废轮胎中试回转窑热解炭特性分析

采用中试回转窑热解装置对废轮胎进行了热解研究，在450—650℃热解试验温度范围内，热解炭产率约为39%—44%。热解炭的工业及元素分析显示，热解炭中灰分含量高达10％以上；含量最多的金属元素是Zn和Fe；热解炭S含量2．2%—2．6％左右，轮胎原料中S元素约75%留在热解炭中，因此热解过程中排放出的气体硫化物很少。此外，探讨了热解炭孔容积分布和温度对比表面积的影响，在450—550℃，热解炭比表面积随热解温度升高而增大；温度继续升高，比表面积变化不大，在孔半径约为25nm处，热解炭比孔容积有最大值。     

花生壳和松木屑固定床低温热解特性的实验研究

分别以花生壳和松木屑为原料在固定床上进行低温热解实验,探究热解温度对热解产物产率的影响。利用气相色谱-质谱联用仪(GC-MS)对热解所得生物油组分进行定性分析,并对生物油中的愈创木酚进行定量分析。结果表明:花生壳和松木屑热解过程中半焦的产率都随热解温度的升高而降低;生物油的产率都随热解温度的升高先升高后降低,且都在500℃达到最大值,最大产率分别为13.14%和20.41%;热解气体的产率都随热解温度的升高而升高。两种生物质热解生物油中各类组分的含量随热解温度的升高发生不同的变化,其中愈创木酚的含量都随热解温度的升高先升高后降低,并在400℃达到最大值。     

烘焙预处理对杉木成型燃料理化性质及热解特性的影响

以杉木成型燃料为原料,研究在不同烘焙温度(200℃、230℃、260℃和290℃)对其烘焙产物及热解特性的影响。结果表明:随着烘焙温度的升高,杉木成型燃料的质量产率和能量产率逐渐降低,跌落强度和耐久性逐渐减小,一些含氧官能团的吸收峰逐渐变弱,氧元素含量大幅降低而高位热值逐渐升高,疏水性明显增强。热解实验结果显示,在260℃和290℃烘焙样品中半纤维素对应的热解肩峰逐渐消失;随着烘焙温度的升高,生物质炭产率明显升高,而生物油产率逐渐下降。同时,烘焙预处理大幅降低了生物油中酸类组分的相对含量,显著提高了酚类组分的相对含量。因此,烘焙预处理对杉木成型燃料理化性质及热解特性产生了显著影响,需根据具体应用环境选取合适的烘焙条件。     

生物质热解炭化及其成型提质研究

在不同温度下对木屑进行热解实验,分析热解炭的特性,对热解炭进行压缩成型并分析成型炭的品质特性及燃烧特性。结果表明:随着热解温度的升高,生物炭的热值由最初的22.46增至29.40 MJ/kg,同时生物炭中无机元素含有率降低,含氧官能团逐渐减少,生物炭的疏水性能得到改善。而成型炭块的体积密度、抗压强度均随热解温度的升高先有所降低后又明显升高,成型炭的能量密度也有明显提升。550～650℃下热解木屑,制备得到的生物炭热值较高,碱金属元素含量较低,压缩后成型炭具有较好的燃烧性能,是一种较为理想的成型燃料。     

竹屑热解过程及产物特征研究

以竹屑为原料,选择250~950℃温度范围,在小型固定床反应器上探究竹材热解过程及产物特征。研究发现:随着热解温度的升高,固体焦炭产率减小,气体产率规律与之相反,液体产率先增后减,且在450℃时达到最大(52.28%)。固体焦炭中化学官能团的种类随温度的升高逐渐减少,含量随之减小,650℃之后除苯环结构外,基本无其他官能团,说明竹屑热解主要发生在650℃之前。在较低温度下,热解油中以呋喃类、醛酮类、酚类等含氧化合物为主,气体产物中主要以CO、CO_2为主,当温度超过750℃后,热解油以萘、苊等多环芳烃为主要含量,由于挥发分的二次裂解加剧,使CO和H_2体积分数增大,CH_4比例随温度变化缓慢。     

废弃皮革与秸秆共热解产物及特性的影响

文中通过采用对废弃皮革和秸秆组分分析、热重分析和自制固定床热解反应探究废弃皮革对秸秆热解过程的影响。实验研究表明:水稻秸秆和废弃皮革的热分解过程比较相似,都具有3个基本过程,且主要都发生在200～550℃温度之间;与废弃皮革相比而言,水稻秸秆在热解过程中产生的挥发组分较高,且生物炭产率较低。当热解温度为500℃时,两者的液体生物油产率同时达到最大,分别为38.39%和47.37%。废弃皮革和水稻秸秆在热解过程中存在着重要的交互作用。当皮革和秸秆混合比例为1:1时,两者之间的相互影响作用较为明显,可以显著提高生物油的产率并抑制生物炭的产生;共热解的生物油产率达50%。这说明合适比例的皮革掺混对于秸秆热解过程具有一定的促进作用,且皮革对废弃秸秆的资源化和能源化利用具有积极影响。     

生物油热解及燃烧特性分析

对由木粉热解所得的生物油样品分别进行了氮气与氧气气氛下不同升温速率的热重分析试验.结果表明:生物油的热解分为两个阶段,第一阶段为生物油中低沸点有机物的挥发以及各组分间反应生成各类产物的过程,第二阶段为各种重组分的裂解过程;生物油的燃烧分为3个阶段,即前期的挥发与裂解和最后焦炭的燃烧过程.提高升温速率使氮气气氛中生物油样品的初始失重温度、失重峰值温度及对应的最大失重速率均有所增大,且在较高升温速率(20℃min)下,较少含炭残余物形成.随升温速率升高,生物油着火温度提高,最终失重率无变化.最后根据热重数据对热解与燃烧各段反应进行了动力学拟合.     

玉米秸秆成型颗粒热解炭抗压强度和收缩特性实验

文章在300～800℃的热解温度下制备了玉米秸秆成型颗粒热解炭,并分析了这些热解炭的抗压强度和收缩特性。分析结果表明:当热解温度为300～700℃时,热解炭的径向和轴向收缩率均随着热解温度的升高而增大;同一热解温度下,径向收缩率均大于轴向收缩率,径向收缩率从12.3%增大到24.2%,轴向收缩率从9.1%增大到18.4%;当热解温度升高到800℃时,热解炭的径向和轴向收缩率均略有回降;当热解温度为300～600℃时,热解炭的抗压强度约为1 MPa,当热解温度为600～800℃时,热解炭的抗压强度约为2 MPa;热解炭的径向抗压强度略大于轴向抗压强度。     

不同类型秸秆生物炭的燃烧特性与动力学分析

研究不同热解温度、粒度、种类的秸秆生物炭的燃烧特性,并进行动力学分析。结果表明,随着热解温度升高,秸秆生物炭的固定碳、C和高位热值均增加,综合燃烧指数减小,燃烧向高温区移动,活化能增大。随着升温速率增高,生物炭综合燃烧指数增大,活化能降低。生物炭着火温度为260～395℃,燃尽温度为480～555℃,500℃制备的生物炭燃烧特性最好,活化能为48～65 kJ/mol。超微生物炭的着火温度、燃尽温度和活化能最低,综合燃烧指数最高,棉花秸秆生物炭更适合作固体燃料。     

烘焙预处理对秸秆热解产物品质及能量分布的影响

以玉米秸秆为原料,研究烘焙温度(220、250和280℃)对秸秆热解产物产率、品质和能量分布的影响。结果表明:秸秆经220、250和280℃烘焙后,热解生物油水分相比原样分别降低11.4%、28.3%和41.8%;与此同时,生物油中酸类产物逐渐减少,酚类产物逐渐增多,生物油热值明显增大。烘焙对热解气中CH_4和H_2有一定促进作用,可燃气的热值逐渐增大。烘焙对生物质炭的化学组分无明显影响,但随着生物质炭产率的增大,其能量产率逐渐增大。烘焙脱氧预处理可改善生物油的品质、提高可燃气的热值、增大生物质炭的能量产率。     

麦秆酶解残渣热解特性及动力学分析

对比分析了麦秆及其酶解残渣的基础物化特性,利用热重−红外联用技术研究了酶解残渣的热解反应过程及其主要气体产物的析出特性,并用混合反应模型计算了酶解残渣热解过程的表观动力学参数。结果表明,麦秆酶解残渣是一种富含木质素的高灰分、低热值的生物质原料,与麦秆原料相比,其热解过程相对平缓,主要失重温度区间为200℃ ~ 800℃,最大失重峰为350℃,与木质素的热解特性相近;提高升温速率可以使酶解残渣热解反应剩余产物质量明显减少,最大失重速率提高;热解主要气体产物中CH4析出的温度区间为400℃ ~ 700℃,CO和CO2在380℃、450℃和650℃都存在析出峰。动力学分析结果表明,酶解残渣热解过程在低温区（200℃ ~ 350℃）和高温区（350℃ ~ 800℃）分别遵循一级和二级反应动力学规律。     

Study of bio-oil and bio-char production from algae by slow pyrolysis

This study examined bio-oil and bio-char fuel produced from Spirulina Sp. by slow pyrolysis. A thermogravimetric analyser (TGA) was used to investigate the pyrolytic characteristics and essential components of algae. It was found that the temperature for the maximum degradation, 322 °C, is lower than that of other biomass. With our fixed-bed reactor, 125 g of dried Spirulina Sp. algae was fed under a nitrogen atmosphere until the temperature reached a set temperature between 450 and 600 °C. It was found that the suitable temperature to obtain bio-char and bio-oil were at approximately 500 and 550 °C respectively. The bio-oil components were identified by a gas chromatography/mass spectrometry (GC–MS). The saturated functional carbon of the bio-oil was in a range of heavy naphtha, kerosene and diesel oil. The energy consumption ratio (ECR) of bio-oil and bio-char was calculated, and the net energy output was positive. The ECR had an average value of 0.49.     

Valorisation of lignocellulosic biomass investigating different pyrolysis temperatures

Presently, sugarcane bagasse (SB) and oat hulls (OH) have a distinctive potential as a renewable source of biomass, due to its global availability, which is advantageous for producing liquid and gaseous fuels by thermochemical processes. Thermo-Catalytic Reforming (TCR) is a pyrolysis based technology for generating energy vectors (char, bio-oil and syngas) from biomass wastes. This work aims to study the conversion of SB and OH into fuels, using TCR in a 2 kg/h continuous pilot-scale reactor at different pyrolysis temperatures. The pyrolysis temperatures were studied at 400, 450 and 500 °C, while the subsequent reforming temperature remained constant at 500 °C. The bio-oil contained the highest calorific value of 33.4 and 33.5 MJ/kg for SB and OH, respectively at 500 °C pyrolysis temperature, which represented a notable increase compared to the raw material calorific value of SB and OH (16.4 and 16.0 MJ/kg, respectively), this was the result of deoxygenation reactions occurring. Furthermore, the increment of the pyrolysis temperature improved the water content, total acid number (TAN), viscosity and density of the bio-oil. The syngas and the biochar properties did not change significantly with the increase of the pyrolysis temperature. In order to use TCR bio-oil as an engine fuel, it is necessary to carry out some upgrading treatments; or blend it with fossil fuels if it is to be used as a transportation fuel. Overall, TCR is a promising future route for the valorisation of lignocellulosic residues to produce energy vectors.     

Bio-fuels from Agricutural Residues

Abstract

Bio-fuels, such as bio-oil, bio-char, and bio-gas, can be obtained from agricultural residues. Agricultural residues are potential renewable energy resources such as biogas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis processes. Pyrolysis process of agricultural residues are the most common and convenient methods for conversion into bio-oil and bio-char. When the pyrolysis temperature increased, the bio-char yield decreased. The bio-char yield increased with increasing particle size of the sample. The yield of bio-oil from pyrolysis of the samples increased with temperature. Anaerobic biogas production is an effective process for conversion of a broad variety of agricultural biomass to methane to substitute natural gas and medium calorific value gases.     

Pyrolysis of Alternanthera philoxeroides (alligator weed): Effect of pyrolysis parameter on product yield and characterization of liquid product and bio char

In the present work, fast pyrolysis of Alternanthera philoxeroides was evaluated with a focus to study the chemical and physical characteristics of bio-oil produced and to determine its practicability as a transportation fuel. Pyrolysis of A.philoxeroides was conducted inside a semi batch quartz glass reactor to determine the effect of different operating conditions on the pyrolysis product yield. The thermal pyrolysis of A. philoxeroides were performed at a temperature range from 350 to 550 °C at a constant heating rate of 25 °C/min & under nitrogen atmosphere at a flow rate of 0.1 L/min, which yielded a total 40.10 wt.% of bio-oil at 450 °C. Later, some more sets of experiments were also performed to see the effect on pyrolysis product yield with change in operating conditions like varying heating rates (50 °C/min, 75 °C/min & 100 °C/min) and different flow rates of nitrogen (0.2, 0.3, 0.4 & 0.5 L/min). The yield of bio-oil during different heating rate (25, 50, 75 and 100 °C/min) was found to be more (43.15 wt.%) at a constant heating rate of 50 °C/min with 0.2 L/min N₂ gas flow rate and at a fixed pyrolysis temperature of 450 °C. The High Heating Value (HHV) value of bio-oil (8.88 MJ/kg) was very less due to presence of oxygen in the biomass. However, the high heating value of bio-char (20.41 MJ/kg) was more, and has the potential to be used as a solid fuel. The thermal degradation of A. philoxeroides was studied in TGA under inert atmosphere. The characterization of bio-oil was done by elemental analyser (CHNS/O analyser), FT-IR, & GC/MS. The char was characterized by elemental analyser (CHNS/O analysis), SEM, BET and FT-IR techniques. The chemical characterization showed that the bio-oil could be used as a transportation fuel if upgraded or blended with other fuels. The bio-oil can also be used as feedstock for different chemicals. The bio-char obtained from A. philoxeroides can be used for adsorption purposes because of its high surface area.     

Potential evolution of Turkish agricultural residues as bio-gas,bio-char and bio-oil sources

A study has been conducted to evaluate the potential power production from the pyrolysis for bio-oil and bio-char, and anaerobic digestion (for bio-gas), of agricultural residues in Turkey. Agricultural residues are potential renewable energy resources such as bio-gas from anaerobic digestion, bio-oil from pyrolysis, and bio-char from carbonization and slow pyrolysis processes. Anaerobic bio-gas production is an effective process for conversion of a broad variety of agricultural biomass to methane to substitute natural gas and medium calorific value gases. When the pyrolysis temperature increased the bio-char yield decreased. The bio-char yield increased with increasing particle size of the sample. Thermochemical conversion processes of biomass are the most common and convenient methods for conversion into energy. Among the processes of energy production from biomass, pyrolysis is the most popular thermal conversion process.     

炭化活化温度对活性炭-CaCl2复合吸附剂性能的影响

为研究并开发高性能的吸附剂,本文以CaCl₂和杉木木屑为原料,采用炭化活化造孔的方法制备复合吸附剂,考察了炭化活化温度对复合吸附剂性能的影响,炭化活化温度分别选择400℃、500℃、600℃和700℃。扫描电镜照片和元素分布图表明,复合吸附剂具有发达的孔隙结构而且CaCl₂分布均匀。NH₃吸附性能实验表明,吸附剂4 h的NH₃吸附量随炭化活化温度的升高而增加。而对于吸附制冷而言,500℃炭化活化温度下制备的复合吸附剂具有最好的性能,其30 min的吸附量达到0.488 g/g。     

燃气热泵系统在过渡季节制备生活热水的性能研究

研究了燃气热泵（GHP）系统在过渡季节制备生活热水的性能特性,分析了发动机余热回收对GHP系统性能的影响。在不同环境温度（15 ~ 24℃）和进水温度（37.7 ~ 47.8℃）下,考察回收与不回收发动机余热模式对生活热水制热量（${{\dot{Q}}_{\text{h}}}$）、耗气功率（P_gas）及一次能源利用率（${{r}_{\text{PER}}}$）的影响规律。结果表明,随着环境温度的升高,P_gas减小,而${{\dot{Q}}_{\text{h}}}$和${{r}_{\text{PER}}}$呈现递增的趋势;随着进水温度的升高,P_gas增大,而${{\dot{Q}}_{\text{h}}}$和${{r}_{\text{PER}}}$呈现递减的趋势。其中环境温度20 ~ 24℃与进水温度37.7 ~ 47.8℃为${{\dot{Q}}_{\text{h}}}$的不敏感区间,在环境温度为24℃和进水温度为37.7℃条件下,${{r}_{\text{PER}}}$高达2.004。GHP系统的余热回收量分别占总制热量和发动机总余热的25.00% ~ 30.16%和62.17% ~ 71.56%,系统的余热利用率高。     

Development of a bifunctional Ni/HZSM-5 catalyst for converting prairie cordgrass to hydrocarbon biofuel

Ni/HZSM-5 catalysts were prepared using the impregnation method. The HZSM-5 and impregnated Ni/HZSM-5 catalysts were characterized by Brunauer–Emmett–Teller and X-ray diffraction. The HZSM-5 and Ni/HZSM-5 catalysts were used for prairie cordgrass (PCG) thermal conversion in a two-stage catalytic pyrolysis system. The products contained gas, bio-oil, and bio-char. The gas and bio-oil were analyzed by gas chromatography and gas chromatography–mass spectrometry separately. Higher heating values and elemental composition of bio-char were determined. The results indicated that 12% Ni/HZSM-5 treatment yielded the highest amount of gasoline fraction for hydrocarbons and showed a robust ability to upgrade bio-oil vapor.     

核桃壳热裂解产物有机结构演变规律

采用TG-FTIR、Py-GC/MS对核桃壳热裂解过程及产物进行研究,利用1H-NMR和13C-NMR对热解炭结构进行分析,探讨热裂解产物有机结构演变规律。结果表明:核桃壳热裂解分为干燥脱水,快速热裂解和残余物缓慢热裂解三个阶段,快速热裂解阶段是主反应阶段,失重可达总失重的89%。不同热解温度下的液态产物成分不同,且随着热裂解温度的升高,低温下形成的热解液会发生二次反应生成新的热解液成分,热解温度由400℃升至600℃,液态产物完成了由酚类、醇类、酸类向酯类、芳香类的转化。升温核桃壳热裂解过程中的气态产物为H_2O,CO_2,CH_4和CO,在357℃时达到最大产量。随着热解温度由300℃升高到800℃,核桃壳热解炭由以苯环、烷烃链、甲氧基、羟基、羰基为主要结构转化为90%以上的芳香结构。