保温时间与粒度对稻秆和棉秆热解产物组成及能量转化影响

热解炭化技术的开发对秸秆的能源化利用具有重要意义。试验研究了保温时间与粒度对水稻和棉花秸秆热解产物理化特性及能源转化的影响。结果表明,保温时间从0到120 min中,秸秆生物炭产率先降低后略增加,热解气中CH_4、C_nH_m和H_2百分含量增加,其高位热值和能量转化率增加,而生物炭的pH值、电导率、灰分、固定碳、C、高位热值增加,保温时间为90 min的生物炭的炭化程度最好。秸秆中能量有1.5%~5.4%保留在热解气中,有50%~57%保留在生物炭中。不同粒度相比,粗粉秸秆的生物炭的炭产率、挥发分、H、O、N及碳转化率最高,细粉秸秆热解气中CO和CH_4百分含量、高位热值和能量转化率最高,而超微秸秆生物炭的pH值、灰分、C最高。棉花秸秆生物炭的挥发分、固定碳、C、H、碳转化率、高位热值和能量转化率高于水稻秸秆生物炭。     

秸秆热解工艺优化与生物炭理化特性分析

以肥料化利用为目标,优化秸秆热解工艺,实现秸秆生物炭的高值化利用。该研究以水稻、小麦、玉米、油菜和棉花秸秆为原料,以炭化温度、保温时间和升温速率为因素进行正交试验,采用综合评分法优化热解工艺,并分析最优工艺条件下生物炭的理化特性。结果表明,影响秸秆生物炭品质因素的主次顺序为炭化温度、保温时间、升温速率。以生物炭的肥料化利用为目标,5种秸秆炭化的最优工艺参数组合是炭化温度500℃、保温时间30 min、升温速率10℃/min。在最优工艺条件下,5种秸秆生物炭的炭产率约为32%~38%,固定碳的质量分数大于45%,C元素的质量分数大于53%,N元素的质量分数为0.7%~2.5%,K元素的质量分数为3.41%~6.81%。生物炭表面有含氧官能团且内部有丰富的介孔结构。该研究为秸秆生物炭的肥料化利用提供数据支撑。     

内加热连续式生物质炭化中试设备炭化温度优化试验

为分析内源加热与分段连续热解技术工艺条件下不同物料的热解炭化特性,探明炭化工艺参数对生物炭理化性质、生物炭得率及设备生产率的影响规律,以玉米秸秆、玉米芯和花生壳为原料,进行了设备生产工艺试验。试验结果表明,引风机转速为725 r/min,通过自动调节各进风口开度,使炉内负压维持在60 Pa左右时,不同炭化温度下的生物炭理化性质、设备生产率和生物炭得率均表现出较大差异,其中,固定碳含量和灰分等指标存在显著性差异(P0.05),玉米秸秆对炭化工艺参数最敏感。通过多指标综合评价分析,结合生产实际,玉米秸秆、玉米芯和花生壳的推荐炭化温度分别为550~600、600~650和600~650℃。该研究可为内加热连续式生物质炭化设备的推广应用提供重要的技术支撑。     

小麦秸秆生物炭对高氯代苯的吸附过程与机制研究

以小麦秸秆为原料,分别在三种温度(400℃、500℃、600℃)下制备小麦秸秆生物炭,并标记为WSB400、WSB500、WSB600。分析了秸秆炭的元素组成,表征了其结构和表面特征,研究了秸秆炭对五氯苯和六氯苯的吸附动力学和吸附等温线。结果表明,升温热解使得小麦秸秆有机组分炭化、极性官能团消除,炭化程度增强;三种秸秆炭均可快速高效地吸附高氯代苯,且对六氯苯的吸附要快于五氯苯,假二级动力学方程能更好地拟合秸秆炭对氯苯的吸附动力学过程;不同秸秆炭对氯苯的饱和吸附量大小顺序为WSB400WSB500WSB600;对吸附等温线进行分析可得,随着秸秆炭制备温度的升高,其对氯苯的吸附等温曲线由线性变为非线性,吸附机理则由以分配作用为主过渡到分配作用与表面吸附共同作用。     

热解温度对玉米秸秆炭产率及理化特性的影响

【目的】通过对不同热解温度条件下玉米秸秆炭理化特性的分析,探索玉米秸秆炭具有较高利用价值的炭化温度。【方法】以玉米秸秆为原料,采用低氧升温炭化法,在不同热解温度下 (100℃、200℃、300℃、400℃、500℃、600℃、700℃、800℃) 分别炭化2 h,制备生物炭,收集并测定了固体产物生物炭产率及特性。【结果】生物炭的产率随热解温度的升高逐渐降低。生物炭全碳含量和碳氮比随热解温度升高而升高,全氮含量在400℃以后随热解温度升高而降低。阳离子交换量 (CEC) 在400℃～600℃达到较高水平,为70.87～83.48 cmol/kg。随热解温度升高,玉米秸秆炭表面碱性含氧官能团增加、酸性含氧官能团减少,pH随着热解温度的升高逐渐增加,当温度达到400℃及400℃以上时呈碱性甚至强碱性。红外光谱分析表明,热解温度达到500℃时,纤维素和半纤维素已经完全分解;高温热解使玉米秸秆中–CH₃、–CH₂、–OH、–C=O间发生缔合或消除,促进芳香基团的形成。随着热解温度的升高,玉米秸秆炭的比表面积和比孔容均是先变大后变小,孔径先变小后变大,在400℃～600℃条件下,玉米秸秆炭的孔隙相对较为丰富,不同热解温度下玉米秸秆炭的比表面积和比孔容呈极显著正相关关系(P < 0.01)。【结论】综合各项指标,玉米秸秆的最佳热解温度为400℃～500℃,此温度下制备的生物炭产出率相对较高,氮、碳养分损失少,生物炭的理化性能和养分利用均达到最优。     

秸秆炭定向调控工艺优化试验

秸秆炭化是秸秆综合利用的重要技术路径,秸秆炭品质是市场化推广的主要指标,其生产工艺调控是关键。该研究依托连续式作物秸秆炭化联产系统,设计炭化工艺正交试验,对生产的秸秆炭测算其热工特性参数和燃烧特性参数,以秸秆炭产量、燃料比、碱性指数和无量纲综合燃烧指数等指标为秸秆炭的品质评价指标,利用灰色关联分析法和综合品质评分法对评价指标和影响因素进行分析,通过CCD中心复合试验设计的响应面法优化秸秆炭定向调控生产工艺。研究结果表明:温度是影响秸秆炭品质的首要因素,除秸秆炭产量外的五种秸秆炭品质评价指标重要性排序为,综合燃烧指数、碳氢原子含量比、燃料比、碱性指数、高位热值,生产的秸秆炭品质稳定,接近于烟煤燃烧品质。CCD响应曲面优化后的最佳工艺参数为,铡切后的玉米秸秆经600℃保温炭化50 min后,秸秆炭产量为53.05%,其综合燃烧指数为0.726 6。经验证试验,试验值与预测值相差不足0.2%,拟合模型和响应曲面优化法准确可行,且最优炭化工艺生产的秸秆炭燃烧品质有大幅度提升。通过该研究的炭化工艺可定向调控秸秆炭品质,形成了可复制推广的高品质燃料化秸秆炭精准定向调控方法,为连续式生物质炭化设备的推广应用提供支撑。     

不同热解温度制备的水稻秸秆生物炭理化特性分析

以不同热解温度(100～800℃)制备的水稻秸秆生物炭为研究对象,研究在不同热解温度下制成的生物炭的理化特性。结果表明,热解温度为100～300℃制成的水稻秸秆生物炭呈弱酸性,400℃以上时呈碱性;水稻秸秆生物炭表面碱性含氧官能团数量随着热解温度的升高而增加、酸性含氧官能团则减少;水稻秸秆生物炭中的官能团C=C、C-O-C、-OH和-C=O在较高的热解温度下发生缔合或消除,促进了芳香基团的形成;随着热解温度的升高,水稻秸秆生物炭的阳离子交换量(CEC)、比表面积、孔径、比孔容、氮气吸附量和颗粒表面的分型维数(D1)均先增加后降低,阳离子交换量(CEC)在300～500℃时、其它性状在400～600℃之间达到最大值;以不同热解温度制成的水稻秸秆生物炭颗粒的孔隙结构均以孔隙宽度2～50 nm的中孔为主。随热解温度的升高,水稻秸秆生物炭的产率逐渐降低;400～500℃炭化2 h,生物炭产率最高,其孔隙结构最为复杂,所以可以认为400～500℃是水稻秸秆炭化的最佳温度。     

秸秆热解炭化多联产技术应用模式及效益分析

通过秸秆热解多联产技术,能够将废弃的秸秆转化为燃气和生物炭等,既能提供清洁能源,改善用能结构,又能有效还田和固碳,具有较好的推广应用潜力。分析内加热式移动床生物质炭气联产技术、外加热式移动床生物质热解炭气联产技术、外加热式移动床生物质热解炭气油联产技术的工艺参数,提出了适宜自然村、村镇社区和规模化应用等3种不同规模用户的秸秆热解炭化生产技术应用模式,并以不同规模秸秆利用量为例,得到消耗每吨秸秆的纯利润分别为87、135和141元/t,销售利润率20%左右,温室气体碳排放交易可增加8%左右的纯收益,经济与环境效益良好。     

不同来源生物质废弃物热解炭化农业应用潜力分析:生物质炭产率、性质及促生效应

  【目的】  中国农业生物质废弃物种类多、数量大,且存在病原菌、农药和抗生素残留等潜在生态和环境风险。热解炭化作为一种废弃物的安全处理方法,其生物质炭的循环得率、性质及其土壤改良和促进作物生长的效应还需系统的比较研究。  【方法】  本研究选取作物生产来源的原生生物质、养殖业来源的次生生物质、食品加工处理的残余生物质等共26种生物质废弃物原料,在同一条件下炭化,分析不同来源原料热解后生物质炭产出率与性质。以小白菜 (Brassica campestris L. ssp.) 为试材进行盆栽试验,研究生物质炭对作物生长及土壤改良效应,进而评估这些废弃物炭化农业循环的应用潜力。  【结果】  供试26种废弃物炭化后的生物质炭产出率介于22%～71%,有机碳循环回收率介于22%～81%,氮素循环回收率介于21%～67%。26种废弃物生物质炭的pH和阳离子交换量差异较小 (变异系数10%左右),总有机碳、氮、水分、灰分含量等差异较大,变异系数在60%～70%;而不同原料生物质炭的电导率和溶解性有机碳含量变化极大,变异系数大于90%。生物质炭盆栽试验中,生物炭添加1%,小白菜生物量提升效应介于–34%～314%,变异系数大于100%;小白菜品质提升效应介于–14%～228%,变异系数为59%;土壤肥力提升效应介于20%～360%,特别是土壤有效磷含量提升幅度在0～24倍,均值为359%。同时,生物质炭产出率与生物质炭中灰分呈显著正相关,生物质炭的碳氮回收率与原料中碳氮含量呈显著正相关;不同原料热解炭化的质量回收率、碳氮回收率与小白菜产量及品质等指标间变化差异较大,在小白菜产量效应和品质效应间,部分生物质炭存在抵消作用,而另一部分生物质炭表现为协同作用。  【结论】  综合考虑热解炭化的生物质炭化循环率及碳氮回收循环率和土壤质量–植物生长协同提升效应,供试26种原料中,蚕砂、稻壳牛粪、骨粉、双孢菇渣、兔粪、羊粪和玉米渣的炭化循环率和土壤质量–植物生长协同提升幅度较高 (> 50%),为优先炭化农业利用的生物质废弃物;而木糖渣、稻壳粉、椰渣、高粱酒渣、核桃皮、蚓粪和红茶渣等废弃物热解炭化,因炭化循环率较低,或者土壤质量–植物生长提升的不一致效应,认为不宜炭化农业利用;而其余废弃物热解炭化后的效应介于上述两类之间,具有较高的炭化循环率和一定程度的土壤质量–植物生长协同提升效应,属于可炭化农业利用的生物质废弃物。     

秸秆类生物质气炭联产全生命周期评价

为探究秸秆类生物质热解转化生物炭及热解气过程的能源转化过程的效率、经济性及温室气体排放,该文依据全生命周期评价分析原理,建立秸秆类生物质气炭联产全生命周期3E(economic,energy and environment)模型,对以玉米秸秆为原料的生物质气炭联产过程进行全生命周期分析,评价范围从作物种植到生物气炭产物的利用,系统分为玉米作物种植阶段、秸秆从田间到转化工厂的收储运阶段、生物质气炭转化阶段、生物质气炭应用阶段等4个阶段,并对比分析了横流移动床生物质气炭联产和竖流移动床生物质气炭联产2种工艺技术优劣。结果表明,横流移动床生物质气炭联产的净能量6 542.2 MJ/t,能量产出投入比为4.5,其中,居能源消费的前三位的是种植氮肥、种植农机油耗、热解电耗,分别占总能耗的30.8%、20.4%、17.2%;气炭联产转化的总成本319.4元/t,其中热解气炭转化阶段成本最高,约占总成本34.0%,产品收入567.6元/t,纯利润248.2元/t;能源消耗过程的温室气体CO_2当量排放量18.05 g/MJ,经生物炭还田固碳,CO_2当量减排量约为40 g/MJ。竖流移动床生物质气炭联产技术能源效益较横流略低,但经济效益较高,2种生物质热解气炭联产技术各具优势,可根据产品应用特点选择最适宜的转化工艺方案。2种气炭联产技术具有一定的经济效益,而且均有较大的节能、减少温室气体排放的效益,具有一定的推广应用价值。     

Inductively coupled plasma optical emission spectrometric determination of minerals in thyme honeys and their contribution to geographical discrimination

Twenty-four Spanish thyme honey samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Twenty-four minerals were quantified for each honey. The elements Al, As, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, Pb, S, Se, Si, Sr, and Zn were detected in all samples; seven elements are very abundant (Ca, K, Mg, Na, P, S, and Si), and six are not abundant (Al, Cu, Fe, Li, Mn, and Zn). Eleven of them are trace elements (As, Ba, Cd, Co, Cr, Ni, Mo, Pb, Se, Sr, and V) at <1 mg kg(-)(1). Classification of thyme honeys according to their origin (coast, mountains) was achieved by pattern recognition techniques on the mineral data. By means of principal component analysis, a good separation by geographical origin is obtained when scores for the two first principal components are plotted. Classification functions of 11 metals (Al, As, Cr, Cu, K, Li, Mg, Na, P, S, and V) were obtained using stepwise discriminant analysis and applied to classify correctly approximately 100% of the honey samples.     

The Transfer of Chemical Elements within a Heath-Ecosystem (Calluna vulgaris) in Northwest Germany

The purpose of this investigation was to describe the element budget of a heathland area in Northwest Germany by measuring the fluxes of elements within the ecosystem. The following fluxes were considered: input by precipitation, canopy-drip, mineralisation, ion uptake, litterfall, output with seepage water. The elements H, Na, K, Ca, Mg, Mn, Fe, Al, S, P, CI, NO, NH, N_org were analysed, the period of investigation was one year. The results demonstrate the high importance of deposited nutrients like N (especially No3), Ca and Mg for the element budget and the stability of a heath-ecosystem. The internal turnover of K, Ca, Mg and Mn within the ecosystem mainly took place by leaching. No leaching was found for N, P, AI, Fe, S, CI, Na. For these elements litterfall was the dominant internal way of cycling. The humus layer was a sink for total-N, NO, Ca, Mg, Mn, Fe and S. NO, Ca, Mg, Mn and S were removed from the percolating solution, while for Fe and especially N and Mn an inhibition of mineralisation was found. The element balance for the mineral soil showed that this part is a sink for Hand a source mainly for Al, Ca and Mg, less for K and Na. From the cation/anion balance of the storage changes in mineral soil the ecosystem-internal H ion production was calculated as 0.4 keq per ha and year. It may be traced back to an uptake of NH, and dissociation of fulvic acids in the mineral soil. The results are discussed with respect to the development, stability and management of heath-ecosystems.     

典型土垫旱耕人为土主要常量元素的迁移富集特征、成因及其意义

土壤中元素含量的分布特征反映了多个成土因素综合作用下土壤演变过程的结果。研究在黄土高原区关中平原西部地区采集两个典型的土垫旱耕人为土剖面,研究常量元素K、Na、Ca、Mg、P、Fe、Al、Ti的分布特征及其成因。结果表明,土垫旱耕人为土剖面中,K、Fe、Al、Ti呈中高型分布,Ca、P、Na、Mg呈中低型分布。各元素的迁移能力表现为:Ca最强,P、Na、Mg、K次之,Fe、Al、Ti比较稳定。Ca、P、Na、Mg在剖面上的中低型分布主要是由自然环境下元素自身的淋溶迁移引起;稳定元素Fe、Al、Ti和弱迁移元素K在黏化B层(2Bt1层、2Bt2层)和干润淋溶土表层(2A层)的峰值则主要是由于暖湿气候条件下碳酸盐的强烈淋溶而呈现的相对富集。研究表明,关中地区典型土垫旱耕人为土元素地球化学特征的形成主要受控于气候的变化,人为作用的影响主要体现在有机碳和磷等养分元素在表层的富集上。     

青藏高原土壤主量元素在2800米高程梯度上的分异特征

There are a series of special mountain soils on the Tibetan Plateau of China in an alpine environment for the high altitude. However, very few studies have focused on major soil elements in relation to soil formation in this area. Aluminum (Al), iron (Fe), calcium (Ca), sodium (Na), potassium (K) and magnesium (Mg) contents of 237 topsoil samples covering a 2.8-km altitudinal gradient in uncultivated areas along the Qinghai-Tibet Railway of China were measured using inductively coupled plasma atomic emission spectroscopy. The spatial distribution of the elements and its relationship to the parent rocks and climatic parameters were analyzed. Soils along the gradient are derived from a range of parent materials, but most are less than 30 cm deep with little development (Cambisols). Soil Al, Fe and Mg contents showed a decreasing trend from the start station (Xining Station) to end station (Lhasa Station) of the Qinghai-Tibet Railway, whereas soil K and Na contents were relative stable from Xining Station to the Kunlun Mountains and then increased gradually. Soil Ca content was lower in the southern part of Tanggula Mountains. The major soil element contents clearly reflected the parent rock and climatic influences. Soils with higher Ca content appeared in areas with Ca-Mg carbonate rocks, soils with higher Al were found in areas with silicate-rich and high-Al silicate clastic rocks and silicate-rich aluminosilicate loose sediments. Soils with higher K and Na contents appeared in areas with high-K, high-Na and silicate-rich aluminosilicate rocks. Soil Na and K contents were affected by temperature, whereas the contents of Mg, Fe, Ca and Al were more affected by precipitation. Soil Na and K contents increased with increasing temperatures, whereas the contents of Mg, Fe, Ca and Al decreased with increasing precipitation. This analysis provides a relationship between soil properties and rapidly changing environmental conditions. The data can be used to investigate the effect of the climate or land use change on soil properties.     

棉花秸秆炭微波裂解生产设备研制

为了提高棉花秸秆的循环利用效率,分析不同参数对微波裂解棉花秸秆生产秸秆炭的产炭率的影响,该文研制了一套微波裂解设备。微波裂解设备主要由气液处理系统、裂解腔、惰性气体供应系统、恒温控制等组成,工作时微波裂解腔中的磁控管对棉花秸秆的裂解过程提供能量,使棉花秸秆达到炭化的效果。以棉花秸秆的炭产率为指标,以棉花秸秆含水率、炭化时间、微波功率为影响因素,通过Box-Behnken中心组合试验方法对微波裂解设备在裂解棉花秸秆过程中的试验因素进行三因素三水平二次回归试验。分析各因素对产炭率的影响,同时对影响因素进行综合优化。结果表明,棉花秸秆含水率和微波功率对棉花秆秸产炭率影响显著(P<0.01),最优参数组合为含水率11%、炭化时间6min、微波功率1.8 kW。验证试验结果表明,在最优参数条件下,棉花秸秆产炭率为30.9%,与理论值的相对误差为0.71%。研究结果可为棉花秸秆炭微波裂解生产设备的设计和作业参数优化提供参考。     

Batch‐Determined Elements Release from Wood Ash Mixed with an Acidic Forest Soil Sample

Abstract

A serial batch leaching experiment was carried out to evaluate the release of elements from wood ash mixed with a strongly acidic forest soil sample. Wood ash application resulted in increased leachate pH, dissolved organic carbon (DOC), and electrical conductivity (EC). Increasing application of wood ash increased cumulative release of inorganic carbon (IC), chloride (Cl), nitrate (NO₃), sulfate (SO₄), potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), manganese (Mn), phosphorus (P), and copper (Cu). Release of NO₃, P, iron (Fe), aluminum (Al), Cu, and lead (Pb) continued. Large amounts of DOC, K, Ca, and SO₄ were mobilized. Inorganic C, Fe, and Mg were released in moderate quantities. Manganese, Na, Al, Cl, and NO₃ were released in limited amounts. Amounts of leached P, Pb, and Cu were lower. The mixed order equation adequately described the release of elements in the soil‐ash mixture. Accumulation of elevated amounts of trace elements does not appear to be a problem when higher wood ash rates are avoided. Wood ash should be applied in split application to avoid short‐term concentrated alkaline and salty conditions that could interfere with plant growth.     

Ability of the earthworms Aporrectodea rosea and Aporrectodea trapezoides to increase plant growth and the foliar concentration of elements in wheat (Triticum aestivum cv. spear) in a sandy loam soil

In a greenhouse study, the ability of the earthworms Aporrectodea rosea and A. trapezoides to influence the foliar concentration of elements and the growth of wheat plants was assessed 27 days after sowing in a sandy loam soil. The presence of A. rosea and A. trapezoides (at densities equivalent to 314 and 471 m^-2, respectively) caused a significant increase in the shoot dry weight of wheat. The presence of A. rosea and A. trapezoides (at densities equivalent to 314 and 157 m^-2, respectively) was also associated with a significant increase in the root dry weight of wheat. The presence of A. rosea caused a significant increase in the foliar concentration of Ca, Cu, K, Mn, N, Na, and P, but did not influence the foliar concentration of Al, B, Fe, Mo, Mg, S, and Zn. The presence of A. trapezoides was associated with a significant increase in the foliar concentration of Al, Ca, Fe, K, Mn, N, and Na, but did not influence the foliar concentration of B, Cu, Mo, Mg, P, S, and Zn. These results demonstrate the potential of A. rosea and A. trapezoides to increase the growth of wheat in a sandy loam soil and suggest that the mechanism by which they increased plant growth was, in part, through increasing the availability and uptake of nutrients from this soil.     

Impact of man's activities on the chemical composition of the sediments of lakes superior and Huron

The concentrations of organic matter, major elements and trace elements were determined at 15 core locations in Lake Superior and Huron. The chemical compositions of the cores are related to sediment particle size, Eh, pH, chronology and location. Concentrations of Si, Al, Ca, Mg, K, Na, and Ti, which represent the major mineral species in the sediments, are generally uniform in each core. Surface enrichments of Hg, Pb, Zn, Cu, Ni, Co, Cd, Cr, Be, V, As, Org-C, and N at many of the locations are attributed to anthropogenic inputs of these elements in recent years. Concentration profiles of Fe, Mn, P, and S are influenced by migration of these elements in the pore waters. High anthropogenic Cu loadings in Lake Superior were related to Cu mining activities in the lake basin, while high anthropogenic inputs of Ni to the Lake Huron sediments were related to Ni contamination from the Sudbury area. Sediment loading calculations show that the anthropogenic inputs of trace and nutrient elements are related to the sedimentation rate, that the inputs are dispersed over wide areas of the lakes and that inputs to Lake Superior have increased significantly since 1955. Evidence is presented that atmospheric inputs are an important source of contaminants.     

淹水条件下土壤中元素迁移的地球化学特征

本文研究了淹水条件下水稻土的两种主要母土的元素活化迁移规律及其地球化学特征。结果表明，淹水条件下淋溶迁移元素来源于不同的母体；铁，锰，钙，镁等元素的活化作用加强，迁移能力增加，元素的迁移序列中锰的迁移能力已接近钙，镁等活泼元素；两种土壤中元素的迁移序列不同。性质相似的元素在迁移过程中具有相似的行为，相互之间有很好的相关性，因而在统计区分中位置靠近。引起元素在土壤中活化迁移的过程包括还原，重碳酸化，