盐酸洗涤与烘焙预处理对甜高粱秸秆热解生物油组分的影响

针对生物质热解生物油氧含量高、腐蚀性强、化合物种类繁多等问题,该研究提出以盐酸洗涤和烘焙预处理相结合的方式来提高生物油品质。甜高粱秸秆预处理前后的物化特性表明单纯酸洗有利于挥发分的生成,单独烘焙预处理降低了H/C以及O/C,使能量产率达95.13%,并促进了炭的生成;酸洗-烘焙联合预处理对生物炭和不可冷凝气体都有一定的促进作用。采用管式炉热解装置制备生物油,利用气相色谱质谱联用仪(GC-MS)分析甜高粱秸秆样品热解生物油成分,结果表明:酸洗、烘焙和联合预处理使甜高粱秸秆热解生物油中化合物的种类分别在111种基础上减少了62、58和68种,酮类、酸类和呋喃类的含量均降低;酸洗对酮类中丙酮的降低作用明显,而烘焙预处理促进了酚类的生成,酸洗-烘焙显著减少乙酸的产量并促进糖类化合物的生成,尤其对珍贵稀有的D-阿洛糖促进作用显著;同时,酸洗、酸洗-烘焙预处理还分别促进了新物质壬酸和戊酸的生成;单纯烘焙有利于提高生物质中富含-OH官能团的纤维素相对含量,从而使生物油中酚类含量明显升高,生物油中虽没有形成新物质,但对pH值改善较为明显。该研究可为生物质热解生物油品质的提高及高值化产物的定向热解提供参考。     

有机酸处理条件对玉米秸秆热解特性的影响

酸洗预处理能有效改善K^+对生物质热解的影响,该文利用热重分析仪和裂解-气相色谱质谱联用仪进行了玉米秸秆的热解试验,研究了不同有机酸酸洗浓度(3%、5%和7%)、酸洗温度(25、50和75℃)和酸洗时间(1、2和3 h)对玉米秸秆热解特性的影响。结果表明:酸洗能显著降低玉米秸秆内在K^+的含量;经过不同条件的有机酸洗预处理后,玉米秸秆的TG/DTG(thermogravimetry/differential thermogravimetry)曲线均向高温段移动,最大热解速率随着酸洗浓度和酸洗温度的增加逐渐增大,随着酸洗时间的增加先增大后降低,在酸洗温度为75℃时,最大热解速率达到最大值15.49%/min;与此同时,玉米秸秆热解主要产物为酚类、酮类和呋喃类化合物,酸洗后,其酚类物质产率明显增加,在酸洗浓度为7%时达到最大值16.75%,而酮类和呋喃类化合物产率减少,分别在酸洗时间为1 h和酸洗浓度为7%时达到最小值0.10%和7.13%。酸洗后,焦炭产率减少,在酸洗浓度为3%时达到最小值18.79%。通过研究不同处理条件下有机酸对玉米秸秆热解特性的影响,为生物质预处理中酸溶液的选择提供了参考。     

酸洗脱矿对浮萍热解产物特性的影响

对高含灰浮萍进行酸洗脱矿处理,然后使用固定床反应装置在400~900℃下进行热解试验,研究酸洗脱矿处理对固、液、气三相产物产率及组成的影响。结果表明,酸洗处理可以有效的脱除生物质中绝大部分碱和碱土金属以及大部分的磷,并大幅提高浮萍C含量和热值,显著提升了样品的燃料特性。热解试验结果表明酸洗后浮萍固体和气体产率分别降低了1.43%~8.02%和2.81%~19.89%,液体产率提高了1.63%~16.72%,且液体产率和固体产率变化趋势在700~900℃更为显著。酸洗减少了主要气体CO、CO₂、CH₄、H₂的产率,但对CO2减幅更为显著,因此气体中可燃组分比例增加且气体热值相比原样增加5%~155%;酸洗显著提升了热解炭中固定碳和C含量且灰分和O含量显著降低,焦炭品质得到了极大地改善;此外,酸洗使得热解油中酚类、呋喃类和羰基化合物含量有所降低,但在400~600℃时使醇醚含量显著增加。     

烘焙对生物质热解产物特性的影响

烘焙可有效地降低生物质中的水分和氧,对其热解过程有显著的影响。该文主要研究了烘焙温度（200,230,260,290℃）对生物质热解过程及产物特性的影响行为及影响机制;研究发现烘焙能改善热解产物的品质,随着烘焙温度的升高,热解合成气中CO含量由48%逐渐减少到34%,CH4和H2增加,其中H2含量最大增加了77.4%,而液体产物中,乙酸和水分含量逐渐减小,水分含量最大减少了42.8%,而酚类产物的含量明显增加,有利于生物油品质的提高。该研究为烘焙技术的发展和生物质高效热化学转化提供科学参考。     

改性生物质炭对棉秆热解挥发分析出特性的影响

生物质焦炭由于其复杂的结构特点和无机矿物质的存在,使得其对快速热解过程中挥发分的析出有着重要的影响。此外生物质本身所含的大量金属盐也促进了焦炭与挥发分的反应。该文通过酸洗和负载Na、K、Mg、Fe金属氯盐等探讨棉杆热解焦炭对生物质热解特性的影响。试验温度为500℃,研究发现棉秆热解炭对酸类、脂类和醛类有明显抑制作用;对酚类、呋喃类以及糖类有促进作用;酸洗以及负载不同金属盐后生物炭的存在使得生物油的产量降低,而气体产率增加;金属离子对酚类富集作用顺序为:KNaFeMg,Fe Cl3的添加有利于氢气的增加,氢气体积分数达12.96%,而KCl和Mg Cl2对CO的生成促进作用明显,产量分别为49.22%和49.38%;金属离子对挥发分裂解影响要强于单纯增加下层催化段焦炭质量。     

温度对竹材烘焙过程中气固液三相产物组成及特性的影响

烘焙预处理可有效降低生物质原料的含水率和O/C比、提高能量密度、可磨性和疏水性,进而减少热解油中水分和含氧化合物的含量,改善生物油的稳定性和品质。该文采用程序控温管式炉、热重-红外联用仪(TGA-FTIR)和快速热解-气质联用仪(PY-GC/MS)等开展生物质烘焙试验研究,研究烘焙温度(210、240、270和300℃)对毛竹烘焙过程中气、固、液三相产物的特性影响。试验结果表明:(1)烘焙固体产物:随烘焙温度升高,固体产物中固定碳和C元素含量显著增加,使得原料的热值从18.85 MJ/kg增加至23.12 MJ/kg,能量密度增加;O元素含量显著减少,使得O/C比值从0.74降低至0.42。(2)烘焙气体产物:烘焙气体成分主要为H_2O、CO_2、CO和CH_4组成,其中CO_2含量最高,其次为H_2O、CH_4和CO,所有气体产物含量随烘焙温度的升高而逐渐增加。(3)烘焙液体产物:烘焙液体产物主要由酸类、酮类、呋喃类、酚类以及醛类等有机物构成,其中酸类、酚类和呋喃类相对含量较高,最高可达20.34%、22.05%和31.42%,酮类、醛类含量相对较少,分别占10.43%与8.26%,随烘焙温度升高,酸类含量先增加后减少,呋喃类、酚类、酮类含量逐渐增加,醛类含量变化规律不显著。(4)基于对烘焙气、固、液体产物分析可知,竹材中的氧元素主要以H_2O、CO_2、CO和有机酸等形式脱除,烘焙预处理能有效提高竹材能量密度,去除水分与含氧化合物,提高烘焙固体产物的利用价值。研究结果可为竹材能源化利用提供参考。     

烘焙与HZSM-5催化剂联用改善柏木热解产物品质

为研究烘焙与催化剂对生物质热解产物特性的耦合影响机制,该文选用HZSM-5催化剂,对不同温度（200、230、260、290℃）烘焙后的柏木进行热解试验。结果发现,将烘焙与HZSM-5催化剂联用后,随着烘焙温度的升高,催化热解后积碳量呈下降趋势,最高降低了62.6%;气体产物中CO的体积分数从53.69%降低至40.84%,H2和CO2的体积分数分别增大了43.1%和35.04%,CH4的体积分数整体变化不明显;液体产物中,酸类物质大幅减少,芳香烃类产物显著增多,酚类产物发生富集;结果表明,烘焙与HZSM-5催化剂的联用有效地改善了快速热解产物尤其是生物油的品质。但是也要指出,烘焙温度过高时,积碳量增多、芳香烃类产物减少,因此柏木适宜的烘焙温度应该选择在230～260℃之间。     

纤维素木聚糖和木质素含量对生物质热解特性及产物的影响

采用热重法研究了纤维素、木聚糖和木质素含量对生物质热解特性的影响,分析了三组分相互混合热解时的交互作用规律,及其对热解动力学参数的影响;同时,在生物质真空热解液化系统上考察了三组分含量对热解液化产物分布及生物油组成的影响。结果表明,纤维素热解较为剧烈,生物油中芳香族、糖类、醛类和醇类含量较高;木聚糖的热稳定性较差,生物油中芳香族、酮类和酸类物质较多;木质素热解较为平缓且固体残留物较多,生物油成分主要为芳香族化合物。纤维素对活化能和指前因子的影响较大,木聚糖和木质素对反应级数的影响较大;纤维素的热解有利于减少固体残留物,而木质素的热解产物有利于促进糖类的分解;木聚糖对纤维素的热解具有明显的抑制作用;木聚糖能促进木质素的低温热解,两者混合热解对生物油组成影响较小。因此,高纤维素含量的生物质可以获得更高的生物油产率,且适量的木质素有利于促进纤维素的分解,为进一步提高生物油产率和品质提供了理论依据。     

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。     

生物质水蒸气氛围烘焙对后续热解影响

为了探究余热烟气中水蒸气对生物质烘焙及后续热解影响,该研究以榆木为研究对象,在立式炉中进行不同氛围（氮气及氮气-水蒸气）和不同温度（200、230、260、290 ℃）的烘焙试验,然后利用热重-质谱联用仪（TG-MS）和热裂解-色谱质谱联用仪（Py-GC/MS）进行惰性氛围的热解试验。结果表明：榆木在烘焙过程中发生了脱水、脱羰基、脱甲基反应,水蒸气的存在对后续热解油中乙酸的去除更有利。在所有样品中氮气氛围下290 ℃烘焙样品的失重速率峰值最低,仅为0.3%/℃。同时水蒸气的存在使氮气-水蒸气烘焙样品的最大失重峰后移。在热解主反应区,200、290 ℃烘焙温度下,水蒸气会提高热解反应活化能,而230、260 ℃烘焙温度下热解反应活化能却降低。此外,同一烘焙温度下水蒸气会抑制热解过程中H2、CH4、H2O、CO和CO2的生成。研究结果可为复杂气氛对生物质烘焙以及后续热解影响的研究提供参考。     

超富集植物热解中氯对重金属迁移特性的影响

为了研究超富集植物热解中氯对重金属迁移特性的影响,该文考察了在管式反应炉上N2气氛中,不同温度下无机氯（NaCl）和有机氯（PVC）的加入对重金属迁移特性的影响。结果表明,无论NaCl,还是PVC,都将增加重金属的挥发。对于Cd、Pb,有机氯的影响大于无机氯,而对于Zn、Mn和Cu,NaCl添加剂对其挥发特性比PVC添加剂的影响大。除Cd外,在400～700°С温度范围内,相同含量氯下重金属的挥发随温度的升高变化不大,只有700°С以上挥发率的差别比较明显。在温度为900°С时,不论是否加入氯,Cd、Pb和Zn的挥发率都达到100%。在试验范围内,Mn和Cu的最大挥发率为66.15%和66.99%,底渣中Mn和Cu含量较多。     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

滨岸排污口对潮滩沉积物中重金属的影响研究

通过对排污口附近及对照点的潮滩沉积物中重金属Zn ,Cu ,Cr和Pb的含量分析发现:各采样点沉积物中的重金属含量均高于环境背景值,平均含量约为环境背景值的2～3倍,排污口附近潮滩沉积物中重金属的含量明显高于对照点潮滩沉积物中的含量;各采样点的柱状沉积物中重金属的含量随深度的变化呈现出一定的变化规律;在垃圾填埋场附近高中低潮滩由于距离排污口的远近不同,表层沉积物中重金属的含量依次降低;对各采样点沉积物中重金属含量的相关性分析发现各点沉积物中累积的重金属的来源有所不同:在排污口附近潮滩的沉积物中重金属主要来源于排污口排放的污水,而对照点朝阳农场潮滩沉积物中重金属主要来源于自然的本底输入或海水外源输入     

Use of Reference Soils in Determinations of 0.01 M Calcium Chloride Available Metals

There are few readily available standard reference soils for which 0.01 M calcium chloride (CaCl₂) soil extraction available metals data are available. This study assessed the ease with which new available metals data could be generated for reference soils. Data on 0.01 M CaCl₂ available elements for four reference soils from the Wageningen Evaluating Programs for Analytical Laboratories and three reference soils from the Australasian Soil and Plant Analysis Council proficiency testing program are presented. It is difficult to generate new 0.01 M CaCl₂ available metal values for standard reference soils, because trace element concentrations are low and measurements have relatively high variability. We suggest that laboratories can use reference soils as quality control samples in the analysis of 0.01 M CaCl₂ available metals by reporting recoveries for major elements (e.g., potassium [K], magnesium [Mg], and sodium [Na], for which reference values are of high reliability) to provide assurance of acceptable extraction efficiency.     

Accumulation of cadmium and other metals in organs of plants growing around metal smelters in Japan

Abstract

It is well known that some plants can adapt to a high concentration of metals that would be lethal to other plant species and also accumulate toxic metals in their body up to a very high level (Peterson 1983). Athyrium yokoscense communities are often observed on highly polluted soils with heavy metals originating from mining or smelting facilities. A. yokoscense and some species of plants which can grow vigorously on highly polluted soils have attracted the attention of miners and investigators as indicator plants for mining areas (Honjo 1990; Nishizono et al. 1987).     

Relationship Between Extractable Metals in Acid Soils and Metals Taken Up by Tea Plants

Abstract

The accumulation of heavy metals in plants is related to concentrations andchemical fractions of the metals in soils. Understanding chemical fractions and availabilities of the metals in soils is necessary for management of the soils. In this study, the concentrations of copper (Cu), cadmium (Cd), lead (Pb), and zinc (Zn) in tea leaves were compared with the total and extractable contents of these heavy metals in 32 surface soil samples collected from different tea plantations in Zhejiang province, China. The five chemical fractions (exchangeable, carbonate‐bound, organic matter‐bound, oxides‐bound, and residual forms) of the metals in the soils were characterized. Five different extraction methods were also used to extract soil labile metals. Total heavy metal contents of the soils ranged from 17.0 to 84.0 mgCukg^?1, 0.03 to 1.09 mg Cd kg^?1, 3.43 to 31.2 mg Pb kg^?1, and 31.0 to 132.0 mg Zn kg^?1. The concentrations of exchangeable and carbonate‐bound fractions of the metals depended mainly on the pH, and those of organic matter‐bound, oxides‐bound, and residual forms of the metals were clearly controlled by their total concentrations in the soils. Extractable fractions may be preferable to total metal content as a predictor of bioconcentrations of the metals in both old and mature tea leaves. The metals in the tea leaves appeared to be mostly from the exchangeable fractions. The amount of available metals extracted by 0.01 mol L^?1 CaCl₂, NH₄OAc, and DTPA‐TEA is appropriate extractants for the prediction of metals uptake into tea plants. The results indicate that long‐term plantation of tea can cause sol acidification and elevated concentrations of bioavailable heavy metals in the soil and, hence, aggravate the risk of heavy metals to tea plants.     

汾河流域土壤重金属垂直分布规律及地域差异

山西汾河流域按土属采土样１７４０个，测定镍、铬、铅、锌、砷、铜、汞、镉八种元素的含量。探讨了垂直分布及各地形部位贡献大小和地域差异。在中高山地、山地、低山丘陵、丘陵阶地、二级阶地和平原盆地六个地形部位中，土壤重金属元素含量均未超过土壤污染起始值。各元素不同地形部位贡献大小为：中高山地汞大、山地铜大、低山丘陵铬大，丘陵阶地铅、镍、铜大，二级阶地汞大、锌小，平原盆地镉、汞大、铜小。故二级阶地和平原盆地应施用铜、锌微肥和防止汞、镉污染。地域差异研究表明：东西两山山地土壤多数元素含量差异不显著，利用较为一致。南北两盆地污染重点在太原盆地。上述研究结果为土壤环境质量评价、土壤污染防治和预测，工矿企业合理布局，农业生产结构调整提供了科学依据。     

砂质土壤不同粒径颗粒中有机碳、养分和重金属状况

用分散、筛分和悬浮相结合的物理方法，研究了砂质土壤中养分和重金属在不同粒径有机、无机颗粒中的分布。研究表明，砂质土壤中Cd、Co、Cr、Cu、Ni、Pb、Zn和Mn在颗粒状有机质（POM）有明显的富集，富集程度以Cu和Zn最为明显。粒径较小（0．05～1mm）的POM组分中重金属的平均富集高于粒径较大（〉1mm）的POM组分。POM中重金属的富集因土壤重金属污染水平和重金属类型而异，并与土壤重金属的积累呈正相关。分析数据表明，土壤POM中重金属的积累不完全是植物分解残留的结果，土壤POM对重金属有强吸持能力可能是POM中重金属富集的主要原因之一。     

土壤重金属形态对径流中重金属流失的影响

土壤重金属的积累可促进地表径流中重金属的流失,流失量与土壤中重金属的形态有关。田间观测和室内模拟淋洗试验的结果都表明,径流或淋出液中重金属主要来源于土壤的交换态(包括水可溶态)重金属;土壤重金属总量与径流中重金属浓度相关不明显;用稀盐(0.01mol/LCaCl2)和1mol/LNH4OAc提取的土壤重金属量与径流和淋出液中重金属浓度都呈显著的相关,可较好地表征土壤中重金属流失潜力。     

Sources of bioavailable trace metals for earthworms from a Zn-, Pb- and Cd-contaminated soil

The sources of bioavailable metals for earthworms were investigated in a Zn-, Pb- and Cd-contaminated soil. Selective sequential extractions (SSE) of metals were performed on soil samples with different amounts of contamination and compared with the body burden concentration of metals in two earthworm species: Aporrectodea caliginosa and Lumbricus rubellus. The most labile forms (water extractable and exchangeable) of metals were poorly related with metal accumulation by the earthworms, except for Cd, whereas the moderately available forms (acid-soluble, bound to iron oxides and organic matter) were related to the pattern of metal accumulation by earthworms. This indicates that the ingestion of metals bound to soil components is likely to be a more important uptake route than the dermal uptake of dissolved ions for metals entering the body tissue of earthworms.