污泥水热炭化中碳氮固定率的影响因素分析

为探究污泥水热炭化工艺中碳和氮固定率与影响因素间的关系,采用三因素三水平Box-Behnken试验设计,拟合响应面模型,研究了水热温度(150～250℃)、含固率(5%～15%)、反应时间(2～6 h)与污泥水热炭化工艺中碳氮固定率的关系。结果表明,多元二次方程可用于描述碳和氮的固定率与上述影响因素间的定量关系(R2分别为0.9925和0.9903)。污泥水热炭化中碳与氮固定率分别为36.6%～52.9%和20.4%～42.5%。水热温度与反应时间对碳和氮固定率均呈负相关,含固率则呈正相关。3个因素对碳固定率的显著影响(p0.05)大小依次为:水热温度含固率反应时间,而氮固定率仅受水热温度的显著影响(p0.05)。水热温度(≤169℃)与含固率(≥7%)的交互耦合可维持较高的碳固定水平(≥50%),而降低水热温度是获得较高氮固定率的关键。该研究结果可为水热炭化技术应用于污泥处理领域提供参考。     

酸碱预处理对西瓜皮微波水热炭化产物特性的影响

为了探究预处理下西瓜皮微波水热(microwavehydrothermal,MHT)温度对炭化产物资源化的影响,该研究对其干燥处理、酸处理和碱处理后进行不同MHT温度试验,分析炭化产物的特性及其可能的应用。结果表明,在MHT温度为130～190℃之间,碱处理在MHT温度为170℃所得水热炭的产率最高达86.01%,明显高于干燥处理和酸处理对应产率(P0.05)。然而,其热值小于17 MJ/kg,不具有作为燃料的潜力。干燥处理和酸处理不仅能获得符合标煤的水热炭,而且能够得到高附加值的5-羟甲基糠醛(5-hydroxymethylfurfural,HMF)和糠醛(furfural,FF)。对比干燥处理产物情况,酸处理能够在MHT温度为130℃时得到3.3%的HMF产率以及在150℃下得到相同产率的FF。经济性分析表明在MHT温度为130℃下酸处理1 t新鲜西瓜皮可得炭化产物的价值约为6 607元,且工艺能耗仅为66元/t。该研究结果可为预处理下西瓜皮资源化转化以及MHT工艺的实际应用提供参考。     

玉米秸秆连续干馏条件下能量平衡分析

为分析外源加热与分段连续干馏技术工艺条件下的生物质热解特性,以玉米秸秆为原料,通过自行开发的生物质连续热解炭气油联产平台,开展了生物质连续干馏试验测试,分析了炭气油三态产物的理化性质、组分分布和受工艺参数影响的基本规律,并在此基础上进行了系统热量衡算和能量平衡分析。结果表明,连续热解条件下,玉米秸秆炭品质受物料在反应室的滞留时间影响大,滞留时间一般应不低于30 min,热解气热值可达到15~20 MJ/m~3,热解油组分极其复杂;玉米秸秆炭携带热量最多,约占产物总能量的47.88%,热解气占产物总能量的36.17%,木焦油和轻油分别占13.14%和1.74%;连续热解系统能耗比为0.97,能量回收率为75.7%。该研究可为外加热分段连续式生物质炭化设备的开发和推广应用提供重要的基础支撑。     

葡萄糖水热过程中焦炭结构演变特性

为了解生物质水热炭化过程中焦炭的形成机制及其理化结构的演变机理,该文以葡萄糖为原料,利用高温高压反应釜,对葡萄糖在水热环境中炭化的反应过程和焦炭的表面物理结构及微观化学组成进行了系统的分析。研究发现,葡萄糖经过水热处理,可以获得富含炭微球的无定形水热焦炭,这些炭微球粒径分布在0.6～7 μm之间,而通过控制水热过程的温度、葡萄糖添加量和停留时间,则可对其收率、形貌、化学组成等理化性质产生重要影响。在220℃,4 h,6 g/100 mL的水热条件下,炭微球粒径最小且均匀,平均粒径约为1.54 μm;在220℃,4 h,12 g/100 mL的水热条件下,焦炭收率最高为38.92%。水热焦炭中含有大量的芳香环结构和含氧官能团,具有很强的亲水性,其表面碳化程度高于内核。水热焦炭的形成主要是一系列脱水、聚合、凝结、芳香化、胶体作用的结果。研究结果为生物质水热法制备炭微球的过程控制提供参考。     

生物质连续炭化中试系统产物特性及其运行效果评估

为分析中试规模条件下的生物质连续炭化特性并系统评估中试设备运行性能,以棉秆、稻壳和果木剪枝等典型农林废弃物为原料,进行了生物质连续炭化中试系统生产测试,分析了炭化温度对产物理化性质、组分分布和产率的影响规律,并在此基础上对设备运行过程、能量平衡、能量转化效率和应用前景等进行了系统评估。结果表明:系统运行过程中温度和压力控制精准,物料滞留时间为36 min,炭化温度分别为550、600、650℃时,炭化温度对产物特性与产率影响明显,炭化温度越高生物炭中固定碳含量越高,650℃时的果木剪枝炭化比550℃时固定炭含量提高12.7百分点;炭化温度越高热解气产率越大,650℃时果木剪枝炭化比550℃时产气率提高7.8百分点;炭化温度在600℃时处理棉秆,系统能量转化效率为74.10%,能流分析表明,此条件下部分燃气回用加热可支撑系统热解。该研究为生物质连续炭化工程装备的开发和示范推广提供了重要技术支撑。     

生物质连续热解炭气油联产中试系统开发

针对目前多数生物质炭化设备生产连续性差、能耗高、生产过程中存在焦油水洗二次污染等问题,结合生物质炭化技术最新进展和农林剩余物原料特征,提出了生物质连续热解炭气油联产工艺方案,引入连续分段热解、多级组合除尘脱焦和燃油/燃气回用加热工艺方法.在此基础上,重点突破了多线螺旋抄板物料均匀有序输送、多腔旋流梯级高效换热、保温沉降密封出炭、系统压力与气体组分耦合预警等技术,开发了生物质连续热解中试生产系统.运行检测结果表明:系统运行稳定可靠,温度控制精度为±16℃,反应室压力控制精度为±-25 Pa,以花生壳为原料,原料处理量为28.2 kg/h,生物炭得率为31.3％,热解气产率29.6％,液体产物产率19.8％,热解气低位热值为16.3 MJ/m3,各项技术指标均达到了系统设计目标与要求.该中试系统的开发为设备放大及示范应用奠定了重要基础.     

天然微藻水热炭理化特性及热解动力学研究

为探索天然微藻资源化的利用途径,该文以天然栅藻为原料,采用傅立叶转换红外线光谱分析, X射线衍射分析,X射线荧光光谱分析,环境扫描电子显微镜与热重分析仪对水热炭进行测试分析。研究结果表明,随着水热温度的升高,水热炭产率从47.29%(180℃)降低至43.01%(240%);水热炭的O/C摩尔比从1.45减小至0.28,碳化程度加强,水热炭具有应用于固体燃料的潜力。鉴于水热炭含有大量灰分,其热值为8.43～9.67 MJ/kg,因此脱灰预处理是必要的过程。经过水热碳化处理,天然栅藻的比表面积从4.36 m~2/g增加到35.26 m~2/g。热解动力学结果表明随着水热温度的提高,水热炭的热稳定性增强。研究结果对天然微藻的资源化利用提供了一定的理论参考。     

水热生物炭燃烧特性与动力学分析

采用热重法对锯末、玉米秸秆水热生物炭燃烧特性及动力学进行了研究,考察了不同升温速率(10、20、40℃/min)对燃烧特性的影响,分析了它们的燃烧特性及动力学参数。结果表明:1)水热炭化前后生物质燃烧质量损失集中在挥发分和固定碳燃烧阶段,升温速率快,着火温度、燃尽温度高,整体向高温区转移,综合燃烧特性指数越大;2)40℃/min时,锯末水热生物炭综合燃烧特性指数远大于玉米秸秆,在其余升温速率下区别不明显;3)以20℃/min相同升温速率时,锯末、玉米秸秆水热生物综合炭燃烧特性相对于未炭化生物质下降27%、13%;4)采用一级反应动力学模型和积分法对水热生物炭燃烧动力学进行了研究,一级反应动力学能很好的描述2种生物炭的燃烧动力学,相关系数(R2)均高于0.9,挥发分阶段活化能大于固定碳阶段的活化能。研究结果可为水热生物炭的燃烧应用能提供理论指导。     

水热炭化温度和时间对鸡粪生物质炭性质的影响

水热炭化被认为是极具潜力的安全处置与资源化利用鸡粪的技术措施之一。该研究将鸡粪在190和260℃水热炭化处理不同时间(1、6和12 h),收集并测定固体产物生物质炭特性,目的在于了解水热炭化反应温度和时间对鸡粪生物质炭特性的影响。结果表明,鸡粪经过水热炭化处理后,46%~56%的干物质转化为生物质炭,C、P质量分数分别增加了5%和59%以上,而H、O、N、K质量分数则分别降低了9%~18%、26%~65%、19%~37%和92%~97%。表面电荷量降低,p H值依变性也减弱,其中有效阳离子交换量降低了50%~90%。生物质炭中1~5μm孔隙显著减少,主要形成1和100μm左右的孔隙。总体来看,水热炭化反应温度越高,反应时间越长,这些指标提高或降低的幅度越大,生物质炭的炭化程度越高;比起反应时间,反应温度对生物质炭性质的影响更大。该文还讨论了鸡粪生物质炭作为土壤调理剂的应用价值与潜力,研究结果可为鸡粪生物质炭在土壤改良等方面的应用提供基础数据。     

中国生物质燃料乙醇项目能量生产效率评估

为了对玉米和木薯乙醇的能量和可再生能量生产效率进行评估，该文统计了玉米和木薯乙醇生命周期能耗，并用市场价值量法按照主副产品的能耗进行了分配。计算出玉米和木薯燃料乙醇的净能量和净可再生能量。并计算了单产和化肥用量变化时的净能量和净可再生能量的变化。计算结果显示，玉米、木薯乙醇的净能量分别为1.472 MJ/L和2.417 MJ/L，净可再生能量分别为1.474 MJ/L和2.459 MJ/L。使用玉米、木薯生产燃料乙醇在能量生产和再生能量生产上都是可行的，木薯乙醇比玉米乙醇可行性更高，单产和化肥用量是提高能源利用和再生能源的关键因素，加强副产品的开发和使用有机肥代替化肥有利于提高系统的能效，提高系统的可再生性。     

木屑及其水热炭的热解特性和动力学对比

为全面了解木屑及其水热炭的差异,获取更多关于水热炭作为化工燃料的使用特性。该文使用热重分析仪和傅里叶红外光谱仪对比研究了木屑及其水热炭在热解过程(10℃/min升温速率)中的失重特性及其官能团变化,分析了升温速率(10、20、30℃/min)对2种样品热解失重过程的影响,采用DAEM(分布活化能模型)计算了2种样品不同转化率下的活化能。结果表明:1)在200℃反应6 h得到的木屑水热炭,化学结构与木屑相似。2)在热解过程(10℃/min升温速率)中,木屑与水热炭最大失重速率分别为0.817%/℃和1.224%/℃,温度为353.57℃和363.42℃;不同终温下半焦红外光谱分析发现,水热炭更易解聚,其碳化速度更快。3)对比3种不同升温速率下2种样品的失重曲线可知,水热处理没有影响热滞后现象,样品焦炭生成量与升温速率无关,焦炭生成量平均值水热炭大于木屑。4)DAEM模型适用于2种样品热解反应活化能的求解,木屑及其水热炭活化能分别为99.33~252.72 k J/mol和63.77~211.68 k J/mol,当转化率在0.30到0.80范围时,木屑的活化能高于水热炭。研究结果为木屑水热炭热化学转化制备焦炭提供理论依据。     

木质纤维素生物质厌氧发酵沼渣热化学转化利用研究进展

厌氧发酵技术可以将木质纤维素生物质转化为沼气,并伴随副产物沼渣产生。随着大型沼气工程的发展,大量沼渣排放已成为厌氧发酵技术推广应用的主要限制因素之一,亟须对沼渣进行快速有效处理。其中,沼渣的热化学转化利用符合大型沼气工程发展趋势,是当前的研究热点之一。首先分析木质纤维素沼渣的原料特性与热化学转化潜力;再对沼渣成型燃料、热解以及水热炭化等领域的研究现状进行分析,着重对沼渣衍生产物特性、热化学转化过程中存在的问题以及与厌氧发酵结合的潜在优势等方面进行讨论;最后,对沼渣热化学转化的发展趋势进行了展望。木质纤维素生物质厌氧发酵与沼渣热化学转化结合的应用模式研究对大型沼气工程推广应用具有一定的科学意义。     

Labile water soluble components govern the short-term microbial decay of hydrochar from sewage sludge

Due to higher proportions of labile carbon (C) compounds the suitability of biochar produced by hydrothermal carbonization (HTC) for C sequestration is questionable. We hypothesized that pre-treatment with water would reduce the biological decay of hydrochar from sewage sludge. Unwashed and washed feedstock and hydrochar were incubated in a short-term experiment. The kinetics of the biological decomposition of the materials was calculated on the basis of a double exponential model and the C sequestration potential using the CANDY Carbon Balance (CCB) model. Biological decomposition of the carbonized materials was governed by the percentage of labile C compounds. Mean residence time of a fast (MRT_fast) and slow decay pool (MRT_slow) of unwashed hydrochars varied clearly (MRT_fast: 0.8 – 5.0 months and the MRT_slow: 5.0–18.6 months). The pre-treatment with water removed labile hydrochar C and reduced the biological accessibility. MRT_fast and MRT_slow was increased by intensive washings (MRT_fast: 5.0–7.4 months and the MRT_slow: 14.9 months). High synthesis coefficients suggest that hydrochar C was humified and transferred into stabilized SOC. The results clearly show that once adsorbed components were eliminated, and as compared to pyrolysed biochar hydrochar from sewage sludge may also be useful for soil C sequestration.     

低氧烟道环境制备污泥活性炭

为降低污泥制备活性炭的成本,以高温低氧烟道气为媒介,研究了活化时间、温度、蒸气含量以及氧含量对污泥活性炭性能的影响规律,结果表明：活化温度、活化时间及水蒸气流量的最佳值分别为800°C、90 min和34.8%,该条件下污泥活性炭比表面积、产率、甲基橙及亚甲基蓝吸附值分别为：246.3 m2/g、46%、14.8 mg/g、18.1 mg/g。因而,高温低氧烟气直接用于物理活化法制备污泥活性炭,活化气量（水蒸汽）不够,产品活性炭的性能差,活化温度高达800°C,运行成本仍偏高。将湿污泥用ZnCl2按1∶1浸渍16 h后活化炭化,在活化温度、活化时间、氧含量分别为550°C、90 min、2%时,污泥活性炭的产率为59%,其比表面积和亚甲基蓝吸附值分别达516.1 m2/g和129.8 mg/g,孔体积为0.29 cm3/g,微孔体积为0.16 cm3/g,平均孔径为3.95 nm,性能较好。氧气能促进活性炭微孔的形成与发展,最佳的氧含量为2%~4%。与无氧条件下制备的污泥活性炭相比,氧含量为4%时制得的污泥活性炭的比表面积增加了6.82%,亚甲基蓝吸附值提高了2.75倍。该研究表明：高温烟气作为热源、保护气和活化气,结合化学活化法,可将脱水湿污泥直接制成污泥活性炭。该结果可为低成本制备污泥活性炭、实现污泥处理的资源化利用提供一定的参考。     

Earthworms can modify effects of hydrochar on growth of Plantago lanceolata and performance of arbuscular mycorrhizal fungi

Hydrothermal carbonization (HTC) is a method to produce carbonized material at relatively low temperatures (180–250 °C) under pressure and aqueous conditions. The product is called hydrochar and can be used as a soil amendment. However, applied in high dosages it may have detrimental effects on plants or soil biota. The potential impact of hydrochar amendment on beneficial soil organisms such as arbuscular mycorrhizal fungi (AMF) and earthworms and their interactions are not well understood. The goal of the present study was to determine effects of hydrochar on plant growth and soil biota and to evaluate interactions of earthworms and hydrochar on plant and AMF performance and to identify underlying mechanisms. In a greenhouse experiment, we investigated the effect of hydrochar at different addition rates (control, 1% and 10%, v/v) with or without the earthworm Aporrectodea caliginosa on the growth of Plantago lanceolata L. and the performance of its AMF. We observed a positive interaction between earthworms and 10% hydrochar on shoot and root biomass: added as a single treatment hydrochar had a negative effect on plant growth at this dosage, but plant biomass increased significantly when hydrochar was added together with earthworms. Root colonization by AMF increased significantly with increasing concentration of hydrochar, but was not affected by earthworms. Contrastingly, extraradical hyphal length of AMF was reduced by earthworms, but not affected by hydrochar. Thus, hydrochar and earthworms affected the performance of AMF, albeit of different AMF structures and in different directions. Our results indicate that earthworms may play an important role in alleviating the negative impacts of high dosages of hydrochar on plant growth; such interactions should move into focus of future research on potential effects of HTC materials.     

污泥施用对土壤及小麦生理特性的影响

以兰州市安宁区污水处理厂污泥为研究对象,采用盆栽方法研究污泥施用后对土壤pH值的影响,对土壤中重金属Cu、Zn、Pb含量的影响以及对小麦叶片叶绿素含量和脯氨酸含量特性的影响。结果表明,污泥施用后土壤的pH值显著下降,并呈递减趋势。不同污泥施加量土壤中3种重金属元素的含量均远低于我国土壤环境质量二级标准（GB15618—1995）中碱性土壤的限制性标准值。3种小麦叶片的叶绿素总含量随污泥浓度的增加而增加,污泥在混配土壤中的干重比为15%时3种小麦均达到最大值,随着污泥施加量的进一步加大出现下降。污泥施用后3种小麦叶绿素a/b值与对照相比无显著变化,小麦叶片中脯氨酸含量比对照有大幅的增加。低污泥施加量时（5%、10%和15%）,3种小麦叶片中脯氨酸含量随施加量增加而增加,但高污泥施加量时（25%和35%）的脯氨酸含量无显著增加,污泥中污染物胁迫超过小麦耐受限值后,小麦生理代谢出现反常。土壤中3种重金属元素的含量与3种小麦体内脯氨酸含量均呈极显著正相关关系,土壤的pH值与3种小麦的叶绿素总含量和脯氨酸含量均呈负相关关系。综合考虑污泥施用对小麦生理特性的影响,对小麦的耕种土壤中一次性施用污泥时,污泥在混配土壤中的干重比应限量在15%以下。     

Effects of sewage sludge stabilization on fertilizer value and greenhouse gas emissions after soil application

Application of sewage sludge on agricultural land becomes more and more common in many parts of the world in order to recycle the nutrients from the sludge. A range of sewage sludge stabilization techniques are available to make the sludge more stable prior to storage, transportation, and application. These stabilization techniques include dewatering, drying, anaerobic digestion, composting, and reed bed sludge treatment. However, very few studies have investigated the effect of these techniques after the sludge has been applied to agricultural land. The objective of the current study was therefore to investigate the effect of sewage sludge stabilization techniques on the C and N mineralization and gaseous emissions from soil. A soil incubation was conducted to determine the rate of C and N mineralization and N₂O and CH₄ emissions of sewage sludge stabilized using different techniques. Unstabilized sludge released up to 90% of their C content as CO₂, part of which could be caused by release of CO₂ from carbonates. Compared with this, sludge stabilization including anaerobic digestion and drying resulted in a reduction of the C mineralization rate of about 40%. Liming reduced C mineralization with around 29%, while treatment in a reed bed system reduced it by 74%. The current study thus clearly demonstrated that stabilization techniques resulted in sludge that was more stable once they were applied to agricultural land. Stabilization also reduced the N immobilization phase, potentially improving the value of the sludge as a fertilizer. Emissions of CH₄ were also reduced through sludge stabilization and mainly occurred after application of easily degradable sludge types, which is likely to have enhanced the creation of anaerobic microsites. The stabilization processes also decreased emissions of N₂O. The results for both CH₄ and N₂O indicate that the stabilization tends to reduce the chance of developing conditions where these gases could be produced.     

污泥及秸秆生物质固体燃料制备中试工艺及燃烧特性

为实现污泥的无害化和资源化处置,该文利用处理量为24t/d的中试试验台,进行了化学调理剂添加比例、脱水时间、秸秆尺寸等工艺参数对污泥制备固体燃料性能影响的研究。结果表明:以Fe3+和Ca2+为调理剂,污泥及秸秆等生物质制备固体燃料最佳的铁钙比及燃料压滤最优时间分别为1∶4～1∶2和6h;化学调质法制备的污泥固体燃料存在一个脱水极限,在脱水压力为1.2MPa、秸秆或木屑添加质量比为10%时,污泥固体燃料的质量含水率最低为40%～50%;同等条件下,秸秆越长,燃料脱水性能越好;燃料着火点低,约500K,完全燃烧温度范围窄,燃烧性能好,可做替代燃料使用。该文研究成果对降低污泥处理成本、实现污泥的无害化、资源化处置具有重要的理论意义和实用价值。     

Carbon sequestration potential of hydrothermal carbonization char (hydrochar) in two contrasting soils; results of a 1-year field study

Soil amendment with hydrochar produced by hydrothermal carbonization of biomass is suggested as a simple, cheap, and effective method for increasing soil C. We traced C derived from corn silage hydrochar (δ¹³C of ?13?‰) added to “coarse” and “fine” textured soils (δ¹³C of ?27?‰ for native soil C (SOC)) over two cropping seasons. Respiration rates increased in both soils (p?<?0.001) following hydrochar addition, and most of this extra respiration was derived from hydrochar C. Dissolved losses accounted for ~5 % of added hydrochar C (p?<?0.001). After 1 year, 33?±?8 % of the added hydrochar C was lost from both soils. Decomposition rates for the roughly two thirds of hydrochar that remained were very low, with half-life for less estimated at 19 years. In addition, hydrochar-amended soils preserved 15?±?4 % more native SOC compared to controls (negative priming). Hydrochar negatively affected plant height (p?<?0.01) and biomass (p?<?0.05) in the first but not the second crop grown on both soils. Our results confirm previous laboratory studies showing that initially, hydrochar decomposes rapidly and limits plant growth. However, the negative priming effect and persistence of added hydrochar C after 1 year highlight its soil C sequestration potential, at least on decadal timescales.