Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Breaking the temperature limit of hydrothermal carbonization of lignocellulosic biomass by decoupling temperature and pressure

Hydrothermal carbonization(HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption have limited the development of HTC technology. In conventional batch reactors, the temperature and pressure are typically coupled at saturated states. In this study, a decoupled temperature and pressure hydrothermal(DTPH) reaction system was developed to decrease the temperature of the HTC reaction of lignocellulosic biomass(rice straw and poplar leaves). The properties of hydrochars were analyzed by scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), Raman spectroscopy, X-ray diffraction(XRD), thermogravimetric analyzer(TGA), etc. to propose the reaction mechanism. The results showed that the HTC reaction of lignocellulosic biomass could be realized at a low temperature of 200℃ in the DTPH process, breaking the temperature limit(230℃) in the conventional process. The DTPH method could break the barrier of the crystalline structure of cellulose in the lignocellulosic biomass with high cellulose content, realizing the carbonization of cellulose and hemicellulose with the dehydration, unsaturated bond formation, and aromatization. The produced hydrochar had an appearance of carbon microspheres, with high calorific values, abundant oxygen-containing functional groups, a certain degree of graphitization, and good thermal stability. Cellulose acts not only as a barrier to protect itself and hemicellulose from decomposition, but also as a key precursor for the formation of carbon microspheres. This study shows a promising method for synthesizing carbon materials from lignocellulosic biomass with a carbon-negative effect.

Hydrochar Pelletization towards Solid Biofuel from Biowaste Hydrothermal Carbonization

Hydrothermal carbonization is highly applicable to high moisture biomass upgrading due to the fact that moist-ure involved can be directly used as reaction media under the subcritical-water region.With this,value-added utilization of hydrochar as solid fuel with high carbon and energy density is one of the important pathways for biomass conversion.In this review,the dewatering properties of hydrochar after the hydrothermal carbonization of biowaste,coalification degree with elemental composition and evolution,pelletization of hydrochar to enhance the mechanical properties and density,coupled with the combustion properties of hydrochar biofuel were discussed with various biomass and carbonization parameters.Potential applications for the co-combustion with coal,cleaner properties and energy balance for biowaste hydrothermal carbonization were presented as well as the challenges.

Preparation and Characterization of Carbon Microspheres From Waste Cotton Textiles By Hydrothermal Carbonization

Carbon microspheres were prepared from waste cotton fibers by hydrothermal carbonization(HTC)with the addition of copper sulphate in this work.The important influence factors,temperature,concentration of copper sulphate,resident time were explored here.The smooth and regular carbon microspheres could be formed at 330°C with 0.15 wt%copper sulphate after 6 h from waste cotton fibers.The crystal structures of cotton fibers were destructed in a short resident time with 0.15 wt%copper sulphate from SEM images and XRD patterns of solid products.This strategy provides a new,mild and efficient method to prepare carbon microspheres from waste cotton fibers by HTC.FTIR spectra verified that the abundant functional groups existed on the surface of synthesized carbon microspheres.From XPS and element analysis results,the copper sulphate participated in the forming process of carbon microspheres indeed.The presence of copper sulphate in the carbon microspheres provided a possibility for the application in antibacterial field.Besides,the catalytic mechanism of copper sulphate on the hydrolysis and carbonization of waste cotton fibers were also discussed.In conclusion,the copper sulphate is an efficient agent for preparing carbon microspheres by HTC from waste cotton fibers.

NMR studies of stock process water and reaction pathways in hydrothermal carbonization of furfural residue

Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques(~1H and ^(13)C NMR,~1H-~1H COSY and ~1H-^(13)C HSQC etc.) especially 1D selective gradient total correlation spectroscopy(TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions(180-240 ℃ at 8 h, and 1-24 h at 240 ℃) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.

Hydrothermal Carbonization of Nonylphenol Ethoxylates Waste Liquid for Energy Source Generation

Nonylphenol polyethoxylates (NPEOs) are widely used as nonionic surfactants in many industry fields. High concentration NPEOs waste water is produced in some production processes. It is often treated to realize reduction by distillation. Therefore, NPEOs waste liquid with higher concentration is produced and it is difficult to be treated by traditional water treatment process. In this study, hydrothermal carbonization process was used to convert NPEOs waste liquid to carbonaceous product (hydrochar) with sulfuric acid as additive in 24 h at 200°C. The hydrochar was characterized by scanning electron microscope, Fourier-transform infrared spectrometer and thermogravimetric analysis. The element composition and the high heat value of the hydrochar were similar to lignite, showing that it could be used as an alternative fuel.

Upgrading the Quality of Solid Fuel Made from Nyamplung (Calophyllum inophyllum) Wastes Using Hydrothermal Carbonization Treatment

One of the major problems faced in managing biomass waste to higher quality products is choosing the right technology.Wastes are used as an alternative fuel,with increase in the calorific value.Hydrothermal carbonization(HTC)is a biomass conversion technology,used to obtain solid fuel.This study aims to utilize of Calophyllum inophyllum as an alternative solid fuel through HTC.The calorific value and proximate of the hydrochar will be determined and analyzed to find out its quality.The experiments were carried out at temperature variations of 160℃,190℃,and 220℃ and holding times of 30 and 60 minutes.The results show that an increase in temperature and holding time causes a decline in the moisture content 1.87%,volatile matter 54.03%,and ash content 12.35%,respectively,leading to elevations in the fixed carbon at 31.75%.In addition,the highest calorific value of 4149 Kcal/Kg was produced at a temperature of 220℃,within a holding time of 60 minutes.The results showed a significant increase in the quality of solid fuels between 3500–4611 Kcal/Kg in accordance with the American Standard Testing and Materials(ASTM).Therefore,this research leads to an important finding that Calophyllum inophyllum waste through the HTC process can be used as an alternative fuel to substitute lignite coal,which is environmentally friendly.

Hydrothermal Carbonization of Deciduous Biomass(Alnus incana)and Pelletization Prospects

Thermal treatment of biomass has been attracting attention for a decade or so, especially torrefaction. However, for the past few years, wet pyrolysis, also known as hydrothermal carbonization (HTC), has been getting some attention. Hydrothermal carbonization is a thermal treatment of biomass in the presence of water in a temperature range of 180°C - 260°C. This method of treating biomass has some benefits which others do not, such as it can handle extremely wet biomass. However, treating biomass may not be enough for practical use. It may need to be transported and stored. Thus, this study explored the idea of pelletizing the HTC biomass. The mechanical strength of the HTC pellets was found to be 93%, whereas, higher heating value (HHV) (dry basis) was found to be 4% higher than the corresponding white pellets. The initial results with some limited parameters indicated that it would be possible to pelletize without binder. However, extensive research on energy balance and economic assessment would be necessary to achieve economic feasibility.

鄂尔多斯盆地富县地区马家沟组热液改造特征与研究意义

构造—热事件对油气生成、储集层演化和成藏有重要的控制作用,但是鄂尔多斯盆地构造—热事件对碳酸盐岩的影响研究较少。以富县地区奥陶系马家沟组储集层为例,通过岩心及薄片观察,利用阴极发光、包裹体测温、碳氧稳定同位素、锶同位素、电子探针微区元素分析、稀土元素分析,岩石学与地球化学研究充分结合,识别出区内存在2期与燕山期热事件相关的胶结作用:第Ⅰ期以缝洞内鞍形白云石发育为特征,其δ^(13)C值和δ^(18)O值均较偏负,锶同位素值较正常海相灰岩高,稀土元素Eu和La负异常,元素分析显示FeO含量异常高、MnO含量较高、SrO含量较高、K_(2)O及Na_(2)O含量低,胶结物包裹体均一温度高;第Ⅱ期以缝孔洞内石英充填及交代和切割鞍形白云石的裂缝方解石发育为特征,其δ^(13)C值与奥陶系碳酸盐岩背景值接近、δ^(18)O值总体偏低,锶同位素值更高,稀土元素展现出特别的La负异常和Eu正异常,元素分析MnO及FeO含量较高,部分K_(2)O及Na_(2)O含量较高,石英包裹体均一温度高。第Ⅰ期流体为早白垩世拉张断裂作用下上覆石炭—二叠系地层有机流体、奥陶系地层内部流体、少量深部流体三者联合作用形成;第Ⅱ期流体为早白垩世拉张断裂作用下深部流体与少量奥陶系地层内部流体两者联合作用形成,深部流体穿越了下伏马家沟组内蒸发盐岩地层。早白垩世热事件对奥陶系碳酸盐岩储集层的影响具有双向性:第Ⅰ期热流体活动多为建设性,与大规模油气生成的时间一致,裂缝和溶蚀孔洞可构成油气有效输导和储集空间;第Ⅱ期热流体活动以孔隙和裂缝充填为主,多为破坏性,但规模较小。

活性碳负载纳米金属氧化物对AP热分解的催化性能

采用水热法制备了两种纳米金属氧化物(纳米CuO和纳米Fe_(2)O_(3)颗粒),将纳米CuO和纳米Fe_(2)O_(3)负载在活性碳上,制备成CuO@C、Fe_(2)O_(3)@C复合材料,并将其作为催化剂与高氯酸铵(AP)混合制备成混合物样品AP/CuO、AP/CuO@C、AP/Fe_(2)O_(3)、AP/Fe_(2)O_(3)@C;通过扫描电子显微镜(SEM)、差示扫描量热仪(DSC)、热重-微分热重分析(TG-DTG)和热重-红外光谱(TG-FTIR)联用等技术研究了4种催化剂对AP热分解的催化机理及分解动力学特性。结果表明,4种催化剂均将AP的两步分解反应催化为单放热峰,在5 K/min升温速率下,AP的分解峰温较纯AP分别提前90.1、73.4、65.4和69℃;AP/CuO@C分解主要气相产物有HCl、CO_(2)、N_(2)O、HNO_(3)和NO_(2),其中NO_(2)含量最高;AP/Fe_(2)O_(3)@C分解主要气相产物中CO_(2)含量显著提升,NO_(2)含量稍有降低。

γ-Al_(2)O_(3)载体的水热合成及其加氢性能

以ρ-Al_(2)O_(3)和NH4HCO3为原料,采用水热法合成出γ-Al_(2)O_(3)的前驱体碳酸铝铵(AACH),考察了原料配比和反应时间对合成产物的影响,利用X射线衍射仪、物理吸附分析仪、化学吸附仪对2种不同前驱体制得的载体进行表征,并对2种载体制得的催化剂进行了加氢脱硫脱氮性能评价。结果表明:在n(HCO_(3)^(-))/n(Al^(3+))为1.5∶1.0,100℃反应14 h下制得具有棒状结构、结晶度较好的AACH;相比由传统拟薄水铝石制得的载体,由AACH制得的载体具有较高比表面积和大孔容,有效孔径(4~10 nm)的孔容占比更高,且利于反应进行的中强酸更多,且所制备催化剂的脱硫脱氮活性更佳。

N掺杂的红色荧光纳米碳点检测汞离子

以对苯二胺和多巴胺为原料,通过一步水热法合成表面富含氨基基团的氮掺杂碳点(N-CDs),经过离心、过滤以及柱层析对所制备碳点进行提纯。采用高分辨透射电子显微镜和荧光对其进行表征。结果表明:该碳点粒径均一,具有良好的红色发光特性,且在最佳实验条件下,Hg2+对该碳点进行选择性荧光猝灭,其荧光猝灭程度与Hg2+浓度在0.1μM~2.1μM范围内呈现良好的线性关系,检测限为0.01μM。最后,该碳点成功用于实际水样中Hg2+的测定,加标回收率为95.0%~103.1%。

三维多孔碳纳米管-还原氧化石墨烯复合气凝胶应用于高性能对称超级电容器

以羟基化的碳纳米管(CNT-OH)和自制的氧化石墨烯(GO)为原料,通过氧化还原自组装的水热合成策略制备了碳纳米管-还原氧化石墨烯(CNTs-rGO)三维气凝胶,并探究了水热温度对三维气凝胶的影响,利用扫描电子显微镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman)和X射线光电子能谱(XPS)对材料的结构、形貌进行了表征,并对其进行电化学性能测试。其中,在140℃下合成的气凝胶CNTs-rGO展示了最佳的电化学性能,在1 A·g^(-1)电流密度下的比电容高达294.65 F·g^(-1),循环伏安曲线在50 mV·s^(-1)扫速下的形状仍然近似于矩形,展示了良好的可逆性。将其作为正极和负极材料组装的对称超级电容器在功率密度为249.8 W·kg^(-1)时的最大能量密度为3.744 Wh·kg^(-1),在1 A·g^(-1)下循环10 000次后,其电容保持率和库仑效率均约为100%。优异的电化学性能主要归因于CNTs-rGO复合材料疏松多孔的三维立体结构,这保证了离子的快速运输,同时CNTs和rGO的交联结构提高了电导率,充分发挥了CNTs和rGO的化学和电学性能。

中药渣水解炭燃料特性及热解燃烧动力学分析

中药渣因含水率高而处理困难,将中药渣经水热处理后有较好的应用前景。以中药渣为研究对象,采用水热处理获取中药渣水解炭,通过工业分析及元素分析、热重分析及动力学分析研究了水热处理对中药渣水解炭特性的影响。结果表明:随着水热处理温度升高,中药渣水解炭的固定碳及元素C含量、燃料比(水解炭的空气干燥无灰基固定碳与挥发分的质量比)及高位发热量增加,挥发分、元素H及元素O含量明显降低,n_(O)/n_(C)及n_(H)/n_(C)逐渐降低,水解炭性质接近一般动力煤性质。热重分析发现热解过程中,280℃下形成的水解炭在160℃~300℃和300℃~500℃出现较明显的双峰失重峰,其余水热处理温度下形成的水解炭仅在275℃~400℃出现一个极明显失重峰。随着水热处理温度的升高,水解炭热解活化能由69.56 kJ/mol降至40.55 kJ/mol。水解炭燃烧过程主要经历四个阶段,180℃~295℃主要是小分子挥发分热解阶段,其活化能为63.65 kJ/mol~105.02 kJ/mol;295℃~390℃主要是小分子挥发分主要燃烧阶段,其活化能为10.78 kJ/mol~35.76 kJ/mol;390℃~410℃主要是大分子挥发分析出与燃烧阶段,其活化能为117.08 kJ/mol~201.61 kJ/mol;410℃~520℃主要是固定碳与焦炭的燃烧以及少量矿物与无机化合物的热分解阶段,其活化能为22.18 kJ/mol~92.10 kJ/mol。随着水热处理温度升高,水解炭燃烧同一阶段的指前因子与活化能变化趋势一致。水解炭的可燃性指数、着火指数以及综合燃烧指数随着水热处理温度升高、水热时间增加以及固液比的增大而减小,固液比为1 g:15 mL且在220℃下水热1 h获得水解炭的燃烧性能较好,综合燃烧指数为3.55×10^(-10)/(min^(2)·℃^(3)),可为高湿固废水热燃料化的应用提供参考。

KOH共热法和水热活化法制备多孔竹活性炭的比较

我国竹材资源丰富,以竹废料为原料,制备可用于超级电容器电极材料的竹活性炭,有助于推动竹产业发展,助力国家“双碳”目标实现。在本研究中,分别采用KOH共热和水热处理对竹粉进行活化,并对制备的竹活性炭进行电化学性能、比表面积、表面微观形貌等测试。实验结果表明,KOH共热活化法的最佳条件为炭化温度350℃,活化温度900℃,升温速率2℃/min,碱炭质量比4∶1;制备的活性炭比表面积为3 299 m2/g, 0.5 A/g电流密度下的比电容为287.8 F/g, 5 000次充放电测试后,电容保持率为95%~105%。水热活化法的最佳条件为KOH质量分数20%,反应温度150℃,反应时间12 h,制备的活性炭比表面积为192.91 m2/g, 0.5 A/g电流密度下的比电容为170.4 F/g,电容保持率为88.89%。2种方法制备的活性炭孔径结构都是以微孔为主,中孔混合分布,含有少量大孔;2种活性炭均含有双层或多层石墨烯结构,但水热活化法制备的活性炭石墨化程度更高,制备条件更温和。研究结果既可为超级电容器用活性炭的研究提供了理论思路,也有效地扩展了竹材的应用领域。

水热炭在吸附有机/无机污染物中的应用研究进展

水热炭材料作为一种新型碳材料,具有含氧官能团丰富、堆积密度高、热稳定性强和导电导热性优良等特点,在催化和吸附、储能材料领域具有潜在的应用价值,尤其适用于吸附各种污染物。首先介绍了水热炭的分类和制备,根据尺寸可以分为水热炭量子点和水热微球。其次综述了水热炭的酸洗改性、碱洗改性、官能团化改性以及对污染物的吸附性能和机理。改性水热炭对污染物吸附的机理包括物理吸附和化学吸附,其中物理吸附主要由范德华力所引起的分子间作用,化学吸附主要包括络合配位、离子交换、静电吸引、氧化还原反应等;最后针对水热炭现存问题进行讨论与展望,以期为改性水热炭吸附去除污染物的广泛应用提供理论支撑。

亚东-谷露断裂带中北段地热流体碳硫硼同位素特征

亚东—谷露断裂带中北段地热系统深循环过程十分复杂,对该区域地热资源的评估具有较大影响。加深对地热水起源、演化和循环过程的研究,对地热资源的勘探和开发具有较大的意义。地热流体中碳硫硼稳定同位素特征分析是研究地热水来源、地热水循环深度和地热水作用过程的方法之一。对亚东—谷露断裂带中北段地热水进行了系统性采样,测量了碳硫硼同位素。进行了碳硫硼同位素分析,结果显示:稳定同位素特征源于地热流体对围岩和地层的淋滤作用和水-岩相互作用。该地热系统中碳的主要来源为碳酸盐的溶解,与区域上分布的碳酸盐地层有关。谷露和续迈地热田δ^(34)S具有较大的分散性,显示出硫来源的非单一性,δ^(34)S均在大气碳酸盐和蒸发碳酸盐范围内,δ^(34)S同位素的来源为大气降水和热储层中的硫酸盐矿物。谷露地热田具有较低的δ^(11)B值和较低的Cl/B比值,较高的硼含量,且硼含量和硼同位素值相对集中,表明硼主要源于地热流体对围岩的淋滤作用。大气降水和冰雪融水中硼含量极少,主要起到对地热水中硼含量的稀释作用,不改变地热水中的δ^(11)B值。本研究的结果验证了亚东—谷露断裂带中北段地热系统地下热水的起源主要为大气降水,在深循环过程中存在少量岩浆流体的混入。

玉米秸秆水热生物炭施用对土壤重金属Cd生物有效性和微生物群落的影响

为了探究玉米秸秆水热生物炭(简称水热炭)施用对镉(Cd)污染土壤的修复效果及作用机制,通过盆栽试验,分析了不同水热炭在不同添加率下(1%和3%)对土壤Cd生物有效性和作物吸收的影响,并探究了不同条件下的微生物群落结构。结果表明:与对照相比,水热炭施用显著提高了土壤有机质和溶解性有机碳含量,土壤中二乙烯三胺五乙酸提取的Cd(DTPA-Cd)和油菜叶片Cd含量分别降低了5.01%~20.98%和10.82%~34.16%。提高水热温度和水热炭添加率有助于降低土壤DTPA-Cd含量。此外,施用水热炭显著增强了根际土壤细菌的多样性和丰度,且明显改变了微生物群落结构。与对照组相比,施用水热炭显著降低了根际土壤中Actinobacteriota的相对丰度,提高了Proteobacteria和Bacteroidota的相对丰度。冗余分析表明土壤溶解性有机碳含量是影响根际土壤细菌群落结构的关键因素。因此,水热炭对重金属污染土壤有很大的修复潜力,但其对土壤重金属的长期效应有待进一步研究。

水热法制备ZrO_(2)催化甘油酯交换反应性能

采用水热法制备了ZrO_(2)催化剂,用于催化甘油(GLY)与碳酸二甲酯(DMC)酯交换反应合成碳酸甘油酯(GC)。考察了焙烧温度对催化剂性能的影响,并采用粉末X射线衍射(XRD)、N_(2)等温吸附-脱附、程序升温脱附(TPD)等手段对ZrO_(2)催化剂进行了表征。结果表明,ZrO_(2)催化性能高度依赖于其表面中强碱性位点密度,当焙烧温度为600℃时,所制备的ZrO_(2)-600催化剂表面中强碱性位点密度较大;在反应温度90℃下反应90 min, GLY转化率为96.1%,GC选择性为86.2%。重复使用第3次时,由于ZrO_(2)表面碱性位点密度减小、孔道坍塌以及部分ZrO_(2)样品溶解在DMC中,GLY转化率和GC选择性均显著下降。

秸秆水热碳化液修饰二氧化钛去除农村生活污水尾水中抗生素的动力学特征研究

为探究秸秆水热碳化液修饰二氧化钛纳米球(SHCS&TiO_(2))去除抗生素的动力学特征,以实际农村生活污水尾水为目标处理水体,以磺胺嘧啶和红霉素为典型目标污染物,采用时间梯度实验研究和动力学模拟进行分析。结果表明:1)SHCS&TiO_(2)去除两种抗生素的动力学特征有明显差异。去除磺胺嘧啶反应主要发生在前10 min,去除速率为2.11~2.37 mg/(L·min),最终去除率为72.6%~89.5%。去除红霉素反应主要发生在0~20、120~240 min,去除速率分别为1.65~2.34、0.32~0.42 mg/(L·min),最终去除率达到100.0%。2)Behnajady-Modirshahla-Ghanbary反应动力学模型模拟结果最佳。3)去除机制是吸附和催化共同作用,且催化起主要作用。