以磷酸法木质素基活性炭为原料,三聚氯胺为氮源、KOH为活化剂,采用同步掺杂方式制备了氮掺杂活性炭(NAC).通过BET、XRD、拉曼光谱和XPS表征手段测试了改性后活性炭的结构及其组分,并通过电化学表征手段,测试了其作为超级电容器电极材料在几种不同性质电解液中的性能,初步探究了电解液对电极材料电化学性能的影响机制.实验结果表明:改性后的活性炭具有丰富的孔结构,比表面积达到2 332 m2/g,微孔孔容为1.37 cm3/g,中孔孔容为0.74 cm3/g,平均孔径为2.79 nm,含氮元素7.5％,其中类石墨型氮(N-Q)结构达到34.6％.丰富的孔结构和氮含量大幅提升了活性炭的电化学性能,其在水系电解液中展现出了高比电容,在1 A/g的电流密度下比电容最高可达424 F/g;在有机系电解液中,尽管其在1 A/g的电流密度下比电容最高仅为87 F/g,由于其工作电压窗口更宽(0～2.5 V),因此具备了更高的能量密度.对结果进行分析,发现:活性炭电极材料在水系电解液中的性能主要受电解液水合离子半径影响,而在有机系电解液中的性能主要受电解液黏度的影响.

以成型、烘焙处理后的玉米秸秆为原料,磷酸作为活化剂制备了玉米秸秆基活性炭,并对活性炭样品进行表征.同时以碘吸附值、亚甲基蓝吸附值和焦糖脱色率为指标测定其吸附性能,并对制备条件进行优化.实验结果表明:玉米秸秆制备活性炭的最佳工艺条件为浸渍比即m(55％H3PO4)∶m(玉米秸秆)为4∶1、活化温度400℃、活化时间100 min,此条件下活性炭的得率为47.78％,制得的活性炭具有良好的吸附性能,碘吸附值、亚甲基蓝吸附值及焦糖脱色率分别达到864 mg/g、210 mg/g和100％.活性炭比表面积可达1 105 m2/g,总孔容积为0.745 cm3/g,微孔孔容为0.287 cm3/g,中孔孔容为0.354 cm3/g,孔径分布集中于5 nm以内,约占73.56％,平均孔径为2.697 nm.FT-IR分析显示:在活化过程中磷酸与玉米秸秆发生交联作用,生成的活性炭损失了玉米秸秆的部分官能团.

木质素是无定型态的高度交联的多酚芳香族聚合物,来源广泛,碳含量丰富,适合用于多孔炭材料的制备.将木质素用于制备多孔炭是实现资源化利用,解决木质素难以大量高效利用而造成环境污染问题的重要途径.本文主要介绍了近些年来,以木质素为炭前驱体,通过物理、化学活化法制备出的以微孔为主的活性炭及采用模板法制备出的介孔炭材料工艺研究情况,对比分析了不同方法制备的多孔炭材料的孔道结构及形貌特点,以及其应用在吸附、催化和电化学方面取得的进展.

以杨木木质素为原料,采用磷酸活化法制备中孔发达的活性炭,并利用孔结构分析、XRD、拉曼光谱,研究了活化温度(400～900℃),以及磷酸与木质素质量比(浸渍比,1:1～4:1)对活性炭LAC-x-y(x代表浸渍比值,y代表活化湿度)结构的影响,通过电化学表征手段,探讨了炭材料的电化学性能与其结构的关系.孔结构分析结果表明:提升温度和浸渍比有利于活性炭中孔的形成,但过高的温度会导致孔隙结构的坍塌,过高的浸渍比会导致灰分的增加,从而导致活性炭性能降低.XRD和拉曼光谱结果表明:提升温度有助于提高活性炭的石墨化程度,而增加浸渍比会导致石墨化程度的降低.在活化温度为800℃、浸渍比为2:1的条件下,制得的活性炭LAC-2-800表现出最佳的结构性能,比表面积1031 m2/g,中孔率61％,平均孔径3.31 nm.使用该活性炭作为超级电容器电极材料时,在1 A/g的电流密度下比电容达到165 F/g,且在10 A/g的电流密度下比电容仍有136 F/g.在1 A/g的电流密度下,在循环5000次后,比电容值能保持在初始值的78.1％.

为满足汽车国六排放标准,以木屑为原料、磷酸为活化剂,制备了碳罐用高丁烷工作容量成型活性炭.在制备过程中通过烘焙提质、粒度调控对原料进行预处理,并采用了真空捏合、模孔设计、高温活化等工艺.考察了烘焙温度、原料粒度、浸渍比、真空捏合时间、活化温度、活化时间等制备条件对活性炭性能的影响.结果 表明:原料经250℃烘焙、破碎至粒度小于0.2 mm及使用孔径为2.5 mm的模具成型,可明显提高制备活性炭的性能;当磷酸与原料浸渍比为1.5∶1,真空捏合为60 min、活化温度为500℃、活化时间为120 min时,制备的活性炭碘吸附值为1028 mg·g-1、亚甲基蓝吸附值为270 mg·g-1、强度为92.4％、丁烷工作容量为152 g·L-1、BET比表面积为1547.63 m2·g-1,性能可达到碳罐用活性炭TGZ1500指标要求.

CS2是一种典型的工业化学毒物,对人体和环境危害极大,目前常用去除方法为活性炭吸附.笔者采用动态吸附装置研究活性炭对CS2吸附?脱附性能,考察温度、气体流速、CS2浓度和气流湿度对活性炭吸附?脱附CS2的影响.结果表明:活性炭对CS2吸附量和残存量随着吸附温度的升高而降低.当流速小于625 mL/min,随着流速的增加,活性炭对CS2吸附量增加,残存量降低;当流速大于625 mL/min,随着流速的增加,活性炭对CS2的吸附量降低,残存量增加.活性炭对CS2吸附量随着CS2质量浓度增加而增加.但当CS2质量浓度小于1643 mg/m3时,随着质量浓度的增加,残存量增加;当CS2质量浓度大于1643 mg/m3,随着质量浓度的增加,残存量降低.随着湿度的增加,活性炭对CS2吸附量降低,残存量增加.综合上述研究结果可以得出:吸附温度、气体流速、CS2浓度和湿度等工况条件对活性炭CS2吸附量和残存量均有较大影响,其中CS2浓度对吸附的影响最大,而脱附残存量主要与吸附温度和CS2浓度有关.为实现活性炭高效吸附和脱附,最佳工艺条件为:干燥状态下,吸附温度25℃,流速小于625 mL/min,CS2质量浓度为1643 mg/m3.

以玉米芯木质素为原料,采用磷酸活化法制备木质素基活性炭;并以亚甲基蓝吸附值为考察指标,通过Plackett-Burman设计、最陡爬坡实验和中心复合设计方法,探究了不同工艺条件在活性炭制备过程中的交互作用及最优工艺参数.结果发现:Plackett-Burman设计筛选得到的3个最重要因素分别为浸渍比、活化温度和活化时间;通过最陡爬坡实验确定了其最佳中心点区域;中心复合设计(CCD)和响应面分析(RSM)得到的最佳工艺条件为浸渍比3:1(g:g)、活化温度563℃和活化时间2.75 h.通过验证实验表明:在上述优化工艺及磷酸质量分数60％、浸渍时间12 h、浸渍温度90℃条件下,木质素基活性炭的孔径主要集中在2～10 nm,BET比表面积为1436 m2/g,总孔容为1.041 cm3/g,微孔孔容为0.3856 cm3/g,亚甲基蓝吸附值为240 mg/g.

活性炭拥有独特的物理化学特性,广泛应用于工业、民用及国防等诸多领域,具有不可替代的重要作用.普通的活性炭已经不能满足人类在生产和生活中日益扩大的需求,所以进一步研究活性炭改性技术成为目前的热点.总结了活性炭在化学改性(氧化改性、还原改性、酸碱改性、金属负载改性和等离子体改性)和物理改性(高温热处理改性和微波改性)两方面取得的研究成果,比较了不同改性方法的技术特征,并对活性炭改性技术的未来发展进行了展望.

研究了磷酸在不同加热温度下生成聚合磷酸的水溶性和酸溶性.结果表明:随着加热温度的升高,磷酸形成的聚合磷酸的溶解性下降,水溶解度和酸溶解度分别从98.71％和98.93％降低至73.12％和74.80％.以商品磷酸法木质活性炭为样品,以常规水洗除灰为对照,研究了酸洗、加热洗涤、添加氧化剂次氯酸、离心脱水方式等对活性炭灰分及其吸附性能的影响,并对洗涤后的活性炭样品进行比表面积及孔结构测定,确定了适宜的洗涤条件:洗涤温度为80℃,使用5％HCl并添加次氯酸洗2次,水洗3次,洗涤过程均用离心脱水方式.洗涤过后,活性炭样品的灰分从常规水洗除灰的6.24％降低至1.49％;此时活性炭的比表面积1503 m2/g、孔径3.656 nm、孔容积1.361 cm3/g、碘吸附值975 mg/g、亚甲基蓝吸附值277.5 mg/g、焦糖脱色率110％,相比水洗除灰均有所增大.因此,活化过程在较低温度下进行并使用上述组合除灰工艺可制备出低灰分磷酸法木质活性炭.

分别以纤维素、木质素、杉木屑与核桃壳为原料,经过炭化后在Ni的催化作用下于1400℃下进行了石墨化反应,并以X射线衍射(XRD)、Raman光谱和高分辨率透射电镜(HRTEM)分析了产物的石墨化程度.研究结果表明:纤维素在生物质的石墨化过程中起主要作用,在相同处理条件下,由纤维素得到的产物石墨化程度最高,由木质素得到的产物石墨化程度最低,杉木屑和核桃壳2种生物质原料得到的产物石墨化程度介于纤维素和木质素之间,不同原料石墨化程度的显著差异可能是由于原料结构的差异造成的.同时电导率测试结果表明:20 MPa条件下,由纤维素得到的产物的电导率为54 S/cm,而由木质素得到的产物仅为31 S/cm,与石墨化程度的高低相对应.纤维素/木质素混合物的石墨化程度介于纤维素和木质素之间,两者不同质量比对混合物的石墨化程度影响不大.

以竹材加工剩余物为原料,在不添加活化剂的条件下,开展了微正压热解自活化制备活性炭的研究,通过热重-质谱分析、热解炭化和热解自活化对比,以及热解自活化尾气监测,探究热解过程中活性炭孔隙结构的形成机制.研究结果发现:热解过程产生的水蒸气和二氧化碳可以与固相炭发生气化成孔反应,制得高吸附性能的竹材活性炭;热解气体、均匀活化、气-炭可逆反应平衡状态、活化剂的扩散速率及气-炭反应速率是竹材活性炭孔隙结构和吸附性能的主要影响机制;控制热解自活化压力为0.12 MPa,在900℃(升温速率15℃/min)热解6h,制得活性炭得率为15.22％,BET比表面积(SBET)1 108 m2/g,微孔容积(kic)为0.407 em3/g,介孔容积(Vmes)为0.085 em3/g,碘和亚甲基蓝的吸附值分别为1 438和300 mg/g,同时副产高H2、CO含量和高CO/CO2比例的费托合成原料气.

As one of the important forestry renewable resources,bamboo is grown without pesticides or chemical fertil?izers,and plays a critical role in the balance of oxygen and carbon dioxide in the atmosphere. It grows rapidly and can be harvested in 3-5 years,which produces 35% more oxygen than an equivalent volume of trees.Bamboo can be used to prepare activated carbon instead of wood,which would save precious wood resources. In this study, the activated carbon with high adsorption performance was prepared from bamboo flour by the phosphoric acid activation and mold?ing before the steam activation. The properties of the activated carbon were characterized by the iodine adsorption val?ue,methylene blue adsorption value,N2adsorption?desorption isotherm,carbon disulfide dynamic adsorption capaci?ty,et al. The results showed that the optimum preparation condition was the phosphoric acid impregnation ratio of 1.2:1,activation time of 20 min,activation temperature of 450℃,steam activation temperature of 875℃,activation time of 1 h and flow rate of 3.0 mL/min. Under these conditions, the activated carbon had the BET specific surface area of 1 264.60 m2/g,total pore volume of 1.227 cm3/g,average pore size of 3.88 nm,iodine adsorption value of 1 452.96 mg/g,methylene blue adsorption value of 307.5 mg/g,strength of 91.76% and yield of 30.42%. Under the dynamic drying and 30% relative humidity conditions,the unit mass adsorption of activated carbon on carbon disulfide were 0.416 g/g and 0.390 g/g,respectively. The adsorption capacity of the activated carbon on carbon disulfide was mainly related to the pore structure of the activated carbon. The activated carbon with high micropores,small average pore diameter and high iodine adsorption value were more favorable for the adsorption of carbon disulfide. Due to the relatively low apparent density of bamboo, the strength of the prepared activated carbon was inferior to the coconut shell activated carbon.

Lignin is one of the three recalcitrant components of lignocellulosic renewable biomass and the most abundant heterogeneous aromatic structural biopolymer on the earth. Lignin has a high carbon content over 50 %,and is one of the potential ideal precursors for carbon materials.Mesoporous carbon with high specific surface area and big pore size has wide applications on biomedical devices, catalysis, supercapacitors and so on. Therefore, the synthesis of mesoporous carbon materials has successfully concentrated attention and efforts by scientists worldwide. Nano-casting techniques are available method to prepare mesoporous carbons. Herein, some common strategies for pore dimension adjusting such as hard template route, soft template route and dual template route were reviewed.Finally,the recent research progress on the preparation of lignin-derived mesoporous carbon materials by using template strategy was emphatically introduced.

This study developed a new pre-treatment method of polyphenol in oil-tea camellia seed oil through the accumulation of CNTs.On the basis of investigating the physico-chemical property of CNTs,adsorption medium,desorption solution on the adsorption and desorption of polyphenol standard product,we took purified CNTs as adsorbent,which were 20 ～30 nm in diameter and carried much-COOH,1∶10 as material/liquid ratio.and the adsorption conditions were as follows:shaking table at constant temperature of 10 ℃ by 2 h,the velocity was 100r/min.After that CNTs were desorpted by 20 mL actone added with ultrasonic,which repeated 3 times.Finally we found that the compensate factor of the method which was used to compensate for incomplete adsorption and desorption was 2.032.When the concentration of polyphenol in oil-tea camellia seed oil was between 4.4 and 93.0 μg/g,the absorbance of desorption solution presented a good linear relationship with the concentration of polyphenol in oil-tea camellia seed oil,the correlation coefficient (r2) was 0.935 1.The minimum determination limit of the method was 3.24 μg/g and the recoveries were between 87.99％ and 110.95％ with relative standard deviation (RSD,n =6) between 8.38％ and 10.74％.There's no significant difference between the results of this method and those of Dio-SPE (P ＞ 0.05).The results showed that the method which taken CNTs as adsorbent to analysis the polyphenol in oil-tea camellia seed oil had the advantage of high stability and accuracy,which provided a new mode of polyphenol determination in oil-tea camellia seed oil.

The coated liquid was prepared with ethyl cellulose as coating material and ethanol as the solvent by dissolving at 50 ℃.In order to prepare activated carbon products coated by EC,the coated liquid was uniformly sprayed on the surface of formed activated carbon before heat treatment.The influences of the mass fraction of coated liquid, spray volume and heat treatment temperature on the strength and adsorption properties of coated activated carbon were studied.It was found that under the mass fraction of coated liquid was 4.23%,the weight of activated carbon was 30 g,the spray volume was 20 mL,and the heat treatment temperature was 140 ℃,the strength of the coated activated carbon reached 93.66% and increased 7.35 percentage points compared with that of raw activated carbon and the butane working capacity reached 86.0 g/L and decreased by 9.6 g/L, a thin film with thickness 3-4 μm was formed on the surface of the activated carbon.EC coating did not change the pore structure of activated carbon, but it would affect the wet ability of activated carbon surface, the water contact angle of coated activated carbon was 89.76°, which of the raw activated carbon was 15.41°, and it meant the hydrophobic performance was significantly improved.The surface of the activated carbon products prepared by this method was smooth,no dust,and the shape kept well.

Sustainable lignin-derived mesoporous carbon for supercapacitors by simultaneously employing MgO nanoparticles and Pluronic F127 as templates.

The effect of high-temperature reforming method on the performance of commercial wooden molding activated carbon materials prepared by phosphoric acid activation was studied .The effects of different heating and cooling modes , reforming temperature and reforming time on the strength of activated carbon materials were investigated .The results showed that when the activated carbon were heated to 800 ℃by rapid heating-up and reformed for 30-75 min before rapid cooling ( fast heating/fast cooling (FH/FC)),the strength of activated carbon increased by 5.75%-6.39%and the yield of activated carbon maintained more than 83.54%which was higher efficiency than that by the method of gradient increased temperature /natural drop (GI/ND) in temperature .The pore structure and adsorption capacity of activated carbon after reforming at 800 ℃for 30 and 60 min were also studied.The results showed that the specific surface area and total pore volume of activated carbon decreased by about 400 m2/g and 0.3 m3/g, respectively.The proportion of pores with pore size distribution smaller than 1.2 nm was increased. The adsorption capacity of methylene blue showed a small decrement .The adsorption capacity of iodine was slightly increased . The butane working capacity was decreased less than 15%.After high-temperature reforming , the ignition point of activated carbon significantly was increased .When activated carbon reformed for 60 min at 800 ℃, its ignition temperature improved by more than 100 ℃.It mainly related to the reduction of the amount of oxygen functional groups on the surface of activated carbon after high-temperature reforming .

This paper is aimed at studying the effect of refining processes on the quality of the camellia see d oil, and understanding the rule of phenols in camellia oil during refining. The camellia oil was sampled in local oil-tea camellia seed oil manufacturer, which was from 3 refining processes including squeezed oil refining process, leached oil refining process and squeezed oil’s moderate refining process. The refining processes of squeezed oil included water washing, bleaching, deodorization, and dewaxing, the refining processes of leached oil included alkaline refining, water washing, bleaching, deodorization, and dewaxing, while the moderate refining processes of squeezed oil included degumming, alkaline refining, washing, and dewaxing. The total phenol content (TPC), phenolic compound (PC), oxidation resistance coefficient (AA) and oxidation induction time of these oil samples were detected. The results showed that, the TPC was higher in squeezed oil than that in leached oil, which were 103.06 and 48.52 μg/g, respectively. The TPC was declined by 88.9%, 86.7% and 63.81% after refining processes of squeezed oil, leached oil, and moderate refining processes of squeezed oil, respectively. The AA was declined by 88.3%, 93.51% and 83.25%, respectively in the 3 refining processes. Moderate refining process was better at the retention of TPC and AA in the study than traditional refining processes. The TPC and AA were 37.82 μg/g and 9.33%respectively in moderate refined oil, while 11.41 μg/g and 4.71% respectively in traditional refined oil. The same conclusion was got in the results of PC. There was only a small amount of cinnamic acid that was detected by high-performance liquid phase chromatography (HPLC) in the leached camellia oil after refining, while 3 PCs were detected in the squeezed oil after refining, which included benzoic acid, cinnamic acid and rutin, with the contents of 4.7, 1.58 and 0.22 μg/g, respectively. Nine PCs were detected in squeezed oil after moderate refining process, including tannic acid, chlorogenic acid, catechin, epicatechin, trans-cinnamic acid, rutin hydrate, coumarin, homovanillic acid, gallic acid and o-vanillic acid. The PCs with the highest content in squeezed oil after moderate refining process were tannic acid whose content was 4.57 μg/g and chlorogenic acid whose content was 3.26 μg/g. The oxidation stability of oils could be increased by refining processes. The oxidation induction time of oil before and after the moderate refining process was 8.56 and 11.66 h, respectively, with an increase of 26.63%, while the oxidation induction time of oil before and after the refining process was 8.14 and 10.42 h, respectively, with an increase of 21.83%. The conclusion is that moderate refining process is better at the retention of nutritional ingredients like PC, and the oil from moderate refining process will have higher oxidation stability. The results of the study provide the method of reserving nutrients in the oil-tea camellia seed oil, and the reference for the selection of refining processes and conditions for manufacturer. The correlation of single polyphenol and antioxidant stability of the oil will be studied in the future, and the determination of antioxidant activity will be improved in future research, too.

Volatile organic compounds(VOCs) is an important class of atmospheric pollutants,and the consequential environmental pollution problems have got wide attention. Activated carbon adsorption method is an effective method for controlling the pollution caused by VOCs. This paper embarks from the introduction of VOCs treatment technology,introducing the use of activated carbon adsorption method in the treatment of VOCs briefly. By summarizing the process technology and existing problems of treating VOCs by activated carbon,the thermal pressure swing adsorption,electric swing adsorption,with advantages of the high efficiency,energy conservation and environmental protection have good prospects for development in the treatment of VOCs. In addition,to provide a theoretical basis for improvement and development a special activated carbon for VOCs treatment,the influence of the surface chemical properties of activated carbon,the physical properties of the adsorbate,and the operating conditions of VOCs on activated carbon adsorption were analyzed. Based on the summarization of the existing research progresses,the development trend of the technology in removal of VOCs by activated carbon adsorption method was forecasted. The measures of improving process, coupling with other VOCs treatment technology,and developing varieties of activated carbons and diverse recovery equipment to accommodate the emissions of VOCs from different fields will be the research hotspots in the future.

Using camellia oleifera shell as raw material,technology and mechanism of removing ash from camel-lia oleifera shell charcoal were explored by the method of hydrochloric acid washing.The results showed that the ash content gradually increased with an increase in carbonized temperature and a decrease in acid washing time, however,after acid washing for more than 2 h,ash content was not significantly changed.In the process of re-moving ash from camellia oleifera shell charcoal using hydrochloric acid washing,de-ashing reaction mainly oc-curred on the surface of charcoal and effective pore expanding was not be formed.Pore structure of all charcoal was not well-developed in the experiment range of carbonization temperature,hydrochloric acid washing could significantly reduce the ash content but hardly benefit the formation of new pore structure.After camellia oleif-era shell charcoal were activated by steam,acid washing could decrease ash content and also increase about 20%pore volume without changing the pole size by removing inorganic substances blocking porous channel.