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2023年 第51卷  第2期

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摘要:
生物质“热溶富碳”(Thermal Dissolution based Carbon Enrichment, TDCE)是利用非/弱极性有机溶剂在温和条件(350 ℃、氮气氛围)下对木质纤维素类生物质废弃物进行热萃取,经过一系列脱氧和芳构化反应,获得的目标固体产物Soluble和Deposit具有无水、无灰、高热值等优点,同时该技术还具有溶剂不参与化学反应,可回收循环利用的优势。因此,热溶富碳是实现生物质能源转化的有效途径之一。本综述首先介绍了目前生物质利用的各类方式;然后重点综述了生物质热溶富碳影响因素、反应机理以及产物利用途径。在“碳中和”的国家战略背景下,生物质热溶富碳技术具有较明显的经济价值和社会意义。
摘要:
结合矿源腐植酸(HA)产率高及生化HA活性高的特点,本研究提出将低阶煤与生物质共热氧化制备复合型HA(MIXHA)的想法。将黑龙江褐煤(HL)及麦秸秆(WS)的混合物(MIX)在10%的HNO3溶液中进行了共热氧化,制备了MIXHA。通过SEM、FT-IR、13C NMR等分析,重点从HA的宏观形貌及微观结构对比了MIXHA与HL、WS分别单独制备的矿源HA、生化HA,分析HL与WS在共热氧化过程的协同作用。结果表明,MIXHA含量高于理论值, HNO3分子的分解产生的活性氧原子、氮氧化物进攻HL与WS的分子结构,由于氢键重排、糖苷键断裂、交联等作用,WS纤维素与半纤维素产生的大量烷基自由基结合在HL缩合芳环上被氧化产生的醌基、羧基的邻对位,从而将芳香环上的质子碳转化为脂肪取代碳。得到的MIXHA含氧官能团丰富、活性高,FT-IR谱图具有明显的特征峰。本研究为低阶煤与农林废弃物的分级、资源化利用提供了一种新思路。
摘要:
本研究以共沉淀法制备的α-Fe2O3催化剂为前驱体,通过调变碳化温度和碳化时间制备了不同物相组成的系列催化剂,采用XRD、Mössbauer谱、XPS和Raman光谱等技术考察了催化剂体相和表面物相组成,在此基础上研究了不同条件下(不同CO转化率和H2O分压)催化剂的物相组成与催化剂性能之间的关系,重点探究了费托合成条件下CO2生成的活性相。结果表明,升高碳化温度和延长碳化时间有利于Fe3O4向碳化铁转变。在典型的费托合成条件下,催化剂的活性受到碳化铁含量和积炭程度的共同影响。当H2O分压较低时,动力学因素限制了水煤气变换(WGS)反应的进行,CO2选择性仅受CO转化率的影响,Fe3O4含量变化对CO2选择性无明显影响;而在较高的H2O分压下,随着催化剂中Fe3O4含量增加, CO2选择性也随之增加。本文初步阐明了Fe3O4是铁基费托合成催化剂中WGS反应的主要活性相,为认识Fe基费托合成催化剂CO2生成的活性相提供了新的信息,为新型低CO2选择性费托合成工业催化剂的设计奠定了基础。
摘要:
采用机械球磨法制备NiMo催化剂,通过XRD、XPS等表征其结构,探究Ni/(Ni+Mo)比对催化剂组成和结构及菲加氢性能的影响。结果表明,该法制备的催化剂活性组分Ni和Mo的分散性好,为孔径集中分布于2−10 nm的介孔催化剂。随Ni/(Ni+Mo)比增加,催化剂的比表面积和MoIV含量呈现出先增加后降低趋势,均于0.33处达到最高。适量Ni促进Mo硫化形成NiMoS活性相,过量的Ni会形成NixSy,覆盖活性位点,降低加氢活性。恒定Ni/(Ni+Mo)比为0.33,催化剂的比表面积随Ni、Mo含量增加明显降低,而MoIV含量增加。增加硫化剂硫代硫酸铵(ATS)的用量,可同时提高催化剂的比表面积和MoIV的含量。Ni/(Ni+Mo)比对菲转化率的影响表现出与催化剂中MoIV含量相一致的变化趋势,当Ni/(Ni+Mo)比为0.33时,菲转化率达最高值74.7%。在该比例下,Ni、Mo含量及S/Mo比分别增至4.8%、16%和4.5时,菲的转化率达96.5%,八氢菲和全氢菲的总选择性和产率分别为83.9%和80.9%,且菲主要从侧环进行深度加氢形成全氢菲。
摘要:
采用双模板剂合成了ZSM-23分子筛,并制备ZSM-23-Al2O3复合载体,通过引入Al2O3调控Pt/ZSM-23催化剂的正十六烷(n-C16)加氢异构性能。采用XRD、SEM、TEM、N2物理吸附-脱附及NH3-TPD等方法探讨Al2O3对催化剂结构性质和化学性质的影响。结果表明,引入Al2O3可以提高Pt在复合载体上的分散度,降低催化剂的酸性位点浓度,有效调控了催化剂的金属-酸性浓度平衡(CPt/CA)。适宜的金属-酸性浓度平衡有利于提高对异构产物的选择性并抑制裂化副反应。Al2O3同时对ZSM-23晶粒起到了分散作用,改善了其分子筛纳米晶粒团聚现象,增加了ZSM-23中孔口的暴露数量,促进反应物和中间体的扩散。复合载体催化剂呈现了出色的异构选择性,其中,Pt/(9Z-1Al)催化剂由于具有适宜的金属-酸性浓度平衡呈现最高的异构产物收率,可达60%,明显高于Pt/ZSM-23催化剂的异构体收率(42%)。反应温度低于310 ℃时,Pt/ZSM-23催化剂的吸附模型符合孔口吸附,而高温时则为锁钥吸附。引入Al2O3后ZSM-23有更多相邻孔口暴露,吸附模型以锁钥择形为主,导致了7/8Me-C15异构产物的大量生成。
摘要:
A highly efficient cerium-modified Cu/hexagonal mesoporous silica (xCe-Cu/HMS) catalyst for the vapor-phase hydrogenation of dimethyl oxalate (DMO) into ethylene glycol (EG) was prepared using an ammonia evaporation method. The Ce promoter can significantly improve the performance of the catalyst, and the best catalytic performance was obtained after the introduction of 1.2% Ce promoter on Cu/HMS. The DMO conversion and EG selectivity got to 99.6% and 96.3%, respectively, under moderate conditions (200 °C, 2.0 MPa, H2/DMO = 100 and LHSVDMO = 1.2 h−1). Characterization results revealed that Ce modification can enhance the interaction between Cu and the support, improve the dispersion of Cu on HMS, and maintain the appropriate ratio of Cu+/(Cu++Cu0). In this study, a simple and low-cost method was used to synthesize Ce-modified Cu-HMS catalysts, which showed excellent catalytic performance in conversion of DMO to EG under moderate conditions.
摘要:
Hydrogen production from electrolyzed water driven by sustainable energy is an effective way to achieve the hydrogen economy with zero carbon emission. Alkaline electrocatalytic hydrogen evolution reaction (HER) is one of the main energy transforming processes in the field of electrolytic water technology. The development of active and cost-effective nonprecious catalytic electrodes is of great importance to alkaline hydrogen evolution reaction. Amorphous nanosized nickel-boron alloy particles (NiB-COS) have been obtained by using chitosan oligosaccharides (COS) as a stabilizer via chemical reduction method. The as-prepared electrocatalysts have been used for the hydrogen evolution reaction (HER). The electrocatalysts have been characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma analysis (ICP) and X-ray photoelectron spectroscopy (XPS). NiB-COS displays a significant increase in hydrogen evolution reaction properties in alkaline media, affording low overpotentials of 49.4 mV at 10 mA/cm2 and 15.1 mV onset overpotential for the hydrogen evolution reaction. Tafel slope of NiB-COS is 86.1 mV/dec. Remarkably, the formation of a nickel-boron alloyed phase and the decrease of particle size are helpful to improve HER activity of NiB-COS. The experimental data indicated that the NiB-COS showed excellent long-term stability as a very active electrocatalyst.
摘要:
In this work we report the feasible modification of graphitic carbon nitride (g-C3N4) polymer through a post-functionalization progress. The resultant photocatalyst exhibits boron doping and mesoporous structure with a high surface area of 125 m2/g, leading in an increased surface activity for photocatalytic water splitting reaction. X-ray diffraction, X-ray photoelectron spectroscopy, PL emission spectra and UV-Vis spectra were used to detect the properties of as-prepared samples. Based on X-ray photoelectron spectroscopy analysis, boron is proposed to dope in the g-C3N4 lattice. Optical studies indicated that boron doped g-C3N4 exhibits enhanced and extended light absorbance in the visible-light region and a much lower intensity of PL emission spectra compared to pure g-C3N4. As a result, boron doped g-C3N4 shows activity of 10.2 times higher than the pristine g-C3N4 for photocatalytic hydrogen evolution. This work may provide a way to design efficient and mesoporous photocatalysts through post modification.
摘要:
本实验制备了一种Z型含氮缺陷的石墨相氮化碳(LaFeO3/CQDs-g-C3Nx)复合光催化剂。利用X射线衍射(XRD)、紫外-可见光漫反射(UV-Vis DRS)、光致发光光谱(PL)、扫描电镜(SEM)、透射电镜(TEM)以及X射线光电子能谱(XPS)等手段对催化剂进行了表征。结果表明,氮缺陷和CQDs的引入能增强光生载流子的迁移效率。LaFeO3/CQDs-g-C3Nx复合材料对罗丹明B(RhB)的光催化降解率是纯g-C3N4的3.98倍,并具有良好的光催化稳定性。同时对抗生素和其他有机污染物也表现出良好的降解能力。
摘要:
采用等体积浸渍法制备了Mn/Fe负载椰壳活性炭碳基催化剂Mn-Fe/HAC。在固定床实验台上研究了反应温度、体积空速(GHSV)和烟气组分(O2、CO、SO2和Hg0)对其脱硝脱汞性能的影响,并结合N2吸附-脱附、NH3-TPD、H2-TPR、Hg-TPD以及瞬态反应测试,分析其脱硝脱汞机理。结果表明,Mn/Fe负载可以明显促进碳基催化剂低温脱硝活性,添加Fe可提高催化剂表面的酸性位点数量和还原能力,促进催化剂活性,进一步拓宽其脱硝温度窗口;7Mn0.5Fe/HAC催化剂在160−220 ℃下的脱硝效率可达95%,且在100−220 ℃下Mn和Fe负载碳基催化剂脱汞效率基本稳定在100%。7Mn0.5Fe/HAC催化剂脱硝效率随着GHSV增加而逐渐降低,而脱汞效率则保持稳定。无O2条件下Mn/Fe催化剂脱硝效率较低(约为50%),而当烟气中O2含量大于6%,其脱硝效率可稳定在95%以上。Hg0浓度对Mn/Fe负载碳基催化剂脱硝性能影响不大,CO有一定抑制作用,而高浓度SO2抑制作用较为显著。Mn和Fe共负载可提高抗硫性,在含150 μL/L SO2模拟烟气下,7Mn0.5Fe/HAC催化剂在180 ℃的脱硝效率仍可稳定在80%以上。Mn/Fe负载碳基催化剂脱硝遵循E-R机理,即NH3先吸附于活性位点,再与气态NO反应,最终将NO还原为N2;而脱汞遵循L-H机理,即Hg0先吸附于活性位点,形成吸附态Hg0,然后与活性氧以及吸附态NO2与SO2反应分别生成HgO、Hg(NO3)2和HgSO4
摘要:
本研究通过吸附实验探究了140−220 ℃下NaHCO3对SeO2的吸附性能,通过一系列表征解析了吸附后样品中硒的总量、价态和形态,结合密度泛函理论计算,探讨了NaHCO3对SeO2的吸附机理。结果表明,NaHCO3对SeO2的吸附性能随温度的升高而增加,在吸附过程中同时发生NaHCO3向Na2CO3的分解反应,分解后产生的Na2CO3吸附活性更强。SeO2吸附过程属于SeO2中Se原子与Na2CO3表面O原子成键的化学吸附,吸附产物以亚硒酸盐为主。
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本研究采用液相离子交换法,用不同浓度的CuCl2对NH4Y分子筛进行离子交换制得系列CuNH4Y-x分子筛吸附剂,并通过固定床吸附穿透实验及一系列表征手段探究了Cu的价态和负载量对乙烯/乙烷吸附分离性能的影响。吸附穿透实验结果表明,Cu(I)NH4Y0.10的乙烯吸附量明显高于Cu(II)NH4Y0.10,且Cu(I)NH4Y系列吸附剂的乙烯吸附量随着Cu负载量的增加呈现先增加后减小的趋势。H2-TPR和HRTEM表明,当Cu的负载量较低时,高度分散落位于Y分子筛超笼中的Cu(I)物种是乙烯有效吸附位点。然而,当Cu的负载量较高时,部分Cu物种发生团聚,造成对乙烯吸附能力的减弱。DFT密度泛函理论计算表明相比于Cu(II)NH4Y吸附剂,乙烯更容易吸附在Cu(I)NH4Y吸附剂上。该研究结果可为乙烯分离用高效Cu离子改性分子筛吸附剂的开发提供重要理论依据与指导。
摘要:
链烃裂解在热解/气化过程中大量存在,其中,轻质链烃反应时间短并且存在多种反应路径,难以通过实验的方式对单一演变路径进行准确的检测和分析。本研究选用Gaussian及其配套软件对C2系列链烃(包括乙烷、乙烯和乙炔)的反应位点进行了预测,并对上述链烃在H/OH/O自由基及水分子作用下的碳链裂解机理进行研究。结果表明,自由基对乙烷的C原子及H原子均可发起进攻,而对于乙烯和乙炔的进攻则主要集中在C原子。在上述三种自由基中,OH自由基对不饱和烃的裂解效果最佳,而H自由基对于饱和烃的裂解效果更好,该结果反映了实际过程中水蒸气对于C2系列链烃化合物的碳链断裂具有积极作用。此外,对比乙烯和乙炔与OH自由基作用的最优路径可以发现,CH2CH2OH在低于1200 K的环境中比CH2CHO更容易裂解,而在高于1200 K的环境中则是CH2CHO裂解更易,从中可以推断出醛类基团对于温度变化的响应速率优于醇类基团。
摘要:
The structure-sensitive of Cu catalyst for furfural hydrogenation to furfuryl alcohol was explored by employing Cu(111) and Cu(211) model systems. Herein, the adsorption behavior of reactants and intermediates, and the possible reaction mechanism of furfuryl alcohol formation were investigated. For furfuryl alcohol formation, the preferred pathway is F-CHO + 2H→F-CH2O + H→F-CH2OH, in which the second H addition is the rate-determining step. Meanwhile, Cu(211) surface exhibits higher activity to furfuryl alcohol formation than that on Cu(111) surface. According to our analysis, the undercoordinated sites on the Cu(211) surface could facilitate H2 dissociation and stabilize the adsorbed furfural, thereby promoting the furfural hydrogenation and the furfuryl alcohol formation. This work provides a feasible approach for regulating the catalytic activity and selectivity in furfural conversion.