竹材碱性过氧化氢预处理及其酶水解性能研究

采用碱性过氧化氢（AHP）体系对慈竹进行预处理,研究过氧化氢（H₂O₂）用量对竹材化学组分及酶水解得率的影响。利用X射线衍射（XRD）和傅里叶变换红外光谱仪（FTIR）分析预处理前后物料的物理和化学结构变化,采用二维核磁共振技术研究预处理物料中剩余木质素的化学结构。结果表明：AHP预处理过程中,随着H₂O₂用量（质量分数）的增加,竹材的葡聚糖含量（相对质量百分比）先增加后减少,木聚糖含量基本不变,而木质素含量整体呈减少趋势。AHP预处理能显著提升竹材的酶解效率,在纤维素酶用量为15 FPU/g葡聚糖,H₂O₂用量为7.0%时,预处理竹材的酶水解性能最高,葡聚糖和木聚糖酶水解得率分别为93.9%和100%。研究发现,慈竹木质素脱除率在H₂O₂用量达到2.0%后趋于稳定,为68.8%,继续增加H₂O₂用量,木质素脱除率无明显提升,对预处理竹材中剩余木质素进行2D-HSQC核磁分析,这部分难以脱除的木质素的化学结构为：64%的S单元、33.7%的G单元和61.6%的β——O——4键,其中S/G值为1.90。     

H2O2/[Hnmp]HCOO氧化苯并噻吩类硫化物的量子化学研究

针对质子型离子液体[Hnmp]HCOO在加入H₂O₂后生成的过氧化物[Hnmp]HCOOO氧化苯并噻吩（BT）、二苯并噻吩（DBT）和4,6-二甲基二苯并噻吩（4,6-DMDBT）的氧化脱硫反应,采用密度泛函理论DFT/B3LYP-D3方法考察了这三种硫化物的反应历程。首先通过几何优化得到了[Hnmp]HCOO和[Hnmp]HCOOO的稳定结构,然后考察了[Hnmp]HCOOO氧化BT、DBT和4,6-DMDBT的反应机理,寻找可能的过渡态、中间体,计算各步反应的能量变化。结果表明,[Hnmp]HCOOO先将硫化物氧化成亚砜,然后进一步氧化成砜;在氧化过程中,DBT的反应速率是三者中最快的,与文献的实验结果一致,且H₂O₂/[Hnmp]HCOO体系的脱硫效果优于传统的H₂O₂/HCOOH体系。     

秸秆燃烧过程中KCl分压蒸发模型的建立与应用

为了研究秸秆燃烧中钾（K）类无机物的逸出特性,计算其逸出速率,利用X射线荧光能谱仪（XRF）和X射线衍射仪（XRD）分析玉米秸及其低温灰中K的化学形态,利用同步热分析仪（STA）研究秸秆及其灰中主要K类无机物在高温过程的逸出特性,建立KCl在多孔介质中逸出和在熔融相中分压的蒸发模型,并应用模型计算秸秆灰中KCl的蒸发速率。结果表明：秸秆低温灰中的K主要以KCl、K₂SO₄形态存在,两者约占灰总量的13%;常用燃烧温度下,KCl主要以蒸发形式逸出;KCl与K₂SO₄的共熔,可降低KCl在熔融相中的蒸气压;秸秆灰中KCl蒸发速率的计算值与实验值吻合良好。     

基于TEM、FT-IR和XPS的PODE2-4/柴油混合燃料颗粒物特性

基于透射电镜（TEM）、傅里叶变换红外光谱（FT-IR）和X射线光电子能谱（XPS）试验对不同掺混比例与不同负荷下的聚甲氧基二甲醚(PODE_2-4)/柴油混合燃料排气颗粒物的理化特性变化规律进行研究.TEM与分形理论分析表明,当PODE_2-4掺混比例增加或负荷减少时,颗粒物的整体尺寸变小,排列更紧密,分形维数变大.FT-IR分析发现,当PODE_2-4掺混比例或负荷增加时,当量峰高比比值减少,颗粒物表面脂肪族碳氢官能团相对含量降低.XPS试验表明,随着PODE_2-4掺混比例的增加或负荷的减小,颗粒物表面的氧、碳元素物质的量比与碳原子杂化比比值增加,羟基、羰基以及总含氧官能团含量增大.结果表明:PODE_2-4掺混比例的增加和负荷的减小影响颗粒物的纳观结构和氧化活性,使其更易于被氧化,有利于颗粒物捕集器的再生.     

Preparation and characterization of PEO based Li1.5Al0.5Ge1.5(PO4)3 solid composite electrolyte

以聚环氧乙烷（PEO）为黏结剂,离子导电性的Li_1.5Al_0.5Ge_1.5(PO₄)₃（LAGP）为主相,乙腈为溶剂,按照EO/Li,摩尔比为13,变化LiN(CF₃SO₂)₂（LiTFSI）中Li⁺ 与LAGP中Li⁺ 的比例,通过溶液浇注法制备得到LAGP-PEO(LiTFSI)固体复合电解质。用X射线衍射、扫描电镜（SEM）和电化学阻抗（EIS）等方法对固体复合电解质的形貌、结构和电导率进行表征。结果表明,LAGP可与PEO(LiTFSI)部分络合并均匀分散于PEO(LITFSI)内,整个体系内存有三个主体相,即PEO(LiTFSI)的复合相、LAGP晶相以及PEO与两种锂盐的过渡相。通过阻抗谱图发现,当质量比w(LAGP)∶w(PEO)=6∶4时,LAGP-PEO(LiTFSI) 固体复合电解质具有最高的室温电导率,为2.68×10^-5 S/cm,在333 K时,达到1.86×10^-4 S/cm,接近LAGP的电导率水平。这说明固体复合电解质中加入LAGP即降低了PEO的结晶度,LAGP自身的电导率也有一定贡献。     

不同预处理方式对芒萁、商陆厌氧消化性能的影响

采用酸（1.5% H₂SO₄）、碱（2% NaOH）、水热（180℃）三种方式分别对芒萁、商陆进行预处理,考查不同预处理方式对芒萁、商陆厌氧消化性能的影响。结果表明：不同预处理方式对原料木质素去除效果不同,去除率大小依次为碱处理 > 酸处理 > 水热处理,其中碱处理条件下芒萁木质素去除率为52.84%,商陆为48.62%。碱处理条件下原料甲烷产率亦最高,分别为芒萁134.62 mL/g VS、商陆260.40 mL/g VS,相比未处理分别提升53.62%、79.38%;稀酸和水热处理条件下芒萁木质素去除率较低,分别为23.61%、4.52%,商陆则分别为31.68%、5.67%。另外,稀酸和水热处理对芒萁产甲烷也有较好的提升作用,相比未处理分别提升33.08%、38.62%,但对商陆产甲烷并没有明显的改善作用（酸处理仅提升7.83%、水热处理降低3.42%）。相比酸处理和水热处理,碱处理具有更好的预处理效果,商陆比芒萁具有更好的产甲烷潜力。     

应用于储热领域的混合钠基废盐热物性分析

近年来工业废盐的堆积量剧增引发一系列环境问题。废盐的处置方法已成为制约废盐资源化利用的瓶颈。针对以NaCl和Na₂SO₄为主要成分的工业废盐(杂质离子包含钙、镁、钾等金属离子),本工作提出利用钠基废盐作为储热材料的处置思路并对其热性能进行分析。采用分子动力学方法,分析废盐中主要杂质对钠基盐体系热物性影响。进一步通过高温熔融法制备二元钠基共晶盐NaCl-Na₂SO₄,分别添加质量分数为1%和5%的KCl模拟含有微量K+废盐,研究其对混合盐热物性影响。结果表明K⁺对钠基盐的热物性有显著提升,含有1%和5%KCl的混合钠基盐相比二元钠基共晶盐的相变潜热分别提高了64%和60%,导热系数提高了2～3倍。K⁺的存在有利于废盐热物性改善,为该类固废资源化利用提供了途径。     

铁基载氧体的污泥化学链气化过程中氮迁移热力学模拟与实验研究

基于吉布斯自由能最小化原理,采用HSC Chemistry 6.0软件,对污泥化学链气化过程中NO_x前驱物（NH₃和HCN）与Fe₂O₃载氧体的氧化还原行为进行了热力学模拟。基于污泥热解实验中NO_x前驱物的含量,计算载氧体与污泥的摩尔比（OC/SS）对NH₃、HCN以及NH₃和HCN混合气氧化过程的影响。热力学模拟结果表明：Fe₂O₃能显著促进NO_x前驱物的氧化和裂解,主要生成N₂,几乎无NO_x生成;当NH₃、HCN以及混合气（NH₃和HCN）分别作为还原剂时,其最优OC/SS分别为0.02、0.04和0.05;由于HCN还原性强于NH₃,其氧化速率较快。基于Fe₂O₃/Al₂O₃混合物（FeAl）载氧体,实验对比了污泥化学链气化与污泥热解过程中NO_x前驱物的释放特性,发现Fe₂O₃能显著降低烟气中NO_x前驱物的产率,NH₃和HCN产率分别下降32%和62%。实验结果与热力学模拟结果一致。     

柴油机排气的O2-NO2对碳烟氧化的协同效应

柴油机排气温度低于873 K时难以直接氧化碳烟,使得柴油机颗粒捕集器（DPF）要实现低温、高效率的再生面临严峻考验．为了明确DPF内O₂-NO₂快速氧化碳烟的反应机制,基于量子化学与化学动力学,采用微观机理结合宏观分析的手段,探究了O₂-NO₂协同氧化碳烟的机理,并对碳烟的氧化进行定性与定量分析．研究表明：O₂-NO₂对碳烟的活性位有竞争吸附作用,NO₂的吸附能明显高于O₂,但O₂与碳烟更易形成C（O）及活性O*.NO₂易与O₂产生的C（O）反应,生成的NO3-可有效氧化活性C*,实现O₂-NO₂对碳烟氧化的协同效应;中等温度为742 K时,O₂与芘基（A4-）反应生成A4O的量保持最多,且O₂与NO₂摩尔分数比为1/2时,A4-的10 s...     

Electrochemical thermal stability of the LiFePO4/LiNi0.8Co0.15Al0.05O2 blend cathode material for lithium ion batteries

为了改善LiNi_0.8Co_0.15Al_0.05O₂正极材料的电化学热稳定性能,加入LiFePO₄共混制成了LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂锂离子电池用混合正极材料。使用X射线衍射（XRD）和扫描电子显微镜（SEM）表征了结构和形貌,测试了电化学性能。结果显示,简单球磨的混合LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂正极材料中,纳米LiFePO₄粒子包覆在LiNi_0.8Co_0.15Al_0.05O₂粒子表面提高了混合正极材料在充放电过程中的电化学稳定性和结构稳定性。LiFePO₄/LiNi_0.8Co_0.15Al_0.05O₂混合正极材料在50 ℃下循环100周容量保持率为82.0%,明显地优于单一LiNi_0.8Co_0.15Al_0.05O₂材料的72.9%。     

废旧三元锂离子电池正极有价金属的回收工艺研究

随着电动汽车和大规模储能市场的快速发展,锂离子电池的销量快速增长,随之产生的废旧锂离子电池数量也日益增长。其中,三元正极锂离子电池含有锂、镍、钴、锰等有价金属,具有较高的回收价值。本文以废旧三元锂离子电池正极片为原料,采用高温热处理法去除正极中的粘结剂和导电碳,以提高有价金属在酸液浸出的回收率。重点考察了高温热处理的温度和时间对有价金属酸浸出率的影响。结果表明:当三元正极热处理温度为650℃、时间为120 min时,正极中粘结剂和导电碳分解完全;在酸浸实验中,在硫酸浓度为4 mol/L,H₂O₂体积含量为11.1%、固液比为55.5g/L、反应温度为80℃、反应时间为2 h条件下,锂、镍、钴、锰的浸出率分别达到99.5%、98.9%、98.7%、98.7%。     

Preparation and thermal stability of ternary sulfate molten salt

以硫酸钠、硫酸钾和硫酸镁为原料,采用在硫酸钠-硫酸钾二元共晶盐中加入硫酸镁的方法制备三元硫酸熔盐。应用TG-DSC联用分析仪、热常数分析仪、X射线衍射仪以及热循环法对复合熔盐的熔点、相变潜热、热导率、比热容、分解点以及热稳定性进行表征。结果表明：所制备的三元硫酸熔盐熔点分布在667.5～669.7 ℃之间,较二元熔盐熔点降低了160 ℃左右,硫酸镁含量为30%（质量分数）的三元硫酸熔盐相变潜热值最大为94.3 J/g,比热容最大为1.13 J/(g·K)（720℃≤T≤800℃）,导热系数为0.41 W/(m·K),分解温度为1070 ℃,经50次热循环后,相变潜热值降低约4.34%,熔点和物相保持基本恒定,具有良好的热稳定性。该研究为硫酸盐作为高温传热蓄热介质提供了依据。     

蒽醌-2-羧酸作为光催化剂催化解聚木质素

木质素是自然界中丰富的可再生芳香碳资源,其解聚得到的单体可以作为重要的化工原料。以蒽醌-2-羧酸作为光催化剂,在硝基苯存在和LED光源照射下,5 h内木质素模型化合物中β-O-4键有80%的转化率。对于木质素β-O-4多聚体,该体系也表现出了光催化活性,将蒽醌-2-羧酸负载在非均相载体上,在光催化降解中也可以获得77%的底物转化率。该反应涉及了木质素β-O-4中C_α—C_β键和C_β—O键的断裂,在催化剂的作用下,首先发生C_α—OH的脱氢,随后经过分子内的断键和重新成键生成苯甲醛和愈创木酚。本研究加深了对光催化木质素氧化过程中C—C键断裂过程的认识,有助于理解木质素的解聚机制。     

Two-step steam pretreatment of softwood by dilute H2SO4 impregnation for ethanol production

Fuel ethanol can be produced from softwood through hydrolysis in an enzymatic process. Prior to enzymatic hydrolysis of the softwood, pretreatment is necessary. In this study two-step steam pretreatment by dilute H₂SO₄ impregnation to improve the overall sugar and ethanol yield has been investigated. The first pretreatment step was performed under conditions of low severity (180°C, 10 min, 0.5% H₂SO₄) to optimise the amount of hydrolysed hemicellulose. In the second step the washed solid material from the first pretreatment step was impregnated again with H₂SO₄ and pretreated under conditions of higher severity to hydrolyse a portion of the cellulose, and to make the cellulose more accessible to enzymatic attack. A wide range of conditions was used to determine the most favourable combination. The temperatures investigated were between 180°C and 220°C, the residence times were 2, 5 and 10 min and the concentrations of H₂SO₄ were 1% and 2%.

The effects of pretreatment were assessed by both enzymatic hydrolysis of the solids and with simultaneous saccharification and fermentation (SSF) of the whole slurry, after the second pretreatment step. For each set of pretreatment conditions the liquid fraction was fermented to determine any inhibiting effects. The ethanol yield using the SSF configuration reached 65% of the theoretical value while the sugar yield using the SHF configuration reached 77%. Maximum yields were obtained when the second pretreatment step was performed at 200°C for 2 min with 2% H₂SO₄. This form of two-step steam pretreatment is a promising method of increasing the overall yield in the wood-to-ethanol process.     

Effect of Na2SO4 additive in positive electrodes on the performance of sealed lead-acid cells for electric scooter applications

This study investigated the effects of Na₂SO₄ additive in the positive electrode on the performance of sealed lead-acid cells. The additive Na₂SO₄ in the cured plates can reduce the 4BS crystal size, which produces a smaller -PbO₂ and β-PbO₂ crystal size in the formed plates, which will have a larger surface area. The plate's chemical composition is independent of the amount of Na₂SO₄ additive in the positive electrodes. Plate composition relies only on the cure temperature conditions. Increasing amounts of Na₂SO₄ additive to the positive electrode will not decrease the crystal size appreciably. The optimal amount of Na₂SO₄ additive is 0.01–0.05 M, which produces the smallest crystal size and largest specific surface area. Cells with Na₂SO₄ additive in the positive plates have a smaller surface area, causing a higher initial capacity and average capacity per cycle for both testing methods: the standard cycle testing and the electric scooter (ES) driving pattern cycle testing. The initial capacity and average capacity can be increased up to 4% in the standard cycle testing and up to 8% in the ES driving pattern cycle testing.     

Electrochemistry of poly(vinylferrocene) modified electrodes in aqueous acidic media

A cyclic voltammetric study of the electrochemistry and chemical stability of the poly(vinylferrocene) (PVFc) redox couple, coated on a gold substrate, in aqueous solutions of H₂SO₄, HClO₄ and HCl was carried out. It was found that the anodic peak potential (E_pa) did not depend on the acid concentration in the range (1.0 × 10⁻² to 1.0 × 10⁻⁷ mol L⁻¹). However, the E_pa values shifted linearly to less positive potentials when investigated in more concentrated acid solutions in the range 1–5 mol L⁻¹. The slope of the E_pa versus acid concentration graph was found to be in the order H₂SO₄ > HCl > HClO₄. In this regard PVFc behaved very similar to 1,1′-bis(11-mercaptoundecyl)ferrocene (Fc(C₁₁SH)₂) except for its chemical stability. In H₂SO₄ media the PVFc was found to be much less stable than 1,1′-Fc(C₁₁SH)₂. The dependence of E_pa on acid concentration could be used to monitor state of charge of lead-acid batteries. However, for this application Fc(C₁₁SH)₂ would be a better choice because of its superior chemical stability.     

Studies on cerium (Ce/Ce)–vanadium(V/V) redox flow cell—cyclic voltammogram response of Ce/Ce redox couple in H2SO4 solution

A novel Ce⁴⁺/Ce³⁺–V²⁺/V³⁺ redox flow cell has been designed. The electrochemical responses of higher concentration Ce⁴⁺/Ce³⁺ couple in H₂SO₄ solution were investigated via cyclic voltammetry. The normal potential and the kinetic parameters for anodic oxidation of Ce³⁺ and cathodic reduction of Ce⁴⁺ were measured. The results showed the surface of platinum electrode was fully covered with type I oxide that inhibited the reduction of Ce⁴⁺. The reversibility of the Ce⁴⁺/Ce³⁺ couple improved with the increase of H₂SO₄ concentration. Different electrochemically active substances existed at various state of charge (SOC) and the reversibility of the Ce⁴⁺/Ce³⁺ couple at the carbon electrode was superior to platinum.     

Activity and corrosion of tungsten carbide recombination electrodes during lead/acid battery operation

The oxidation of the tungsten carbide (WC) catalyst in recombination electrodes partially immersed in H₂SO₄ solution was investigated when the electrodes operated in an atmosphere of oxygen and hydrogen. It has been established that after a long operation period (400 h) 60 to 70% of the catalysts, depending on the initial active surface of WC, may be oxidized to WO_x, whereby the rate of recombination decreases about three times. It is assumed that the oxidation of WC is due to the H₂O₂ formed as an intermediate product of the recombination of hydrogen and oxygen. Silver accelerates the decomposition of H₂O₂ and hence the use of a WC—Ag mixture as catalyst in the recombination electrodes reduces strongly the carbide corrosion.     

Proton conductivity and chemical stability of Li2SO4 based electrolyte in a H2S–air fuel cell

Proton conductivity of Li₂SO₄-Al₂O₃ (LA) based electrolyte was determined under non-reducing dynamic conditions using current interruption technique. The performance of LA as electrolyte has been examined at 600 °C in a H₂S fuel cell with MoS₂-NiS as anode catalyst and NiO as cathode catalyst. XRD and XPS results show that Li₂SO₄ is not stable when heated in pure H₂S as it is reduced to Li₂S by hydrogen produced in equilibrium amounts from the thermal decomposition of H₂S. In contrast, under dynamic operation in a H₂S fuel cell the concentration of H₂ is much lower, the reduction reaction does not occur and, surprisingly, Li₂SO₄ is a chemically stable electrolyte.