表面改性铁刨花活化过硫酸盐降解水体中的对硝基苯酚

以机加工废料铁刨花为原料,采用盐溶液吸氧腐蚀的绿色制备方法,在铁刨花表面原位合成γ-FeOOH层,并用X射线衍射(XRD)对其物象进行表征。以对硝基苯酚(4-NP)为目标污染物,研究γ-FeOOH@Fe复合材料活化过硫酸钾(K₂S₂O₈)降解污染物的性能。结果表明,γ-FeOOH@Fe复合材料活化K₂S₂O₈降解4-NP的效率明显优于单纯的铁刨花,在室温条件下,当pH值为7.0、4-NP初始质量浓度为10 mg/L、K₂S₂O₈质量浓度为40 mg/L、γ-FeOOH@Fe投加量为2 g/L时,反应24 min后,4-NP降解率达到92.3%;水中无机阴离子H₂PO₄-和HCO₃^-对γ-FeOOH@Fe活化K₂S₂O₈降解4-NP表现出不同...     

不同活化过硫酸盐体系深度处理制浆造纸废水研究

采用光-Na₂S₂O₈、热-Na₂S₂O₈、Fe²⁺-Na₂S₂O₈、光/Fe³⁺-Na₂S₂O₈、以及超声-Na₂S₂O₈等5种活化体系对造纸废水深度处理中有机物降解的效果进行了研究,考察了pH、温度、初始Na₂S₂O₈浓度、Fe²⁺浓度、Fe³⁺浓度以及超声频率对造纸废水COD降解的影响。结果表明：5种体系对造纸废水COD降解效率比较为：热-Na₂S₂O₈（84.2%）>光/Fe³⁺-Na₂S...     

Na2S2O3·5H2O复合材料的制备及循环稳定性能

为了解决Na₂S₂O₃·5H₂O存在的过冷度过大导致不结晶的问题,提高复合相变材料的循环稳定性并抑制相分离现象,以CaSO₄和1-萘酚（C₁₀H₈O）为成核剂;聚丙烯酸钠（PAAS）和羧甲基纤维素钠（CMC）为增稠剂进行改良,通过步冷曲线和差示扫描量热法（DSC）对复合相变材料进行了研究。实验结果表明：加入质量分数为1%和5%的CaSO₄、0.5%和3%的C₁₀H₈O对Na₂S₂O₃·5H₂O有较好的成核作用。萘酚体系在加入增稠剂后降温冷却时不出现结晶现象。对于CaSO₄体系,增稠剂PAAS效果优于CMC,Na₂S₂O₃·5H₂O+1%CaSO₄+2%PAAS复合材料相变温度47.7℃,相变潜热为200.4J/g;Na₂S₂O₃·5H₂O+5%CaSO₄+2%PAAS复合材料相变温度48.2℃,相变潜热为213.4J/g;经过100次高低温循环后,1%CaSO₄的复合材料相变温度47.6℃,相变潜热为192.4J/g,相较循环前相变潜热降低了3.99%。5%CaSO₄的复合材料相变温度47.8℃,相变潜热211.2J/g,相比循环前下降1.03%。5% CaSO₄体系较优于1% CaSO₄体系,循环前后潜热值、相变温度变化不大,循环稳定性良好。     

交联型PUA复合乳液的合成、表征与性能探究

采用半连续法以异佛尔酮二异氰酸酯（IPDI）、聚醚210、二羟甲基丙酸（DMPA）等为聚氨酯原料,甲基丙烯酸甲酯（MMA）和丙烯酸丁酯（BA）为丙烯酸酯类单体,甲基丙烯酸羟丙酯（HPMA）为偶联剂,过硫酸钾（K₂S₂O₈）为引发剂,三羟甲基丙烷（TMP）为交联剂,合成了具有明显核壳结构的丙烯酸酯改性水性聚氨酯（PUA）乳液。通过傅里叶红外光谱和透射电镜对聚合物结构和乳胶粒形态进行表征,并通过接触角（CA）、力学性能测试,差示量热扫描（DSC）和热重分析（TG）等手段研究了乳胶膜的性能。结果显示,当TMP用量为0.8%时,乳胶粒呈核壳结构,乳液稳定性能好,乳胶膜的拉伸强度达到12.5MPa,对水的静态接触角为96°,耐水性和耐热性也有显著提高。     

PAN-H1.6Mn1.6O4锂离子筛膜的制备及在卤水中吸附性能

采用亲水的PAN为成膜材料,制备了掺杂H_1.6Mn_1.6O₄的PAN-H_1.6Mn_1.6O₄锂离子筛膜。通过SEM、Li⁺静态吸附实验、（NH₄）₂S₂O₈对锂的洗脱实验和卤水中吸附实验,研究了锂离子筛的添加量对PAN-H_1.6Mn_1.6O₄锂离子筛膜结构、Li⁺吸附-洗脱性能的影响。结果表明,PAN浓度为10%（质量）,H_1.6Mn_1.6O₄的添加量为50%（质量）时,PAN-H_1.6Mn_1.6O₄离子筛膜的吸附量为17.45 mg·g^-1,达到粉末状吸附量的88.0%。以（NH₄）₂S₂O₈为洗脱剂,当浓度为0.3 mol·L^-1、液固比为600:1、时间为12 h时,锂洗脱量为17.23 mg·g^-1,锰溶损率仅为1.14%。在含有Na⁺、K⁺、Mg²⁺和Ca²⁺的罗布泊老卤卤水中,锂离子筛膜对Li⁺有很高的选择性。在卤水中进行10次吸附与解吸循环,吸附量从11.64 mg·g^-1下降到10.94 mg·g^-1,吸附容量仅损失6.0%。总体结果表明亲水性载体对H_1.6Mn_1.6O₄吸附容量影响较小,温和的洗脱剂对锂离子筛膜的化学稳定性有利。     

天然水体总磷测定的消解方法改进研究

水体中总磷的含量是测定水质的一项重要指标。本文针对硫酸-硝酸、过硫酸钾-高温高压消解法的缺陷,研究发现过硫酸钾-消解仪法可以缩短消解时间且操作方便、水样及试剂用量少。过硫酸钾-消解仪法的消解优化条件为：水样5.00mL、K₂S₂O₈投加量为1.5mL、消解温度150℃、消解时间70min,消解效果与硫酸-硝酸消解法一致。     

硝化腐植酸基离子印迹聚合物的制备及吸附性能研究

以腐植酸为原料、浓硝酸为氧化剂合成硝化腐植酸（NA）,再以硝化腐植酸为基质、N-异丙基丙烯酰胺（NIPAM）为功能单体、Pb（NO₃）₂为模板、N,N-亚甲基双丙烯酰胺（MBA）为交联剂、过硫酸钾（K₂S₂O₈）与亚硫酸氢钠（NaHSO₃）为复合引发剂,经过沉淀聚合法制备铅离子印迹聚合物IIPs。利用SEM、FT-IR、TG-DSC表征所得产物,探究产物的结构与性能,并通过紫外-可见分光光度法（UV-Vis）研究了IIPs的吸附性能。结果表明,IIPs对Pb²⁺的最大吸附量为21.71 mg/g,该吸附过程符合二级动力学模型和Langmuir热力学模型;IIPs最佳循环次数为7次;在竞争离子Cu²⁺和Cd²⁺存在时,选择性系数分别为6.97(Pb²⁺/Cu²⁺)和7.36(Pb²⁺/Cd²⁺)。     

Preparation and performance of a new sulfonate copolymer scale inhibitor

用水作溶剂,（NH₄）₂S₂O₈/NaHSO₃氧化还原体系作为引发剂,以2-丙烯酰胺基-2-甲基丙烷磺酸（AMPS）、马来酸酐（MA）为单体,与自制的聚乙二醇-衣康酸酯通过溶液聚合制备了一种新型磺酸基聚合物阻垢剂。用红外光谱和热分析方法对聚合物进行了表征和分析。探讨了单体配比、引发剂用量、反应温度对聚合物阻垢性能的影响。结果表明,该共聚物对于碳酸钙盐具有优异的阻垢效果。阻垢剂用量为15 mg/L时,对碳酸钙的阻垢率可达到95%以上。     

In2O3/Ag：ZnIn2S4“Type Ⅱ”型异质结构材料的制备及可见光催化性能

采用低温油浴的方法,制备出具有“Type Ⅱ”异质结构的In₂O₃/Ag:ZnIn₂S₄复合材料光催化剂。使用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis DRS）以及光电化学测试（PEC）等技术对物相、形貌结构、元素化合状态、光响应特性等方面进行探究。在可见光照射下进行光解水制氢和光降解甲基橙（MO）实验来评价光催化剂的光催化活性,结果表明,粉末状光催化剂 In₂O₃/40.0%（质量分数）Ag:ZnIn₂S₄的光催化制氢速率达到 21.85 μmol·h^-1,约是In₂O₃和Ag:ZnIn₂S₄的57.5倍和1.5倍。在可见光下的降解MO实验中,In₂O₃/40.0% Ag:ZnIn₂S₄光降解速率为0.3466 min^-1,分别约是In₂O₃和Ag:ZnIn₂S₄的105倍和2.1倍。这主要归因于In₂O₃和Ag:ZnIn₂S₄之间形成的“Type Ⅱ”异质结构,促使光生载流子的快速迁移和分离。     

In2O3/Ag：ZnIn2S4“Type Ⅱ”型异质结构材料的制备及可见光催化性能

采用低温油浴的方法,制备出具有“Type Ⅱ”异质结构的In₂O₃/Ag:ZnIn₂S₄复合材料光催化剂。使用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis DRS）以及光电化学测试（PEC）等技术对物相、形貌结构、元素化合状态、光响应特性等方面进行探究。在可见光照射下进行光解水制氢和光降解甲基橙（MO）实验来评价光催化剂的光催化活性,结果表明,粉末状光催化剂 In₂O₃/40.0%（质量分数）Ag:ZnIn₂S₄的光催化制氢速率达到 21.85 μmol·h^-1,约是In₂O₃和Ag:ZnIn₂S₄的57.5倍和1.5倍。在可见光下的降解MO实验中,In₂O₃/40.0% Ag:ZnIn₂S₄光降解速率为0.3466 min^-1,分别约是In₂O₃和Ag:ZnIn₂S₄的105倍和2.1倍。这主要归因于In₂O₃和Ag:ZnIn₂S₄之间形成的“Type Ⅱ”异质结构,促使光生载流子的快速迁移和分离。     

Degradation of pesticides in water using solar advanced oxidation processes

Alachlor, atrazine and diuron dissolved in water at 50, 25 and 30 mg/L, respectively were photodegraded by Fe²⁺/H₂O₂, Fe³⁺/H₂O₂, TiO₂ and TiO₂/Na₂S₂O₈ treatments driven by solar energy at pilot-plant scale using a compound parabolic collector (CPC) photoreactor. All the advanced oxidation processes (AOPs) employed mainly compared the TOC mineralisation rate to evaluate treatment effectiveness. Parent compound disappearance, anion release and oxidant consumption are discussed as a function of treatment time. The use of Fe²⁺ or Fe³⁺ showed no influence on the reaction rate under illumination and the reaction using 10 or 55 mg/L of iron was quite similar. TiO₂/Na₂S₂O₈ showed a quicker reaction rate than TiO₂ and a similar rate compared to photo-Fenton. The main difference found was between TiO₂/Na₂S₂O₈ and photo-Fenton, detected during atrazine degradation, where pesticide transformation into cyanuric acid was confirmed only for TiO₂/Na₂S₂O₈.     

硫酸盐熔融反应法从钛铁矿中提取钛的研究

以海南万宁的钛铁矿和硫酸铵为主要原料,通过熔融反应法使钛铁矿中的钛转化为易溶于稀酸的硫酸氧钛,用稀硫酸浸取,达到提高钛浸取率的目的。考察了硫酸铵加入量、焦硫酸钾加入量、反应温度、稀硫酸浸取浓度对钛浸取率的影响。实验结果表明：硫酸铵和焦硫酸钾的加入量、反应温度对钛浸取率的影响较大。提高钛浸取率的最佳条件为：m（钛铁矿）∶m（硫酸铵）∶m（焦硫酸钾）=1∶6∶0.5,反应温度为450 ℃,保温时间为30 min,稀硫酸浸取浓度为2.32 mol/L,在此条件下钛的浸取率达到96.82%。     

钒铬还原渣酸浸液中钒铬初步分离工艺

钒铬还原渣是钠化提钒过程的典型危险固体废弃物,其资源化利用需求迫切。中国科学院过程工程研究所提出钒铬还原渣硫酸酸解-钒铬初步分离-铬/钒/铁络合深度分离技术路线,并在攀钢集团建成万吨级示范工程。本文重点考察钒铬还原渣酸解液中钒铬初步分离原理及工艺,研究了H₂O₂和Na₂S₂O₈两种氧化剂对沉钒效果的影响,并通过实验确定了最佳工艺条件。结果表明：以H₂O₂为氧化剂时,H₂O₂与钒摩尔比为0.75、氧化温度为60℃、初始溶液pH为2.0、氧化时间为60min、水解温度为95℃、水解时间为2.5h的条件下可得到84.2%的沉钒率;以Na₂S₂O₈为氧化剂时,Na₂S₂O₈与钒摩尔比为0.65、氧化温度为90℃、氧化时间为45min、沉钒初始溶液pH为2.5、沉钒温度为90℃、沉钒时间为2.5h的条件下可获得93.1%的沉钒率。过硫酸钠氧化过程温和,沉钒率高,铬损失小,更适合工业推广应用。采用SEM获得了沉淀产物的微观形貌,煅烧后得到V₂O₅产品,采用XRF获得了产品组成,通过X射线衍射确定得到的V₂O₅产品为正交晶型。     

THE DEHYDRATION OF GARLIC 2. THE EFFECTS OF PRETREATMENTS ON DRYING KINETICS

The kinetics of drying of pretreated garlic slices of thickness 1.5 - 5.0 mm were determined at between 40 and 60°C using an air flow rate of 2.5 m/s. Pretreatmenl consisted in immersion of the slices in water or solutions of K₂CO₃, K₂CO₃ with olive oil, Na₂S₂O₅ or NaOH, at 25°C for 60 or ISO s. The effects of each pretreatmenl on the drying kinetics and the quality of the dried product were evaluated, in the latter case by determining its rehydration ratio. Pretreatment with water or the Na₂S₂O₅ solution gave good results regardless of the thickness of the garlic slices, whereas pretreatment with a dilute NaOH solution gave good resuhs for thin slices (≤2.5 mm). The experimental kinetic data were satisfactorily fitted by a difiusional kinetic model developed in Part 1 of this work.     

Molecular structure–reactivity relationships for the oxidation of sulfur dioxide over supported metal oxide catalysts

The catalytic oxidation of sulfur dioxide to sulfur trioxide over several binary (M_xO_y/TiO₂) and ternary (V₂O₅/M_XO_Y/TiO₂) supported metal oxide catalysts was systematically investigated. The supported metal oxide components were essentially 100% dispersed as surface metal oxide species, as confirmed by Raman spectroscopy characterization. The sulfur dioxide oxidation turnover frequencies of the binary catalysts were all within an order of magnitude (V₂O₅/TiO₂>Fe₂O₃/TiO₂>Re₂O₇/TiO₂  CrO₃/TiO₂  Nb₂O₅/TiO₂>MoO₃/TiO₂  WO₃/TiO₂). An exception was the K₂O/TiO₂ catalysts, which is essentially inactive for sulfur dioxide oxidation. With the exception of K₂O, all of the surface metal oxide species present in the ternary catalysts (i.e., oxides of V, Fe, Re, Cr, Nb, Mo and W) can undergo redox cycles and oxidize SO₂ to SO₃. The turnover frequency for sulfur dioxide oxidation over all of these catalysts is approximately the same at both low and high surface coverages. This indicates that the mechanism of sulfur dioxide oxidation is not sensitive to the coordination of the surface metal oxide species. A comparison of the activities of the ternary catalysts with the corresponding binary catalysts suggests that the surface vanadium oxide and the additive surface metal oxide redox sites act independently without synergistic interactions. The V₂O₅/K₂O/TiO₂ catalyst showed a dramatic reduction in the catalytic activity in comparison to the unpromoted V₂O₅/TiO₂ catalyst. The ability of K₂O to significantly retard the redox potential of the surface vanadia species is primarily responsible for the lower catalytic activity of the ternary catalytic system. The fundamental insights generated from this research can potentially assist in the molecular design of the air pollution control catalysts: (1) the development of catalysts for low temperature oxidation of SO₂ to SO₃ during sulfuric acid manufacture (2) the design of efficient SCR DeNO_x catalysts with minimal SO₂ oxidation activity and (3) improvements in additives for the simultaneous oxidation/sorption of sulfur oxides in petroleum refinery operations.     

内插扭带对鼓泡反应器脱硫脱硝效果的影响

在玻璃鼓泡反应器中进行Na₂S₂O₈和H₂O₂两种混合氧化剂吸收SO₂和NO的实验研究,结果表明：在Na₂S₂O₈氧化剂中加入H₂O₂可以促进脱硫脱硝,考虑溶液的成本以及系统的整体脱硫脱硝总效率,选取质量分数为2%的H₂O₂和10%的Na₂S₂O₈混合液具有较高的性价比。基于数值模拟的方法,将扭带引入鼓泡反应器中,研究扭带直径、厚度和扭率对鼓泡反应器脱硫脱硝效率的影响。数值模拟结果表明,与普通鼓泡反应器相比,加入扭带促进脱硫脱硝的效果。脱硫脱硝效率随着扭带直径和扭带厚度的增大而增大,随着扭带扭率的增大而减小,当扭带的直径从16mm增加到24mm时,系统的脱硫率和脱硝率分别增加了3.88%和3.45%;当扭带的厚度从0.2mm增加到1mm时,系统的脱硫率和脱硝率分别增加了4.27%和1.62%;当扭带的扭率从0.25增加到0.75时,系统的脱硫率和脱硝率分别降低了3.91%和1.90%。     

Removal of nitric oxide from simulated flue gas using aqueous persulfate with activation of ferrous ethylenediaminetetraacetate in the rotating packed bed

Nitric oxide being a major gas pollutant has attracted much attention and various technologies have been developed to reduce NO emission to preserve the environment. Advanced persulfate oxidation technology is a workable and effective choice for wet flue gas denitrification due to its high efficiency and green advantages. However, NO absorption rate is limited and affected by mass transfer limitation of NO and aqueous persulfate in traditional reactors. In this study, a rotating packed bed (RPB) was employed as a gas–liquid absorption device to elevate the NO removal efficiency (η_NO) by aqueous persulfate ((NH₄)₂S₂O₈) activated by ferrous ethylenediaminetetraacetate (Fe²⁺-EDTA). The experimental results regarding the NO absorption were obtained by investigating the effect of various operating parameters on the removal efficiency of NO in RPB. Increasing the concentration of (NH₄)₂S₂O₈ and liquid–gas ratio could promoted the oxidation and absorption of NO while theη_NO decreased with the increase of the gas flow and NO concentration. In addition, improving the high gravity factor increased the η_NO and the total volumetric mass transfer coefficient (K_Gα) which raise the η_NO up to more than 75% under the investigated system. These observations proved that the RPB can enhance the gas–liquid mass transfer process in NO absorption. The correlation formula between K_Gα and the influencing factors was determined by regression calculation, which is used to guide the industrial scale-up application of the system in NO removal. The presence of O₂ also had a negative effect on the NO removal process and through electron spin resonance spectrometer detection and product analysis, it was revealed that Fe²⁺-EDTA activated (NH₄)₂S₂O₈ to produce •SO₄^–, •OH and •O₂^–, played a leading role in the oxidation of NO, to produce NO₃^– as the final product. The obtained results demonstrated a good applicable potential of RPB/PS/Fe²⁺-EDTA in the removal of NO from flue gases.     

KBaB5O9的两步法制备及其过程动力学研究

本文利用溶液法制备了K₂Ba[B₄O₅(OH)₄]₂·8H₂O,并将其进行热处理制备得到了KBaB₅O₉,利用XRD、FT-IR、TG-DTA-DTG对样品进行了表征。分析研究了由K₂Ba[B₄O₅(OH)₄]₂·8H₂O热处理制备KBaB₅O₉过程中的物相变化过程,其物相变化经历脱结晶水、脱羟基、重结晶、再分解、熔融再结晶5个阶段,其中结晶水的脱失分两步进行。运用Kissinger法、Flynn-Wall-Ozawa法、Šatava-Šesták法对K₂Ba[B₄O₅(OH)₄]₂·8H₂O结晶水第二步脱失过程的动力学参数进行了计算,可知K₂Ba[B₄O₅(OH)₄]₂·8H₂O结晶水第二步脱失过程的活化能E_s为151.94 kJ/mol,指前因子的对数值lg A_s为21.25 min^-1,机理函数G(α)=(1-2α/3)-(1-α)^2/3(其中α为转化率)。     

Promotion of palladium-based catalysts on metal monolith for partial oxidation of methane to syngas

Four different modifications of alumina were prepared for use as the support for a Pd catalyst used for the partial oxidation of methane to syngas. The catalysts were washcoated on a metallic monolith in order to determine their activities at high gas flow rates. Compared with the Pd/Al₂O₃ catalyst, enhanced partial oxidation activities were observed with the Pd/CeO₂/Al₂O₃, Pd/CeO₂/BaO/Al₂O₃ and Pd/CeO₂/BaO/SrO/Al₂O₃ catalysts. The palladium particles were better dispersed in the presence of CeO₂ and SrO. Adding BaO, CeO₂ and BaO–CeO₂ to γ-Al₂O₃ prevented the transformation of the alumina phase during the 3-day aging process at 1000 °C, providing the support with some level of thermal stability. The addition of small amounts of SrO to the CeO₂/BaO/Al₂O₃ support enhanced the thermal stability of the Pd particles and minimized their sintering. The triply promoted Pd catalyst studied in this work was effective in carrying out partial oxidation at high temperatures, with BaO and CeO₂ promoting the thermal stability of the support, CeO₂ and SrO dispersing the Pd particles and SrO anchoring the Pd particles strongly to the support. The composition of the catalyst which gave both the highest partial oxidation activity and the best thermal stability was Pd(2)/CeO₂(23)/BaO(11)/SrO(0.8)/Al₂O₃.