DBU-based CO_2 absorption–mineralization system: Reaction process,feasibility and process intensification

Amine-based carbon dioxide(CO_2) capture is still limited by high desorption energy consumption. Fixing CO_2 into carbonate is a safer and more permanent method. In this work, calcium oxide(CaO) is introduced to perform chemical desorption instead of thermal desorption on 1,8-diazabicyclo [5.4.0] undec-7-ene(DBU) aqueous solution after CO_2 absorption. The X-ray diffraction(XRD) patterns of solid products show the formation of calcite calcium carbonate(CaCO_3), which prove the feasibility of this method. The effects of reaction temperature, reaction time and Ca~(2+)/CO_3~(2-) molar ratios on the related reactions in CO_2 absorption–mineralization process and CaCO_3 precipitation are discussed, and purer CaCO_3 is obtained by ultrasonic treatment. The CaCO_3 content can be increased to 95.8% and the CO_2 desorption ratio can achieve 80% by 30 min ultrasonic dispersion treatment under the conditions(40℃, 180 min, Ca~(2+)/CO_3~(2-) molar ratio = 1.0). After five cycles, DBU aqueous solution shows stable CO_2 absorption and mineralization ability. Fourier transform infrared spectroscopy(FT-IR) spectra of the reaction process also indicate the regeneration of the solvent. Compared with thermal desorption, this process is exothermic, almost without no additional heat.     

二氧化碳在双极膜电渗析系统中溶解吸收过程的研究

在二氧化碳捕集、利用和封存（CCUS）技术中,海水固碳技术绿色环保、安全可靠,具有很好的发展前景。其中,双极膜电渗析法海水固碳技术的关键之处在于二氧化碳在系统中的溶解吸收。考察了结晶器中添加晶种、通气体系成分、模拟烟道气流量、双极膜电渗析装置的电流密度对海水固碳过程中二氧化碳溶解吸收效果的影响,结果表明：系统外加晶种、模拟烟道气作为通气体系时更有利于二氧化碳在双极膜电渗析系统中的溶解吸收,促进碳酸钙生成。在上述基础上,随着模拟烟道气流量的增加,二氧化碳的比吸收速率降低,二氧化碳在溶液中大部分转化成碳酸氢根,碳酸根和碳酸钙的生成速率则会降低;随着电渗析装置电流密度的提高,碳酸氢根、碳酸根和碳酸钙的生成速率均会随之提高。该研究为酸性气体在双极膜电渗析系统中溶解吸收和矿化利用提供了指导。     

Desorption of Cl- from Mg-Al layered double hydroxide intercalated with Cl- using CO2 gas and water

Mg-Al layered double hydroxide intercalated with CO_3~(2-)(CO_3·Mg-Al LDH) is effective for treating HCl exhaust gas.HCl reacts with CO_3~(2-) in CO_3·Mg-Al LDH, resulting in the formation of Cl·Mg-Al LDH.We propose that CO_2 can be used for the desorption of Cl~-from Cl·Mg-Al LDH to regenerate CO_3·Mg-Al LDH.Herein,we studied the desorption of a from CI-Mg-Al LDH by adding water to Cl·Mg-Al LDH and blowing CO_2 into it.We also analyzed the effects of temperature and water addition speed on the desorption of CI~-from Cl·Mg-Al LDH.Our results show that the added water adhered to CI·Mg-Al LDH and that CO_2 in the gaseous phase was dissolved in this adhered water,thus generating CO_3~(2-).Therefore,anion exchange occurred between CO_3~(2-) and Cl~-in the Cl·Mg-Al LDH,thus desorbing Cl~-.     

基于阴离子交换反应的NiMn-LDH电极电容性能提升研究

采用一步水热法在泡沫镍网上原位生长镍锰基层状双氢氧化物（NiMn-LDH）纳米片阵列电极,并通过氢氧化钾溶液中浸泡的方式提升电极的容量。采用SEM、XRD、TEM和XPS等手段对浸泡前后的电极材料进行表征。结果表明,在浸泡前后NiMn-LDH电极的形貌没有变化,但在电极材料内部发生了明显的CO₃^2-和OH^-的交换反应,降低体积较大的CO₃^2-在LDH层间的分布数量,使层内空间成为OH^-的“蓄水池”,缩短了电荷存储过程中OH^-的迁移距离,因此电容性能有了明显提升。电化学测试结果表明,在5 mA/cm²电流密度下,电极的比电容从18.0 F/g增加至766.6 F/g（1.69 F/cm²）。将该电极与活性炭组装的全固态不对称超级电容器在功率密度为900 W/kg时,可呈现的能量密度为35.9 W·h/kg,并且器件的循环稳定性良好。     

府谷煤CO2催化气化反应性的研究

加入适宜的催化剂可以提高气化反应速率,降低起始气化温度。为了研究不同阴离子（SO₄^2-、CO₃^2-、Cl^-）盐对府谷煤热失重过程的影响,利用热重分析仪对负载了8种催化剂（K₂CO₃、K₂SO₄、KCl;Na₂CO₃、Na₂SO₄、NaCl;FeSO₄、FeCl₂）的煤样进行了CO₂气化实验,其中每克府谷煤的K⁺、Na⁺、Fe²⁺负载量分别为0.001mol。同时采用升温动力学模型进行了数据拟合。实验结果表明：催化剂对煤与CO₂的低温热解并无明显的催化作用,而在高温气化阶段催化效果显著。对于钾盐和钠盐催化剂,当阳离子相同时,其催化活性顺序为：CO₃^2->SO₄^2->Cl^-。对于铁盐催化剂,FeSO₄的催化活性优于FeCl₂。动力学结果发现：负载催化剂煤样的活化能大小符合上述实验规律,分布在169～232.6kJ/mol之间,相比原煤（267.9kJ/mol）都有一定程度的降低。     

Separation of mixed salts(Cl~-/SO_4~(2-)) by ED based on monovalent anion selective membranes

The industrial products or wastewater rich in the mixed salts(Cl~-/SO_4~(2-)) not only causes the environmental damage, but also induces waste of resource. In this study, an ED stack with monovalent selective AEMs and conventional CEMs was employed to separate the Cl~-and SO_4~(2-)from simulated wastewater. The effect of current density and mass fraction percentage was investigated in order to optimize the experimental conditions during ED process. It was found that at a concentration ratio between NaCl and Na_2SO_4 of 95/5(wt%/wt%) and a current density of40 m A·cm~(-2), a current efficiency of 72%, an energy consumption of 1.6 k W·h·kg~(-1) Na Cl and a Cl~-/SO_4~(2-)concentration(67.5/3.5 g·L~(-1)) were obtained. Hence, it is appropriate and effective to separate Cl~-and SO_4~(2-)by ED using the monovalent selective AEMs.     

Wood液态合金在NaOH溶液中的电化学反应及表面张力变化行为

通过改变液体金属在NaOH溶液中所处的环境介质,利用石墨电极对其施加电场,研究了液态金属的表面张力、界面电化学反应、氧化膜的产生、溶液中电润湿等动态过程。实验发现Wood合金液滴在阳极发生电化学反应产生的氧化膜会迅速减小表面张力并发生铺展,在阴极发生还原反应会使带氧化膜的金属在3 s内恢复到原状,电毛细作用力使氧化膜破裂,各氧化物与NaOH反应产生Sn（OH）₆^2-、SnO₃^2-、SnO₂^2-、PbO₃^2-、Cd（OH）₄^2-使溶液的颜色发生改变,溶液中生成Bi₂O₃-Bi（OH）₃白色共聚物。薄膜电介质层润湿和溶液中电润湿机理在本质上相同,表面张力随着电压的增大而减小并发生明显的电润湿铺展过程,但由于金属液滴通过电化学反应所能吸附的OH^-数量有限,润湿角存在饱和性。     

冬瓜基含TiO2炭气凝胶的制备、表征及其光催化性能

以冬瓜和钛酸四丁酯为原料,采用水热法和冷冻干燥法成功制备出含TiO₂炭气凝胶（WTCA）,研究了其对罗丹明B废水的光催化降解性能,并考察了水中常见无机盐离子对其光催化效果的影响。利用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、拉曼光谱仪（Raman）和荧光光谱仪（FL）等对样品结构和性能进行了表征。XRD、Raman和EDS分析表明复合气凝胶中含有锐钛矿TiO₂和碳元素;SEM和TEM分析表明TiO₂纳米颗粒均匀地负载在具有多级孔洞结构的炭气凝胶的骨架表面;含TiO₂炭气凝胶的光催化活性明显高于纯TiO₂,当负载量达30%时,其对罗丹明B的光催化降解效率最高（降解率达96.11%）。此外,无机盐阴离子对复合气凝胶的光催化效果有一定的抑制作用（CO₃^2- > SO₄^2- > Cl^- > NO₃^-）,而无机盐阳离子Na⁺、K⁺、Ca²⁺和Mg²⁺的抑制作用不明显。     

Preparation and characterization of sulfated TiO2 with rhodium modification used in esterification reaction and decomposition of methyl orange☆

A unique Rh/TiO_2 solid acid catalyst modified with H_2SO_4 was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange(MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium(Rh) nanoparticles were loaded on SO_4~(2-)/TiO_2 via the photo-deposition method. It was found that SO_4~(2-)/Rh–TiO_2 exhibited stronger catalytic activity than SO_4~(2-)/TiO_2. The new catalysts were characterized by X-ray powder diffraction(XRD), Brunauer–Emmett–Teller(BET), Transmission electron microscopy(TEM) and high-resolution(HRTEM), X-ray photoelectron spectroscopy(XPS) and Fourier Transform infrared spectroscopy(FTIR). Results from XRD and BET show that SO_4~(2-)/Rh–TiO_2 has higher specific surface area and smaller pore size than SO42-/TiO_2. The distribution of loaded Rh was found to be uniform with a particle size of 2–4 nm. Data from XPS reveal that Rh primarily exists as Rh~0 and Rh~(3+)in Rh–TiO_2 and SO_4~(2)-/Rh–TiO_2. These valence forms of Rh likely contribute to the enhanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh–TiO_2, and these acidic sites are largely responsible for improving the catalytic performance. This superior SO_4~(2-)/Rh–TiO_2 catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.     

深井降温系统管道结垢微观机理

以深部矿井降温系统管道内壁出现的结垢问题为研究对象,首先采集管道水样进行水质全分析测试,确定管道内成垢性离子并建立化学及数学模型,其次采用第一性原理计算方法研究得到了深部矿井降温系统管道结垢微观机理。结果表明,深井降温系统管道内壁结垢过程包括Ca²⁺和CO₃²⁺的结合结晶及MgCo₃、CaSO₄转化为CaCO₃的转化;理论分析及第一性原理计算结果表明,深井降温系统管道内壁结垢的主要影响因素为成垢性离子（Ca²⁺、HCO^-、Mg²⁺和SO₄^2-）,且和的存在会抑制碳酸钙结垢的产生。该研究对于深部高温热害矿井的降温系统的结垢产生机制以及采取合理的防、除垢措施,保障良好的矿井降温效果和安全生产具有理论指导意义。     

盐湖高锂卤水中硫酸根的分离与锂的迁移

以盐湖高锂卤水为原料,采用化学沉淀法,以无水氯化钙作为沉淀剂,脱除卤水中的硫酸根。详细考察了原料配比（钙离子与硫酸根物质量的比）、加料方式、加料时间、反应时间、搅拌转速和反应温度等条件对除硫率的影响,同时重点研究了反应过程中锂的夹带损失率和生成锂的复盐形式。得到除硫的适宜条件：原料配比为1.2,加料方式为正向加料即氯化钙溶液加入卤水中,反应温度为25 ℃,加料时间为24 min,搅拌转速为150 r/min,反应时间为60 min。在该实验条件下卤水中硫酸根的脱除率达到99.02%,锂的夹带损失率达到27.71%;通过扫描电镜可以得到沉淀产物的形貌,通过XRD表征结果可以说明在分离硫酸根的过程中锂离子主要是以Li₂SO₄·H₂O和LiAl₂（OH）₇（H₂O）₂的形式夹带损失。     

Electrochemical CO2 mineralization for red mud treatment driven by hydrogen-cycled membrane electrolysis

CO₂ mineralization as a promising CO₂ mitigation strategy can employ industrial alkaline solid wastes to achieve net emission reduction of atmospheric CO₂. The red mud is a strong alkalinity waste residue produced from the aluminum industry by the Bayer process which has the potential for the industrial CO₂ large scale treatment. However, limited by complex components of red mud and harsh operating conditions, it is challenging to directly mineralize CO₂ using red mud to recover carbon and sodium resources and to produce mineralized products simultaneously with high economic value efficiently. Herein, we propose a novel electrochemical CO₂ mineralization strategy for red mud treatment driven by hydrogen-cycled membrane electrolysis, realizing mineralization of CO₂ efficiently and recovery of carbon and sodium resources with economic value. The system utilizes H₂ as the redox-active proton carrier to drive the cathode and anode to generate OH^- and H⁺ at low voltage, respectively. The H⁺ plays as a neutralizer for the alkalinity of red mud and the OH^- is used to mineralize CO₂ into generate high-purity NaHCO₃ product. We verify that the system can effectively recover carbon and sodium resources in red mud treatment process, which shows that the average electrolysis efficiency is 95.3% with high-purity (99.4%) NaHCO₃ product obtained. The low electrolysis voltage of 0.453 V is achieved at 10 mA·cm^-2 in this system indicates a potential low energy consumption industrial process. Further, we successfully demonstrate that this process has the ability of direct efficient mineralization of flue gas CO₂ (15% volume) without extra capturing, being a novel potential strategy for carbon neutralization.     

固体酸催化淀粉一锅法制备果葡糖浆的研究

研究了几种负载型固体酸催化剂催化淀粉转化为果葡糖浆的催化效果,其中,超稳Y型分子筛（USY）负载硫酸制备得到的SO₄^2-/USY可以作为双功能催化剂,既催化淀粉水解为葡萄糖,又使葡萄糖异构为果糖,实现了淀粉一锅法制备果葡糖浆的工艺途径,具有良好的催化效果。对催化剂的制备条件进行优化,发现较佳的制备条件为1.5 mol/L H₂SO₄和550℃的焙烧温度。以此为催化剂对反应条件进行优化,获得较佳的反应条件是5%淀粉（淀粉/水）、催化剂用量为淀粉质量的30%、反应温度为150℃、反应时间为1 h、转速400 r/min,得到的果葡糖浆得率为86.18%,含58.34%的葡萄糖和27.84%的果糖。对催化剂进行物理吸附表征,发现USY具有较高的比表面积和孔隙度,通过浸渍焙烧过程能有效使硫酸通过键合作用吸附在USY表面上。对催化剂进行NH₃程序升温脱附和元素分析表征发现,催化剂的重复使用活性降低与含碳有机质沉积和催化活性中心的SO₄^2-流失有关。通过简单的焙烧（除去表面积碳）和硫酸中浸渍活化（增加SO₄^2-）的催化剂再生方法,可以有效地恢复SO₄^2-/USY的催化活性。     

紫外/亚硫酸钠体系对2,4,6-三溴酚的脱溴效果及机理

研究了紫外/亚硫酸钠（UV/SO₃^2-）体系对2,4,6-三溴酚（2,4,6-TBP）的脱溴效果及影响因素,分析了还原体系2,4,6-TBP的脱溴过程、降解机理及降解路径。结果表明：UV/SO₃^2-还原体系对2,4,6-TBP的降解效果明显高于单独UV体系;亚硫酸钠浓度、pH与反应温度均对还原体系目标污染物的降解影响显著。随着亚硫酸钠浓度升高、pH上升及反应温度提高,UV/SO₃^2-体系2,4,6-TBP的降解效果逐渐增加。准一级动力学方程可描述不同亚硫酸钠浓度与反应温度时还原体系对目标污染物的降解过程。水合电子捕获剂的添加可有效抑制2,4,6-TBP的脱溴反应;UV/SO₃^2-体系污染物还原降解速率与溴离子产生率均高于单独UV体系。还原体系中2,4,6-TBP在水合电子作用下逐级脱溴降解为低毒性物质。     

Kinetic studies of the electrolytic reduction of carbon dioxide on the mercury electrode

The reduction of CO₂ to HCOOH has been studied for the Hg electrode in neutral and acidic aqueous solutions in the potential range between −0.8 and −1.9 V(sce). In the neutral pH range all the current is consumed in the production of formic acid, while in acid solutions both HCOOH and H₂ are produced. Steady-state polarization curves, cathodic galvanostatic charging curves. current-efficiency measurements, reaction orders with respect to CO₂ partial pressure, and double-layer variation have been used to determine possible reaction pathways. In neutral solutions the mechanism may be described by a direct reduction of CO₂ in which two consecutive charge-transfer steps occur. In acidic solutions the above process occurs in parallel with the reduction of H₃O⁺ ions. The H atoms formed react in a branching mechanism either with H₃ O⁺ ions and electrons to yield H₂, or with CO₂ to yield eventually HCOOH.     

Chlorine-free emission disposal of spent acid etchant in a three-compartment ceramic membrane reactor

Electrochemical technologies for the on-site treatment of spent acid etchant have received great attention due their ease of operation and economic benefits. On the other hand, a large amount of Cl₂ is generated during the electrolysis process, which leads to potential environmental risks. In the present work, a novel threecompartment ceramic membrane flow reactor, including a cathode chamber, an anode chamber, and a gas absorption chamber was developed. The three chambers were divided by an Al₂O₃ ceramic membrane and a breathable hydrophobic anode diffusion electrode (ADE). The Cl₂ evolution onset potential of the ADE was increased to 1.19 V from 1.05 V of the graphite felt, effectively inhibiting the chlorine evolution reaction (CER). The anode-generated Cl₂ diffused into the gas absorption chamber through the ADE and was eventually consumed by the H₂O₂ adsorbent. Cu could be recovered without emitting chlorine due to the special structure of reactor. The current efficiency of copper precipitation and cathode reduction from Cu²⁺ to Cu⁺ reached 97.7% at a working current of 150 mA. These results indicated that the novel membrane reactor had high potential for application in the copper recovery industry.     

新型纳米SO42-/TiO2催化剂制备及催化合成醋酸丁酯

采用高压水热法合成纳米锐钛矿相TiO₂前驱体,通过H₂SO₄溶液浸渍制备系列新型SO₄^2-/TiO₂催化剂,采用XRD、TG-DTG和TEM对其结构和形貌进行表征,并用于催化醋酸与正丁醇的酯化反应,考察H₂SO₄溶液浓度、浸渍时间和反应时间对酯化率的影响。结果表明,在H₂SO₄浓度1 mol·L^-1、浸渍时间12 h和反应时间180 min条件下,酯化率高达99.2%,催化剂具有优异的催化性能和较佳的重复使用性。     

硫酸根对聚合氮化碳光催化活性的影响

在pH=1条件下分别加入硫酸根、硝酸根、磷酸根对三聚氰胺进行处理,采用高温煅烧法制备了一系列聚合氮化碳材料,并通过X射线衍射（XRD）、扫描电子显微镜（SEM）、紫外-可见漫反射光谱（UV-Vis DRS）等分析手段对样品进行了表征。以罗丹明B（RhB）为污染物,探究了在可见光下聚合氮化碳对RhB的光催化降解性能、稳定性以及降解机理。加入0.12 mol硫酸根处理的聚合氮化碳（CN-0.04SO₄^2-）在45 min内对RhB的降解率为99.1%,其伪一级动力学常数是未加硫酸根的23.0倍,硫酸根能有效地增强聚合氮化碳的光催化活性。CN-0.04SO₄^2-经过3次循环实验对RhB的降解率略有下降,说明其具有良好的稳定性。活性物种捕获实验表明,影响光催化降解RhB的主要活性物种是·O₂^-和·OH。     

On the formation of pyronitrate in molten salts

N₂O₅ reacts with O²⁻ ion in LiCl---KCl eutectic at 450° to give NO₃⁻. By analogy to the salts of the other oxides of Group V, NO₃⁻ can be considered as metanitrate and is expected to give—under appropriate conditions—the corresponding pyro-salt. Experiments are described in which the O²⁻ ion in LiCl---KCl melt is potentiometrically titrated with KNO₃. The titration curves show an inflexion at the composition corresponding to pyronitrate, N₂O₇⁴⁻.

The formation of pyronitrate in KNO₃ melts is also established. Strong oxide-ion donors, eg Na₂O₂ or NaOH, or electrolytically generated O²⁻ ion, react slowly with the melt to produce a compound of less basic character. The reaction is zero-order with respect to O²⁻ and has an activation energy of ca 6·17 Kcal/mole.

Pyronitrate in molten KNO₃ possesses a basicity comparable to that of the carbonate ion in the same melt. It readily lends its oxide ion to strong acids eg, Cr₂O₇²⁻ and PO₃⁻. X-ray diffraction patterns of NO₃⁻-N₂O₇⁴⁻ mixtures show peaks that can be correlated to the new anion.     

粉煤灰源C-S-H吸附U(Ⅵ)性能及机理

以粉煤灰铝回收过程的脱硅液为原料,通过控制钙硅摩尔比的常规沉淀法制备得到大比表面积介孔C-S-H（401 m²·g^-1）,系统研究了初始浓度、投加量、pH和离子强度对C-S-H吸附U（Ⅵ）过程的影响,以及吸附的热动力学特征,并评价了C-S-H去除实际含铀废水中毒性金属的性能。结果表明,通过控制合成条件实现了低品质硅钙渣向高附加值吸附材料的转变。0.75 g·L^-1 C-S-H在pH 2仍具有较高的平衡吸附容量（q_e=67.9 mg·g^-1）,在富含CO₃^2-的碱性溶液中UO₂（H₂O）₅²⁺转变为UO₂（CO₃）₃^4-不利于带负电的C-S-H表面吸附U（Ⅵ）。当C-S-H投加量升高至2～5 g·L^-1,材料对U（Ⅵ）的吸附去除效率即能维持在相对较高水平（C[U（Ⅵ）]_initial=500 mg·L^-1,去除率88.3%～93.5%）,吸附可在数小时内达到平衡,符合拟二级动力学模型和两阶段Weber-Morris方程模型,吸附等温线符合Langmuir模型,吸附机理主要为离子交换（84.6%）和表面络合。材料对含铀废水中的U、Zn、Hg、Mn和Cd均表现出良好的吸附去除性能,因而C-S-H可成为在废水毒性金属去除方面极具应用前景的材料。