直馏航煤吸附脱硫醇的试验研究（Ⅱ）——吸附及脱附试验研究

在自制安装的试验装置,考察了航煤脱硫醇的影响因素,从而筛选出合适的脱硫醇条件。这些因素包括：吸附剂的含水量、吸附温度、吸附空速等。试验结果表明：吸附剂的含水量对吸附性能有明显影响,当吸附剂含水达到3．3％时,硫醇硫脱除率由98．18％降至90．36％,若含水量继续增加,脱除率下降更快;温度对吸附平衡及吸附速率影响较小,以常温操作为宜;空速是影响吸附精制效果的重要因素,对于硫醇硫不大于138μg／g的航煤原料,空速小于3h-1时,可使精制产品硫醇硫不超过20μg／g,而空速小于2h-1时,可使精制产品硫醇硫低于10μg／g。试验还评价了吸附剂再生性能,经220～240℃水蒸气吹脱6h,吸附剂的吸附性能基本恢复。     

Integrated direct air capture and CO<Subscript>2</Subscript> utilization of gas fertilizer based on moisture swing adsorption

A new concept of low-cost direct air capture technology integrated with a fertilization system is proposed, as an alternative to the application of air derived CO₂. A moisture swing sorbent can elevate the CO₂ concentration from 400 parts per million (ppm) to several thousand ppm, and this can be used to cultivate plants. Desorption isotherms were determined and are described well by a Langmuir model. The adsorption rate constant and the desorption rate constant were gained at 25 °C, 35 °C, and 45 °C under 1000 ppm concentration of CO₂. In accelerated cultivation experiments, the effects of CO₂ concentration, light intensity, and spectrum on the CO₂ uptake rate of the plants were investigated. A multi-bed desorption system which is capable of providing a continuous and stable CO₂ supply for a greenhouse is demonstrated based on the desorption characteristic and CO₂ uptake feature of plants. An energy and cost assessment for the integrated system was performed and the results indicated that minimum energy requirements and cost estimate of CO₂ are 35.67 kJ/mol and 34.68 USD/t, respectively. This makes direct air capture a competitive and sustainable carbon source for agriculture.     

Cobalt-Based Cocatalysts for Photocatalytic CO2 Reduction

Conversion of carbon dioxide (CO₂) into valuable chemicals and renewable fuels via photocatalysis represents an eco-friendly route to achieve the goal of carbon neutralization. Although various types of semiconductor materials have been intensively explored, some severe issues, such as rapid charge recombination and sluggish redox reaction kinetics, remain. In this regard, cocatalyst modification by trapping charges and boosting surface reactions is one of the most efficient strategies to improve the efficiency of semiconductor photocatalysts. This review focuses on recent advances in CO₂ photoreduction over cost-effective and earth-abundant cobalt (Co)-based cocatalysts, which are competitive candidates of noble metals for practical applications. First, the functions of Co-based cocatalysts for promoting photocatalytic CO₂ reduction are briefly discussed. Then, different kinds of Co-based cocatalysts, including cobalt oxides and hydroxides, cobalt nitrides and phosphides, cobalt sulfides and selenides, Co single-atom, and Co-based metal–organic frameworks (MOFs), are summarized. The underlying mechanisms of these Co-based cocatalysts for facilitating CO₂ adsorption–activation, boosting charge separation, and modulating intermediate formation are discussed in detail based on experimental characterizations and density functional theory calculations. In addition, the suppression of the competing hydrogen evolution reaction using Co-based cocatalysts to promote the product selectivity of CO₂ reduction is highlighted in some selected examples. Finally, the challenges and future perspectives on constructing more efficient Co-based cocatalysts for practical applications are proposed.

     

Effects of elevated CO(2) levels on root morphological traits and Cd uptakes of two Lolium species under Cd stress

This study was conducted to investigate the combined effects of elevated CO₂ levels and cadmium (Cd) on the root morphological traits and Cd accumulation in Lolium multiflorum Lam. and Lolium perenne L. exposed to two CO₂ levels (360 and 1 000 μl/L) and three Cd levels (0, 4, and 16 mg/L) under hydroponic conditions. The results show that elevated levels of CO₂ increased shoot biomass more, compared to root biomass, but decreased Cd concentrations in all plant tissues. Cd exposure caused toxicity to both Lolium species, as shown by the restrictions of the root morphological parameters including root length, surface area, volume, and tip numbers. These parameters were significantly higher under elevated levels of CO₂ than under ambient CO₂, especially for the number of fine roots. The increases in magnitudes of those parameters triggered by elevated levels of CO₂ under Cd stress were more than those under non-Cd stress, suggesting an ameliorated Cd stress under elevated levels of CO₂. The total Cd uptake per pot, calculated on the basis of biomass, was significantly greater under elevated levels of CO₂ than under ambient CO₂. Ameliorated Cd toxicity, decreased Cd concentration, and altered root morphological traits in both Lolium species under elevated levels of CO₂ may have implications in food safety and phytoremediation.     

Conversion of CO<Subscript>2</Subscript> to useful substances with composite iron,nickel, and copper catalysts

Composite materials of Fe/Al₂O₃, which consist of small particles of iron supported by thermally stable alumina even at 500–700 °C, have been widely used in the water-gas shift reaction for natural gas reforming. Therefore, Fe/Al₂O₃ is one of the promising candidates for re-transformation of exhausted CO₂ into fuels such as alcohols and hydrocarbons. The development of a CO₂ reforming system using the composite materials of Fe/Al₂O₃ through CO₂ reduction to CO, dissociation of water into hydrogen, and methanol synthesis has been investigated. It was found that dry and steam (i.e. wet) reforming of CO₂ produced almost the same amount of CO. At a temperature above 500 °C, maximal and saturated yields of CO and H₂ from CO₂ and water were obtained. However, this CO₂ reforming system requires higher-pressure conditions from several tens to hundreds standard atmospheric pressure in order to achieve high yield and selectivity for methanol production. In this study we developed the modified CO₂ reforming system by the utilization of Ni and/or Cu instead of Fe in order to obtain other types of useful products such as CO, CH₄, and carbon, more efficiently and selectively under atmospheric pressure. When Ni or Cu was used, conversion of CO₂ was reduced to 76%, while 9% of methane was detected in the case of Ni. On the other hand, though the CO₂ conversion reduced half of the Fe, the selectivity of CO from CO₂ increased to 95% in the case of Cu.     

Impact of elevated CO2 concentration under three soil water levels on growth of Cinnamomum camphora

Forest plays very important roles in global system with about 35% land area producing about 70% of total land net production. It is important to consider both elevated CO2 concentrations and different soil moisture when the possible effects of elevated CO2 concentration on trees are assessed. In this study, we grew Cinnamomum camphora seedlings under two CO2 concentrations （350 μmol/mol and 500μmnol/mol） and three soil moisture levels [80%, 60% and 40% FWC （field water capacity）] to focus on the effects of exposure of trees to elevated CO2 on underground and aboveground plant growth, and its dependence on soil moisture. The results indicated that high CO2 concentration has no significant effects on shoot height but significantly impacts shoot weight and ratio of shoot weight to height under three soil moisture levels. The response of root growth to CO2 enrichment is just reversed, there are obvious effects on root length growth, but no effects on root weight growth and ratio of root weight to length. The CO2 enrichment decreased 20.42%, 32.78%, 20.59% of weight ratio of root to shoot under 40%, 60% and 80% FWC soil water conditions, respectively. And elevated CO2 concentration significantly increased the water content in aboveground and underground parts. Then we concluded that high CO2 concentration favours more tree aboveground biomass growth than underground biomass growth under favorable soil water conditions. And CO2 enrichment enhanced lateral growth of shoot and vertical growth of root. The responses of plants to elevated CO2 depend on soil water availability, and plants may benefit more from CO2 enrichment with sufficient water supply.     

XAD-4树脂对水相中邻氨基苯酚的吸附特性研究

研究了XAD-4大孔树脂对水相中邻氨基苯酚的吸附特性。研究内容包括接触时间、pH、吸附剂质量、吸附温度对吸附的影响。树脂能有效地除去水相中的邻氨基苯酚,在pH=3.2～5.2的范围内树脂对邻氨基苯酚均有较大的吸附,其最佳酸度为pH=4.0,吸附率可达97.3%。研究表明Langmuir等温吸附模型能较好地描述吸附过程。用1.5～2.0 mol/L HCl对吸附后的树脂进行再生试验,脱附率可达91.2%。     

Metal Oxide/Nitrogen-Doped Carbon Catalysts Enables Highly Efficient CO2 Electroreduction

The metal oxide/nitrogen-doped carbon (NC) compounds zirconium oxide/NC (ZrO₂/NC) and cerium oxide/NC (CeO₂/NC) were synthesized via the pyrolysis of polyaniline on the metal oxide surface. The characterization of the ZrO₂/NC and CeO₂/NC catalysts showed more active CO₂ reduction reaction activity than that of NC catalyst without metal oxide. Gas chromatography analysis revealed that CO and H₂ were the primary products, and no liquid-phase products were detected via proton nuclear magnetic resonance spectroscopy or high-performance liquid chromatography. The maximum Faraday efficiency of ZrO₂/NC reached 90% at − 0.73 V (vs. RHE), with the current density of CO at 5.5 mA/cm²; this Faraday efficiency value was higher than that of NC (41%), with the current density of CO at 3.1 mA/cm². The interaction between the metal oxide and carbon allowed the efficient formation of defect sites, especially imine-type nitrogen, strengthening the adsorption of the key reaction intermediate CO₂^•− and thus promoting the CO₂ reduction reaction.

     

牡蛎壳对染料废水吸附的研究

以牡蛎壳为原料,通过煅烧方法制备牡蛎壳吸附剂.考查了溶液pH值、牡蛎壳煅烧温度、煅烧时间、粒径、吸附剂用量、初始浓度和吸附时间等因素对直接大红4BS和孔雀石绿吸附性能的影响.结果表明,直接大红4BS和孔雀石绿的最佳pH分别为1.0和8.0.在200℃煅烧5h后,采用100目0.8g吸附剂吸附染料,去除率达最大值.运用三种动力学模型对吸附过程进行拟合,结果表明吸附过程可以很好地用准二级动力学方程描述.吸附等温线用Langmuir方程的拟合效果优于Freundlich方程,吸附剂再生后,可循环使用5次以上.     

Preparation of ultrafine γ-Al2O3 particles in non-ionic water in oil microemulsions

Ultrafine γ-Al₂O₃ particles are synthesized in Triton X-100/n-hexanol/cyclohexane/water water in oil(w/o) microemulsion by mixing two separately prepared microemulsions containing Al(NO)₃ and (NH₄)₂CO₃ respectively. The ultrafine Al₂O₃ particles are characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD) and their size and distribution are measured. The effects of water, surfactant and reactant concentrations on the particle size and distribution are studied. The results show that the particle size and distribution can be changed by varying the preparation conditions, and the size of the microemulsion droplets has a controlling effect on the size of the particles. A possible mechanism of ultrafine particles (UFPs) prepared by microemulsions is proposed.     

Calculation of the Phase Equilibrium of CO_2–Hydrocarbon Binary Mixtures by PR-BM EOS and PR EOS

The phase equilibrium data of CO_2 –hydrocarbon binary mixtures are important for the design and operation of CO_2 flooding, coal liquefaction, and supercritical extraction processes. Numerous pieces of binary phase equilibrium data have been obtained. Thus, models for the accurate calculation of binary and multicomponent mixtures must be developed on the basis of existing data. In this work, 3578 vapor–liquid phase equilibrium data points for 10 CO_2 –hydrocarbon binary mixtures, including CO_2 –butane, CO_2 –pentane, CO_2 –isopentane, CO_2 –hexane, CO_2 –benzene, CO_2 –heptane, CO_2 –octane, CO_2 –nonane, CO_2 –decane, and CO_2 –undecane, were collected. The PR and PR-BM equations of state(EOS) in combination with relevant mixing rules were used to calculate the phase equilibrium data of the CO_2 –hydrocarbon binary mixtures. The binary interaction parameter k ij in the PR EOS was temperature independent, whereas parameters in the PR-BM EOS were functions of temperature. Thus, the phase equilibrium data and other thermodynamic properties of the binary and multicomponent mixtures at different temperatures and pressures can be calculated by using the parameters obtained in this work. The PR-BM EOS performed better than the PR EOS, and the average absolute deviations over the temperature range of 255.98–408.15 K calculated by the PR EOS and PR-BM EOS were less than 5.74% and 3.36%, respectively. The results calculated by the two EOS were compared with those calculated by other models, such as PPR78, PR + LCVM + UNIFAC, KIE + PR EOS + HV, and PSRK. The phase equilibrium data of CO_2 –butane–decane, CO_2 –hexane–decane, and CO_2 –octane–decane ternary mixtures were calculated by the two EOS. The average overall deviations for the CO_2 mole fractions calculated by the two EOS were less than 7.66%.     

Experimental evaluation of the effect of an internal heat exchanger on a transcritical CO2 ejector system

This study presents experimental results focused on a performance comparison of a transcritical CO₂ ejector system without an internal heat exchanger (IHX) (EJE-S) to a transcritical CO₂ ejector system with an IHX (EJE-IHX-S). The comparison includes the effects of changes in operating conditions such as cooling water flow rate and inlet temperature. Experiments are conducted to assess the influence of the IHX on the heating coefficient of performance (COP_r), heating capacity, entrainment ratio, pressure lift, and other parameters. The primary flow rate of the EJE-IHX-S is higher than that of the EJE-S. The pressure lift and actual ejector work recovery are reduced when the IHX is added to the transcritical CO₂ ejector system. Using a more practical performance calculation, the compression ratio in the EJE-S is reduced by 10.0%–12.1%, while that of EJE-IHX-S is reduced only by 5.6%–6.7% compared to that of a conventional transcritical CO₂ system. Experimental results are used to validate the findings that the IHX weakens the contribution of the ejector to the system performance.     

Ultra-Thin Carbon-Doped Bi2WO6 Nanosheets for Enhanced Photocatalytic CO2 Reduction

The photocatalytic reduction of CO₂ is a promising strategy to generate chemical fuels. However, this reaction usually suffers from low photoactivity because of insufficient light absorption and rapid charge recombination. Defect engineering has become an effective approach to improve the photocatalytic activity. Herein, ultra-thin (~ 4.1 nm) carbon-doped Bi₂WO₆ nanosheets were prepared via hydrothermal treatment followed by calcination. The ultra-thin nanosheet structure of the catalyst not only provides more active sites but also shortens the diffusion distance of charge carriers, thereby suppressing charge recombination. Moreover, carbon doping could successfully extend the light absorption range of the catalyst and remarkably promote charge separation, thus inhibiting recombination. As a result, the as-prepared Bi₂WO₆ photocatalyst with ultra-thin nanosheet structure and carbon doping exhibits enhanced photocatalytic CO₂ reduction performance, which is twice that of pristine ultra-thin Bi₂WO₆ nanosheet. This study highlights the importance of defect engineering in photocatalytic energy conversion and provides new insights for fabricating efficient photocatalysts.

     

In-situ characterization of gas-liquid precipitation reaction in a spray using rainbow refractometry

Gas-liquid precipitation reactions in terms of a spray exist widely in energy, chemical, and environmental engineering. In this paper, a rainbow refractometry-based method is used to measure the reaction process of these spray-based gas-liquid precipitation reactions in a non-intrusive way. Rainbow refractometry can simultaneously provide information on thermochemical and physical properties of droplets. A global rainbow measurement system was built to characterize a CO₂ absorption reaction. Rainbow signals of spray droplets of Ca(OH)₂ solutions before and after CO₂ absorption were recorded and processed. Results indicated that the average refractive index of saturated H₂O-Ca(OH)₂ solution was 1.335 69, which accorded with the Abbe measurement. After the absorption reaction, the refractive index of droplets decreased to 1.335 17 which is close to that of water. The reaction extent was therefore reflected in the change of the refractive index of droplets. An extra experiment of CO₂ absorbed by Ba(OH)₂ solutions was conducted. The refractive index of droplets decreased with the reaction process, which acted well as an evolution indicator of the reaction. A heat transfer analysis of the reaction was also carried out. Due to the high heat dissipation performance of fine droplets, the temperature increase in the measurement volume was estimated to be less than 0.61 K, which has almost no effect on the measured results. The rainbow refractometry-based method shows good potential for in-situ characterization of a gas-liquid precipitation reaction.     

应用改性粉煤灰处理含铅废水的研究

对改性粉煤灰处理含铅废水进行了实验研究,结果表明,对铅离子的去除效果优于等量未改性粉煤灰和活性炭。吸附时间、废水的pH值、吸附剂用量、温度以及废水中Pb2＋浓度都能影响改性粉煤灰的吸附效果。最适宜的吸附条件是：在室温,pH=8．0,吸附剂用量为1．0g,Pb2＋含量小于0．005mol／L,吸附15min时,改性粉煤灰对废水中Pb2＋的吸附达到饱和。     

Theoretical study of NO adsorbed on the surface of TiO<Subscript>2</Subscript> (110) cluster model

The chemisorption properties of N¹⁸O adsorption on TiO₂(110) surface were investigated by experimental and theoretical methods. The results of temperature programmed desorption (TPD) indicated that the temperatures of the three desorption peaks of the main N₂ molecules were at (low) temperature of 230 K, 450 K and (high) temperature of 980 K. This meant that N¹⁸O decomposed and recombined during the process of N₂ desorption after N¹⁸O was exposed. Analysis of the stable combination and orbital theory calculation of the surface reaction of NO adsorption on the TiO₂(110) cluster model showed that there was clear preference for the Ti-NO orientation.     

果胶@生物炭-Fe3O4的制备及其对Cu2+的吸附性能

以木屑为原料,高温热解制备生物炭。以聚乙烯醇为粘结剂,采用混合法将生物炭与果胶复合,并负载磁性,经烘干定型制备果胶包覆的磁性生物炭材料（果胶@生物炭-Fe₃O₄）。采用扫描电镜（SEM）、X射线衍射（XRD）及N₂吸附-脱附（BET）等方法对果胶@生物炭-Fe₃O₄进行表征,结合吸附实验分析其对Cu²⁺的吸附特性。结果表明,当生物炭、果胶、Fe₃O₄质量比为5：1：1,溶液pH值为6,吸附24 h,果胶@生物炭-Fe₃O₄对Cu²⁺吸附效果最好;二级动力学方程能较好地描述果胶@生物炭-Fe₃O₄对Cu²⁺的吸附过程,Freundlich模型能较好地拟合其吸附行为;SEM结果显示该材料具有不规则的孔隙结构;XRD分析显示纳米Fe₃O₄是其主要的晶体结构;BET测得其比表面积为25.654 m²·g^-1,平均孔径为20.18 nm。     

Optimization Strategies for Selective CO2 Electroreduction to Fuels

Capturing CO₂ from the atmosphere and converting it into fuels are an efficient strategy to stop the deteriorating greenhouse effect and alleviate the energy crisis. Among various CO₂ conversion approaches, electrocatalytic CO₂ reduction reaction (CO₂RR) has received extensive attention because of its mild operating conditions. However, the high onset potential, low selectivity toward multi-carbon products and poor cruising ability of CO₂RR impede its development. To regulate product distribution, previous studies performed electrocatalyst modification using several universal methods, including composition manipulation, morphology control, surface modification, and defect engineering. Recent studies have revealed that the cathode and electrolytes influence the selectivity of CO₂RR via pH changes and ionic effects, or by directly participating in the reduction pathway as cocatalysts. This review summarizes the state-of-the-art optimization strategies to efficiently enhance CO₂RR selectivity from two main aspects, namely the cathode electrocatalyst and the electrolyte.

     

Effect of CO2 enrichment on the glucosinolate contents under different nitrogen levels in bolting stem of Chinese kale (Brassica alboglabra L.)

The effects of CO₂ enrichment on the growth and glucosinolate (GS) concentrations in the bolting stem of Chinese kale (Brassica alboglabra L.) treated with three nitrogen (N) concentrations (5, 10, and 20 mmol/L) were investigated. Height, stem thickness, and dry weights of the total aerial parts, bolting stems, and roots, as well as the root to shoot ratio, significantly increased as CO₂ concentration was elevated from 350 to 800 μl/L at each N concentration. In the edible part of the bolting stem, 11 individual GSs were identified, including 7 aliphatic and 4 indolyl GSs. GS concentration was affected by the elevated CO₂ concentration, N concentration, and CO₂×N interaction. At 5 and 10 mmol N/L, the concentrations of aliphatic GSs and total GSs significantly increased, whereas those of indolyl GSs were not affected, by elevated atmospheric CO₂. However, at 20 mmol N/L, elevated CO₂ had no significant effects on the concentrations of total GSs and total indolyl GSs, but the concentrations of total aliphatic GSs significantly increased. Moreover, the bolting stem carbon (C) content increased, whereas the N and sulfur (S) contents decreased under elevated CO₂ concentration in the three N treatments, resulting in changes in the C/N and N/S ratios. Also the C/N ratio is not a reliable predictor of change of GS concentration, while the changes in N and S contents and the N/S ratio at the elevated CO₂ concentration may influence the GS concentration in Chinese kale bolting stems. The results demonstrate that high nitrogen supply is beneficial for the growth of Chinese kale, but not for the GS concentration in bolting stems, under elevated CO₂ condition. Project (No. 2007CB109305) supported by the National Basic Research Program (973) of China     

小球藻生物吸附废水中铜的研究

以小球藻作为生物吸附剂,去除水溶液中微量Cu~(2+),研究结果表明小球藻对Cu~(2+)的生物吸附主要经历了快速的吸附和缓慢的吸收两个步骤:pH值是影响Cu~(2+)生物吸附的一个重要影响因素,最佳pH值在6～8之间;离子强度对Cu~(2+)的吸附有一定的抑制作用;小球藻对Cu~(2+)的生物吸附符合Freundlich等温方程。