中国碳捕集、利用与封存技术发展与展望

实现“双碳”目标是我国应对气候变化的重大决策,也是我国生态文明建设的重要内容。碳捕集、利用与封存（Carbon Capture,Utilization and Storage,CCUS）技术是实现“双碳”目标的关键性技术,也是我国达成二氧化碳零排放的保障性措施。本文简要介绍了CCUS主要环节的技术流程,概括了我国CCUS技术的发展历程。从技术水平、国家政策、示范项目情况等多个角度,总结了现阶段我国CCUS技术的整体研究与发展水平。并根据我国能源供给模式、工业发展水平等因素,分析并阐明了我国CCUS技术发展的必要性,以及现阶段CCUS技术发展所面临的挑战。最后本文还从行业角度出发,将CCUS技术与油气、建筑、农业、化工多种重点行业结合,提出了具体可行、互促互利的CO₂转化利用模式,为实现CCUS的商业化运行、保证CCUS技术的可持续发展提供了思路。     

关于焦化行业CO2排放核算方法的探讨

本文分析了适用于焦化行业通用CO₂排放核算方法,在此基础上结合我国焦化行业工艺和原料的特征,采用排放因子法和物料衡算法等两种方法对10家典型焦化企业CO₂排放进行核算。结果表明:物料衡算法能很好地反映不同类型焦化企业的排放特征;排放因子法对我国独立焦化企业存在碳排放量系统性高估的可能。为此,建议我国焦化企业可借鉴德国焦化企业的碳核算经验,采用碳平衡法对不同类型的焦化企业(单元)的碳排放量进行核算,并完善相关的统计和监测技术。     

基于产业链分析的长三角地区CO2与大气污染物排放研究

长三角地区作为我国大气污染较为严重区域之一,如何在保持经济增长的同时减少CO₂与大气污染物的排放已成为一个重要挑战。本研究基于2007年与2012年长三角区域间投入产出表,定量分析了长三角地区省市间贸易引致的二氧化碳和大气污染物排放转移特征和变化趋势。同时,运用产业关联系数法,从前向关联与后向关联双重视角分析了长三角地区减缓CO₂和大气污染物排放的关键行业。研究结果表明,长三角的SO₂、PM_2.5排放总量表现为消费端大于生产端,CO₂、NO_x排放总量表现为生产端大于消费端。安徽省总体呈现为长三角地区贸易的SO₂、NO_x与PM_2.5排放净调出地,而上海与浙江表现为多数污染物排放净调入地。CO₂与大气污染物协同前向减排的关键行业为江苏省、浙江省和安徽省的电力、热力的生产和供应业,安徽省的煤炭开采和洗选业等,可以通过生产端技术革新和能源结构优化来促进减排;CO₂与大气污染物后向协同减排的关键行业为江苏省、浙江省和安徽省的建筑业等,对于这些行业,调整消费结构是有效的减排措施。为更好地制定长三角地区减排与污染防治政策,应当综合考虑行业减排、协同减排等,以确保经济持续增长的同时达到减排目标。     

协同实现降碳减污的管理需求与关键问题

建设人与自然和谐共生的中国式现代化,离不开降碳、减污、扩绿、增长的协同推进。一方面,推动减污降碳协同增效是我国发展阶段使然。与发达国家先解决了国内污染问题再应对气候变化的发展过程不同,我国正处于减污与降碳要求叠加、负重前行的关键期。在生态环境保护结构性、根源性、趋势性压力总体上尚未根本扭转的新发展阶段,协同推进降碳减污是我国经济社会发展全面绿色转型的必然选择。另一方面,同根、同源、同过程的特征使得实现降碳减污协同增效具有可行性。化石能源的燃烧和加工利用同时产生 CO₂ 等温室气体和SO₂、 NOx、颗粒物（PM）、挥发性有机化合物（VOCs）等大气污染物,推动降碳与减污的协同治理能够降低管理成本,获得环境质量改善、气候变化风险降低、低碳经济竞争力提升等多重政策效益,是提高生态环境治理现代化水平的重要途径。     

二氧化碳捕集利用与封存项目纳入碳市场的现状、挑战与对策

二氧化碳捕集、利用与封存（CCUS）被认为是燃煤和燃气电厂以及钢铁、水泥和石化等行业实现碳中和的重要技术选项,而碳市场则是重要的市场化减排机制,提高两者的衔接水平,对于我国“双碳”目标的实现具有重要意义。通过总结国际上CCUS项目与碳市场衔接的成功经验,可以为我国CCUS项目与碳市场衔接提供相关借鉴。本文系统梳理了国内外CCUS项目纳入碳市场的立法、激励政策、CCUS减排核算方法学研究情况,识别出我国在CCUS项目与碳市场衔接方面尚存在法律支撑不足、缺乏激励政策以及CCUS项目碳减排核算方法不准确等一系列问题,最后提出多项建议以推动我国CCUS项目与碳市场的衔接：①完善碳市场监管和法律体系,促进CCUS与碳市场衔接;②研判CCUS优先领域,分阶段促进不同行业CCUS项目纳入碳交易市场;③强化政策激励,打通CCUS与碳市场衔接的投融资与成本疏导路径;④分阶段完善碳交易市场建设,充分发挥碳市场金融属性促进CCUS与碳交易市场衔接;⑤建立完善的监测、报告和核查（MRV）标准体系和证书制度,保证CCUS项目减排量核证的准确性和规范性。     

我国大气环境管理历程与展望

随着大气环境问题从煤烟型向以PM_2.5和O₃为特征的区域复合型污染演变，我国大气污染控制模式从以污染物排放浓度控制为核心、以污染物排放总量控制为核心逐渐走向以大气环境质量改善为核心。特别是近几年，全国各地在空气质量管理、科学精准治污等领域开展一系列积极的探索与实践，取得了显著成效。本文系统回顾了近50年来我国不同阶段大气环境管理工作的特点，重点梳理了2013年《大气污染防治行动计划》实施以来，空气质量管理经验与成绩，结合减污降碳总体部署对我国2035年“美丽中国建设目标基本实现”时的空气质量进行了展望，从PM_2.5与O₃协同控制的角度出发，提出了“十四五”期间我国大气环境管理的总体思路。     

浙江省火电行业主要污染物减排环境效益研究

利用美国环保局开发的新一代空气质量模式系统Models-3,对2010 年浙江省大气污染物进行数值模拟研究,并对SO₂、NO₂ 和PM₁₀ 等大气污染物浓度的模拟结果与监测结果进行了对比分析。结果表明,Models-3 系统能较好地反映浙江省的大气污染情况,模拟值与观测值的变化趋势具有较好的一致性,说明该模式能较好地进行大气污染物的分布特征和变化规律的研究。为定量分析电力行业多污染物协同控制与区域复合型大气污染之间的定量关系,评估不同控制情景下的环境质量效益,应用CMAQ 空气质量模型分别对2010 年基准排放情景和火电行业主要污染物(SO₂、NO_x 和烟尘)的三套减排控制情景,评价环境空气污染物SO₂、NO_x、PM_2.5 和PM₁₀ 状况进行模拟,评价污染物减排的环境效益。三套方案下PM_2.5 浓度下降比例分别为0.53%、0.55% 和0.57%,其中重点区域浓度下降比例分别为4.36%、4.38%和5.9%;PM₁₀ 浓度下降比例分别为0.40%、0.42% 和0.65%,重点区域下降比例分别为3.42%、5.82% 和8.16%;NO_x 浓度下降比例分别为12.4% 和13.3%,重点区域下降比例分别为13.8% 和16.9%;SO₂ 下降比例平均为11.24%,其中重点区域下降比例为14.4%。SO₂、NO_x 和烟(粉)尘协同减排对于浙江地区特别是重点区域的环境空气质量改善有着显著意义。     

污染场地风险管控环境经济政策体系：国外经验与本土实践

快速城市化和工业化给我国带来了大量的场地污染问题,污染场地修复和风险管控成为国土资源可持续利用的重要领域,创新土壤污染防治经济政策,充分发挥市场调节作用是土壤污染防治的内在要求,是破解土壤生态环境问题、推进土壤污染防治管理转型的重要支撑。本文从经济政策的体系、投融资模式与机制等方面展开,对美国、德国、荷兰等发达国家的污染场地风险管控环境经济政策进行了梳理分析,总结其可借鉴的成功经验;介绍了我国污染场地风险管控环境经济政策实施现状,最终从完善调控体系、明晰权责归属、拓宽资金来源、规范资金运营、丰富投融资模式、探索费用效益分析机制等方面提出我国污染场地风险管控环境经济政策体系的改进建议。     

生态环境风险管理与损害赔偿制度现状与展望

我国目前面临的生态环境风险形势复杂严峻，严密防控生态环境风险已成为“十四五”和中长期生态环境保护、美丽中国建设的重要任务之一。本文探讨了生态环境风险的概念、分类，系统梳理了生态环境风险评估与管理、生态环境损害评估与损害赔偿等领域的国内外管理经验与研究进展。在此基础上，重点剖析了我国生态环境风险管理面临的痛点与难点问题，从树立生态环境风险法治管理理念、构建生态环境风险管理战略布局、建立生态环境风险常态化管控体系、加强生态环境风险防控技术支撑、强化经济和社会治理手段助力风险管控、建设生态环境损害赔偿业务化工作体系等六个方面，系统提出了加强我国生态环境风险管理的对策建议，以期为更有效地防范化解重大生态环境风险提供决策参考。     

中国铜产业体系演化的碳中和实现机制研究

本文研究了我国铜产业采选、冶炼、加工和再生等环节的演化趋势,构建了铜产业直接碳排放-能源间接排放-其他间接排放相结合的多层级碳排放核算模型,分析了我国铜产业各环节碳排放演变规律及碳中和实现机制。结果表明：①1980-2020年我国铜精矿、精炼铜、铜加工材、再生铜产品分别增长了6.6倍、 25.1倍、 88.5倍、 37.1倍,受碳中和目标实现对电力需求量增加的影响,预计2060年铜资源消费总量将较2020年提升62.3%,铜资源社会存量将达到3.9亿t,再生铜将于2030年超过原生铜成为主导资源类型。②2020年铜产业的碳排放总量达到2968.2万tCO₂e,其中,采选环节的吨铜碳排放量最高,达到了3.4tCO₂e,是第二位冶炼的2.3倍;冶炼环节的碳排放总量最大,达到铜产业的39.3%;再生环节的降碳效果突出,相较原生采选冶炼环节减少1251.2万tCO₂e;进出口贸易则进一步降低了该产业43.7%的碳排放总量。③预计2060年铜产业碳排放总量将达到1499.8万tCO₂e,通过促进国际贸易、循环经济、技术创新及环境市场建设等举措,可大幅降低产业的碳排放总量,其中国际贸易及循环经济情景的碳减排效果在2030年前均较显著、随后逐渐下降,技术创新及环境市场建设是该产业碳中和目标实现的根本,在2060年的减排潜力分别达到535.9万t及607.9万t。为了更好地促进该产业可持续发展及“双碳”目标实现,建议依托国内国际双循环格局合理调控铜产业结构,秉持全生命周期理念加快构建铜产业绿色供应链,紧随碳中和发展趋势促进资源循环减污降碳协同增效。     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Performance of lime-BHA solidified plating sludge in the presence of Na2SiO3 and Na2CO3

This research investigated the performance of lime-BHA (black rice husk ash) solidified plating sludge with 2 wt% NaO from Na(2)SiO(3) and Na(2)CO(3) at the level of 0, 30 and 50 wt%. The sludge was evaluated for strength development, leachability, solution chemistry and microstructure. The lime-BHA solidified plating sludge with Na(2)SiO(3) and Na(2)CO(3) had higher early strength when compared to the control. The addition of Na(2)SiO(3) and Na(2)CO(3) increased the OH(-) concentration and decreased the Ca(2+) and heavy metal ions in solution after the first minute. The XRD patterns showed that the addition of Na(2)SiO(3) resulted in the formation of calcium silicate hydrates, while the addition of Na(2)CO(3) resulted in CaCO(3). The heavy metals from the plating sludge, especially Zn, were immobilized in calcium zincate and calcium zinc silicate forms for the lime-BHA with and without Na(2)SiO(3) solidified wastes, while samples with Na(2)CO(3) contained Zn that was fixed in the form of CaZnCO(3). The cumulative leaching of Fe, Cr and Zn from the lime-BHA solidified plating sludge decreased significantly when activators were added, especially Na(2)CO(3).     

A model for the CO2 capture potential

Global warming is a result of increasing anthropogenic CO₂ emissions, and the consequences will be dramatic climate changes if no action is taken. One of the main global challenges in the years to come is therefore to reduce the CO₂ emissions.Increasing energy efficiency and a transition to renewable energy as the major energy source can reduce CO₂ emissions, but such measures can only lead to significant emission reductions in the long-term. Carbon capture and storage (CCS) is a promising technological option for reducing CO₂ emissions on a shorter time scale.A model to calculate the CO₂ capture potential has been developed, and it is estimated that 25 billion tonnes CO₂ can be captured and stored within the EU by 2050. Globally, 236 billion tonnes CO₂ can be captured and stored by 2050. The calculations indicate that wide implementation of CCS can reduce CO₂ emissions by 54% in the EU and 33% globally in 2050 compared to emission levels today.Such a reduction in emissions is not sufficient to stabilize the climate. Therefore, the strategy to achieve the necessary CO₂ emissions reductions must be a combination of (1) increasing energy efficiency, (2) switching from fossil fuel to renewable energy sources, and (3) wide implementation of CCS.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.     

Advanced oxidation treatment of pulp mill effluent for TOC and toxicity removals

Pulp mill effluent was treated by different advanced oxidation processes (AOPs) consisting of UV, UV/H2O2, TiO2-assisted photo-catalysis (UV/TiO2) and UV/H2O2/TiO2 in lab-scale reactors for total organic carbon (TOC) and toxicity removals. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC and toxicity removals were investigated. Almost every method resulted in some degree of TOC and toxicity removal from the pulp mill effluent. However, the TiO2-assisted photo-catalysis (UV/TiO2) resulted in the highest TOC and toxicity removals under alkaline conditions when compared with the other AOPs tested. Approximately, 79.6% TOC and 94% toxicity removals were obtained by the TiO2-assisted photo-catalysis (UV/TiO2) with a titanium dioxide concentration of 0.75gl(-1) at pH 11 within 60min.     

Photocatalytic Production of Methane and Hydrogen Through Reduction of Carbon Dioxide with Water Using Titania Pellets

This paper presents an experimental study on employing a pellet form of catalyst in photo-reduction of carbon dioxide with water. Water was first absorbed into titania pellets. Highly purified carbon dioxide gas was then discharged into a reactor containing the wet pellets, which were then illuminated continuously for 65 hours using UVC lamps. Analysing the products accumulated in the reactor confirmed that methane and hydrogen were produced through photo-reduction of carbon dioxide with water. No other hydrocarbons were detected. Increasing the temperature in the reactor has showed little change on the amount of methane produced.     

Thermodynamic and Economic Aspects of the Hard Coal Based Oxyfuel Cycle

The present study shows a new approach in modelling the hard coal fired Oxyfuel Cycle on the whole. The static process model comprises an Oxyfuel combustion principle applied to an existing state-of-the-art hard coal power plant located in Rostock, Germany. It includes the air separation unit and the flue gas liquefaction unit, which are modelled in detail. As one of the main advances to previous work, the closed simulation of all components in one model delivers a coherent solution with a significantly reduced number of assumptions. The model needs no interfaces between different stand alone simulation tools or manual iteration and transfer of internal variables. Results from a thermodynamic and economic feasibility study on this process are shown and areas relevant for future research are identified.

The present study shows the feasibility and prospective key figures of the technology under realistic, comparable and reproducible assumptions and boundary conditions. The basic engineering of the process with a detailed study of the necessary gas separation and flue gas handling technologies is undertaken in the effort to a first stage optimisation of the process.

The flowsheet tool Aspen Plus (TM) was used to simulate the overall process. This particular tool was chosen because it offers an advanced data library on chemical substances and allows the calculation of phase equilibria and real gas behaviour during air separation and flue gas liquefaction. Emissions, coal consumption and investment costs of the Oxyfuel power plant are compared to those of the original state-of-the-art hard coal power plant which is used as the reference case.     

Treatment of Dichloromethane Using Gliding Arc Plasma

Decomposition of dichloromethane (CH₂Cl₂) using a gliding plasma was examined and reported in this paper. The effects of initial concentrations of CH₂Cl₂, total gas flow rates, and input frequency have been studied to evaluate the performance of gliding arc on CH₂Cl₂ decomposition. Using atmospheric pressure air as the carrier gas, experimental results indicate that the maximum conversion of CH₂Cl₂ was 95.1% at a total gas flow rate of 180 L/hr containing 1% by volume of CH₂Cl₂. The reaction occurred at an exothermic condition and gaseous products are dominated by CO, CHCl₃, and Cl₂. CO₂ and CCl₄ are also detected in the product stream in small amounts. The conversion of CH₂Cl₂ increases with the increasing applied voltage and decreasing total gas flow rate.     

Optimizing Li2O-2B2O3 coating layer on LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material for high-performance lithium-ion batteries

ABSTRACT

In this paper, a wet chemical method is used to coat LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) cathode material by Li₂O-2B₂O₃ (LBO) layer for Lithium-ion batteries (LIBs). For performance optimization, the effects of different contents (thicknesses) of LBO coating layers on NCM811 particle surface on the morphologies, structures, compositions, and electrochemical properties of the corresponding LIBs are studied using XRD, SEM, TEM, and electrochemical measurements. Coin LIBs are assembled with such coated NCM811 cathode materials for performance validation. Results show that LBO coating layer does not change the original lattice structure of the bulk material, it can only adhere to the surface of the bulk material. After coating, NCM811 shows a good crystallinity and the ordered layered structure. TEM images show that the thickness of LBO coating is increased with increasing LBO content, and that the appropriate LBO coating thickness and uniform coating state are conducive to the improvement of the electrochemical properties of NCM811 cathode materials. Particularly, NCM811 with LBO coating content of 1000 ppm shows the best performance compared to other coating contents. In this case, the coating thickness is relatively uniform, which is about 40～100 nm, giving a good first charge-discharge capacity of 214.1mAh/g, and a high Coulomb efficiency of 90.06%. After 50 cycles, the capacity retention rate of LIBs still keeps as high as 99.64%. Therefore, LBO coating can improve the performance of NCM811 and then the lithium-ion batteries.     

Photo-oxidation of NO using an exterior paint--screening of various commercial titania in powder pressed and paint films

The present work aims to evaluate the photocatalytic activity of photo-TiO(2) from various producers (Evonik, Kemira, Kronos, Millennium, Sachtleben and Tayca), in the form of powder pressed films and upon incorporation in a water-based paint, for outdoor NO abatement. The photocatalytic activity of the different samples was evaluated in terms of NO conversion and selectivity towards nitrite and nitrate ions following approximately the ISO 22197-1:2007(E) standard. The highest yields obtained for powder pressed films were achieved with VLP7000 (0.70), followed by VLP7101 (0.55) and UVLP7500 (0.55), all from Kronos. On the other hand, when incorporated in paint films, the highest yields were obtained with PC500 and PC105 from Millennium and UV100 from Sachtleben (ca. 0.15). The paint matrix plays an important role on the photocatalytic activity. In particular, the time for steady state is one or two orders of magnitude higher when the photocatalysts are incorporated in paint films in relation to the powder pressed films. The paint films were activated following the procedure recommended by the above-mentioned standard. However, the photocatalytic activity of films incorporating P25 (Evonik) was displayed only when higher power radiation and higher humidity conditions were used. This allowed for similar levels of photocatalytic activity as the other paint films.