O2/CO2气氛下氮反应机理的研究

选取CH4、O2、CO2、Ar、NO、NH3，等气体，作为混合气和煤粉一起送入一维沉降炉内，以模拟O2／CO2气氛下煤中燃料氮、循环NO以及二者的相互作用对NO排放的影响，结果显示，在还原性气氛下NH3、HCN、CH4、CO与循环NO间的反应是NO排放下降的主要因素，且煤焦与NO的异相反应、吸附反应对NO的降解效果要明显高于氧化性气氛，同时，CO2体积分数的增加使得燃料中氮的氧化率升高，循环NO的降解率下降；氧化性气氛下随CO2体积分数的增加，燃料中氮的氧化率也增加，但循环NO的降解率升高．当CO2体积分数不变时，其对NO降解的作用随循环NO体积分数的增加愈加明显，在循环NO也不变且CO2体积分数较低时，随过量空气系数的增加，循环NO的降解率下降，而CO2体积分数较高时则出现相反情况。     

污泥与煤在CO2/O2及N2/O2气氛条件下的混燃特性分析

采集了广州具有代表性的市政污泥,利用热重法对单一污泥、煤及其混合样品在CO_2/O_2及N_2/O_2气氛条件下进行了TG(热重)实验,同时计算了污泥和煤的4个燃烧特性指数,获得了燃烧的动力学参数.实验结果表明,污泥燃烧有4个燃烧阶段,包括水分析出、挥发分析出与燃烧、固定碳的燃烧和无机盐类挥发分解,其中,挥发分析出与燃烧是污泥燃烧的主要阶段;煤掺烧污泥可以提高煤的着火性能.在CO_2/O_2及N_2/O_2燃烧气氛下,增加O_2浓度,污泥与煤混合样的热重曲线整体向低温区移动,微商热重曲线峰值增大,峰宽变小,燃烧性能增强.在CO_2/O_2气氛下,O_2浓度从30%增加到60%时,污泥的挥发分释放特性指数D、可燃性指数C、燃尽指数Cb、综合燃烧特性指数S分别增加了45%、12%、18%、6%.相同O_2浓度条件下,污泥与煤在CO_2/O_2气氛下的着火性能较N_2/O_2气氛滞后,最大峰值变小,高浓度的CO_2抑制其混合样的燃烧.采用Coats-Redfern方程计算得到3个燃烧阶段反应的动力学参数,其中,增加O_2浓度,污泥与煤混合样品的质量平均表观反应活化能Em减小,并且O_2浓度越高越有利于燃烧反应的进行.污泥与煤混合燃烧取n=2可以对挥发分燃烧与固定碳燃尽峰峰前与峰后的反应模型进行描述.     

负载量对氨水吸收CO2的影响规律及添加剂的作用研究

进行了氨法脱碳过程中吸收剂中CO2负载量对CO2脱除率影响的实验研究.结果发现,CO2脱除率随着负载量的增大而显著减小,高负载量(≥0.4)时,增加吸收液中总氨质量分数(吸收液中所有包含氨分子和铵离子的物质,并统一换算成NH3的质量分数)并不能有效地提高CO2的脱除率.同时,分别对有机和无机添加剂进行筛选,选取哌嗪(P...     

土壤质地对自养固碳微生物及其同化碳的影响

自养微生物可同化大气中的CO2并将其转化为土壤有机碳,对提高农田土壤的碳吸收和碳储存有重要意义,然而土壤质地对自养固碳微生物功能种群及其同化碳的影响机制还不清楚.本研究选取亚热带地区同一母质发育而成的两种质地水稻土壤(壤质黏土和砂质黏壤土),通过14C-CO2连续标记技术结合室内模拟培养实验,探讨土壤质地对自养微生物同化碳(14C-SOC)、自养微生物截留碳(14C-MBC)和自养微生物可溶性碳(14C-DOC)的影响.以固碳功能基因(cbb L基因)作为指示基因,结合PCR和克隆测序技术,分析不同质地土壤自养固碳微生物群落结构和多样性的差异.结果表明,壤质黏土14C-SOC、14C-MBC和14C-DOC平均含量分别为133.81、40.16和8.10 mg·kg-1,均显著高于砂质黏壤土14C-SOC(104.95 mg·kg-1)、14C-MBC(33.26 mg·kg-1)和14C-DOC(4.18 mg·kg-1)平均含量(P0.05),说明土壤质地显著影响了土壤自养微生物碳同化量以及自养微生物同化碳在土壤中的转化.稀疏曲线、细菌cbb L基因文库覆盖度以及多样性指数分析结果显示壤质黏土固碳细菌群落多样性高于砂质黏壤土.系统发育分析表明,壤质黏土细菌cbb L基因序列与Rhodoblastus acidophilus、Blastochloris viridis、Thauera humireducens、Mehylibium sp.、Variovorax sp.等具有一定的同源性,而砂质黏壤土cbb L基因序列主要与根瘤菌和放线菌同源.可见,土壤质地对自养固碳微生物群落结构和多样性产生了深刻的影响,壤质黏土中较高的黏粒含量、土壤养分含量和阳离子交换量可能有利于维持更高的自养固碳微生物多样性和活性,从而导致不同质地土壤自养微生物碳同化量及其转化存在显著差异.     

河流CO2与CH4排放研究进展

河流作为连接海-陆两大碳库的主要通道,其水-气界面二氧化碳(CO_2)与甲烷(CH_4)排放构成全球碳循环的重要环节,对全球气候变暖的贡献不容小觑.明确河流水体CO_2与CH_4产排过程、时空特征以及控制因素是认识河流生态学功能以及其对变化环境响应的重要内容.基于当前河流CO_2与CH_4排放研究进展,构建河流碳排放动力学概念框架(内源代谢、陆源输入),并从全球尺度、区域尺度、流域尺度综述了河流碳排放时空变异性特征以及存在的研究不足.在理解碳排放动力学概念框架和时空变异特征的基础上,构建了河流CO_2与CH_4动力学控制因子分层框架(内部因子:有机质、温度、营养盐;外部因子:水文、地貌、人类活动),深入探讨了河流碳排放的关键影响因素.最后,根据当前研究中存在的不足,提出河流碳排放应将纳入区域陆地碳平衡过程,今后研究重点应包括流域尺度上河流CO_2与CH_4内源产生与陆源输入相对贡献的量化研究、不同界面CO_2与CH_4产生与排放过程研究、高时空分辨率的监测数据的补充以及变化环境与人类活动干扰下河流碳排放的响应过程等,为理解河流生态学过程及生态系统功能提供基础,同时为我国进一步深入开展相关研究提供借鉴.     

CO2 emission reduction for Japanese petrochemicals

Energy efficiency in the Japanese industry is one of the highest in the world. As a consequence, reduction of CO₂ emissions is considered to be difficult and costly. However little attention has been paid as of yet to changes related to so-called non-energy use of fossil fuels. The analysis in this paper suggests that a large number of options exist for emission reduction in the Japanese petrochemical industry. This includes the introduction of biomass feedstocks, the introduction of new catalytic production processes, and changes in waste handling. The use of bioplastics and the use of CO₂ feedstocks seem costly options for GHG emission reduction that should not be applied on the short term. Japanese GHG emissions can be reduced by 7.7% if the optimal set of emission mitigation options is applied. About 60 Mt emission reduction (4.9%) can be achieved by changes on the supply side, another 35 Mt emission reduction (2.8%) can be achieved by changes in waste management. While changes in waste management can be implemented before 2010, biomass introduction on the supply side will probably require a longer lead-time. About half of the emission reduction is cost–effective, but will require further technology development. The other half can be achieved at a cost level of 10,000 yen/t CO₂ (80 US$/t CO₂). The latter part is based on proven technology that is currently not cost–effective.     

Eutectic mixture promoted CO2 sorption on MgO-TiO2 composite at elevated temperature

The development of carbon dioxide(CO_2) sorbents that can operate at elevated temperatures is significant for the advancement of pre-combustion capture technologies.Recently, promoter-based systems composed of alkali/alkaline earth metal nitrates and/or carbonates have been considered as next-generation solid sorbents due to their improved CO_2 uptake and kinetics. However, obtaining stable MgO sorbents against temperature swing regeneration still remained challenging. Herein, we report MgO-TiO_2 solid sorbents promoted by eutectic mixture(KNO_3 and LiNO_3) for elevated temperature CO_2 sorption. The developed sorbents show improved CO_2 sorption capacity, which may be attributed to the alternative CO_2 sorption pathway provided by the ionization of highly dispersed MgO in the eutectic mixture. The MgO-TiO_2 framework was also shown to assist in retaining the MgO configuration by constraining its interaction with CO_2. Furthermore, it is demonstrated that constructing composite structures is essential to improve the CO_2 sorption characteristics,mainly recyclability, at elevated temperatures. The developed promoter integrated sorbents showed exceptionally high CO_2 sorption capacity of 30 wt.% at an elevated temperature(300°C) with pronounced stability under temperature swing operation.     

CO2 adsorption using TiO2 composite polymeric membranes: A kinetic study

CO₂ is the main greenhouse gas which causes global climatic changes on larger scale. Many techniques have been utilised to capture CO₂. Membrane gas separation is a fast growing CO₂ capture technique, particularly gas separation by composite membranes. The separation of CO₂ by a membrane is not just a process to physically sieve out of CO₂ through the controlled membrane pore size. It mainly depends upon diffusion and solubility of gases, particularly for composite dense membranes. The blended components in composite membranes have a high capability to adsorb CO₂. The adsorption kinetics of the gases may directly affect diffusion and solubility. In this study, we have investigated the adsorption behaviour of CO₂ in pure and composite membranes to explore the complete understanding of diffusion and solubility of CO₂ through membranes. Pure cellulose acetate (CA) and cellulose acetate-titania nanoparticle (CA-TiO₂) composite membranes were fabricated and characterised using SEM and FTIR analysis. The results indicated that the blended CA-TiO₂ membrane adsorbed more quantity of CO₂ gas as compared to pure CA membrane. The high CO₂ adsorption capacity may enhance the diffusion and solubility of CO₂ in the CA-TiO₂ composite membrane, which results in a better CO₂ separation. The experimental data was modelled by Pseudo first-order, pseudo second order and intra particle diffusion models. According to correlation factor R², the Pseudo second order model was fitted well with experimental data. The intra particle diffusion model revealed that adsorption in dense membranes was not solely consisting of intra particle diffusion.     

Spherical Bi2O3/ATO catalyst with N2 pre-reduction electrocatalytic reduction of CO2 to formic acid

To achieve carbon neutrality,the Chinese government needs to gain a comprehensive understanding of the sources and drivers of greenhouse gas (GHG) emissions,particularly at the county level.Anji County in eastern China is a typical example of an industrial transformation from quarrying to a low-carbon economy.This study analyzed the decoupling types and structural characteristics of GHG emissions and the driving factors of carbon dioxide(CO₂) emissions in the Anji from 2006 to 2019,an...     

MgO-based adsorbents for CO2 adsorption: Influence of structural and textural properties on the CO2 adsorption performance

A series of MgO-based adsorbents were prepared through solution–combustion synthesis and ball-milling process.The prepared MgO-based powders were characterized using X-ray diffraction,scanning electron microscopy,N_2 physisorption measurements,and employed as potential adsorbents for CO_2 adsorption.The influence of structural and textural properties of these adsorbents over the CO_2 adsorption behaviour was also investigated.The results showed that MgO-based products prepared by solution–combustion and ball-milling processes,were highly porous,fluffy,nanocrystalline structures in nature,which are unique physico-chemical properties that significantly contribute to enhance their CO_2 adsorption.It was found that the MgO synthesized by solution combustion process,using a molar ratio of urea to magnesium nitrate(2:1),and treated by ball-milling during 2.5 hr(MgO-BM2.5h),exhibited the maximum CO_2 adsorption capacity of 1.611 mmol/g at 25℃ and 1 atm,mainly via chemisorption.The CO_2 adsorption behaviour on the MgO-based adsorbents was correlated to their improved specific surface area,total pore volume,pore size distribution and crystallinity.The reusability of synthesized MgO-BM2.5h was confirmed by five consecutive CO_2adsorption–desorption times,without any significant loss of performance,that supports the potential of MgO-based adsorbent.The results confirmed that the special features of MgO prepared by solution–combustion and treated by ball-milling during 2.5 hr are favorable to be used as effective MgO-based adsorbent in post-combustion CO_2 capture technologies.     

小浪底水库影响下的黄河花园口站和小浪底站pCO2特征及扩散通量

于2011年11月至2012年10月在黄河小浪底站和花园口站进行连续采样分析,根据亨利定律计算出表层水体二氧化碳分压(p CO2),研究了在小浪底水库"水沙调控"的影响下黄河花园口站和小浪底站表层水体p CO2特征及水-气CO2通量.结果表明,在小浪底水库正常调度期间,小浪底站表层水体p CO2在82~195 Pa之间,花园口站表层水体p CO2在99~228 Pa之间,且花园口站表层水体p CO2均高于同期的小浪底站;在小浪底水库调水调沙期间,两个水文站均表现为水库泄水期间的表层水体p CO2明显低于水库排沙期间的表层水体p CO2.无论是在小浪底水库正常调度期间还是在调水调沙期间,两个水文站表层水体p CO2均与DIC含量呈现显著的正相关关系.8、9月Ep CO2/AOU的比值高于生物好氧呼吸作用控制水体p CO2的理论下限0.62,因此8、9月生物好氧呼吸作用对水体p CO2的贡献比较明显.从全年来看小浪底站和花园口站平均水-气CO2扩散通量分别为0.486μmol·(m2·s)-1和0.588μmol·(m2·s)-1;在水库正常调度期间花园口站水-气CO2扩散通量明显高于同期的小浪底站;在小浪底水库调水调沙期间两个水文站均表现为水库泄水期间的水-气CO2扩散通量明显低于水库排沙期间的水-气CO2扩散通量.     

笼养肉鸡生长过程NH3、N2 O、CH4和CO2的排放

为确定规模化笼养肉鸡生产过程NH3、N2O、CH4和CO2的排放因子,并探讨不同生长阶段排放特征,本研究选择山东某商业化肉鸡养殖场,利用INNOVA 1312多气体分析仪-连续采样测试系统和风机风量现场测定系统(FANS),对肉鸡舍NH3、N2O、CH4和CO2的排放进行为期42 d的测定,确定了肉鸡整个生产过程气体的平均排放因子和累积排放因子.结果表明,整个肉鸡生产过程中NH3排放因子呈现出先升高后降低的趋势,变化范围在8.5～342.1 mg·(d·bird)-1,平均为137.9mg·(d·bird)-1[48.6 g·(d.AU)-1],CH4和CO2排放因子随着日龄的增加而增大,CH4排放因子的变化范围在19.5～351.9mg·(d·bird)-1之间,平均为154.5 mg·(d·bird)-1[54.4 g·(d.AU)-1],CO2的排放因子在2.2～152.9 g·(d·bird)-1之间变化,平均为65.9 g·(d·bird)-1[23.2 kg·(d.AU)-1],整个生产过程没有监测到N2O的排放;肉鸡的NH3累计排放因子为(5.65±1.02)g·(bird·life cycle)-1,第1阶段(0～17 d)、第2阶段(18～27 d)和第3生长阶段(28～42 d)氨气排放占总排放的比例分别为33.6%、36.4%和29.9%,第2阶段的NH3累计排放因子显著高于第1和第3生长阶段;CH4和CO2的累计排放因子分别为(6.30±0.16)g·(bird·life cycle)-1和(2.68±0.18)kg·(bird·life cycle)-1,第3阶段的CH4和CO2累计排放因子显著大于1和2阶段,占总排放量的50%以上.研究结果为控制气体排放提供了数据基础.     

乙醇胺热降解-氧化降解循环过程及SO2在其中的影响

使用半连续式不锈钢搅拌反应釜,研究了质量分数30%的乙醇胺(MEA)水溶液(CO2负载量0.4 mol·mol-1)的热降解-氧化降解循环过程,旨在探讨循环过程对MEA降解的影响,以及SO2对MEA热降解、氧化降解和循环过程产生的影响.其中,热降解的实验条件为120℃,降解时间为2周,在密闭反应器内进行;氧化降解的实验条件为55℃,约121.59 kPa,向溶液中持续通入模拟烟气,总气量为7.5 L·min-1,其中包括2%CO2、0~150 ppm SO2和空气.实验结果表明,在先进行热降解再进行氧化降解的过程中,MEA的热降解产物N-(2-羟乙基)乙二胺等会在氧化降解的过程中发生进一步反应,且原本氧化降解中生成的亚硝酸根会有部分进一步被氧化,生成硝酸根.在循环过程中,MEA的整体降解程度比单独进行热降解、氧化降解实验中有所提高.研究表明,添加亚硫酸根会加剧热降解中的氨气生成量,而在氧化降解中,SO2又表现出了明显的抑制作用.在循环过程中,这两者均有体现,SO2仍起到一定的抑制降解的作用.     

屋顶绿化二氧化碳减排效益的研究

屋顶绿化不仅能够美化城市环境,而且对城市二氧化碳减排具有一定作用。文章利用自行设计的熏气装置对几种常见屋顶绿化植物进行CO2熏气实验,测定其对CO2的吸收速率和影响因素;实验结果表明,红叶石楠、红继木和石榴等绿化植物对CO2具有显著的吸收能力,其中红叶石楠的吸收速率最高,达7.058 L/(m.2d),绿化植物对CO2的吸收速率受屋面温度影响较大,温度超过34℃时吸收速率快速减小;在实验观测基础上,结合武汉城市区域气候特征、建筑物荷载能力、屋顶绿化可用面积等信息,分析得到武汉市进行规模化屋顶绿化之后,每年可吸收转化CO21.696×106t,相当于一个194 MW火力发电厂一年的CO2排放量,屋顶绿化的发展前景较可观。     

DBU醇溶液对CO_2吸收量的影响研究

本文考察了CO2体积分数、温度、气体流量、吸收液喷雾量、DBU体积分数等因素对CO2吸收量的影响.研究结果表明:各因素对CO2吸收量的影响大小顺序为CO2体积分数温度气体流量吸收液喷雾量DBU体积分数,DBU醇溶液喷雾吸收CO2的最佳条件是CO2体积分数15%、温度30℃、气体流量2.7 L·min-1、吸收液喷雾量30 m L·min-1、DBU体积分数5%,此时CO2吸收量为1.095 mol·mol-1.     

Breakthrough CO2 adsorption in bio-based activated carbons

In this work, the effects of different methods of activation on CO₂ adsorption performance of activated carbon were studied. Activated carbons were prepared from biochar, obtained from fast pyrolysis of white wood, using three different activation methods of steam activation, CO₂ activation and Potassium hydroxide (KOH) activation. CO₂ adsorption behavior of the produced activated carbons was studied in a fixed-bed reactor set-up at atmospheric pressure, temperature range of 25–65°C and inlet CO₂ concentration range of 10–30 mol% in He to determine the effects of the surface area, porosity and surface chemistry on adsorption capacity of the samples. Characterization of the micropore and mesopore texture was carried out using N₂ and CO₂ adsorption at 77 and 273 K, respectively. Central composite design was used to evaluate the combined effects of temperature and concentration of CO₂ on the adsorption behavior of the adsorbents. The KOH activated carbon with a total micropore volume of 0.62 cm³/g and surface area of 1400 m²/g had the highest CO₂ adsorption capacity of 1.8 mol/kg due to its microporous structure and high surface area under the optimized experimental conditions of 30 mol% CO₂ and 25°C. The performance of the adsorbents in multi-cyclic adsorption process was also assessed and the adsorption capacity of KOH and CO₂ activated carbons remained remarkably stable after 50 cycles with low temperature (160°C) regeneration.     

碳酸酐酶及其矿化捕获CO2研究

自然条件下CO₂水化速率十分缓慢,而CA(carbonic anhydrase,碳酸酐酶)作为一种以锌为活性中心的球状金属酶,可逆催化CO₂生成碳酸氢盐的水合反应,同时能加速该进程的反应速率,并且产物碳酸氢盐和氢根离子无毒害作用,是未来解决环境中CO₂吸收、贮存的可行技术. 但现阶段CA的大规模工业化生产和应用仍有诸多难点亟待解决:CA在使用时稳定性和活性均较低,易受到多种环境因素(如温度、pH、其他溶剂等)的影响;没有合适的含CA的生物载体;工业生产酶成本高昂且固载困难等. 这些问题也是目前CA研究的热点领域. 研究表明,常用的载体材料包括壳聚糖、无机纳米微粒、多孔材料、聚氨酯泡沫等, 这些材料各有优点,并且都能与CA较好地结合,固载CA的活性及稳定性也都不同程度的优于游离态CA,其中CA固载于无孔二氧化硅纳米颗粒上的热稳定性较好. 常用的结合方法有共价结合、吸附结合和交联结合,其中共价结合可以解决CA重复使用时的解吸和漏出问题. 对CA捕获CO₂实际应用中的诸多问题也正在积极解决:①混合气温度过高时,筛选热稳定性较高的菌种,或直接编码表达这类CA,亦或将CA与其他溶解CO₂能力强的溶剂(如胺液、MEA、MEDA等)配合使用;②针对液态膜易挥发的缺点,可以增加聚砜类增湿器;③对于捕获过程中HCO₃-不断增多的问题,可以加入Ca(OH)₂中和或是用离子置换装置去除.      

Pt-Cu/TiO2{001}纳米片用于CO2加氢制甲醇反应的研究

以高暴露{001}晶面的TiO₂纳米片为载体,利用共还原法负载0.5%的Pt和一定量的Cu得到Pt-Cu/TiO₂{001}催化剂,并在P=3.0 MPa,T=200~300℃,V（N₂）：V（H₂）：V（CO₂）=8：69：23,空速（WHSV）=3600 mL·g^-1·h^-1反应条件下评价了催化剂催化CO₂加氢制甲醇的反应性能.XRD、XPS、EPR和CO₂-TPD等的表征表明,与催化剂Cu/TiO₂相比,引入Pt后,催化剂由于金属Pt的电子促进作用使负载的金属与载体之间的相互作用更强,进而有利于稳定Cu颗粒尺寸且载体形成了更多缺陷（如氧空位、Ti³⁺）.因此,Pt-Cu/TiO₂{001}催化剂的金属与载体界面上的活性位点更多,从而表现出更好的CO₂活化能力和甲醇生成性能.     

流化床O2/CO2气氛下添加SiO2对燃煤PM2.5的控制

采用小型流化床研究了在O2/CO2气氛下添加SiO2对PM2.5(空气动力学直径小于2.5 μm的颗粒物)的控制,试验在1123 K、O2/CO2气氛下进行,并采用荷电低压撞击器(ELPI)采集和分析燃烧后的PM2.5.结果表明,添加SiO2是燃烧过程中影响PM2.5生成的重要因素.添加SiO2后,生成PM1的质量浓度均降低,而PM1-2.5的质量浓度均略有增加;PM2.5质量粒径分布均呈双峰分布,峰值分别出现在0.2 μm和2.0μm左右.随着SiO2添加量的增加,PM2.5中的S、K、Na、Cu和Pb元素的含量呈减少的趋势;随着颗粒粒径减小,S、K、Na、Cu和Pb元素的含量有增高的趋势.     

低浓度CO2在聚苯胺/Y分子筛复合材料上的吸附

根据原位聚合方法将不同量的苯胺分别聚合在Y分子筛上,得到3种聚苯胺(PANI)/Y分子筛复合材料PANI-Y~(-1)、PANI-Y-2及PANI-Y-3,用傅立叶红外及氮气吸附实验表征了材料的结构特征,探讨了复合材料对常压下低浓度CO_2的吸附及再生性能.结果表明,苯胺在Y分子筛上成功聚合,复合材料的比表面积分别为52、54和35 m2·g~(-1),孔道由大孔和少量中孔组成,微孔极少.PANI负载量越大,材料的孔容越低.20℃下,初始体积分数为10%的CO_2在复合材料与Y分子筛上的吸附符合Logistic模型,吸附量的顺序为PANI-Y-2(2.09 mmol·g~(-1))PANI-Y-3(1.79 mmol·g~(-1))PANI-Y~(-1)(1.07 mmol·g~(-1))Y分子筛(0.80 mmol·g~(-1)),复合材料对CO_2的吸附受PANI负载量和比表面积的共同影响.在2%~10%的范围内,CO_2在复合材料上的吸附量随初始体积分数增加而增加;在25~65℃下,吸附量随温度升高而降低.80℃下,PANI-Y-2的4次热再生效率较差,仅68%;采用氨水/热再生相结合的方式脱附CO_2,再生率提高到94%.