Removal of phosphorus and sulfur from yellow phosphorus off-gas by metal-modified activated carbon

In order to provide comprehensive utilization of high concentration CO for mono-carbon (C1) chemical industry, the purification of yellow phosphorus off-gas is of great concern. In this research, activated carbon (AC) modified by different impregnants were used for removal of PH₃, H₂S, SO₂, COS, and CS₂ in yellow phosphorus off-gas. For the removal of PH₃, AC impregnated with 0.10 mol L⁻¹ CuAc₂ was proved to be the best adsorbent. And removal efficiency of H₂S could be significantly enhanced by AC impregnated with 7% Na₂CO₃. The results of plant experiments suggested that the total concentration of the impurities in yellow phosphorus off-gas was less than 1 mg Nm⁻³ after purification operation. The metal-modified activated carbon (MMAC) was systematically characterized in terms of XPS, TGA, and DTA. The adsorption reaction mechanism was also investigated. As a result, the yellow phosphorus off-gas purified in this study can be used as a raw material gas in the C1 chemical industry.     

CO2泄漏对稻田水基础水质指标的影响研究

碳捕集与封存（CCS）技术是当前抑制大气中CO₂过快增长的有效方法,但在CCS项目实施过程中仍存在CO₂泄漏而影响地表环境及生态的风险.本研究以龙粳31号和龙稻18号为实验对象,模拟研究地质封存CO₂以不同速率泄漏对稻田水环境基础水质指标D_CO2、pH、DO和ORP的影响,探讨稻田水对地质封存CO₂泄漏的响应规律.结果表明：CO₂泄漏对稻田水的D_CO2、pH、DO和ORP长期影响显著,不同CO₂泄漏速率对稻田水质指标的影响差异显著.在各指标平衡后,稻田水各水质指标均呈现明显的日变化规律,其中D_CO2呈早晚高、午间低的先减后增规律,而pH、DO和ORP均呈早晚低、午间高的先增后减规律.根据各指标差异性分析,建议将稻田水D_CO2作为稻田系统CO₂泄漏监测的主要指标,将pH、DO、ORP作为CO₂泄漏监测的辅助指标.     

利用高通量测序对封存CO2泄漏情景下土壤细菌的研究

全球CO2浓度不断升高的背景下,地质封存CO2为控制大气CO2浓度上升提供了全新的思路,但封存CO2潜在的泄漏风险也对生态系统产生重大威胁.土壤微生物与土壤健康密切联系.鉴于目前地质封存CO2泄漏对土壤微生物影响的研究鲜有报道,本研究通过模拟地质封存CO2泄漏情景,利用Miseq平台Illumina第二代高通量测序土壤细菌16S rRNA基因,结合相关生物信息学分析,初步探讨了封存CO2泄漏情景下农田土壤细菌群落丰富度、多样性和群落结构的变化.试验共获得15个土壤样本的43 017个OTU共486 645条读数,生物学分析结果表明,封存CO2泄漏通量和时间不同的情景下,农田土壤细菌丰富度和细菌群落多样性的变化存在差异,初步推测CO2泄漏量增大和泄漏时间持续更长的情景下,土壤细菌丰富度和多样性下降幅度较大,土壤细菌群落中优势菌群向若干细菌集中,其中土壤酸杆菌门细菌相对增多可能作为地质封存CO2泄漏对土壤生态系统影响的生物监测指标.     

深部储层中CO2沿断层泄漏量的影响因素

CGS（CO₂地质储存）是CO₂减排的重要手段之一,天然裂隙的存在则是CGS的潜在风险.CO₂地质储存过程中储层上覆盖层及其浅部含水层是防止CO₂泄漏的天然屏障,为了探究深部咸水层中CO₂沿断层的泄漏过程并获得断层渗透率及储层中超临界CO₂流体初始条件（初始饱和度、初始泄漏压力）对CO₂沿断层泄漏速率和泄漏量的影响程度,依据鄂尔多斯CO₂灌注工程示范区资料,使用多相、多组分溶质运移数值模拟软件TOUGH2建立了2D概念模型.结果表明,深部咸水层中的CO₂在压力差和浓度差的作用下沿断层发生泄漏,到达浅部含水层后开始发生侧向运移,100 a内运移了约200 m的水平距离;由于浮力的作用,CO₂集中在含水层顶板处,有效地防止了CO₂向外泄漏.影响因素分析表明,100 a内断层渗透性能为低渗、中渗和高渗条件时,CO₂累积泄漏量分别为0、1 050和3 000 t;CO₂初始饱和度分别为0.20、0.50和0.99时,CO₂累积泄漏量分别为550、1 050和1 650 t;初始泄漏压力分别为17.3、17.6和18.1 MPa时,CO₂累积泄漏量则分别为900、1 050和1 400 t.除此之外,断层渗透性、CO₂初始气体饱和度和初始泄漏压力对CO₂泄漏的影响还体现在泄漏发生时间和平均泄漏速率上.研究显示,各因素对CO₂沿断层泄漏过程的影响程度表现为断层渗透性能> CO₂初始饱和度> CO₂初始泄漏压力.      

加油站油类污染物自然衰减现场试验研究

利用自行设计制作的一套土壤气体取样监测装置,在北京地区某加油站开展了包气带内石油类污染物自然衰减的现场试验研究.在现场对包气带内的土壤气体样本进行采集,并对样本中的VOC含量及O2、CO2含量进行了检测分析.2个阶段的检测结果表明,经过381 d的自然衰减,污染点位的TVOC浓度减少了99.2%,BTEX的气相浓度占TVOC的比例由17.0%降至12.1%;O2和CO2含量在G3点位呈现出随着土壤深度的增加,O2含量逐渐减少、CO2含量逐渐增加的变化趋势.通过对试验结果的分析得出以下结论:①第一次检测结果表明G3点位附近存在一定的土壤污染,经过381 d的自然衰减,G3点位土壤中的BTEX含量已降至保护环境的标准以下,该污染现场的环境监控措施可以解除;②对造成该点污染的原因进行推断,可以判定污染为短期污染源导致,不存在持续的泄漏源;③自然衰减能够有效清除土壤中污染物,可以作为北京市同类污染场地有效的治理手段加以考虑;④检测污染土壤中O2和CO2含量的变化是判断有机污染物需氧降解的有效手段.     

瓦里关气相色谱法大气CO_2和CH_4在线观测数据处理分析

加强我国本底站温室气体数据资源的科学管理与共享,首先应保证观测全流程的标准化和规范化,确立数据处理和质量控制方法.我国青海瓦里关全球本底站自1994年开始了气相色谱-氢火焰离子化检测器法(GC-FID)大气CO2和CH4在线观测,本文详细讨论了该系统原始资料采集、数据信息合并、时间序列检查、观测员级质量控制和专家级质量控制等流程.利用局部近似回归法对大气CO2和CH4数据进行本底值筛分,获得CO2本底数据百分比约占有效数据的72%、CH4占44%.在线观测的CO2和CH4月平均浓度与同期瓶采样分析结果基本一致,相对偏差均在±0.5%以内.经流程化处理和质控的瓦里关大气CO2和CH4本底浓度变化资料已进入全球同化数据库(Globalview-CO2、Globalview-CH4),报送世界温室气体数据中心(WDCGG)并应用于世界气象组织(WMO)温室气体公报和联合国政府间气候变化专门委员会(IPCC)评估.     

The oxycoal process with cryogenic oxygen supply

Due to its large reserves, coal is expected to continue to play an important role in the future. However, specific and absolute CO₂ emissions are among the highest when burning coal for power generation. Therefore, the capture of CO₂ from power plants may contribute significantly in reducing global CO₂ emissions. This review deals with the oxyfuel process, where pure oxygen is used for burning coal, resulting in a flue gas with high CO₂ concentrations. After further conditioning, the highly concentrated CO₂ is compressed and transported in the liquid state to, for example, geological storages. The enormous oxygen demand is generated in an air-separation unit by a cryogenic process, which is the only available state-of-the-art technology. The generation of oxygen and the purification and liquefaction of the CO₂-enriched flue gas consumes significant auxiliary power. Therefore, the overall net efficiency is expected to be lowered by 8 to 12 percentage points, corresponding to a 21 to 36% increase in fuel consumption. Oxygen combustion is associated with higher temperatures compared with conventional air combustion. Both the fuel properties as well as limitations of steam and metal temperatures of the various heat exchanger sections of the steam generator require a moderation of the temperatures during combustion and in the subsequent heat-transfer sections. This is done by means of flue gas recirculation. The interdependencies among fuel properties, the amount and the temperature of the recycled flue gas, and the resulting oxygen concentration in the combustion atmosphere are investigated. Expected effects of the modified flue gas composition in comparison with the air-fired case are studied theoretically and experimentally. The different atmosphere resulting from oxygen-fired combustion gives rise to various questions related to firing, in particular, with regard to the combustion mechanism, pollutant reduction, the risk of corrosion, and the properties of the fly ash or the deposits that form. In particular, detailed nitrogen and sulphur chemistry was investigated by combustion tests in a laboratory-scale facility. Oxidant staging, in order to reduce NO formation, turned out to work with similar effectiveness as for conventional air combustion. With regard to sulphur, a considerable increase in the SO₂ concentration was found, as expected. However, the H₂S concentration in the combustion atmosphere increased as well. Further results were achieved with a pilot-scale test facility, where acid dew points were measured and deposition probes were exposed to the combustion environment. Besides CO₂ and water vapour, the flue gas contains impurities like sulphur species, nitrogen oxides, argon, nitrogen, and oxygen. The CO₂ liquefaction is strongly affected by these impurities in terms of the auxiliary power requirement and the CO₂ capture rate. Furthermore, the impurity of the liquefied CO₂ is affected as well. Since the requirements on the liquid CO₂ with regard to geological storage or enhanced oil recovery are currently undefined, the effects of possible flue gas treatment and the design of the liquefaction plant are studied over a wide range.     

CO2封存泄漏的稻田土壤细菌监测指标筛选研究

为研究CO₂地质封存过程中CO₂泄漏对水稻及稻田土壤的风险影响,利用CO₂模拟泄漏平台,研究了不同CO₂泄漏速率下水稻生长、稻田土壤性质与土壤细菌组成及多样性的变化特征.结果表明：随着CO₂泄漏速率的增加,稻田土壤pH显著降低,电导率显著增加,水稻生长受到明显抑制;稻田土壤细菌的丰富度指数和多样性指数均有增加,均匀度指数有所降低.CO₂泄漏显著改变了稻田土壤细菌组成,稻田土壤的优势菌门中变形菌门、拟杆菌门与绿弯菌门的相对丰度总体降低,而酸杆菌门与放线菌门的相对丰度总体升高;稻田土壤优势菌属中RB41、MND1、厌氧粘菌属及鞘脂单胞菌属的丰度总体升高,而硝化螺旋菌属的丰度总体降低;稀有细菌中CO₂泄漏下全部出现的有粘胶球形菌门、柔膜菌门及双头菌属、硫杆菌属,CO₂泄漏后全部消亡的为假单胞菌属.建议将变形菌门的减少和酸杆菌门的增加,以及RB41、MND1及厌氧粘菌属的增加作为稻田土壤CO₂泄漏监测的推荐指标.     

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.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

包气带水气二相流CO2运移规律

利用土柱实验装置模拟CO₂在土壤中的迁移转化规律,重点研究湿润峰处水、气二相间污染物转化实验土柱长1m,过饱和CO2溶液浓度为748mg/L.分析表明水相运移受对流、弥散、反应及水-气质量传输机制控制,气相运移受对流、扩散和水-气质量传输机制控制.对土柱中水气二相动态条件下的取样方法进行了探索,确定了CO₂在渗透湿润峰水-气二相间分配系数为0.00061,表明水相向气相有一定传输,但不显著.可进一步为低中水平放射性废物地质处置安全评价及固体废物填埋处置环境影响评价提供定量科学依据.     

氮输入对沼泽湿地碳平衡的影响

以小叶章沼泽化草甸为对象,利用静态箱-气相色谱法,在三江平原进行野外原位试验,研究氮输入对沼泽湿地碳平衡及其各分量的影响.氮素输入后,沼泽湿地生态系统总初级生产力提高,生物量增大,分别比对照处理增加了10%和26.8%.同时,CH₄和生态系统呼吸CO₂排放量提高,而生态系统CO₂净交换(NEE)和净碳(CO₂和CH₄都转化成对应的碳)交换降低,CO₂、CH₄和NEE的季节变化动态未改变.2004年整个生长季氮输入处理的CO₂和CH₄排放量分别比对照处理升高了34%和145%,NEE和净碳交换分别降低了70%和81.6%,但整个生长季2个处理仍然表现为碳的净吸收.氮输入没有改变沼泽湿地碳“汇”的功能,只是减弱了其作为碳“汇”的功能.     

新安江水库二氧化碳排放的时空变化特征

新安江水库是我国华东地区最大的水库,面积580 km2,平均深度30 m,水库水体处于中贫营养状态.为了研究新安江水库中CO_2排放的时空变化特征,2014年12月至2015年12月采用静态浮箱法收集水库表面以分子扩散方式排放的CO_2,使用气相色谱仪分析CO_2浓度.结果表明,新安江水库CO_2排放通量从上游入库河流[(120.39±135.41)mg·(m~2·h)~(-1)]至库区主体[(36.65~61.94)mg·(m~2·h)~(-1)]呈下降趋势,而大坝下游河流中CO_2排放通量[(1 535.00±1 447.46)mg·(m~2·h)~(-1)]显著增加,约分别是上游入库河流和库区主体的13倍和25~42倍.但随着与大坝距离增加,大坝下游河流中CO_2排放通量显著下降,如7 km处的CO_2排放通量仅为出库水体处的20%.在库区主体中,CO_2排放通量具有明显的季节变化:CO_2排放通量在秋、冬季时为正值,最大值出现在冬季(12月或1月),说明此时库区表层水体是CO_2排放源;而CO_2排放通量在春、夏季为负值,最小值出现在春季(3、4或5月),说明此时库区表层水体是CO_2吸收汇,这可能与春、夏季时水体中藻类繁殖有关.所以,在调查水库表面CO_2排放时,应对水库的上游入库河流、库区主体和坝下河流进行全面长期的观测,才能避免低估水库中CO_2排放总量.     

京津冀区域生产和消费CO2排放的时空特点分析

区分消费和生产二氧化碳排放是对开放的经济区域进行排放责任划分的基础,日渐受到政策制定者的关注.利用经济投入产出-生命周期分析模型,对京津冀区域1997年、2002年和2007年的消费和生产二氧化碳排放时空特征及二氧化碳排放平衡进行分析.结果表明,京津冀区域消费和生产二氧化碳排放呈约4%的年均增长;贸易隐含二氧化碳排放比例为30%~83%,并以国内贸易隐含二氧化碳排放为主;河北的消费和生产二氧化碳排放占区域主导,增速和二氧化碳排放强度高于北京和天津;京津冀区域为二氧化碳排放净流入区域,存在部分排放责任转移;京津为二氧化碳排放净转入地区,冀为二氧化碳排放净转出地区;京津冀三地二氧化碳排放关键部门分布集中且相似度较高,可以考虑区域联合控制.其中,电力、蒸汽、热水生产和供应业和金属冶炼及压延加工业对二氧化碳排放的依赖性最大,承担较大的其他部门的二氧化碳排放责任.投入产出分析解析了地区生产和消费二氧化碳排放情况,有利于区域减排的精细化管理和制定相应对策,并促进区域减排合作.     

Soil warming effect on net ecosystem exchange of carbon dioxide during the transition from winter carbon source to spring carbon sink in a temperate urban lawn

The significant warming in urban environment caused by the combined effects of global warming and heat island has stimulated widely development of urban vegetations. However, it is less known of the climate feedback of urban lawn in warmed environment. Soil warming effect on net ecosystem exchange (NEE) of carbon dioxide during the transition period from winter to spring was investigated in a temperate urban lawn in Beijing, China. The NEE (negative for uptake) under soil warming treatment (temperature was about 5℃ higher than the ambient treatment as a control) was -0.71 μmol/(m².sec), the ecosytem was a CO₂ sink under soil warming treatment, the lawn ecosystem under the control was a CO₂ source (0.13 μmol/(m².sec)), indicating that the lawn ecosystem would provide a negative feedback to global warming. There was no significant effect of soil warming on nocturnal NEE (i.e., ecosystem respiration), although the soil temperature sensitivity (Q₁₀) of ecosystem respiration under soil warming treatment was 3.86, much lower than that in the control (7.03). The CO₂ uptake was significantly increased by soil warming treatment that was attributed to about 100% increase of α (apparent quantum yield) and A_max (maximum rate of photosynthesis). Our results indicated that the response of photosynthesis in urban lawn is much more sensitive to global warming than respiration in the transition period.     

固定化碳酸酐酶在立式反应器催化吸收模拟烟气中CO2的实验研究

利用海藻酸钠包埋和戊二醛交联法固定碳酸酐酶,并在立式反应器进行了固定化酶吸收CO2的特性实验.实验结果表明:固定化酶的酶活力回收率是56.3%;固定化酶显著加快模拟烟气中CO2的吸收;载酶量小时,气体流量是影响吸收CO2效果的主要因素,气体流量增大,载酶量成为主要因素;气体流量增大,载酶量对反应终止p H的影响减小;载酶量增大,气体流量对反应终止p H的影响减小;气体流量增大,CO2吸收效率下降,载酶量提高,CO2吸收效率上升;气体流量为650 m L·min-1和载酶量为1 mg时,固定化酶催化吸收CO2效果显著;固定化酶具有较高的操作稳定性;SEM显示反应后的固定化酶表面出现大量形状不规则的小孔,空隙结构变得发达.     

Adsorption of carbon dioxide on amine-modified TiO2 nanotubes

TiO2 nanotubes (TiNT) were prepared by a hydrothermal treatment and modified by three kinds of amines,namely ethylenediamine,polyetherimide and tetraethylenepentamine (TEPA),to study their CO2 adsorption properties from gas streams.The resultant samples were characterized by X-ray diffraction,transmission electron microscopy,and infrared spectroscopy,as well as low temperature N 2 adsorption.CO2 capture was investigated in a dynamic packed column at 30℃.TEPA-modified TiO2 nanotubes showed the highest adsorption capacity of 167.64 mg/g because it had the highest amino-group content among the three amines.CO2 fixation on TiNT impregnated by TEPA was investigated at 30,50,and 70℃,and the adsorption capacity increased slightly with temperature.Following the adsorption step,the sorbents were regenerated by temperature programmed desorption,and the TiNT-TEPA sample,as CO2 sorbent,was found to be readily regenerated and energy-efficient.The cycle test also revealed that the TiNT-TEPA adsorbent is fairly stable,with only a 5% drop in the adsorption capacity after 10 adsorption/desorption cycles.In addition,the CO2 adsorption behavior was investigated with the deactivation model,and which showed an excellent prediction for the TiNT-TEPA breakthrough curves.     

半干旱草原地-气温室气体交换速率测定

重点介绍采用静态箱 -气相色谱法测定低交换速率的半干旱草原地 -气间温室气体交换速率的采样分析系统的配置及操作 .将静态采样箱置于采样点 ,用 50 cm³或 100 cm³的塑料注射器现场取样 ,转存于气袋中并送到实验室分析 .用改进了的进样系统并装有 FID和 ECD的气相色谱仪 ( GC)分析其中的 CH₄、CO₂ 和 N₂O浓度 ,计算出地 -气痕量温室气体的交换速率 .对内蒙古羊草草原、草甸草原 N₂O、CO₂ 和 CH₄交换速率日变化规律实测结果分析表明 ,该方法简便易行、准确可靠 .     

基于生命周期评价的钢铁厂碱渣固碳技术比较研究

本研究以3种钢铁厂碱渣直接法固碳技术为研究对象,该技术将钢渣进行碳酸化处理,可快速永久地将CO2固化储存在钢渣中,气固相反应可分别在高压釜、泥浆反应器和超重力旋转床的水溶液中一步完成,并将其分别定义为T1、T2、T3.通过Umberto软件建立生命周期模型,对3种技术的资源环境影响进行评估.结果表明,T1的环境影响最高,其次为T3,T2的环境影响最小.技术评价显示,T3在技术效率、资源消耗、环境影响方面具有较好的综合效益.敏感性分析表明,加热效率的敏感性系数分别为0.97、0.97和0.46.转换率与温室气体排放的关系分别呈上升、倒U型和下降的变化趋势.提高加热效率、合理利用热源及选择合适的技术效率,将有利于技术优化,减少技术的环境影响,提高固碳效率.     

Sorbents with high efficiency for CO2 capture based on amines-supported carbon for biogas upgrading

Sorbents for CO_2 capture have been prepared by wet impregnation of a commercial active carbon(Ketjen-black, Akzo Nobel) with two CO_2-philic compounds, polyethylenimine(PEI)and tetraethylenepentamine(TEPA), respectively. The effects of amine amount(from 10 to70 wt.%), CO_2 concentration in the feed, sorption temperature and gas hourly space velocity on the CO_2 capture performance have been investigated. The sorption capacity has been evaluated using the breakthrough method, with a fixed bed reactor equipped with on line gas chromatograph. The samples have been characterized by N_2 adsorption–desorption,scanning electron microscopy and energy dispersive X-ray(SEM/EDX). A promising CO_2 sorption capacity of 6.90 mmol/gsorbenthas been obtained with 70 wt.% of supported TEPA at 70℃ under a stream containing 80 vol% of CO_2. Sorption tests, carried out with simulated biogas compositions(CH_4/CO_2mixtures), have revealed an appreciable CO_2 separation selectivity; stable performance was maintained for 20 adsorption–desorption cycles.