CO2乳液置换开采天然气水合物研究进展

CO₂置换开采及封存的碳汇是降低我国南海水合物产业化开采成本的重要路径,不仅能保障粤港澳大湾区经济建设所需的能源供给,而且能降低大湾区过量的碳排放,与气态、液态CO₂相比,注入CO₂乳液置换效率更高。综述CO₂乳液在置换开采甲烷水合物中的应用,以及乳液的稳定性问题,讨论CO₂乳液开采南海水合物的优势及难点,并对下一步CO₂乳液法置换开采南海水合物进行分析,为未来天然气水合物开采及同步碳封存提供参考和建议。     

三轴应力下CO2置换开采天然气水合物实验研究

为模拟海域真实环境,在三轴应力、氯化钠体系以及水合物储层富水状态的条件下,开展针对氯化钠体系、储层初始饱和度以及置换压应力对液态CO₂置换开采海域天然气水合物的实验。研究表明：在三轴应力以及孔隙度约46.70%的条件下,氯化钠体系对CH₄置换效率影响较小,但对CO₂水合物合成表现出抑制作用;储层初始饱和度与CH₄置换效率之间是负相关关系且高的储层含水率更有利于CO₂封存;CH₄置换效率随着置换压应力的增长有一定幅度的提高,置换压应力的增大为CO₂水合物合成提供了高的驱动力,进而提高了CO₂封存效率。     

水合物法分离CO2工艺研究进展

随着温室效应加剧,CO₂减排行动已迫在眉睫。水合物法分离CO₂工艺作为一种发展前景广阔的新型CO₂分离技术,为CO₂减排提供了一种解决思路。水合物法分离CO₂工艺相比于化学吸收、物理吸附、深冷分离和膜分离等技术具有分离效率高、过程简单无副产物、条件温和的优势,为减缓CO₂排放增加对环境造成的影响提供了一个中短期解决方案,以此为前提将允许人类继续使用化石燃料直至可再生能源技术广泛应用。本文综合分析了国内外的相关文献,介绍了水合物法分离CO₂工艺的基本原理,并比较了水合物法分离CO₂不同工艺的优劣之处,为进一步优化水合物法分离CO₂工艺提供指导。     

利用水合物法分离捕集二氧化碳研究进展

我国是以煤炭为主要能源的国家,面临着严峻的碳减排挑战。相对于传统气体分离技术,水合物法CO₂分离捕集技术具有环境友好、工艺简单、能耗低等特点,被认为是具有应用前景的CO₂分离捕集技术,因而被广泛研究。综合调研了国内外水合物法分离捕集CO₂的研究,从热力学、动力学、微观分析、分离工艺及分离装备、成本比较等方面对相关研究进行了系统分析及综合评价,并详细讨论了水合物平衡条件和不同类型添加剂对水合物平衡条件的影响。为进一步开发水合物法CO₂分离捕集技术的研究提供指导。     

天然气水合物气藏开发技术探讨

天然气水合物是本世纪最具开发前景的替代能源，开发天然气水合物资源，对我国宏观能源战略决策和可持续发展具有重大的现实意义。文章概述了天然气水合物气藏的特点和国外水合物气藏勘探项目的进展．对热激发技术、降压技术和化学试剂技术等3种技术进行了对比分析，并着重研究了微波加热技术和CO2置换技术。微波加热技术的优点是作用速度快、设备简单、灵活性高、不会对储层造成任何污染。CO2置换技术的优点是利用天然气水合物生成和分解的机理，不仅考虑了经济地开采资源，并且还提出了在开采后消除对海底环境产生有害影响的对策。     

基于碳捕集系统半闭式S-CO2布雷顿循环性能分析

针对高温钙基碳捕集技术回收储存过程中未利用CO₂的超临界、流量大等特点的问题,采用半闭式超临界二氧化碳(S-CO₂)布雷顿循环系统取代传统CO₂回收系统,以降低由于碳捕集系统所造成的热量损失。利用Aspen Plus软件搭建耦合钙循环碳捕集的燃气轮机发电模型,在其CO₂回收系统中耦合S-CO₂布雷顿循环系统和跨临界二氧化碳(T-CO₂)布雷顿循环系统,使用精准度更高的REFPROR物性方法研究主压缩机出口压力、透平入口温度、透平入口压力及分流系数对循环系统净做功的影响。结果表明：CO₂回收系统中耦合S-CO₂布雷顿循环系统可以使全厂热效率提升1.7%,全厂■效率为26.98%;采用分流纯净烟气的方法作为S-CO₂布雷顿循环系统的热源,可使同一热源的热效率提升6.7%。     

TSR炉喷吹CO2热力学分析及工业试验

从热力学角度对CO₂用于不锈钢冶炼可行性进行了分析,通过热力学计算研究,发现在C含量不低于0.25%时,将CO₂用于不锈钢冶炼是可行的。建立了喷吹CO₂冶炼410S不锈钢工艺模型,该模型能够较好拟合实际应用CO₂冶炼过程。并通过70 t TSR炉工业试验结果进行验证。试验结果表明：CO₂用于不锈钢冶炼具有强化脱碳及减少铬烧损的效果,与原工艺相比,同期C含量降低0.011%,Cr含量提高0.144%。     

热激励的CO_2置换CH_4水合物的实验研究

CO_2置换CH_4水合物具有在开采天然气水合物的同时储藏CO_2的功能.天然气水合物因其可燃烧、燃烧后污染小、储量巨大等特点被认为是未来最有可能的能源替代品,但CO_2置换天然气水合物存在反应周期长、置换速率低的缺点.提出了一种借助CO_2水合物生成热量激励CH_4水合物分解的方法,在低温、高压的纯水体系中,研究了温度为275.15 K,置换压力分别为2.3、2.5、2.8、3.0 MPa时有热激励和无热激励两种置换反应的区别.研究结果表明,有热激励的置换反应,由于提供了额外的热量,使CH_4水合物更易分解,从而加速了置换反应的发生,提高了置换速率.     

基于Cu2O光阴极的光电催化CO2还原研究

光电催化CO₂还原制备碳氢燃料是缓解当前能源和环境危机的潜在策略。现阶段，光电极的构建依然是光电催化CO₂技术的关键点。由于Cu基催化剂具有低成本、高C2+选择性、高稳定性等适宜CO₂还原应用的特性，构建新型Cu基光电极仍是CO₂还原研究领域中研究热点。本文从P型Cu₂O光阴极入手，系统研究了电沉积工况与光电催化CO₂还原反应之间构效关系。研究结果表明，在恒温环境中，施加0.5 mA/cm²恒电流密度可获得结晶度良好的Cu₂O光阴极，并实现C2产物的合成。其中，乙醇的选择性可达5.3%。本文研究结果可为设计和制造具有高活性的光电催化CO₂还原光电阴极提供可行策略。     

天然气联合循环电厂燃烧后CO2捕集一体化技术经济评价

  目的  近年来,天然气发电在我国构建清洁能源体系中扮演着重要角色,预计到2025年“十四五”规划期结束时,中国气电装机容量将会突破150 GW。二氧化碳捕集利用是气电实现“双碳”目标的关键路径之一。  方法  为此,设立1个600 MW等级天然气联合循环发电（NGCC）、1个CO₂捕集和压缩（PCC）的综合工厂作为模拟对象。  结果  模拟研究表明:设计CO₂全烟气量捕集、90%效率、CO₂压缩提纯率为99.5%,燃气发电总出力输出下降了约16.05%,厂用电率增加5.55%,循环冷却水需求增加了约50.52%。  结论  通过经济分析显示,综合工厂的静态投资成本比单一发电厂的成本高54.28%,电力均等化运营成本（LCOE）增加了15.96%,给二氧化碳捕集的部署和发展带来了非常大的困难。但其中天然气价格仍然是影响电厂运营成本的最主要因素。     

二氧化碳-氮气混合气体在微粉硅胶中生成水合物的 实验研究

空气中CO₂含量的增加导致了全球气候变暖问题。气体水合物能够有效分离出电厂尾气中的CO₂,对改善环境具有重要意义。考察了微粉硅胶（silica gel）中80mol% N₂与20mol% CO₂混合气体水合物形成特性,选取压力范围为6.0 ~ 8.0 MPa,温度范围为 -20 ~ -5℃。研究发现,N₂与CO₂混合气进入反应釜后,直接生成水合物,诱导时间小于1 min。压力越高、温度越低,生成水合物的相对气体消耗量越大,最大的相对气体消耗量为0.115 (mol/mol),水的转化率最大为77.02mol%,前30 min水合物生成速率与压力无关。水合物气体消耗量越大,反应釜中剩余N₂组分的含量越大,最大为90.95mol%。水合物生成驱动力越低,水合物中CO₂ 组分越高。在6.0 MPa、-5℃下,水合物中CO₂组分最大为65.70mol%。     

Anthropogenic emissions of CO2 and CH4 in an urban environment

Regular observations of atmospheric mixing-ratios of carbon dioxide and methane in the urban atmosphere, combined with analyses of their carbon-isotope composition (δ¹³C, δ¹⁴C), provide a powerful tool for assessing both the source strength and source partitioning of those gases, as well as their changes with respect to time. Intense surface fluxes of CO₂ and CH₄, associated with anthropogenic activities result in elevated levels of these gases in the local atmosphere as well as in modifications of their carbon-isotope compositions. Regular measurements of concentration and carbon-isotope composition of atmospheric CO₂, carried out in Krakow over the past two decades, were extended to the period 1995–2000 and also to atmospheric mixing-ratios of CH₄ and its carbon-isotope composition. Radiocarbon concentrations (δ¹⁴C) in atmospheric CO₂ recorded at Krakow are systematically lower than the regional background levels. This effect stems from the addition of ¹⁴C-free CO₂ into the local atmosphere, originating from the burning of fossil fuels. The fossil-fuel component in the local budget of atmospheric carbon calculated using a three-component mixing model decreased from ca. 27.5 ppm in 1989 to ca. 10 ppm in 1994. The seasonal fluctuations of this component (winter–summer) are of similar magnitude. A gradually decreasing difference between the ¹⁴CO₂ content in the local atmosphere and the regional background observed after 1991 is attributed to the reduced consumption of ¹⁴C-free fuels, mostly coal, in southern Poland and the Krakow municipal area. The linear regression of δ¹³C values of methane plotted versus reciprocal concentration, performed for the data available for Krakow sampling site, yields the average δ¹³C signature of the local source of methane as being equal to −54.2‰. This value agrees very well with the measured isotope signature of natural gas being used in Krakow (−54.4±0.6‰) and points to leakages in the distribution network of this gas as the main anthropogenic source of CH₄ in the local atmosphere.     

Why does CO2 hydrate disposed of in the ocean in the hydrate-formation region dissolve in seawater?

The fate of CO₂ hydrate disposed of in the ocean is analyzed based on thermodynamic theory. It is found that CO₂ hydrate and seawater form a stable system only when (a) the system pressure p and temperature T fall within the hydrate-formation region in the ocean (i.e. p > 4.5MPa and T < 283 K) and (b) seawater is saturated or supersaturated with respect to CO₂. At ocean depths below 440 m, the pressure and temperature required for system stability are satisfied. However, since seawater is highly unsaturated with respect to CO₂, the requirement for full thermodynamic stability cannot be met because the hydrate and seawater are not in chemical equilibrium and the chemical potential for CO₂ in the hydrate is larger than that in seawater. Therefore, the hydrate is unstable and dissolves in seawater. Thus, CO₂ hydrate disposed of in the ocean may not be a long-lived entity in the ocean as was predicted previously by many investigators. The results of our study have been confirmed by laboratory simulations.     

羧甲基纤维素钠对CH4水合物形成过程的影响

羧甲基纤维素钠（CMC-Na）是水基钻井液中的重要组分,为研究CMC-Na对天然气水合物热力学和动力学的影响,实验测量了质量浓度介于0.5%～1.5%的CMC-Na溶液中甲烷水合物的相平衡条件,以及275.2 K、6 MPa的初始条件下CMC-Na溶液中甲烷水合物的形成过程。研究结果表明,CMC-Na对甲烷水合物的热力学稳定性具有微弱的抑制作用,相同压力下相平衡温度降低了0.1～0.2 K。CMC-Na溶液中形成的甲烷水合物为Ⅰ型,水合物数为5.84～5.90。在CMC-Na溶液中,甲烷水合物形成所需的诱导时间大大缩短,表明CMC-Na对甲烷水合物的形成过程具有促进作用。在CMC-Na溶液中水合物生成所需气体消耗量呈阶段式增长。水合物转化率低于35%的情况下,已经生成的水合物没有对搅拌器叶片形成持续附着进而卡住搅拌器。因此,CMC-Na对甲烷水合物的热力学稳定性具有一定的负面影响,对水合物的形成具有一定的促进作用。另外,CMC-Na能够降低水合物生成过程中搅拌扭矩的波动,对维持搅拌的正常运行具有重要作用。     

CO2单井增强地热系统取热性能研究

为提高闭式单井系统取热性能,提出一种CO2单井增强地热系统（CO2-SEGS）。建立井筒流动换热和储层热-流-固耦合的数学模型,考虑CO2可压缩性以及井纵向压力传递特性,对比分析了水和CO2在SEGS中的取热性能,研究系统取热性能与封隔间距、井筒保温的关系。结果表明：（1）额定循环流量下,井口生产温度从134.09℃降低至116.06℃;CO2在采出过程中降压膨胀做功,产生明显的温降效应,中心管井口温度比底部低约57℃。（2）井筒不同位置处CO2的密度、热容差异很大,当循环流量小于50 kg/s时,依靠浮升力作用,SEGS可实现自主循环运行,无需额外泵功。（3）当水和CO2的流量分别为15 kg/s和40 kg/s时,两者年均取热速率近似相等,CO2的采出温度比水低约40℃,而压力损耗远小于水。（4）SEGS取热性能与封隔间距以及中心管保温性能呈正相关。研究结果可为SEGS系统的开发提供参考。     

Expulsive force in the development of CO2 sequestration: application of SC-CO2 jet in oil and gas extraction

With the rapid development of global economy, an increasing amount of attention has been paid to the emission of greenhouse gases, especially CO₂. In recent years, dominated by the governments around the world, several significant projects of CO₂ sequestration have been conducted. However, due to the huge investment and poor economic effects, the sustainability of those projects is not satisfactory. Supercritical CO₂ (SC-CO₂) has prominent advantages in well drilling, fracturing, displacement, storage, plug and scale removal within tubing and casing, which could bring considerable economic benefits along with CO₂ sequestration. In this paper, based on physicochemical properties of SC-CO₂ fluid, a detailed analysis of technical advantages of SC-CO₂ applied in oil and gas development is illustrated. Furthermore, the implementation processes of SC-CO₂ are also proposed. For the first time, a recycling process is presented in which oil and gas are extracted and the CO₂ generated could be restored underground, thus an integrated technology system is formed. Considering the recent interests in the development of enhancing hydrocarbon recoveries and CO₂ sequestration, this approach provides a promising technique that can achieve these two goals simultaneously.     

Natural gas fired combined cycle power plant with CO2 capture

A natural gas (NG) fired power plant is designed with virtually zero emissions of pollutants, including CO₂. The plant operates in a gas turbine-steam turbine combined cycle mode. NG is fired in highly enriched oxygen (99.7%) and recycled CO₂ from the flue gas. Liquid oxygen (LOX) is supplied by an on-site air separation unit (ASU). By cross-integrating the ASU with the CO₂ capture unit, the energy consumption for CO₂ capture is significantly reduced. The exergy of LOX is used to liquefy CO₂ from the flue gas, thereby saving compression energy and also delivering product CO₂ in a saleable form. By applying a new technique, the gas turbine efficiency is increased by about 2.9%. The net thermal efficiency (electricity out/heat input) is estimated at 45%, compared to a plant without CO₂ capture of 54%. However, the relatively modest efficiency loss is amply compensated by producing saleable byproducts, and by the virtue that the plant is pollution free, including NO_x, SO₂ and particulate matter. In fact, the plant needs no smokestack. Besides electricity, the byproducts of the plant are condensed CO₂, NO₂ and Ar, and if operated in cogeneration mode, steam.