不同CO2捕集技术的CO2耦合绿氢制甲醇工艺研究

大量的化石燃料燃烧导致温室气体排放增加,全球气候变暖。世界各国以全球协约的方式减排CO₂,我国也由此提出“碳达峰·碳中和”目标。CO₂捕集以及转化制液体燃料和化学品是双碳目标下行之有效的碳减排措施之一,不仅可以实现CO₂的资源化利用,同时也缓解了国家能源安全问题。本文以燃煤电厂烟气CO₂捕集和CO₂合成甲醇为研究对象,分析了基于四种不同CO₂捕集技术的CO₂耦合绿氢制甲醇工艺。对四种不同CO₂捕集技术的CO₂制甲醇工艺进行了严格的稳态建模和模拟,分析和比较了不同CO₂捕集技术情景下的CO₂制甲醇工艺的技术和经济性能。结果表明,MEA、PCS、DMC和GMS情景的单位甲醇能耗分别是7.81、5.48、5.91和4.66 GJ/ t CH₃OH,GMS情景的单位能耗最低,其次是PCS情景,但随着更高效相变吸收剂的开发,PCS情景的单位甲醇产品的能耗将降低至2.29~2.58 GJ/t CH₃OH。四种情景的总生产成本分别是4314、4204、4279和4367 CNY/ t CH₃OH,PCS情景的成本最低,更具有经济优势。综合分析表明PCS情景的性能表现最好,为可用于燃煤电厂最佳的碳捕集技术,为CO₂高效合成燃料化学品提供方向,缓解化石燃料短缺和环境污染问题。     

CO2捕集技术的研究进展

介绍了近年来二氧化碳捕集技术路线和国内外的有关研究项目,分析了各种方法的分离原理及优缺点。并对二氧化碳捕捉技术发展前景进行了展望。     

CO2的回收和捕集技术进展

本文介绍了几种常用的CO2:回收利用方法及世界各大公司利用这些方法进行改进的效果,从而提高了CO2的回收利用率.     

烟道气中CO2捕集技术探讨

阐述了电厂烟道气中CO2捕集回收的各种工艺方法，并简要分析了各种捕集回收工艺中存在的问题，然后对二氧化碳捕捉技术发展前景进行了展望。     

一种低能耗捕集CO2煤基甲醇和电力联产过程设计

传统的煤制甲醇过程所需合成气的氢碳比为2.1左右,而煤气化粗合成气氢碳比仅为0.7左右,因此需要将部分合成气进行变换来调节氢碳比。然而,变换气与未变换气混合后使得CO₂浓度降低,从而导致CO₂捕集能耗增加。提出了一种低能耗捕集CO₂煤基甲醇和电力联产过程。新联产过程中部分粗合成气首先经过变换,将CO转变为H₂和CO₂,CO₂浓度提高,在此时进行CO₂捕集可实现捕集能耗的降低。经CO₂捕集后,得到富H₂气体,富H₂气体分流后与另一部分煤气化粗合成气混合调节甲醇合成的氢碳比。对新的过程进行了建模、模拟与分析。结果表明相比传统的带CO₂捕集的煤制甲醇和IGCC发电过程,新的联产过程的能量节约率可达到16.5%,CO₂捕集能耗下降30.3%。     

生物质制甲醇系统CO2捕集过程的设计模拟及技术经济性分析

通过ASPEN PLUS过程系统建模模拟,设计了生物质制甲醇系统中CO2的捕集工艺流程,并分析了其技术经济性能,研究了不同CO2捕集率的成本及其对生物质制甲醇能耗、水耗的影响。结果表明,捕集率为85%时生物质制甲醇系统CO2捕集封存较佳,单位捕集量的成本最低,有效能耗为453 MJ/t、水耗为193 kg/t、成本为135元/t,远低于直接从大气中捕集CO2。虽然这将使生物质制甲醇的生产成本增加154元/t,但当CO2减排补贴价格为40~50元/t时,则可抵消该部分成本增量。     

氨法捕集CO2工艺研究进展

介绍了CO2捕集回收的工艺方法，简要分析了氨法捕集回收工艺存在的问题，以期利用化工模拟软件优化研究工艺参数，从而降低吸收成本。     

CO2捕集与合成甲醇利用技术的研究进展

二氧化碳(CO₂)是主要的人为产生的温室气体之一，其排放量的不断增加，引起了社会各界的广泛关注。近年来，科学家不断尝试从源头上减少CO₂的排放，但没有取得明显的效果。实际上, CO₂既是温室气体的主要来源，也是有用的碳源。因此，如何捕集和有效利用CO₂也是近年来许多学者一直在探索的研究方向。本文综述了吸收法、吸附法、膜分离法等主要的CO₂捕集方法；从CO₂的利用、H2的来源、CO₂加氢合成甲醇工艺等方面介绍了CO₂加氢合成甲醇的研究进展，为缓解CO₂排放提供参考思路。     

电厂CO2捕集工艺夹点分析与过程集成节能

电厂一乙醇胺（MEA）法烟气CO2捕集（CCS）工艺换热网络能量流密集,固有能耗高,对该工艺进行过程集成节能研究,具有重要意义。对CO2捕集工艺换热网络的夹点分析说明该换热网络存在跨越夹点的热量传递。冷热物流的总复合曲线特征说明了CO2捕集工艺固有能耗高的特性。对换热网络进行调优并提出了节能技术方案：（1）在夹点之上利用MEA贫液的部分高温位热量加热预吸附塔再生气;(2)采用MEA再生塔产生的湿CO2混合物作为驱动热源,跨越夹点设置一台氨吸收式制冷机以替代CO2液化所需部分制冷量。基于过程集成节能提出的换热集成节能措施可有效降低CO2捕集工艺固有能耗,使蒸汽耗量降低21%,冷却水耗量降低17.2%,CO2液化所需低温冷却公用工程降低43.4%。     

低温甲醇洗碳捕集改进与优化

减少CO₂排放对环境保护尤为重要。传统低温甲醇洗工艺中大量被贫甲醇吸收的CO₂由于被N₂稀释而直接作为尾气排放进大气中。为探究工艺改进空间,本研究基于Aspen Plus对一传统低温甲醇洗工艺进行模拟,物性方法选用CPA (Cubic-Plus-Association)模型并对该模型的二元交互系数进行回归修正,后与实际数据进行对比确保模型的准确性。对于工艺改进,首先在传统低温甲醇洗工艺的基础上采用四级增压热闪蒸和降压闪蒸相结合的方式进行一次改进以用于CO₂捕集,并对相关参数进行优化以进一步降低系统公用工程消耗。结果显示,虽然一次改进工艺的CO₂产量是传统工艺的3.3倍,但系统能量消耗增加了2.12%,系统(火用)消耗增加了17.81%。接着,在一次改进工艺的基础上采用“半贫液+透平回收”相结合技术进一步进行节能改进,二次改进工艺的CO₂产量不仅与一次改进工艺相当,系统能量消耗和系统(火用)消耗相比于传统低温甲醇洗工艺也分别降低了17.16%和5.85%。     

二氧化碳捕集技术及应用分析

分析了CO2捕集技术及现状。CO2捕集是CCS的关键技术单元之一,针对不同的CO2气源,国内外研究开发了多种技术。许多CO2捕集技术已经工业化,其中燃烧后烟气中CO2的捕集技术主要是以一乙醇胺(MEA)为基础的胺法;燃烧前的CO2捕集技术主要应用于IGCC电厂,一般需要对煤气中CO进行部分变换,变换后脱碳可采用成熟技术,如Selexol(NHD)等。富氧燃烧则是在中试成功的基础上,进行更大规模的工业示范。国内外大型煤制油化工项目主要采用低温甲醇洗脱除CO2,如果设置CO2产品塔,则可以获得体积分数98%以上的CO2。天然气脱碳主要采用MDEA技术。另外还有低温法、PSA、膜分离等CO2捕集技术及化学链燃烧等一些正在研发的技术。     

CO2 utilization for methanol production; Optimal pathways with minimum GHG reduction cost

Mitigating CO₂ emissions from industries and other sectors of our economy is a critical component of building a sustainable economy. This paper investigates two different methanol synthesis routes based on CO₂ utilization (CO₂ capture and utilization [CCU], and tri-reforming of methane [TRM]), and compares the results with the conventional methanol production using natural gas as the feedstock (NG-MeOH). A comprehensive techno-economic analysis (TEA) model that includes the findings of the life cycle assessment (LCA) models of methanol production using various CO₂ utilization pathways is conducted. Economic analysis is conducted by developing a cost model that is connected to the simulation models for each production route. Compared to the conventional process (with a GHG emission of 0.6 kg CO₂/kg MeOH), the lifecycle GHG reduction of 1.75 and 0.41 kg CO₂/kg MeOH are achievable in the CCU and TRM pathways, respectively. Furthermore, the results indicate that, under current market conditions and hydrogen production costs, methanol production via CO₂ hydrogenation will result in a cost approximately three times higher than that of the conventional process. The integrated TEA–LCA model shows that this increased cost of production equates to a required life cycle GHG reduction credit of $279 to $422 per tonne of CO₂ utilized, depending on construction material and selected pathway. Additionally, when compared to the CO₂ hydrogenation route, the tri-reforming process (TRM-MeOH) can result in a 42% cost savings. Furthermore, a minimum financial support of $56 per tonne utilized CO₂ will be required to make the TRM-MeOH process economically viable.     

Recent progress of green sorbents-based technologies for low concentration CO2 capture

The increased concentration of CO₂ due to continuous breathing and no discharge of human beings in the manned closed space, like spacecraft and submarines, can be a threat to health and safety. Effective removal of low concentration CO₂ from the manned closed space is essential to meet the requirements of long-term space or deep-sea exploration, which is an international frontier and trend. Ionic liquids (ILs), as a widespread and green solvent, already showed its excellent performance on CO₂ capture and absorption, indicating its potential application in low concentration CO₂ capture. In this review, we first summarized the current methods and strategies for direct capture from low concentration CO₂ in both the atmosphere and manned closed spaces. Then, the multi-scale simulation methods of CO₂ capture by ionic liquids are described in detail, including screening ionic liquids by COSMO-RS methods, capture mechanism by density functional theory and molecular dynamics simulation, and absorption process by computational fluid dynamics simulation. Lastly, some typical IL-based green technologies for low concentration CO₂ capture, such as functionalized ILs, co-solvent systems with ILs, and supported materials based on ILs, are introduced, and analyzed the subtle possibility in manned closed spaces. Finally, we look forward to the technology and development of low concentration CO₂ capture, which can meet the needs of human survival in closed space and proposed that supported materials with ionic liquids have great advantages and infinite possibilities in the vital area.     

低温甲醇脱碳工艺热力学模型和过程模拟研究

为了进行含高压气体和强极性物质的体系的低温甲醇脱碳工艺的模拟研究,建立相应的热力学模型.采用Soave-Redlich-Kwong(SRK)立方型状态方程,结合Huron-Vidal混合规则和非随机双流体Non-Random-Two-Liquid(NRTL)活度系数模型建立的热力学模型,从气体溶解度和气液平衡数据拟合获...     

CO2 capture by methanol,ionic liquid,and their binary mixtures: Experiments,modeling, and process simulation

The CO₂ solubility data in the ionic liquid (IL) 1‐allyl‐3‐methylimidazolium bis(trifluoromethyl sulfonyl)imide, methanol (MeOH), and their mixture with different combinations at temperatures of 313.2, 333.2, and 353.2 K and pressures up to 6.50 MPa were measured experimentally. New group binary interaction parameters of the predictive universal quasichemical functional‐group activity coefficient (UNIFAC)‐Lei model, which has been continually advanced by our group, were introduced by correlating the experimental data of this work and the literature. The consistency between experimental data and predicted results proves the reliability of UNIFAC‐Lei model for CO₂‐IL‐organic solvent systems. The newly obtained parameters were incorporated into the UNIFAC property model of Aspen Plus software to optimize a conceptual process developed for the purification of a CO₂‐containing gas stream. The simulation results indicate that the use of IL either mixed with MeOH or purely considerably lowers the process power consumption and improves the process performance in terms of CO₂ capture rate and solvent loss. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2168–2180, 2018     

耦合膜分离的新型CO2低温捕集系统性能优化

CO₂捕集作为温室气体排放控制的有效手段已成为重要研究课题。作为新兴捕集技术之一,低温CO₂捕集因产品纯度高、无附加污染等优势受到关注。然而,该技术能耗和捕集率对于气体中CO₂浓度十分敏感,对于高CO₂浓度气体可获得较高的CO₂捕集率和较低能耗水平。基于此,本文提出了耦合膜分离的新型CO₂低温捕集系统,通过膜材料选择渗透性实现待捕集气体CO₂浓度主动调控,并在最优浓度下进行CO₂低温捕集。首先基于不同传统低温捕集系统特点,对比分析了不同耦合系统模式,从而确定了最优耦合系统结构。针对最优耦合系统进行了运行参数优化,并分别基于实现系统捕集能耗最低与捕集率最高的目标,获得了膜渗透侧CO₂浓度与进气CO₂浓度间的关系式,为该耦合系统中膜组件选型提供指导。研究表明,本文提出的耦合系统捕集能耗为1.92MJ/kgCO₂,相比于传统单一低温系统捕集能耗可降低16.5%。     

混合胺溶剂吸收CO_2的内冷流程模拟

为降低醇胺溶液吸收法捕集分离CO_2的能耗问题,采用在吸收塔增加内部冷却即内冷的方法,使用乙醇胺和甲基二乙醇胺混合溶剂水溶液,采用化工模拟软件AMSIM进行了CO_2吸收的过程模拟。分析了内冷位置、一级和二级内冷的冷却量、贫液流量和混合溶液浓度对捕集能耗的影响。结果表明采用混合胺溶剂和内冷流程的CO_2捕集能耗比乙醇胺传统流程的能耗降低了17%,说明将捕集溶剂和捕集流程结合起来进行研究,可以明显降低CO_2捕集能耗。     

Strategies for CO2 capture from different CO2 emission sources by vacuum swing adsorption technology☆

Different VSA(Vacuum Swing Adsorption) cycles and process schemes have been evaluated to find suitable process configurations for effectively separating CO2 from flue gases from different industrial sectors. The cycles were studied using an adsorption simulator developed in our research group, which has been successfully used to predict experimental results over several years. Commercial zeolite APGIII and granular activated carbon were used as the adsorbents. Three-bed VSA cycles with- and without-product purge and 2-stage VSA systems have been investigated. It was found that for a feed gas containing 15% CO2(representing flue gas from power plants), high CO2 purities and recoveries could be obtained using a three-bed zeolite APGIII VSA unit for one stage capture, but with more stringent conditions such as deeper vacuum pressures of 1–3 k Pa. 2-stage VSA process operated in series allowed us to use simple process steps and operate at more realistic vacuum pressures. With a vacuum pressure of 10 k Pa, final CO2 purity of 95.3% with a recovery of 98.2% were obtained at specific power consumption of 0.55 MJ·(kg CO2)-1from feed gas containing15% CO2. These numbers compare very well with those obtained from a single stage process operating at1 k Pa vacuum pressure. The feed CO2 concentration was very influential in determining the desorption pressure necessary to achieve high separation efficiency. For feed gases containing N 30% CO2, a singlestage VSA capture process operating at moderate vacuum pressure and without a product purge, can achieve very high product purities and recoveries.     

蒸汽活化钙基吸收剂联合脱碳脱硫特性

利用管式炉（TF）、蒸汽发生器和热重分析仪（TGA）研究了钙基吸收剂联合脱碳脱硫以及水合特性,并通过N2吸附实验对不同烧结程度以及水合前后样品的孔隙结构进行了测量。结果表明,无水合时,40次碳化循环后的样品碳化活性降至18%,但仍具有44%的硫化活性,比新鲜剂仅低4%,说明脱碳失效剂仍是良好的脱硫剂。碳循环失效剂经蒸汽活化后其碳化活性可提高至68%左右,且具有与新鲜剂类似的活性下降规律。每两次碳化循环后进行一次蒸汽活化,可使样品保持65%的平均转化率。蒸汽活化后吸收剂硫化率可提高至80%,远高于新鲜剂,由电镜扫描实验发现这是由于水合时颗粒产生了大的裂缝和破碎,提供了大量产物可自由生长的外表面积。不考虑颗粒磨损,利用钙基吸收剂先循环脱碳再蒸汽活化最后脱硫是一项联合脱除烟气中CO₂和SO₂的新方法。