变压吸附分离提纯CO_2技术的应用

本文叙述了变压吸附提纯ＣＯ２技术的基本原理和工艺过程，介绍了我国ＰＳＡ－ＣＯ２的开发过程及发展前景，对已开发的ＰＳＡ－ＣＯ２工业装置的生产成本和经济性进行了分析     

Adsorption of H2, CO2, CH4, CO,N2 and H2O in Activated Carbon and Zeolite for Hydrogen Production

Abstract

The design of a layered pressure swing adsorption unit to treat a specified off-gas stream is based on the properties of the adsorbent materials. In this work we provide adsorption equilibrium and kinetics of the pure gases in a SMR off-gas: H₂O, CO₂, CH₄, CO, N₂, and H₂ on two different adsorbents: activated carbon and zeolite. Data were measured gravimetrically at 303–343 K and 0–7 bar. Water adsorption was only measured in the activated carbon at 303 K and kinetics was evaluated by measuring a breakthrough curve with high relative humidity.     

CO2 Adsorption and Desorption for CO2 Enrichment at Low-Concentrations Using Zeolite 13X

Adsorption of CO₂ using zeolite 13X as adsorbent has been studied extensively, but little attention has been paid to CO₂ adsorption at very low concentrations such as in the ambient air. Furthermore, there is almost no information on CO₂ desorption characteristics. In a carbon enrichment for plant stimulation system, ambient CO₂ is enriched from 400 to 1000 ppm to provide an enriched CO₂ stream for plant growth in greenhouses. To provide essential design data, systematic performance tests were carried out to evaluate both the adsorption and desorption capacity, enrichment factor, moisture content, and cyclic performance. It was found that the adsorption capacity and CO₂ concentration in the enriched air are a function of adsorption temperature and the difference of adsorption and desorption temperatures, for a given adsorbent loading at a properly selected gas flow rate.     

Preparation and characterization of CO2-selective Pebax/NaY mixed matrix membranes

CO₂-selective Pebax/NaY mixed matrix membranes (MMMs) were prepared by incorporating NaY zeolite into Pebax matrix. The morphology, chemical groups, thermal stability, and microstructure of the MMMs were investigated by scanning electron microscope, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction, respectively. The effects of zeolite loading amount, permeation temperature and pressure on the CO₂/N₂ separation performance of the resultant membranes were studied. The as-prepared MMMs are much superior to the pristine Pebax membranes in terms of permeability and selectivity. The CO₂ permeability and CO₂/N₂ selectivity can respectively reach to 131.8 Barrer and 130.8 for MMMs made by the starting materials containing 40 wt % NaY. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48398.     

变压吸附气体分离技术应用及展望窥探

为了深入探究变压吸附气体分离技术,分析了技术工作原理,依据此原理,研究此项技术在H_2、CO_2、C0、氯乙烯精馏尾气的回收与提取中的应用方法,并探究参数指标变化下气体回收与提取纯度的影响。基于变压吸附技术应用现状,气体吸附提取纯度仍有上升空间,具有较高的研发应用前景。     

Adsorption thermodynamics of CO2 on nitrogen-doped biochar synthesized with moderate temperature ionic liquid

The purpose of this work was to investigate the thermodynamic characteristics of carbon dioxide (CO₂) adsorption on a promising nitrogen-doped biochar at constant temperature and isopiestic pressure. The biochar was prepared as a CO₂ adsorbent based on catalytic pyrolysis of pristine coconut shells using urea as the nitrogen source and moderate temperature ionic liquid as a catalyst. The results showed that CO₂ adsorption on the biochar was a spontaneous, dominantly physical, exothermic, and entropy decrement process that could be well described by the slip model and the dual-site Langmuir model. Those thermodynamic parameters, including interface potential, exhibited a series of interesting tendencies with the changes in adsorption temperature and pressure. Under the conditions of 273 K and 100 kPa, the adsorption capacity and the interface potential were 4.6 mmol/g and −16.7 J/g, respectively. And the site energy ranged from 2.57 to 5.13 kJ/mol in the test conditions, which became narrow with increasing temperature. The temperature exhibited positive effects on interface potential, enthalpy change, entropy change, enthalpy change, internal energy change but negative effects on adsorption capacity, Gibbs free energy change, and Helmholtz free energy change. Interestingly, the pressure exhibited the opposite effect trends. The peak pressure with maximum temperature effect at a given temperature and the peak temperature with maximum pressure effect at a given pressure were found to exist for some thermodynamic parameters. These exhibited a different but significantly beneficial perspective to understand the mass and energy transfer during CO₂ adsorption on the biochar at constant temperature and isopiestic pressure, which have rarely been reported before.     

CO2/CH4/N2在沸石13X-APG上的吸附平衡

采用磁悬浮热天平测量了CO₂、CH₄与N₂在沸石13X-APG上的吸附等温线,温度为293、303、333和363 K,压力为0～500 kPa。对吸附平衡实验数据采用multi-site Langmuir模型和Sips模型进行拟合,均得到良好的拟合效果,非线性回归得到吸附热等模型参数,可为变压吸附工艺过程的开发提供基础热力学数据。将沸石13X-APG吸附分离性能与文献中报道的吸附材料(如沸石分子筛、活性炭、金属有机骨架材料和介孔硅分子筛)性能相比较。通过比较CO₂、CH₄与N₂吸附容量以及相对分离系数,探讨CO₂/CH₄(垃圾填埋气或者CO₂强化煤层甲烷回收气)体系、CO₂/N₂(燃煤电厂、水泥厂以及焦炭厂烟道气)体系以及CH₄/N₂(煤层气)体系吸附分离的高效材料,为未来二氧化碳吸附捕集和甲烷吸附回收提供基础数据。     

变压吸附工艺的研究与进展

论述了国外变压吸附在气体分离研究及技术的最新进展 ,对其工艺流程设计存在的问题进行了阐述 ,并分析了变压吸附工艺的应用及发展方向。     

烟气中CO2化学吸收法脱除技术分析与进展

介绍了烟气中CO2化学吸收法脱除技术,分析了其存在的技术难点,并对该技术的研究进展进行了论述;最后提出了化学吸收法脱除技术研究中两种值得关注的研究方向。     

变压吸附处理二组分有机废气

变压吸附(PSA)处理挥发性有机气体是一个新的领域。以活性炭CAN-230为吸附剂,采用两塔三步骤变压吸附过程对甲苯、二甲苯混合气体进行处理,考察了脱附压力、湿度等因素对处理效果的影响以及甲苯、二甲苯之间的相互影响。结果表明:采用常压吸附、真空脱附的变压吸附过程处理甲苯、二甲苯二组分废气时,脱附压力不宜高于0.03 MPa;相对湿度在50%以下时,对处理效果的影响不大,当相对湿度大于60%时,水蒸汽对有机气体的吸附有很强的抑制作用,净化气的浓度随湿度增大而增大;甲苯、二甲苯之间存在竞争吸附,进气中一种物质浓度的增大会使得另一种物质在净化气中的浓度升高。     

MER型沸石吸附分离CO2/CH4的分子模拟

MER型沸石在吸附分离CO₂/CH₄方面展现出良好的工业应用前景,受到广泛关注,但还缺乏理论基础数据。本文采用巨正则蒙特卡洛（GCMC）模拟方法,以全硅MER型沸石作为对照,模拟分析了CO₂/CH₄在Na⁺、K⁺、Cs⁺和Ca²⁺交换的MER型沸石中的吸附分离行为。结果表明：不同阳离子交换的MER型沸石对CO₂和CH₄的吸附符合Langmuir-Freundlich吸附等温线模型,平衡吸附量的大小顺序为：Ca-MER＞Na-MER＞K-MER＞Cs-MER,与沸石的自由体积和比表面积大小顺序一致,且近似成线性关系,选用高价阳离子MER型沸石可以提高吸附量;CO₂和CH₄主要分布在沸石的pau笼中,在d8R笼和ste笼中也有少量分布;骨架外阳离子与CO₂的强吸附作用和独特的八元环窗口孔径是MER型沸石对CO₂/CH₄混合组分表现出超高吸附选择性的原因,吸附选择性高达1000以上。综合吸附量、吸附热和吸附选择性分析指出,Na-MER和K-MER型沸石是优良的CO₂吸附剂。本研究为MER型沸石吸附分离CO₂/CH₄提供了理论依据和实验指导。     

工业尾气变压吸附提纯一氧化碳中试

Using pressure swing adsorption （PSA） technology to purify carbon monoxide （CO） discharged from industrial gases is a high-efficiency and economical method. In this article, a four-bed PSA experiment for CO purification was improved and optimized, in which a set of 120 m^3·h^-1 pilot-scale PSA device was developed to purify CO from industrial tail gases, a set of control systems suitable for industry production was developed, and the influences of the operating parameters on CO purification were investigated. The experimental results indicated that the pilot-scale PSA device could produce qualified product gas and get high CO recovery ratio under optimized conditions. The research may provide reliable fundamental data, for industrial scale utilization of CO, from industrial tail gases, and have strong market competitive power and a broad promoted application prospect.     

活性炭对CO_2的吸附与解吸研究进展

本文介绍了工业上CO2的主要来源及应用,以及工业上分离、回收CO2的常用方法。同时介绍了活性炭在变压吸附分离气体领域的应用,以及变压吸附过程中吸附剂再生的常用方法。详细综述了活性炭的孔结构、表面化学结构等因素对CO2的吸附及解吸性能影响的研究进展。     

Adsorption of CO2 on Zeolite 13X and Activated Carbon with Higher Surface Area

In this work, adsorption isotherms and adsorption kinetics of CO₂ on zeolite 13X and activated carbon with high surface area (AC-h) were studied. The adsorption isotherms and kinetic curves of CO₂ on the adsorbents were separately measured at 328 K, 318 K, 308 K, and 298 K and with a pressure range of 0–30 bar by means of the gravimetric adsorption method. The mass transfer constants and adsorption activation energy E_a of CO₂ on the adsorbents were estimated separately. Results showed that at very low pressure the amounts adsorbed of CO₂ on the zeolite 13X was higher than that on the AC-h, while at higher pressure, the amounts adsorbed of CO₂ on the AC-h was higher than that on the zeolite 13X since the AC-h has a larger surface area and a larger total pore volume compared to the zeolite 13X. The adsorption kinetics of CO₂ can be well described by the linear driving force (LDF) model. With the increase of temperature, the mass transfer constants of CO₂ adsorption on both samples increased. The adsorption activation energy E_a for CO₂ on the two adsorbents decreased with the increase of pressure. Furthermore, at low pressure the E_a for CO₂ adsorption on the zeolite 13X was slightly lower than that on the AC-h, while at higher pressure the E_a for CO₂ adsorption on the zeolite 13X was higher than that on the AC-h.     

应用于烟气中CO2捕集的固体吸附材料研究进展

固体吸附法捕集二氧化碳技术具有吸/脱附性能优良、设备轻便灵活、环保和低成本的优势，被认为是实现电厂烟气中碳捕集最具前景的技术之一。国内外学者对于可应用于电厂烟气中二氧化碳捕集的固体吸附材料开展了大量的研究并取得一定进展。该文综述了近些年沸石分子筛、金属有机框架材料（MOFs）和活性炭（ACs）等吸附材料的研究现状；归纳并分析了各类吸附材料的应用优势和在工程应用中存在的问题；总结了各类材料吸附性能的主要影响因素和吸附机理等。最后，展望了固体吸附材料的发展方向。     

吸附分离CH4/N2可行性研究

The separation between methane and nitrogen is an inevitable and important task in the C1 chemical technology and the utilization of methane from coalbed, yet it is considered to be one of the tough tasks in the field of separation. Pressure swing adsorption is a preferable technology if an adsorbent that allowing a large coefficient of separation for the CH4/N2 system is available. The separation coefficients between CH4 and N2 were obtained on analyzing the breakthrough curves measured experimentally with nine adsorbents. A technique of measuring the temperature-pulse was incorporated in the experiments, and the reliability of the result was improved. Superactivated carbon with large surface area and plenty of micropores was shown to have the largest separation coefficient and to be promising for the commercial utilization.     

N2和CO在5A分子筛上吸附的气相色谱研究

文中重新推导并简化了采用反相气相色谱法来测定吸附热力学参数的计算公式,并且在不同温度下,对N2和CO在4种5A分子筛上色谱保留时间进行了测定,对测定结果以推导公式为函数作线性回归,并且计算了吸附热力学参数ΔadH,ΔadS和ΔadG。结果表明,保留时间与1/T相关性很好,CO的吸附热随着分子筛Ca2+交换度的增加而增加,随着H+交换度的增加而减少,N2的吸附热则随着Ca2+交换度的增加变化不明显,随着H+交换度的增加而减少;CO和N2的吸附热在-25.36—-29.39 kJ/mol,4种分子筛对N2和CO的吸附熵在-80.01—-73.96J/(mol.K)和-72.13—-60.48 J/(mol.K),吸附G ibbs自由能变分别在-2.98—-4.77 kJ/mol和-9.82—-8.26 kJ/mol。     

13X-APG沸石真空变压变温耦合工艺吸附捕集烟道气中CO2

采用13X-APG沸石吸附捕集烟道气中CO2,并研发了五步循环真空变压变温(VTSA)耦合吸附捕集工艺. 实验测定了循环吸附/解吸过程中吸附剂再生率、烟道气中CO2回收率、产品气量及产品气中CO2纯度,并与传统的真空变压吸附工艺(VSA)和变温吸附工艺(TSA)比较. 由于VTSA在真空解吸的同时加热吸附剂,减少了真空泵的电耗,可在较温和的真空下(约3′103 Pa)操作,附加的吸附剂再生温度也不高,90~150℃下吸附剂再生率达97%以上,CO2回收率达98%以上. 吸附剂捕集CO2的量可提高到1.8 mol/kg,是VSA工艺产品气量的2倍,且产品气中CO2纯度提高到90%以上.     

真空变温吸附捕集干烟道气中CO2的模拟研究

为减缓气候变化,减少CO₂的排放,对真空变温吸附(TVSA)从干烟道气中捕集CO₂进行了系统的研究。以沸石13X为吸附剂,设计了实验室规模的4塔连续进料的TVSA工艺,并建立数学模型进行数值模拟。模拟结果表明,通过四塔TVSA可获得纯度为97.54%,回收率为96.79%的CO₂产品气,其产率为1.7 mol· ( \mathrm{k} \mathrm{g} \text{?} \mathrm{a} \mathrm{d} \mathrm{s} ) ^-1·h^-1,能耗为3.14 \mathrm{M} \mathrm{J} · ( \mathrm{k} \mathrm{g} \text{?} \mathrm{C} {\mathrm{O}}_{\mathrm{2}} {)}_{}^{-\mathrm{1}} 。此外,考察了进料量、循环回流步骤时间、真空度对产品气纯度、回收率、吸附剂产率和工艺能耗的影响,并且分析了塔内压力与温度变化,详细探讨了塔内气固相浓度随轴向的分布。良好的工艺效果表明,TVSA有潜力成为一种能够生产高纯度高回收率的CO₂产品气,并具有良好经济效益的捕碳工艺。     

吸附分离CH4/N2可行性研究

The separation between methane and nitrogen is an inevitable and important task in the C1 chemical technology and the utilization of methane from coalbed, yet it is considered to be one of the tough tasks in the field of separation. Pressure swing adsorption is a preferable technology if an adsorbent that allowing a large coefficient of separation for the CH4/N2 system is available. The separation coefficients between CH4 and N2 were obtained on analyzing the breakthrough curves measured experimentally with nine adsorbents. A technique of measuring the temperature-pulse was incorporated in the experiments, and the reliability of the result was improved.Superactivated carbon with large surface area and plenty of micropores was shown to have the largest separation coefficient and to be promising for the commercial utilization.