规整复合吸附剂真空变压吸附分离CH4/N2工艺模拟与分析

为减少甲烷排放,实现低浓度煤层气有效资源化利用,探究了使用规整复合吸附剂真空变压吸附富集低浓度煤层气的工艺。采用静态容积法测定了甲烷、氮气在规整复合吸附剂上的吸附等温线,同时建立了包括质量、热量和动量守恒在内的严格吸附床数学模型,设计了三塔连续进料的真空变压吸附工艺并进行模拟。分析了工艺达到循环稳态后吸附床层轴向温度分布和压力变化,并且探究了进料量、解吸压力、原料气中甲烷浓度和吸附压力对纯度、回收率、工艺能耗和吸附剂产率等工艺性能的影响。模拟结果表明,在进料量为100 L·min^-1,解吸压力为0.1 bar（1 bar=0.1 MPa）,原料气甲烷浓度为30%,吸附压力为3 bar时可以生产纯度为59.07%,回收率为93.64%的富CH₄产品气,同时单位能耗为18.70 kJ·mol^-1,吸附剂产率为4.56 mol·h^-1·kg^-1。表明规整吸附剂对CH₄/N₂具有良好的吸附分离效果,能够实现低浓度煤层气中甲烷高效富集。     

真空变压吸附提纯沼气的实验

以煤基碳分子筛为沼气净化吸附剂,借助扫描电镜观察了碳分子筛的表面形貌,并通过物理化学吸附仪表征了碳分子筛的孔径分布。基于静态容积法测定了CO₂与CH₄在碳分子筛的静态吸附量,并估算了CO₂与CH₄在碳分子筛的动力学扩散系数。单塔穿透实验考察了吸附压力与进料流量对原料气中CO₂穿透曲线的影响,选取吸附压力为0.3 MPa,进料流量为4 L·min-1进行两塔六步真空变压吸附提纯沼气的实验研究,并考察了吸附步骤时长与产品气冲洗率对CH₄富集效果的影响。实验结果表明,吸附步骤时长为140 s,冲洗率为0.05时,产品气中CH₄纯度可达98%,收率可达82%。     

快速变压吸附制氢工艺的模拟与分析

目前工业上主要通过变压吸附技术从蒸汽甲烷重整气中制取氢产品气。然而,能源需求量的快速增加使得传统变压吸附技术在产量方面的不足越发明显。为此,进行了快速变压吸附从蒸汽甲烷重整气中制取氢气的模拟研究。采用活性炭和5A分子筛作为吸附剂,并以测得的原料气中各组分在两种吸附剂上的吸附数据为基础,进行了六塔快速变压吸附工艺的数值模拟与分析。在分析了塔内温度、压力和固相的浓度分布后,探究了进料流量、双层吸附剂高度比以及冲洗进料比三个操作参数对于快速变压吸附工艺性能的影响,结果表明：原料气组成为H₂/CH₄/CO/CO₂=76%/3.5%/0.5%/20%,吸附压力为22 bar（1 bar=10⁵ Pa）,解吸吹扫压力为1.0 bar,处理量为0.8875 mol·s^-1,吸附剂床层高度比为0.5∶0.5,冲洗进料比为22.37%时,可获得H₂纯度99.90%,回收率69.88%,此时H₂产量为0.4713 mol·s^-1。相比之下,氢气纯度为99.90%时,尽管PSA工艺回收率为83.40%,但处理量只有0.39 mol·s^-1,因此H₂产量仅为0.2472 mol·s^-1。     

沸石ZSM-5吸附回收低浓度煤层气中CH4

利用高硅疏水性沸石ZSM-5吸附回收低浓度煤层气中的甲烷,对其吸附平衡、吸附动力学以及真空变压吸附分离过程进行了理论和实验研究。通过重量法和穿透曲线法测定了CH₄/N₂单组分及双组分的竞争吸附平衡数据,并采用Multisite Langmuir吸附等温线模型对其进行拟合。结合CH₄和N₂稀释穿透曲线实验数据和等温无动量损失的双分散二级孔结构扩散模型,获得CH₄和N₂在沸石ZSM-5上的微孔扩散系数。建立并求解包含质量、动量及能量传递的固定床吸附分离模型方程,预测了CH₄和N₂在沸石ZSM-5上的竞争吸附穿透曲线。进一步采用ZSM-5吸附剂填充床单柱四步真空变压吸附实验考察了进料浓度、进料流速、进料时间以及吹扫比对分离效果的影响。结果发现沸石ZSM-5对CH₄具有较好的选择性,沸石晶粒内的微孔扩散为吸附速率控制步骤,真空变压吸附工艺可将模拟煤层气中20%的CH₄提纯至31%～41%,回收率为93%～98%。     

高压下煤对CH4/CO2二元气体吸附等温线的研究

研究了晋城和潞安煤在高压下对纯 CH4,CO2 及其二元混合气体的吸附特性 ,在对混合气体绝对吸附量计算公式推导的基础上 ,对绝对吸附等温线进行了研究 .结果表明 :高压下煤对混合气体的吸附介于纯 CH4和 CO2 之间 ,Gibbs吸附等温线和绝对吸附等温线表现出较大的差异 ;煤对混合气体中 CH4和 CO2 的吸附呈现出不同的吸附特点 ;煤对 CO2 优先吸附 ,并且随着压力的升高 ,煤对 CO2 选择性吸附能力增加 .本研究结果对开展注烟道气提高煤层采收率和煤层埋藏CO2 具有一定的指导作用 .     

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.     

Purification of coal mine methane on carbon molecular sieve by vacuum pressure swing adsorption

The vacuum pressure swing adsorption (VPSA) method, as an alternative way to separate the CH₄/N₂ mixture, was adopted to purify methane from coal mine methane. The performance of the VPSA process was investigated experimentally and theoretically with a reactivated carbon molecule sieve as the adsorbent. The computer calculations were compared to the experimental data. The concentrated methane with 79% purity could be collected directly during the high-pressure adsorption step with 93% recovery and 0.0720 mL·g^–1·min^–1 productivity, when the composition of raw gas was 10/90 vol% CH₄/N₂, which is of great significance for the utility of low quality energy gas.     

真空变压吸附分离CH4/N2/O2实验、模拟与安评

针对CH₄/N₂/O₂混合物脱氧效果差以及安全性低等问题,采用实验室自制活性炭为吸附剂,通过数值模拟和实验进行了双塔真空变压吸附（VPSA）分离25% CH₄/59% N₂/16% O₂混合物的工艺研究。通过考察进料流量和置换流量对甲烷产品纯度和回收率的影响,实验验证了数值模型的准确性。在模拟和实验的基础上,对VPSA工艺全流程进行了系统的安全性分析,并针对存在安全隐患的过程,提出一种更为安全的VPSA工艺流程。研究结果表明,通过双塔VPSA可以获得甲烷纯度为51.36%的产品气,甲烷回收率可达85.65%,存在安全隐患的过程主要集中在吸附、均压和终升压步骤,通过原料气的惰化过程,可以实现VPSA工艺的安全操作。     

真空变压吸附分离氮气甲烷的模拟与控制

采用实验室自制的活性炭为吸附剂,进行了真空变压吸附（VPSA）分离氮气/甲烷的实验、模拟和控制研究。建立了一套双塔VPSA实验装置,并将其数学模型建立在gPROMS软件中,通过改变进料气流量做多组对比实验,通过模拟数据和实验数据的对比,验证了数学模型的准确性。通过双塔VPSA的模拟调试,可以将甲烷的纯度由30%提升到80%,同时保证83%的回收率。随后,针对实际生产中不可避免的状态干扰因素,选取了3种常见的扰动状况,以产品气纯度快速回归至80%为控制目标,根据本文所采用的VPSA系统设计了PID控制器,进行了模拟和控制的研究。研究结果表明,引入PID控制器可以使纯度受到扰动影响时较快速地回归至合格纯度,同时保证装置较为稳定的运行。     

Enrichment of CO from syngas with Cu(I)Y adsorbent by five-bed VPSA

Cu(I)Y adsorbent was prepared by reduction of Cu(II)Y which was prepared by ion exchange between the NaY zeolite and a solution of Cu(II) chloride. The dynamic adsorption capacity of Cu(I)Y for CO was calculated by adsorption breakthrough curve measured on a fixed bed at 30°C and 0.006 MPa (g) of CO partial pressure. The calculated CO adsorption capacity was 2.14 mmol/g, 37.5 times as much as that of NaY zeolite. The adsorption breakthrough curve experiment was also simulated with Aspen Adsorption software and the results were approximately consistent with experimental results. Then a five-bed VPSA process for separating CO from syngas on this adsorbent was dynamically simulated with Aspen Adsorption software with the adsorption pressure of 0.68 MPa (g) and the desorption pressure of -0.075 MPa (g). The results showed that CO was enriched from 32.3% to 95.16%–98.12%, and its recovery was 88.47%–99.44%.     

CO2/CH4 Separation by Adsorption using Nanoporous Metal organic Framework Copper‐Benzene‐1,3,5‐tricarboxylate Tablet

Equilibrium data for carbon dioxide and methane adsorption on nanoporous metal organic framework Cu‐BTC powder and tablets were measured in a magnetic suspension balance in the temperature range of 308–373 K and a pressure range of 0–7 bar and fitted with Langmuir model. The tablets adsorption loading is 0.63 mol kg^–1 for methane and 3.1 mol kg^–1 for carbon dioxide at 1 bar and 308 K, while these values are 0.77 and 3.9 mol kg^–1 for powder in the same conditions. Isosteric heats of adsorption were 22.8 and 15.0 kJ mol^–1 for carbon dioxide and methane, respectively, on both adsorbents, which indicates a strong adsorption of carbon dioxide. Also, single and binary breakthrough curves were measured in the same temperature range and atmospheric pressure by using Cu‐BTC tablets as adsorbent. A complete model was used in the simulation of breakthrough curves and good agreement was observed with experimental data.     

煤层气在活性炭和炭分子筛上变压吸附分离

变压吸附分离是有效的气体分离提纯方法,采用合适的吸附剂可对煤层气(CH4/N2混合气体)进行高效分离,节约能耗。在单床吸附装置上测量了CH4/N2混合气体在3种活性炭和4种炭分子筛吸附柱上的穿透曲线,并进行实验研究再生条件对吸附剂分离性能的影响。实验结果表明,7种吸附剂均对CH4/N2混合气具有一定程度的分离能力,且高温真空再生后吸附效果更好;但仍需开发出更有效的吸附剂。     

真空变压吸附捕集烟道气中二氧化碳的模拟、实验及分析

采用工业硅胶作为吸附剂,利用两塔变压吸附装置进行了烟道气变压吸附碳捕集实验。利用gPROMS软件建立两塔变压吸附模型对实验过程进行模拟,对比了实验和模拟的结果,验证了模型的准确性。通过两塔变压吸附可将15%的CO₂富集到74%,收率为91.52%。在模型基础上考察了变压吸附碳捕集过程中进料量、吸附时间、顺放压力与二氧化碳收率、纯度和能耗的关系,定性分析了吸附塔压力和进料量对压缩机能耗的影响。结果表明:增大进料量、延长吸附时间、降低顺放压力,可以有效提高产品气中CO₂浓度,但同时也导致收率的下降,前两者还会造成单位能耗的增加;吸附压力越高,进料流量越大,压缩机能耗越大。     

Predictive equations in gas adsorption kinetics

The experimental method of determining the operative parameters of adsorptive capacity and rate in the gas adsorption kinetics of packed bed sorbents relies upon the linear relationship between gas breakthrough time and sorbent weight. The slope and intercept of the straight line, resulting from such a plot, yields values for the gas saturation capacity and adsorption rate constant of the adsorbent. This relationship is shown in the modified Wheeler adsorption equation, originally derived from a continuity equation of mass balance between the gas entering an adsorbent bed and the sum of the gas adsorbed by plus that penetrating through the bed. We have found that for wellpacked adsorbent beds, the Dubinin-Polanyi equations for predicting adsorption space at equilibrium, based upon prior characterization of an adsorbent with a reference gas, could also be applied to gas flow conditions, and the kinetic capacity of the adsorbent predicted within close limits. Although no theoretical relationship exists for prediction of the adsorption rate constant, recent gas tests at high linear flow velocities have shown experimental evidence of the mass transfer limiting value for the rate constant. The functionalities of the kinetic saturation capacity and the mass transfer limited value for the adsorption rate constant have been incorporated into the modified Wheeler adsorption equation to provide an expanded equation permitting prediction by calculation of the breakthrough time of a gas through a well-packed bed of adsorbent granules.     

ZIF-8浆液法分离CH4/N2的双吸收-吸附塔工艺流程建模与模拟

由于ZIF-8浆液独特的可流动性，可以借鉴传统的吸收-解吸工艺，实现煤层气中甲烷的多级连续高效富集。在单吸收-吸附塔工艺的基础上，为了进一步降低能耗，提出了高低压双吸收-吸附塔新型分离工艺，并对该工艺进行了全流程建模及模拟。采用平衡级法，建立了工艺流程中各单元传质设备的数学模型，包括吸收-吸附塔、闪蒸罐、解吸塔。此外，还进行了灵敏度分析，探究了平衡级数、进料位置、气液比、解吸压力等因素对产品气中甲烷浓度以及回收率等工艺性能的影响。模拟结果表明，当产品气中甲烷浓度达到90.13%（mol）时，回收率为90.25%。并且单位原料气能耗为0.445 kW·h∙m^-3（原料气），低于单塔能耗（0.510 kW·h∙m^-3）。由此，改进的双塔工艺在满足甲烷纯度和回收率的同时，相较于单塔工艺进一步降低了能耗。     

铝基吸附剂固定床分离卤水锂资源过程研究

铝基锂吸附剂是一种非常适用于低锂品位、高镁锂比盐湖卤水提锂的吸附剂,具有无溶损、稳定性高等优点,也是目前唯一一种已投入工业化生产的吸附剂。使用自制的球形铝基锂吸附剂GLDH填充固定床,系统研究了吸附温度、进料流速、初始锂离子浓度和床层高度对GLDH固定床分离卤水锂资源过程中吸附穿透曲线的影响。结果表明：升高温度、增加床层高度、降低初始锂离子浓度和进料流速会导致穿透时间延长、穿透吸附容量升高。采用BDST、Clark、Thomas、Y-N和M-D-R 5种经验模型对锂吸附穿透曲线进行拟合,确定M-D-R模型能够较准确地描述固定床锂吸附过程。     

吸附时间对VPSA分离CH_4/N_2效果的影响

利用三塔真空变压吸附装置,对低浓度原料气CH4/N2分离效果进行实验。研究了均压时间不同时的吸附时间对吸附分离效果的影响,并针对整个吸附装置、每个塔中CH4浓度与吸附时间的关系分别进行分析。实验表明,在一定条件下,吸附时间长短会影响每个塔反应釜内被浓度覆盖的区域变化,即在不被原料气穿透前提下,存在最佳吸附时间。通过分析吸附时间的作用,提高原料气VPSA分离CH4/N2的效果。     

Analysis of purge gas temperature in cyclic TSA process

This study analyzes the effect of an operating parameter on the dynamic behavior by performing dynamic simulations of cyclic thermal swing adsorption (TSA) system, in fixed beds packed with activated carbon as an adsorbent. This TSA process purifies and regenerates the ternary mixtures consisted of benzene, toluene and p-xylene. A mathematical model, considering the dynamic variation and spatial distribution of properties within the bed, has been formulated and described by a set of partial differential algebraic equations. The models are based on non-equilibrium, non-isothermal and non-adiabatic conditions. The breakthrough curves of our simulation model are compared with those of Yun's experiments (1999). The cyclic steady-state (CSS) cycles are obtained for the various cases by cyclic simulation. The influences of the purge gas temperature on breakthrough curves, CSS convergence time, cyclic operating step time, purge gas consumed, regeneration energy requirement and adsorption ability at CSS are also discussed.