制纯氧分子筛

变压吸附(Press Swing Adsorption,PSA)制纯氧具有很好的工业应用前景,但氩气和氧气在制氧分子筛上的吸附选择性接近于1,因而不能分离,不能通过一步PSA制备出纯度高于95%的氧气。氩气和氧气在银离子交换沸石分子筛上的吸附选择性大于1,有可能成为制纯氧分子筛,但目前其选择性还不能满足工业分离的要求。本文介绍了银离子交换沸石分子筛在制纯氧领域的研究进展,并探讨了制纯氧分子筛的研究展望。     

LiX沸石分子筛的铈离子改性研究

采用阳离子交换法对Li X沸石分子筛进行Ce⁽³⁺⁾改性,制得不同Ce(3+)改性,制得不同Ce⁽³⁺⁾交换量的Ce Li X沸石分子筛。通过XRD、SEM、BET、XRF对Ce Li X沸石分子筛进行表征,通过气体吸附仪测得了Ce Li X沸石分子筛在25℃下对氮气、氧气的吸附等温线。结果表明,Ce(3+)交换量的Ce Li X沸石分子筛。通过XRD、SEM、BET、XRF对Ce Li X沸石分子筛进行表征,通过气体吸附仪测得了Ce Li X沸石分子筛在25℃下对氮气、氧气的吸附等温线。结果表明,Ce⁽³⁺⁾通过离子交换法可以替换Li X沸石分子筛中的非骨架Li+,Ce(3+)通过离子交换法可以替换Li X沸石分子筛中的非骨架Li+,Ce⁽³⁺⁾的引入不会改变其原本的晶体结构,且能显著提高Li X沸石分子筛对O2/N2的吸附选择性。     

重叠步骤对真空变压吸附制氧性能的影响

建立了一套半工业性两塔真空变压吸附制氧试验装置,提出了2种循环操作时序,循环一的特征在于具有同时逆向抽真空与清洗、同时逆向抽真空与均压升2个重叠步骤;循环二具有同时逆向抽真空与清洗、同时进气升压与均压升2个重叠步骤.试验结果显示,采用13LiX沸石分子筛,2种循环流程获得体积分数为92.1%的氧气时,回收率分别达到58.9%和64.8%,氧气产率分别为80.9 m3/(h·t)和86.3 m3/(h·t).在较低压比的情况下,2种不同循环流程均能获得较好的制氧性能,吸附塔的最高吸附绝对压力分别约为148 kPa和149 kPa,最高压比分别为3.44和3.39.     

LiX沸石分子筛的铈离子改性研究

采用阳离子交换法对Li X沸石分子筛进行Ce~(3+)改性,制得不同Ce~(3+)交换量的Ce Li X沸石分子筛。通过XRD、SEM、BET、XRF对Ce Li X沸石分子筛进行表征,通过气体吸附仪测得了Ce Li X沸石分子筛在25℃下对氮气、氧气的吸附等温线。结果表明,Ce~(3+)通过离子交换法可以替换Li X沸石分子筛中的非骨架Li+,Ce~(3+)的引入不会改变其原本的晶体结构,且能显著提高Li X沸石分子筛对O2/N2的吸附选择性。     

空分富氧沸石分子筛吸附剂的研究

介绍了国内外目前以PSA技术进行空气分离制备氧气所用沸石分子筛吸附剂的研究状况。从研究结果来看，N2吸附容量和N2／O2分离选择性的提高主要通过对沸石分子筛4A和13X进行离子交换，以对其表面进行改性，从而调整对N2、O2的吸附性能。另外，沸石分子筛制备过程中的硅铝比和成型条件等对N2和O2的吸附也有一定的影响。     

用高性能制氧分子筛变压吸附

对沸石分子筛进行离子交换改性 ,同时严格控制成型活化条件 ,开发出变压吸附空分用系列高性能制氧分子筛。测试其氮、氧静态吸附等温线以及吸附热数据 ,并对数据结果进行分析。这为进一步开发和优化变压吸附制氧过程提供了良好的基础     

变压吸附制纯氧过程阀系数的优化控制

利用电路网络模型,对变压吸附制纯氧阀系数进行优化控制,在碳分子筛为第一级吸附,5A分子筛作为二级吸附工艺中,可得到浓度为99.06%,回收率为28.4%的氧气产品,从而提高了氧气的回收率,增加了单位吸附剂的生产能力,节省了动力消耗.     

固相离子交换法制备Li-Ca-LSX分子筛及其氮氧分离性能的研究

以液相离子交换制得Ca-Na-LSX型分子筛,再采用固相离子交换制备不同交换度的Li-Ca-LSX分子筛。在室温(25℃)下测定了样品对氮气、氧气的静态吸附,得到分子筛氮氧分离系数。结果表明:随着Ca2+交换度从12%增加到92%,Ca-Na-LSX分子筛氮、氧吸附量均增加,氮氧分离系数提高;固相锂离子交换后,Li-Ca-LSX分子筛的Li+交换度从43.3%下降到34.2%,氮吸附量的增幅较大,氮氧分离系数显著提高,当Li+、Ca2+交换度分别为34.2%、60.2%时,分子筛样品的氮氧分离系数达到6.1。     

π型向心径向流吸附器变质量流动特性研究

对径向流吸附器内变压吸附(PSA)制氧的变质量流动规律进行研究,有助于准确掌握吸附过程及床层内的变量因素对制氧性能的影响。对π型向心径向流吸附器建立气固耦合的两相吸附模型,并对其PSA制氧过程进行了数值模拟研究,得到了床层内氧气浓度分布、温度分布以及产品气浓度的变化规律。结果表明：首次循环结束时床层内氧气最高摩尔分数可达66.02%,回收率29.2%。非稳定循环期间,氧气摩尔分数从66.02%升高至 97.5%,回收率从29.2%提高至38.5%。循环达到稳定后,床层内氧气摩尔分数最高可达98.6%,回收率38.9%左右,且达到稳定状态后床层内气固两相温差减小,逐渐达到热平衡。获得了吸附器内部气体与吸附剂两相间的传质、传热过程,为π型向心径向流吸附器用于PSA制氧提供技术支持。     

π型向心径向流吸附器变质量流动特性研究

对径向流吸附器内变压吸附(PSA)制氧的变质量流动规律进行研究,有助于准确掌握吸附过程及床层内的变量因素对制氧性能的影响。对π型向心径向流吸附器建立气固耦合的两相吸附模型,并对其PSA制氧过程进行了数值模拟研究,得到了床层内氧气浓度分布、温度分布以及产品气浓度的变化规律。结果表明:首次循环结束时床层内氧气最高摩尔分数可达66.02%,回收率29.2%。非稳定循环期间,氧气摩尔分数从66.02%升高至97.5%,回收率从29.2%提高至38.5%。循环达到稳定后,床层内氧气摩尔分数最高可达98.6%,回收率38.9%左右,且达到稳定状态后床层内气固两相温差减小,逐渐达到热平衡。获得了吸附器内部气体与吸附剂两相间的传质、传热过程,为π型向心径向流吸附器用于PSA制氧提供技术支持。     

Separation of Campesterol and β‐Sitosterol from a Sterol Mixture

Abstract

By solvent crystallization using diethyl ether as the solvent on sterol mixture, brassicasterol and stigmasterol that contains a side chain with double bond were separated from campesterol and β‐sitosterol with a saturated side chain. The total campesterol and β‐sitosterol content in the liquid phase was more than 97% with a recovery of 12%. Multistage crystallization using acetone as the solvent could increase the recovery of campesterol and β‐sitosterol to 30%. By employing zeolite selective adsorption on the campesterol and β‐sitosterol fraction, β‐sitosterol can be recovered in the liquid phase with a purity of 95.2% and a recovery of 3% (overall recovery 1%). After desorbing in ethanol, campesterol adsorbed on the zeolite can be recovered with a purity of 95.4% and a recovery of 3.7% (overall recovery 1.6%).     

真空变压吸附分离氮气甲烷流程灵敏度分析与优化

首先采用实验室自制椰壳活性炭为吸附剂,进行了氮气/甲烷(65%/35%)原料气的真空变压吸附工艺(VPSA)分离实验。通过对比实验和gPROMS 动态模拟软件的分离效果,对变压吸附数学模型进行了验证,证明了所采用数学模型的准确性。在此基础上,对影响产品气甲烷纯度、回收率的关键决策变量进行了灵敏度分析。分析结果表明:产品气纯度主要由原料气流量和置换气流量来进行调控,产品气回收率则需要关键变量共同的作用才能实现最大化。依据灵敏度分析结果,对两塔分离氮气甲烷混合气的变压吸附工艺进行了动态优化。在最优的工况下,可以将进料组成为35%的甲烷富集到75%,回收率达到97.08%;从而达到对于废混合气的高效回收利用。     

基于双回流变压吸附工艺的空气分离模拟及分析

双回流变压吸附是一种在吸附塔中间位置进料,塔顶和塔底分别采用轻、重组分回流的变压吸附过程,能够同时生产两种高纯度、高回收率的产品气。以实验室自主合成的LiLSX分子筛为吸附剂,利用Aspen Adsorption模拟软件,对进料组成为78%N₂/21%O₂/1%Ar的实际空气进行了两塔双回流变压吸附的模拟研究。模拟结果表明：当原料气为78%N₂/21%O₂/1%Ar,吸附压力为2 bar(1 bar=10⁵ Pa),解吸压力为0.3 bar,进料量为0.4 m³/h,轻组分回流流量为0.095 L/min,重组分回流流量为5.22 L/min时,能够得到体积分数为95.67%的O₂和体积分数为98.25%的N₂,回收率分别为94.60%和99.91%。并且进一步探究了进料位置、吸附时间、轻组分回流流量、重组分产品气流量等因素对O₂和N₂两种产品气纯度和回收率的影响。     

Hydrogen recovery from Tehran refinery off-gas using pressure swing adsorption, gas absorption and membrane separation technologies: Simulation and economic evaluation

Hydrogen recovery from Tehran refinery off-gas was studied using simulation of PSA (pressure swing adsorption), gas absorption processes and modeling as well as simulation of polymeric membrane process. Simulation of PSA process resulted in a product with purity of 0.994 and recovery of 0.789. In this process, mole fraction profiles of all components along the adsorption bed were investigated. Furthermore, the effect of adsorption pressure on hydrogen recovery and purity was examined. By simulation of one-stage membrane process using co-current model, a hydrogen purity of 0.983 and recovery of 0.95 were obtained for stage cut of 0.7. Also, flow rates and mole fractions were investigated both in permeate and retentate. Then, effects of pressure ratio and membrane area on product purity and recovery were studied. In the simulation of the gas absorption process, gasoline was used as a solvent and product with hydrogen purity of 0.95 and recovery of 0.942 was obtained. Also, the effects of solvent flow rate, absorption temperature, and pressure on product purity and recovery were studied. Finally, these three processes were compared economically. The results showed that the PSA process with total cost of US$ 1.29 per 1 kg recovered H₂ is more economical than the other two processes (feed flow rate of 115.99 kmol/h with H₂ purity of 72.4 mol%).     

变压吸附法回收高炉气中CO的研究

采用载铜吸附剂进行了变压吸附回收高炉气中CO的工业侧线试验 ,考察了载铜吸附剂与 5A分子筛分别用于回收高炉气中CO时的产品纯度和CO的回收率 ,试验结果表明 ,载铜吸附剂对高浓度N2 中的CO有很好的选择性 ,其性能优于 5A分子筛。从技术经济角度分析了两步变压吸附法应用于高炉气中CO回收的可行性、环境效应和经济效益。     

Production of argon free oxygen by adsorptive air separation on Ag‐ETS‐10

The purification of different components of air, such as oxygen, nitrogen, and argon, is an important industrial process. Pressure swing adsorption (PSA) is surpassing the traditional cryogenic distillation for many air separation applications, because of its lower energy consumption. Unfortunately, the oxygen product purity in an industrial PSA process is typically limited to 95% due to the presence of argon which always shows the same adsorption equilibrium properties as oxygen on most molecular sieves. Recent work investigating the adsorption of nitrogen, oxygen and argon on the surface of silver‐exchanged Engelhard Titanosilicate‐10 (ETS‐10), indicates that this molecular sieve is promising as an adsorbent capable of producing high‐purity oxygen. High‐purity oxygen (99.7+%) was generated using a bed of Ag‐ETS‐10 granules to separate air (78% N₂, 21% O₂, 1% Ar) at 25°C and 100 kPa, with an O₂ recovery rate greater than 30%. © 2012 American Institute of Chemical Engineers AIChE J, 59: 982–987, 2013     

Separation of methane and nitrogen using ionic liquidic zeolites by pressure vacuum swing adsorption

The separation of methane (CH₄) and nitrogen (N₂) is a significant challenge to the enrichment and utilization of low concentration CH₄ due to the similarity in the physical and chemical properties of the two molecules. In this work, we investigated the separation of CH₄ from N₂ using 100 kg of a new ionic liquidic zeolite (ILZ) material in a 6-bed pilot-scale pressure swing adsorption process. Feed gases with CH₄ concentrations of 5.0% and 16.1% were upgraded to 11.5% and 34.6%, respectively, with CH₄ recoveries higher than 80%. The pilot test results were used to anchor a numerical model that then allowed the efficient investigation of multiple operational parameters including desorption pressure and feed gas flow rates. The numerical model produced CH₄ concentrations for both product streams consistent with those measured in the pilot experiments, with root mean square deviations below 2%. The modeling results revealed that sufficiently low desorption pressures can unexpectedly lead to lower heavy product purities under limited feed gas flow conditions. Furthermore, the optimum feed gas flow rate under which maximum heavy product purity is achieved increases with lower desorption pressure. The maximum CH₄ concentrations increased from 31.8% to 41.5%, as desorption pressures decreased from 22.8 to 12.2 kPa for optimum feed flow rates between 78.2 and 105.5 mol/h. We also demonstrate a method of process optimization based on the bed capacity ratio, ℂ, which provides a scale-independent measure of the degree to which the column is being used effectively. By varying feed flow rate and/or desorption pressure, ℂ values between 0.2 and 0.8 were explored, with maxima in the combined separation performance metric (methane recovery) × (methane purity) occurring for values of ℂ in the range 0.29–0.36. This separation performance optimization by adjusting ℂ provides an effective strategy for integrating and understanding the impact of multiple operating parameters.     

Effects of the Residence Time in Four-Bed Pressure Swing Adsorption Process

Abstract

Hydrogen separation by the four-bed PSA process using layered beds of activated carbon and zeolite 5A was investigated experimentally and theoretically to recover high purity H₂ from steam methane reforming off-gas. The recovery increased with increasing the residence time at given product purity because of the contact time between the impurities and the adsorbents is increased. The difference of increasing the recovery became smaller with increasing the residence time and then the recovery was not increased after 43.6 seconds of the residence time. The minimum residence time exists to obtain the maximum recovery at desired product purity (99.999%+).