变压吸附空分制氮过程的研究

建立了一套中试装置 ,对以商业炭分子筛为吸附剂的变压吸附 (PSA)空分制氮循环过程进行了系统研究 .用所建立的数学模型对相应实验进行模拟并将模型预测与实验数据进行比较 ,结果表明模型是可靠的 .     

Simulation and validation of ethanol removal from water in an adsorption packed bed: Isotherm and mass transfer parameter determination in batch studies

Preferential adsorption of ethanol from ethanol/water mixtures in batch equilibrium and kinetic experiments were carried out on a commercially available activated carbon adsorbent Filtrasorb 600 (F‐600). A model based on finite difference method was developed and employed to determine the mass transfer parameters and equilibrium behaviour for the adsorption of ethanol from simple batch systems. The estimates of the adsorption isotherm along with the mass transfer parameters were used to simulate the transient performance that could be expected in a packed bed under various operating conditions (feed flow rate, feed concentration, and particle size). The applicability of the simulation results were found to be a good match with experimental packed bed experiments over the entire range of operating conditions tested.     

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。     

Vacuum pressure swing adsorption process for coalbed methane enrichment

The enrichment of low concentration coalbed methane using adsorption process with activated carbon adsorbent was studied in this work.Adsorption isotherms of methane,nitrogen and carbon dioxide on activated carbon were measured by volumetric method,meanwhile a series of breakthrough tests with single component,binary components and three components feed mixture has been performed for exploring dynamic adsorption behaviors.Moreover,a rigorous mathematical model of adsorption bed containing mass,energy,and momentum conservation equation as well as dual-site Langmuir model with the Linear driving force model for gas-solid phase mass transfer has been proposed for numerical modeling and simulation of fixed bed breakthrough process and vacuum pressure swing adsorption process.Furthermore,the lumped mass transfer coefficient of methane,nitrogen and carbon dioxide on activated carbon adsorbent has been determined to be 0.3 s~(-1),1.0 s~(-1) and 0.06 s~(-1) by fitting the breakthrough curves using numerical calculation.Additionally,a six bed VPSA process with twelve step cycle sequence has been proposed and investigated for low concentration coalbed methane enrichment.Results demonstrated that the methane molar fraction in feed mixture ranged from 10% to 50% could be enriched to 32.15% to 88.75% methane in heavy product gas with a methane recovery higher than 83%under the adsorption pressure of 3 bar(1 bar=10~5 Pa) and desorption pressure of 0.1 bar.Energy consumption of this VPSA process was varied from 0.165 kW·h·m~(-3) CH_4 to 0.649 kW·h·m~(-3) CH_4.Finally,a dual-stage VPSA process has been successfully developed to upgrade a low concentration coalbed methane containing 20% methane to a target product gas with methane purity higher than 90%,meanwhile the total methane recovery was up to 98.71% with a total energy consumption of 0.504 kW·h·m~(-3) CH_4.     

A COMPARISON OF GAS SEPARATION PERFORMANCE BY DIFFERENT PRESSURE SWING ADSORPTION CYCLES

By simulations using an equilibrium model, a quantative comparison is made for different pressure swing adsorption (PSA) processes for gas separation. The comparison is based on the performance curve, which is defined as the relationship between product purity and product recovery at a fixed feed throughput.

For bed repressurization in the PSA cycle, the use of the light product yields superior separations compared to that using the feed mixture. For the pressure reduction step, it is found that the separation results are better when the heavy-product purge step is used, as compared to that using cocurrent depressurization. For an ultrahigh-purity light product, however, the PSA process using cocurrent depressurization is superior.

A new PSA process is suggested in which the heavy-product purge step is accomplished by using (or pressure-equalizing with) the effluent from another bed which undergoes the countercurrent blowdown step.     

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%).     

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%。     

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。     

乙醇脱水的木薯粉吸附性能研究

使用恒温固定吸附床对乙醇蒸汽脱水的术薯粉吸附剂的气相选择吸附性能进行研究。乙醇原料液的浓度为75％～95％（质量百分数）,使用干燥过的木薯粉作为吸4;什剂,分别测得吸附床不同位置处、不同表观速率、不同吸附剂粒度和不同温度时的乙醇蒸汽的透过曲线并进行了分析。通过木薯粉吸附最终可获得99．7％（质量百分数）的无水乙醇。     

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。     

活性炭吸附脱硫固定床反应器研究

在原油储运过程中挥发的H2S这种恶臭气体不但危害人体健康,还对环境造成很大的污染。文章提出了采用活性炭吸附脱除原油挥发气中H2S的工艺。从理论上探讨了活性炭脱硫机理及固定床内吸附传质动力学,并且建立了活性炭吸附H2S的固定床脱硫反应器数学模型,采用COMSOL Multiphysics软件求解数学模型以预测穿透曲线。同时进行了实验研究,并根据实验数据绘出了穿透曲线,且与模型计算结果进行了比较,二者吻合较好。还进一步探讨了空速、温度和原料气含量对吸附硫容的影响。     

Production of dehydrated fuel ethanol by pressure swing adsorption process in the pilot plant

Fermented ethanol is gaining wide popularity as a car fuel additive. The pressure swing adsorption (PSA) process is attractive for the dehydration of bioethanol on the industrial scale, since its energy consumption is low and it is capable of producing a very pure product. 3 ? zeolite possesses micro-pores which, due to their small size, adsorb water molecules but not ethanol molecules. In this work, up to 2 kL/day of dehydrated ethanol (99.5% by weight) was successfully produced with 3 ? zeolite by the pressure swing adsorption process. The cycles of the PSA process were operated under the following variables: feed flow rate (27–62 Nm³/hr of 93.2% by weight), purge/feed ratio (30–24%), adsorption temperature (130–140 °C) and adsorption pressure (1.2 atm).     

Modelling and simulation of two-bed PSA process for separating H_2 from methane steam reforming

Methane steam reforming is the main hydrogen production method in the industry. The product of methane steam reforming contains H_2, CH_4, CO and CO_2 and is then purified by pressure swing adsorption(PSA) technology. In this study, a layered two-bed PSA process was designed theoretically to purify H_2 from methane steam reforming off gas. The effects of adsorption pressure, adsorption time and purgeto-feed ratio(P/F ratio) on process performance were investigated to design a PSA process with more than99.95% purity and 80% recovery. Since the feed composition of the PSA process changes with the upstream process, the effect of the feed composition on the process performance was discussed as well.The result showed that the increase of CH_4 concentration, which was the weakest adsorbate, would have a negative impact on product purity.     

间歇式吸附与连续式脱附耦合亲和层析法研究

用间歇式吸附和连续式脱附耦合的亲和层析法分离纯化了溶菌酶。采用Langmuir Freundlich方程描述等温吸附线 ,通过间歇式吸附实验结果得到了该方程的相关参数以及蛋白质在吸附剂孔内的扩散系数。以蛋白质回收率和吸附剂利用率为基准比较了间歇式吸附和连续式吸附在操作时间上的差异。结果表明在蛋白质回收率和吸附剂利用率完全相等的情况下 ,间歇式吸附所用时间远小于连续式吸附时间。     

面向烟气NOx净化与回收的新型吸附工艺

合理高效的吸附工艺是决定吸附法净化和回收烟气中NO_x工业可行性的关键工艺环节。提出一种通过外部补充气体实现固定床循环体空间内多次循环解吸NO_x的新型吸附工艺（GVTSA）。基于该工艺,采用Na-ZSM-5分子筛作为吸附剂,以某钢厂烧结机脱硫后烟气为原料（组分）进行了NO_x吸附回收实验研究。结果表明,GVTSA工艺相较传统吸附工艺（TSA工艺、VSA工艺）可获取更高的NO_x回收量,在优选条件下（220℃,-50 kPa）,NO_x回收率达到90%,解吸气中NO₂浓度由原料气的36 mg·m^-3提升到2%以上,NO_x循环吸附量可达0.10 mmol·g^-1,16次吸脱附循环稳定。研究结果可为烟气NO_x治理与资源化工业应用提供参考。     

用于乙醇脱水的生物质吸附性能

The adsorption capability of paddy flour and maize flour for gaseous phase selective adsorption for ethanol dehydration was investigated via a bench-test fixed-bed adsorber at constant temperature. Ethanol concentration in the feed was 93.4% (mass) and each of the dried biomass was used as adsorbent, and breakthrough curves and temperature distribution in adsorptive bed were obtained for different bed depths,superficial velocities, granularities of adsorbent and temperatures. Bed pressure drop curves for different bed depths and superficial velocities were also measured. A product of ethanol purity of 99.5% (mass) could be obtained through both kinds of biomass adsorbent. When 99.5% (mass) of ethanol purity is defined as the breakthrough point, the production capacity for either adsorbent was within 0.0915-0.2256 (gram product/gram adsorbent). Tests on pure ethanol adsorption were also performed to extrapolate the selectivity of both adsorbents.     

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。     

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。     

Process analysis of temperature swing adsorption and temperature vacuum swing adsorption in VOCs recovery from activated carbon

In order to better guide the design of industrial process for purification and recovery of VOCs, temperature swing adsorption (TSA) and temperature vacuum swing adsorption (TVSA) process for VOCs purification and recovery were studied systematically with activated carbon adsorbent. The adsorption and desorption behaviors of benzene on activated carbon in above two processes were investigated systematically. Effects of operating parameters on process performances were further analyzed, including as regeneration temperature, purging feed ratio and hot–cold purging ratio. The results showed that the increase of hot–cold purging ratio (HP/CP) could obtain the same regeneration effect as the increase of desorption temperature. Increasing the feed purge ratio without increasing the hot–cold purging ratio is not conducive to bed regeneration, because a large number of cold purge gases cannot utilize the residual heat of temperature wave, thus reducing the desorption effect of the cooling step on the bed. In addition, the vacuum step can enhance the regeneration ability of hot nitrogen to the bed at the same regeneration temperature, making the bed regeneration of TVSA process more thorough. Temperature in the middle and lower part of the bed in TVSA process was higher and the regeneration was more thorough. In conclusion, TVSA has more obvious advantages than TSA in terms of energy consumption, hot or cold purge volume and bed regeneration.     

叠合式平板亲和膜吸附生物分子的动力学模型

基于吸附动力学方程和吸附质量平衡方程，提出了叠合式平板亲和膜吸附生物分子的动力学模型，采用Ｃｆｒａｎｋ－Ｎｉｃｈｏｌｓｏｎ有限差分隐解法求解联立方程组，考察了弥散系数、进料浓度、吸附反应正向结合速率常数、膜厚、配基浓度以及流速对吸附穿透曲线的影响，并用溶质回收率和配基利用率两个参数对吸爱曲线的操作效果进行一的表征。用文献报导的实验结果对模型的验证表明，法无因次流出浓度小于０．４时，实测结果与模型预