简捷法确定提纯回用氢网络目标值

与只考虑直接回用的氢网络相比,具有提纯单元的氢网络能显著减少新鲜氢气的消耗量,但其设计及求解提纯目标值过程均更为复杂。对于单杂质、提纯单元采用固定浓度模型的提纯回用氢网络,结合此类网络的特点,提出了一种简捷法确定网络目标值。首先假设提纯后氢物流量足够大,由此得出初始提纯夹点。当初始夹点估算正确时,由夹点之下的需求物流和源物流的流量与杂质质量衡算即可得出提纯回用氢网络的目标值;当初始夹点估算不正确时,可以第一次计算结果为基础判断得出正确夹点,再增加一步简单计算,也可得到提纯回用目标值。计算实例表明本文方法计算简单且有效。     

提纯回用氢网络的夹点变化规律

在氢系统中引入提纯装置可以经济有效地提高氢气的回用率,是氢系统中广泛采用的方法。但引入提纯回用过程可能会影响氢系统的夹点位置,还可能使氢系统出现多夹点。由于夹点对系统性能的分析与优化具有极其重要的作用,而夹点位置的变化则会影响到用氢过程的匹配。在氢夹点技术的基础上,通过图示分析法,研究了在不同提纯产品浓度下提纯回用过程的夹点变化规律和趋势,对于考虑提纯回用的氢网络集成具有重要的意义。     

Novel method for targeting the optimal purification feed flow rate of hydrogen network with purification reuse/recycle

The purification reuse/recycle is one effective resource conservation strategy. In this article, a novel conceptual method is proposed to identify the optimal purification feed flow rate (PFFR) and the corresponding maximum hydrogen utility savings (HUS) of the hydrogen network with purification reuse/recycle. In this method, the sources and sink‐tie‐lines are divided into three regions according to the purified product and purification feed. The quantitative relationship between the HUS and the PFFR is analyzed for the sink‐tie‐lines and sources of each region. With the quantitative relationship line between the HUS and the PFFR of each source plotted, the quantitative relationship diagram can be obtained and can be used to identify the pinch point and the HUS for a given PFFR. Furthermore, the optimal PFFR and the maximum HUS can be identified easily. Three cases are studied to illustrate the applicability of the proposed method. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1964–1980, 2013     

储氢提纯和氢网络的耦合优化

基于氢网络的集成以及AB₅型储氢材料LaNi_4.75Fe_0.25及LaNi_4.85Al_0.15的特性,对储氢提纯在氢网络中的应用进行研究。综合考虑LaNi_4.75Fe_0.25及LaNi_4.85Al_0.15储氢/放氢动力学,建立了储氢提纯氢网络的优化方法,根据单位质量储氢材料提纯的节氢能力和公用工程节省量与提纯参数的关系,确定最优提纯氢源浓度、最大公用工程节省量、储氢材料量和吸氢时间。用该方法对某炼厂氢网络和储氢提纯单元进行优化,结果表明,最优提纯氢源浓度为70%,提纯后公用工程可节省23.72%; LaNi_4.85Al_0.15作为储氢提纯材料优于LaNi_4.75Fe_0.25,其消耗量为991.26 kg。     

The opportunity of membrane technology for hydrogen purification in the power to hydrogen (P2H) roadmap: a review

The global energy market is in a transition towards low carbon fuel systems to ensure the sustainable development of our society and economy. This can be achieved by converting the surplus renewable energy into hydrogen gas. The injection of hydrogen (≤10% v/v) in the existing natural gas pipelines is demonstrated to have negligible effects on the pipelines and is a promising solution for hydrogen transportation and storage if the end-user purification technologies for hydrogen recovery from hydrogen enriched natural gas (HENG) are in place. In this review, promising membrane technologies for hydrogen separation is revisited and presented. Dense metallic membranes are highlighted with the ability of producing 99.9999999% (v/v) purity hydrogen product. However, high operating temperature (≥300 °C) incurs high energy penalty, thus, limits its application to hydrogen purification in the power to hydrogen roadmap. Polymeric membranes are a promising candidate for hydrogen separation with its commercial readiness. However, further investigation in the enhancement of H₂/CH₄ selectivity is crucial to improve the separation performance. The potential impacts of impurities in HENG on membrane performance are also discussed. The research and development outlook are presented, highlighting the essence of upscaling the membrane separation processes and the integration of membrane technology with pressure swing adsorption technology.     

氢气网络系统的夹点分析与匹配优化

针对炼化企业的氢气分配网络系统,以最小公用工程氢气用量为目标,综合考虑氢气流量、氢气纯度、有害杂质和压力限制等因素,采用氢夹点方法进行分析,提出了匹配原则对氢气网络系统进行优化.通过实例进行了优化分析与计算.研究表明:氢夹点法是氢气网络优化分析的有效方法,所提出的匹配原则可以实现氢气网络的优化.     

单壁纳米碳管的纯化及其储氢特性

针对半连续氢电弧法制备的单壁纳米碳管提出了一种纯化方法。采用HNO3和H2O2回流水煮的方法对单壁纳米碳管进行了纯化处理，透射电镜观察及热重分析表明样品中的无定形炭、纳米碳颗粒及金属催化剂颗粒等杂质可被有效去除，提纯后单壁纳米碳管的收率约为35％，纯度在95％以上；研究发现该纯化方法对单壁纳米碳管的孔径分布和比表面积有较大影响。采用体积法测定了纯化前后单壁纳米碳管样品的储氢容量，结果表明纯化样品的储氢量为1．65％，比未提纯样品（0．56％）有较大提高。     

A novel graphical method for the integration of hydrogen distribution systems with purification reuse

Increase in refining demand and tighter environmental regulations have led to sharp increases in hydrogen consumption of oil refineries. Hydrogen conservation and effective use are of interest to refineries whose operations and profitability are constrained by hydrogen. Purification is widely used in hydrogen networks of refineries to reduce hydrogen production load. To minimize hydrogen utility consumption, it is necessary to optimize the hydrogen network with purification as a whole. In this paper, for hydrogen purification process, a triangle rule (which can be generalized to polygon rule) is proposed for graphical representation of its mass balance. The proposed procedure treats the product concentration and recovery rate of the purification process as adjustable parameters. An ensuing graphical method is developed for targeting the pinch point and minimum utility consumption of the hydrogen system with purification reuse. This graphical method can be used for any purification devices and in systems with any utility concentration. A refinery case is studied to demonstrate the optimization method.     

变压吸附在氨装置改制氢中的应用

从化学净化法制氢过程的工艺特点出发，总结出了氢气纯度与原料产氢率之间的关系。针对广州分公司合成氨改制氢低负荷运行项目的特点，提出了采用变压吸附的组合净化工艺，并对组合净化工艺的技术可行性进行了初步探讨。     

过氧化氢中无机杂质净化技术进展

综述了过氧化氢中无机杂质的来源和高纯过氧化氢生产中无机杂质的净化技术研究进展,这些技术包括：精馏法、离子交换树脂法、吸附法、结晶法、絮凝法、膜分离技术,以及这些技术的组合净化技术等.精馏净化产品纯度不高,但技术成熟,可工业放大;膜分离净化技术较安全,但膜的寿命短;离子交换树脂工艺简单,净化效率高,但树脂易被氧化.指出以精馏为前净化技术,再与膜分离、树脂法相结合是无机杂质去除技术的发展趋势.     

Pressure swing adsorption/membrane hybrid processes for hydrogen purification with a high recovery

Hydrogen was recovered and purified from coal gasification-produced syngas using two kinds of hybrid processes: a pressure swing adsorption (PSA)-membrane system (a PSA unit followed by a membrane separation unit) and a membrane-PSA system (a membrane separation unit followed by a PSA unit). The PSA operational parameters were adjusted to control the product purity and the membrane operational parameters were adjusted to control the hydrogen recovery so that both a pure hydrogen product (>99.9%) and a high recovery (>90%) were obtained simultaneously. The hybrid hydrogen purification processes were simulated using HYSYS and the processes were evaluated in terms of hydrogen product purity and hydrogen recovery. For comparison, a PSA process and a membrane separation process were also used individually for hydrogen purification. Neither process alone produced high purity hydrogen with a high recovery. The PSA-membrane hybrid process produced hydrogen that was 99.98% pure with a recovery of 91.71%, whereas the membrane-PSA hybrid process produced hydrogen that was 99.99% pure with a recovery of 91.71%. The PSA-membrane hybrid process achieved higher total H₂ recoveries than the membrane-PSA hybrid process under the same H₂ recovery of membrane separation unit. Meanwhile, the membrane-PSA hybrid process achieved a higher total H₂ recovery (97.06%) than PSA-membrane hybrid process (94.35%) at the same H₂ concentration of PSA feed gas (62.57%).

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超纯过氧化氢制备中有机杂质的吸附净化技术进展

介绍了超纯过氧化氢的应用及其生产技术。论述了活性炭的吸附净化机理、工业过氧化氢中有机杂质的产生、危害以及常用的净化除杂技术。在对各种净化技术的优势和不足进行比较的基础上,指出吸附净化技术工艺简单、净化效果好。同时指出了采用活性炭吸附净化技术脱除工业过氧化氢中有机杂质的关键及存在的技术难点。     

气相色谱法测定炼厂氢气组成

炼厂氢气纯度是一项常规分析项目,氢气中杂质组成分析,对炼厂的生产也是一项有意义的工作.介绍了运用色谱技术,采用单外标物、单点校正法,测定氢气中的杂质组成;并采用扣除法,测定氢气纯度的分析方法.该分析方法简便快捷,标样配制简单,分析数据的准确度和精密度高,有很高的应用价值.     

氯碱厂副产氢气的分离提纯方法

从纯化机制入手,介绍了氯碱厂的副产氢气经分离提纯到99．9％及99．9999％以上的方法：低温吸附法、变压吸附法和膜分离法等。     

高含硫天然气净化厂硫化氢气体吸收的影响因素探讨

综合论述了高含硫天然气净化厂对原料气中硫化氢气体吸收处理的方法。普光天然气净化厂在气体吸收溶剂上选择了最新的MDEA脱除溶剂,在工艺上采用了两级吸收的醇胺脱硫和级间冷却技术,充分实现了硫化氢气体的全部吸收。在硫化氢气体吸收过程中,普光天然气净化厂对工艺参数也进行了优化选择,最终实现了节能减排的总方针。     

基于杂质赤字的再生回用水网络集成图示法

将氢网络中基于剩余率的集成优化法扩展至水网络，以杂质浓度为基础进行分析，提出了基于杂质赤字的再生回用水网络图像集成优化方法。该方法无需图像试差和迭代，通过构建浓度-流量图和杂质赤字图，可确定未考虑再生回用的水网络夹点位置及最小新鲜水用量。并在此基础上，考虑再生装置和水网络的优化以及二者的集成，分析水网络的新鲜水节省量与杂质脱除率、再生水源流量及再生废水浓度的定量关系；构建定量关系图确定最小新鲜水用量随各参数的变化关系、夹点位置、最大新鲜水节省量以及一定再生条件下的极限及最优提纯参数。案例分析表明，该方法简单、高效，对于各工况下的水网络，均可使新鲜水消耗量及废水排放量减小，为工艺设计和操作提供重要的参考。     

Combination of Sorption-Enhanced Steam Methane Reforming and Electricity Generation by MCFC: Concept and Numerical Simulation Analysis

Abstract

Reformed gas made by the steam methane reforming(SMR) process is used as fuel feed to MCFC, but it is not as good as pure hydrogen due to the presence of CO₂ and CO. The sorption-enhanced steam methane reforming(SE-SMR) process can reduce CO₂ and CO to a low level and produce high purity hydrogen. Considering the merits of similar operating temperatures (about 500°C) and carbon dioxide recycle, a novel concept of a six-step sorption-enhanced steam methane reforming (SE-SMR) combined with electricity generation by molten carbonate fuel cell (MCFC) is proposed. In the present paper, a cycle of the SE-SMR process, which include the steps of reaction/adsorption, depressurization, gas purges (nitrogen and reformed gas, respectively), and pressurization with reformed gas, is modeled and analyzed. The process stream in the SE-SMR process is used as anode feed in MCFC. According to the result of numerical simulation, a fuel cell grade hydrogen product (above 80% purity) at the SE-SMR temperature of 450°C can be obtained. A carbon dioxide recycle mechanism is developed for cathode feed of MCFC from flue gas by burning with excess air to achieve a proper CO₂/air ratio (about 30:70). The novel electricity generation system, which can operate at lower energy consumption and high purity hydrogen feed is helpful for the MCFC'S performance and life time.     

具有净化单元氢网络的迭代设计方法

提出一种具有净化单元氢网络的迭代设计方法。首先假设净化后源物流的量足够大,将之看作系统的新增源物流即可构成具有净化单元的初始氢网络。运用多氢源匹配方法来设计氢网络,从而得到净化后源物流的用量F_reg和所有未回用的内部源物流合并计算出的净化后源物流的量F_reg^total。比较F_reg和F_reg^total的大小,当F_reg^totalreg时,将F_reg^total作为下一次迭代净化后源物流的量的初值,只需几次迭代即可得到最终设计;当F_reg^total≥F_reg时,将F_reg的值作为最终设计的净化后源物流的用量,按照由F_reg值确定出的净化前源物流的量选取杂质浓度较低的未回用的内部源物流用于净化,对此种情况,不需后续迭代即可得到最终设计。对文献中几个实例的研究表明,该方法设计步骤简单可行,不仅能得到氢消耗目标值,而且还能得到氢网络的具体设计。     

A dual functional staged hydrogen purifier for an integrated fuel processor–fuel cell power system

This paper describes the operation of a dual functional, membrane/catalytic CO_x methanator, hydrogen purifier that is well-suited for an integrated fuel processor/fuel cell power system. In combination with a pressure swing reformer (PSR) and a PEMFC, the system provides high overall efficiency and portability for distributed power or onboard vehicle use. Gas testing results illustrate the ability of the purifier to produce fuel cell purity hydrogen at peak power flux. The durability of this purifier is shown by its ability to meet target hydrogen purity even with a membrane that permeates >3000 ppm CO. Gas purge streams from both fuel cell electrodes are combined with the membrane retentate and combusted in the PSR combustion cycle to provide heat for the reforming reaction leading to high thermal efficiency. Most significantly, it is shown that staging of this purifier, enables recovery of some fraction of the purified hydrogen at pressures substantially approaching that of the feed hydrogen partial pressure. This creates an onboard source of high pressure hydrogen to be optionally fed to a storage device for use during vehicle startup, or to the fuel cell, either directly or via the storage device, under high power load conditions. The beneficial impact of this two-stage, dual functional purifier on membrane cost, dependability and fuel processor/fuel cell integration, will be discussed.