Ni-BaCe0.6Zr0.2Nd0.2O3-δ金属陶瓷双相膜的氢渗透性与稳定性

制备了金属陶瓷双柏Ni-BaCe0.6Zr0.2Nd0.2O3-δ膜,并将其用丁从含氢混合气巾分离氧气,研究了该膜在不同条件下的透氢性能以及膜片在CO2与H2O存在条什卜的透氢稳定性.结果表明,膜片的透氧最随着温度的升高而提高.当使用含3%H2O的原料气时,膜片透氢量是其在干燥气氛时的2～5倍;在900℃,原料气为潮湿80%H2/He的条件卜,膜片的透氢量达到0.073cm3/(min cm2).膜片在含有30%CO2的混合气巾,经100 h寿命实验后,仍然保持较高的渗透稳定性.这些结果表明该双相膜在分离CO2和H2混合气中具有很好的应用前景.     

透氧膜反应器内NiO/MgO催化焦炉煤气重整反应途径

对透氧膜反应器内焦炉煤气(COG)重整反应模型进行分析.通过H2+N2、CH4+N2、CO+N2和H2+CH4+N2混合气在透氧膜反应器内重整反应,以及有无催化剂下重整反应和催化剂床层厚度重整反应实验,推测焦炉煤气重整反应模型:首先焦炉煤气中H2在催化剂活性金属镍颗粒上吸附解离,解离后的氢向高活性位迁移"(三相界面")并与膜表面侧晶格氧(或O2-)反应生成H2O.同时CH4也可能在活性镍颗粒上裂解生成CH3*和H*,反应生成的H2O与膜表面催化剂上裂解的碳反应生成H2和CO.未反应完的H2O在催化剂床层内与剩余CH4反应生成H2和CO.     

汽油自热重整制氢反应过程分析

汽油空气自热重整制氢是解决质子交换膜燃料电池（PEMFC）氢源的重要途径。汽油中组分复杂,特别是碳原子数、分子结构相差很大时,各组分生成焓、汽化热相差很大,热力学分析表明：重整难易有较大差别,重整规律各异;另一方面,它们重整特性又有相似的一面,理论氧碳摩尔比均接近于0.31。以正辛烷自热重整反应作为模型反应,发现重整过程O2/C、H2O/C都显著影响产氢率,高水碳比时产品气废热能否尽量回收也是一个重要因素。理论上,在O2/C=0.5、H2O/C=2.0时存在最优氢产率2.1mol/mol C,这时可以得到40mol%的氢气。在本所开发的GH12汽油重整优质催化剂上,以固定床瓜尖器模拟正辛烷自热重整反应过程,发现实验结果与理论分析吻合良好。据此提出了汽油制氢合理的工艺路线。     

乙醇水蒸气重整制氢催化剂Ni/Al2O3的研究

采用壳多糖螯合、浸渍法制备出Ni/Al2O3催化剂,并用BET、XRD、TG等方法对催化剂的性能、结构进行表征.通过在常压固定床流动体系中进行乙醇水蒸气重整制氢反应,讨论和评价了催化剂的性能.结果表明,10%Ni/Al2O3催化剂对乙醇水蒸气重整制氢表现出较好的活性.在反应温度高于500℃、水醇比为3∶1时,乙醇转化率100%,H2选择性在68%以上,增大水醇比可使H2选择性适度提高.     

Ni-Fe催化剂乙醇部分氧化制氢的研究

研究了Ni Fe催化剂对乙醇部分氧化制氢反应,系统地考察了不同O2/C2H5OH摩尔比及反应温度下催化剂的性能.发现Ni Fe催化剂对乙醇部分氧化制氢具有较好的催化活性,其中组成为Ni50Fe50催化剂最好,最佳的反应条件是O2/C2H5OH=1.0,T=573 K.XRD谱图表明催化剂主要由尖晶石结构的铁酸盐和FeNi3合金相组成. XPS结果说明,催化剂体相以还原态FeNi3合金相为主,表面以氧化态的铁酸盐为主.稳定性考察的结果表明,催化剂经40 h反应后,对氢的选择性明显下降,此时对应的FeNi3物相衍射峰强度也明显降低,表明催化剂对H2选择性的下降与FeNi3物相的转变有关.     

生物乙醇重整制氢反应器

生物乙醇重整制氢是一种具有良好应用前景的制氢技术,是当前低碳能源领域的研究热点.发展生物乙醇重整制氢技术的关键是研发在低温下具有高活性和高选择性的新型重整催化剂,以及开发新式高效的催化反应器.本文着眼于反应器对生物乙醇重整制氢过程的影响,综述了国内外固定床反应器、微通道反应器和膜反应器等生物乙醇重整制氢反应器的研究现状...     

Pt/Al2O3整体催化剂上选择性氧化脱除甲醇重整氢源中CO——副反应对CO脱除效果的影响分析

移动甲醇重整制氢是质子交换膜燃料电池（PEMFC）可行的供氢方式之一，包括水蒸气重整、部分氧化重整和自热重整。甲醇重整制氢方法不同，重整气体积组成在H245％～75％，CO215％～25％，CO1％～10％，H2O10％～20％和N20—20％变化。重整气进入PEMFC之前要经过CO水蒸气变换反应（如果采用水蒸气重整，不需要变换过程），     

RbBr/CsBr-CH3OH/C2H5OH-H2O三元体系的溶解度

采用自制的相平衡研究装置, 测定了RbBr-CH3OH/C2H5OH-H2O和CsBr-CH3OH/C2H5OH-H2O四个三元体系在25、35、45 ℃三个温度下的平衡溶解度;同时得到了四个三元体系饱和溶液中不同盐浓度下的折光率数据. 实验结果表明,在所有的体系中, 随着甲醇或乙醇质量分数的增加, RbBr和CsBr 在水中的溶解度逐渐降低; 并且折光率也逐渐减小. 用经验关联方程对溶解度进行了拟合, 同时给出了CH3OH 和C2H5OH 分别对RbBr和CsBr的盐析率曲线.     

负载型Pt催化剂上生物质水相重整制氢

制备了Al2O3,活性炭(AC),氢型超稳Y分子筛(HUSY)和SiO2载的Pt催化剂.采用N2物理吸附、感应耦合等离子体原子发射光谱和H2化学吸附等手段对催化剂进行了表征,并考察了它们在甘油水相重整反应中的催化性能.重点研究了Pt/AC催化剂上不同多元醇、葡萄糖和其它可溶性糖的水相重整制氢反应.结果表明,在甘油水相重整制氢反应中,负载Pt催化剂的活性在低温(503K)以Pt/AC,Pt/HUSY,Pt/SiO2和Pt/Al2O3的顺序递增,然而在高温(538K)却以Pt/SiO2,Pt/HUSY,PVAC和Pt/Al2O3的顺序递增.在载体为酸性的催化剂Pt/Al2O3和Pt/HUSY上有利于烃的生成;在多元醇水相重整制氢反应中,产物氢的选择性和产率随碳数增加而降低;在葡萄糖水相重整制氢反应中,产物氢的选择性和收率随其浓度增加而降低,烃选择性在葡萄糖浓度为4.6%时最高,这与葡萄糖的缩合和降解等副反应有关.果糖比葡萄糖更难发生水相重整制氢反应.与低级糖麦芽糖和葡萄糖相比,在多糖淀粉的重整制氢反应中氢选择性和收率较高.     

以稀土氧化物为助剂的乙醇水蒸气重整制氢催化剂研究

采用浸渍法,以γ-Al2O3为载体,稀土(Ce,Nd)氧化物为助剂,金属Ni为活性物,制备了用于乙醇水蒸气重整制氢的复合催化剂.该类催化剂在400～550 ℃的较低温度范围内具有较高的氢气产率.不管助剂为何种稀土(Ce,Nd)氧化物,当其含量一定时,活性组分Ni的含量为15%的催化剂均具有最佳活性;当活性组分Ni一定,助剂的含量为10%时,催化剂的产氢率最大.采用10%CeO2/15%Ni/γ-Al2O3催化剂时,乙醇重整制氢的产氢率可达5.2以上.     

High pressure performance of thin Pd–23%Ag/stainless steel composite membranes in water gas shift gas mixtures; influence of dilution, mass transfer and surface effects on the hydrogen flux

The hydrogen permeation and stability of tubular palladium alloy (Pd–23%Ag) composite membranes have been investigated at elevated temperatures and pressures. In our analysis we differentiate between dilution of hydrogen by other gas components, hydrogen depletion along the membrane length, concentration polarization adjacent to the membrane surface, and effects due to surface adsorption, on the hydrogen flux. A maximum H₂ flux of 1223 mL cm⁻² min⁻¹ or 8.4 mol m⁻² s⁻¹ was obtained at 400 °C and 26 bar hydrogen feed pressure, corresponding to a permeance of 6.4 × 10⁻³ mol m⁻² s⁻¹ Pa^−0.5. A good linear relationship was found between hydrogen flux and pressure as predicted for rate controlling bulk diffusion. In a mixture of 50% H₂ + 50% N₂ a maximum H₂ flux of 230 mL cm⁻² min⁻¹ and separation factor of 1400 were achieved at 26 bar. The large reduction in hydrogen flux is mainly caused by the build-up of a hydrogen-depleted concentration polarization layer adjacent to the membrane due to insufficient mass transport in the gas phase. Substituting N₂ with CO₂ results in further reduction of flux, but not as large as for CO where adsorption prevail as the dominating flow controlling factor. In WGS conditions (57.5% H₂, 18.7% CO₂, 3.8% CO, 1.2% CH₄ and 18.7% steam), a H₂ permeance of 1.1 × 10⁻³ mol m⁻² s⁻¹ Pa^−0.5 was found at 400 °C and 26 bar feed pressure. Operating the membrane for 500 h under various conditions (WGS and H₂ + N₂ mixtures) at 26 bars indicated no membrane failure, but a small decrease in flux. A peculiar flux inhibiting effect of long term exposure to high concentration of N₂ was observed. The membrane surface was deformed and expanded after operation, mainly following the topography of the macroporous support.     

Membrane reactor performance of steam reforming of methane using hydrogen-permselective catalytic SiO2 membranes

Hydrogen production by steam reforming of methane using catalytic membrane reactors was investigated first by simulation, then by experimentation. The membrane reactor simulation, using an isothermal and plug-flow model with selective permeation from reactant stream to permeate stream, was conducted to evaluate the effect of permselectivity on membrane reactor performance – such as methane conversion and hydrogen yield – at pressures as high as 1000 kPa. The simulation study, with a target for methane conversion of 0.8, showed that hydrogen yield and production rate have approximately the same dependency on operating conditions, such as reaction pressure, if the permeance ratio of hydrogen over nitrogen ((H₂/N₂)) is larger than 100 and of H₂ over H₂O is larger than 15. Catalytic membrane reactors, consisting of a microporous Ni-doped SiO₂ top layer and a catalytic support, were prepared and applied experimentally for steam reforming of methane at 500 °C. A bimodal catalytic support, which allows large diffusivity and high dispersion of the metal catalyst, was prepared for the enhancement of membrane catalytic activity. Catalytic membranes having H₂ permeances in the range of 2–5 × 10⁻⁶ m³ m⁻² s⁻¹ kPa⁻¹, with H₂/N₂ of 25–500 and H₂/H₂O of 6–15, were examined for steam reforming of methane. Increased performance for the production of hydrogen was experimentally obtained with an increase in reaction-side pressure (as high as 500 kPa), which agreed with the theoretical simulation with no fitting parameters.     

Studies of the Methane Steam Reforming Reaction at High Pressure in a Ceramic Membrane Reactor

The effects of temperature and pressure on the steam reforming of methane 3H2+CO) were investigated in a membrane reactor (MR) with a hydrogen permeable membrane. The studies used a novel silica-based membrane prepared by using the chemical vapor deposition (CVD) technique with a permeance for H2 of 6.0×l0-8 mol·m-2·s-1·Pa-1 at 923 K. The results in a packed-bed reactor (PBR) were compared to those of the membrane reactor at various temperatures (773-923 K) and pressures (1-20 atm, 101.3-2026.5 kPa) using a commercial Ni/MgAl2O4 catalyst. The conversion of methane was improved significantly in the MR by the countercurrent removal of hydrogen at all temperatures and allowed product yields higher than the equilibrium to be obtained. Pressure had a positive effect on the hydrogen yield because of the increase in driving force for the permeance of hydrogen. The yield of hydrogen increased with pressure and reached a value of 73×10-6 mol·g-1·s-1 at 2026.5 kPa and 923 K which was higher by 108% than the value of 35×10-6 mol·g-1·s-1 obtained for the equilibrium yield. The results obtained with the silica-based membrane were similar to those obtained with various other membranes as reported in the literature.     

两步变温法微米晶种诱导合成高性能的T型分子筛膜

在预涂自制微米晶种的多孔管状莫来石支撑体表面上,采用两步变温法诱导合成T型分子筛膜。在溶胶配比nSiO2∶nAl2O3∶nNa2O∶nK2O∶nH2O=1∶0.05∶0.3∶0.1∶30合成条件下,通过变温晶化过程成功制备出高性能的T型分子筛膜。XRD和SEM结果表明,该法可在支撑体表面上较快地形成一层连续致密的纯相T型分子筛膜层,较大缩短了膜合成时间和提高了膜致密性。在优化条件下所合成的膜具有优异的渗透汽化性能,且膜制备的重复性良好。75℃时,在水/异丙醇(10/90,w/w)混合物体系中膜的渗透通量和分离因子分别高达4.25 kg.m-2.h-1,7600;在水/乙醇(10/90,w/w)混合物体系中膜的渗透通量和分离因子分别为2.87 kg.m-2.h-1,1 900。     

A novel method for the preparation of thin dense Pd membrane on macroporous stainless steel tube filter

Thin Pd membranes were in situ deposited on macroporous stainless steel (MPSS) tubes using an improved electroless plating method consisting of material filling in the substrate pores, Pd plating on the filled substrate, and recovery and activation of the substrate pores. The Pd/MPSS composite membranes resulted from the filling materials of both aluminum hydroxide gel and Pd/aluminum hydroxide gel have been studied in detail and compared with each other. The hydrogen permeation mechanism through both membranes may be controlled by surface reactions, while the hydrogen permeation flux and activation energy for the membrane resulted from Pd/aluminum hydroxide gel are higher than these for the membrane resulted from aluminum hydroxide gel. In the case of the former membrane, which is almost pinhole free, the hydrogen permeation flux is as high as 0.302 mol/(m² s) with a pressure difference of 100 kPa at 773 K. Good membrane stability is also proven by the unchanged membrane surface morphology, the steady hydrogen permeance, and the complete hydrogen selectivity. The deposition mechanism of the membrane has been proposed and interpreted in detail.     

Transport of binary water–ethanol mixtures through a multilayer hydrophobic zeolite membrane

Transport of water–ethanol mixtures through a hydrophobic tubular ZSM-5 (Si/Al = 300) zeolite membrane during pervaporation was studied experimentally and theoretically. The zeolite membrane was deposited on a support made of pure titania coated with three intermediate ceramic titania layers. The influence of feed concentration, feed temperature and permeate pressure on permeate fluxes and permeate concentrations was investigated in a wide range. Dusty gas model parameters of the support and all ceramic intermediate layers were calculated on the basis of gas permeation data. Mass transfer resistances and pressure drops in the different membrane layers during pervaporation were calculated for several process conditions. In particular the influence of the undesired but unavoidable pressure drop in the support and the intermediate layers on the effective driving force for pervaporation was evaluated and found to be relevant for predicting the overall process performance. The membrane prepared was found to be suitable for the recovery of highly concentrated ethanol from feed mixtures of relatively low ethanol concentrations at relatively low feed temperatures.     

Methanol steam reforming in a dense Pd–Ag membrane reactor: The pressure and WHSV effects on CO-free H2 production

In this experimental work, a dense tubular Pd–Ag membrane reactor is used for carrying out the methanol steam reforming reaction for producing a CO-free hydrogen stream. A non-commercial Cu/Zn/Mg-based catalyst is used in the lumen side of the membrane reactor and the experimental tests are performed at a reaction temperature of 300 °C and H₂O/CH₃OH feed molar ratio of 3/1. In both co-current and counter-current flow configurations, the effect of the weight hourly space velocity (WHSV) as well as the reaction pressure on the membrane reactor performances in terms of CO-free hydrogen recovery, hydrogen yield and hydrogen selectivity are proposed and discussed.     

Synthesis of industrial scale NaY zeolite membranes and ethanol permeating performance in pervaporation and vapor permeation up to 130 °C and 570 kPa

NaY zeolite tubular membranes in an industrial scale of 80 cm long were synthesized on monolayer and asymmetric porous supports. The quality of synthesized membranes were evaluated by pervaporation (PV) experiments in 80 cm long at 75 °C in a mixture of water (10 wt.%)/ethanol (90 wt.%), resulting in higher permeation fluxes of 5.1 kg m⁻² h⁻¹ in the monolayer type membrane and of 9.1–10.1 kg m⁻² h⁻¹ in the asymmetric-type membranes, respectively. The uniformity with small performance fluctuation in longitudinal direction of the membranes were observed by PV for 10–12 cm long samples at 50 °C in a mixture of methanol (10 wt.%)/MTBE (90 wt.%). The ethanol single component permeation experiments in PV and vapor permeation (VP) up to 130 °C and 570 kPa were performed to determine the relations between the ethanol flux and the ethanol pressure difference across the membrane which is represented by permeance (Π, mol m⁻² s⁻¹ Pa⁻¹) for estimate of potential of ethanol extraction through the present NaY zeolite membranes applying feasible studies. Results indicate that (1) the permeation fluxes are linearly proportional to the driving force of vapor pressure for each sample in VP and PV. The permeances through an asymmetric support type membrane were rather constant of 0.6–1.2 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ in the wide temperature range of 90–130 °C in PV and VP, indicating that the ethanol permeances have weak temperature dependency with the feed at the saturated vapor pressure.

The results of superheating VP experiments showed that ethanol permeation fluxes are increased with increasing of the degree of superheating at a given constant feed vapor pressure. The ethanol permeances are increased with increasing of temperature at a given feed vapor pressure. The superheating VP could be a feasible process in industry.     

聚乙烯醇辐照交联共聚物渗透气化分离膜

研究了聚乙烯醇(PVA)与丙烯酰胺丙烯酸钠共聚物(PcoAANa)的辐照交联共聚物膜用于水-乙醇混合物的渗透气化分离,随着PcoAANa在共聚物中的含量由0%上升到35%,透量及分离系数同时增大,膜材料对混合物中水及乙醇的选择性溶解,对渗透气化过程起重大影响。求出了水、乙醇及其混合物的表现透过活化能.水,乙醇和混合物的平均扩散系数在水含量为40%时出现极大值。