Hydrogen production by steam methane reforming in a membrane reactor equipped with a Pd composite membrane deposited on a porous stainless steel

With the aim of producing hydrogen at low cost and with a high conversion efficiency, steam methane reforming (SMR) was carried out under moderate operating conditions in a Pd-based composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst. A Pd-based composite membrane with a thickness of 4–5 μm was prepared on a tubular stainless steel support (diameter of 12.7 mm, length of 450 mm) using electroless plating (ELP). The Pd-based composite membrane had a hydrogen permeance of 2.4 × 10^?3 mol m^?1 s^?1 Pa^?0.5 and an H₂/N₂ selectivity of 618 at a temperature of 823 K and a pressure difference of 10.1 kPa. The SMR test was conducted at 823 K with a steam-to-carbon ratio of 3.0 and gas hourly space velocity of 1000 h^?1; increasing the pressure difference resulted in enhanced methane conversion, which reached 82% at a pressure difference of 912 kPa. To propose a guideline for membrane design, a process simulation was conducted for conversion enhancement as a function of pressure difference using Aspen HYSYS^®. A stability test for SMR was conducted for ～120 h; the methane conversion, hydrogen production rate, and gas composition were monitored. During the SMR test, the carbon monoxide concentration in the total reformed stream was <1%, indicating that a series of water gas shift reactors was not needed in our membrane reactor system.     

Palladium composite membrane fabricated on rough porous alumina tube without intermediate layer for hydrogen separation

A thin palladium composite membrane without any modified layer was successfully obtained on a rough porous alumina substrate. Prior to the fabrication of palladium membrane, a poly(vinyl) alcohol (PVA) layer was first coated onto the porous substrate by dip-coating technique to improve its surface roughness and pore size. After deposition of palladium membrane on the PVA modified substrate, the polymer layer can be completely removed from the composite membrane by heat treatment. The microstructure of the palladium composite membrane was characterized in detail using SEM, EDXS and XRD analysis. Permeation measurements were carried out using H₂ and N₂ at temperatures of 623 K, 673 K, 723 K and 773 K. The results indicated that the hydrogen permeation flux of 0.238 mol m^?2 s^?1 with H₂ separation factor α(H₂/N₂) of 956 for the as-prepared palladium membrane was obtained at 773 K and 100 kPa. Furthermore, the good membrane stability was proven during the total operation time of 160 h at the temperature range of 623 K–773 K and gas exchange cycles of 30 between hydrogen and nitrogen at 723 K.     

Optimization of hydrogen enrichment via palladium membrane in vacuum environments using Taguchi method and normalized regression analysis

In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H₂, N₂, and CO₂ were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H₂ permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H₂ permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H₂ permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H₂ and 25% N₂, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H₂ permeation flux was 0.185 mol s^?1 m^?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H₂ permeation flux.     

Methane steam reforming in a Pd-Ag membrane reformer: An experimental study on reaction pressure influence at middle temperature

In this experimental work, methane steam reforming (MSR) reaction is performed in a dense Pd-Ag membrane reactor and the influence of pressure on methane conversion, CO_x-free hydrogen recovery and CO_x-free hydrogen production is investigated. The reaction is conducted at 450 °C by supplying nitrogen as a sweep gas in co-current flow configuration with respect to the reactants. Three experimental campaigns are realized in the MR packed with Ni-ZrO catalyst, which showed better performances than Ni-Al₂O₃ used in a previous paper dealing with the same MR system. The first one is directed to keep constant the total pressure in both retentate and permeate sides of the membrane reactor. In the second case study, the total retentate pressure is kept constant at 9.0 bar, while the total permeate pressure is varied between 5.0 and 9.0 bar. As the best result of this work, at 450 °C and 4.0 bar of total pressure difference between retentate and permeate sides, around 65% methane conversion and 1.2 l/h of CO_x-free hydrogen are reached, further recovering 80% CO_x-free hydrogen over the total hydrogen produced during the reaction. Moreover, a study on the influence of hydrogen-rich gas mixtures on the hydrogen permeation through the Pd-Ag membrane is also performed and discussed.     

Optimization analysis of hydrogen separation from an H2/CO2 gas mixture via a palladium membrane with a vacuum using response surface methodology

This study uses a palladium membrane to separate hydrogen from an H₂/CO₂ (90/10 vol%) gas mixture. Three different operating parameters of temperature (320–380 °C), total pressure difference (2–3.5 atm), and vacuum degree (15–49 kPa) on hydrogen are taken into account, and the experiments are designed utilizing a central composite design (CCD). Analysis of variance (ANOVA) is also used to analyze the importance and suitability of the operating factors. Both the H₂ flux and CO₂ (impurity) concentration on the permeate side are the targets in this study. The ANOVA results indicate that the influences of the three factors on the H₂ flux follow the order of vacuum degree, temperature, and total pressure difference. However, for CO₂ transport across the membrane, the parameters rank as total pressure difference > vacuum degree > temperature. The predictions of the maximum H₂ flux and minimum CO₂ concentration by the response surface methodology are close to those by experiments. The maximum H₂ flux is 0.2163 mol s^?1 m^?2, occurring at 380 °C, 3.5 atm total pressure difference, and 49 kPa vacuum degree. Meanwhile, the minimum CO₂ concentration in the permeate stream is t 643.58 ppm with the operations of 320 °C, 2 atm total pressure difference, and 15 kPa vacuum degree. The operation with a vacuum can significantly intensify H₂ permeation, but it also facilitates CO₂ diffusion across the Pd membrane. Therefore, a compromise between the H₂ flux and the impurity in the treated gas should be taken into account, depending on the requirement of the gas product.     

Hydrogen permeation enhancement in a Pd membrane tube system under various vacuum degrees

Hydrogen purification using palladium (Pd) membrane technology has been seen as a potential solution for producing pure hydrogen form hydrogen-rich gas. Compared to traditional practices of operating the permeate side of the membrane at atmospheric pressure, in this study, a vacuum is applied. The effects of various vacuum degrees applied to the permeate side of the Pd membrane are investigated and compared to the results under normal operation without a vacuum. The feed gas used for experiments consists of a mixture of hydrogen (70 vol%) and nitrogen (30 vol%). Three membrane operating temperatures (320, 350, and 380 °C), four pressure differences (2, 3, 4, and 5 atm) across the membrane, and four vacuum degrees (−15, −30, −45, and −53 kPa) applied to the permeate side are considered. For the three operating temperatures, the best improvements in the performance of hydrogen permeation are at 320 and 350 °C when a −53 kPa vacuum is applied, resulting in 79.4% and 79.1% improvements, respectively, compared to normal operations. Increasing temperatures leads to an increase in H₂ permeation both with and without a vacuum; however, best performances of H₂ permeation are observed in cases without a vacuum.     

Fabrication & performance study of a palladium on alumina supported membrane reactor: Natural gas steam reforming,a case study

In this work, a synthetic mixture of natural gas is considered in a steam reforming process for generating hydrogen by using a membrane reactor housing a composite membrane constituted of a Pd-layer (13 μm) supported on alumina. The Pd/Al₂O₃ membrane separates part of the produced hydrogen through its selective permeation, although it shows a relatively low H₂/N₂ ideal selectivity (>200 at 0.5 bar of trans-membrane pressure and T = 425 °C).The steam reforming reaction is performed at 420 °C, by varying the gas hourly space velocity between 4400 h^?1 and 6900 h^?1 and by using two different mixtures containing some common impurities found within natural gas pipeline. Specifically, the effect of N₂ and CO₂ as impurities in the feed line is analyzed. The reaction pressure and steam-to-carbon ratio (S/C) are kept constant at 3.0 bar (abs.) and 3.5/1, respectively.The best performance of the Pd-based membrane reactor is obtained at 420 °C, 3.0 bar and 100 mL/min of sweep-gas, yielding a methane conversion of 55% and hydrogen recovery >90%.     

Diffusion barrier coating using a newly developed blowing coating method for a thermally stable Pd membrane deposited on porous stainless-steel support

In this study, we present an intermetallic diffusion barrier coating using a newly developed blowing coating method for a thermally stable Pd-based composite membrane on porous stainless steel (PSS). A tubular PSS sample with 1/2 inch (12.7 mm) in diameter and 450 mm in length was used for the support. The support was welded with a stainless-steel cap and a 450-mm-long stainless-steel tube for each end. Before the diffusion barrier coating, the large-sized entrance pores were gradually blocked with sub-micron (～500 nm) and nano (50–80 nm) yttria stabilized zirconia (YSZ). 8YSZ, i.e., 8wt.% YSZ, was used for the interdiffusion barrier material and dispersed on the surface of the pre-treated PSS using the blowing coating method. The blowing coating method has 4 steps: (i) spraying the 17 wt. % 8YSZ paste on the surface of the PSS tube, (ii) blowing the paste using compressed air, (iii) drying at room temperature, and (iv) heat treatment at 923 K for 2 h in air. Steps (i) and (ii) were repeated 3 times to have a ～240 nm thick 8YSZ layer. A thin palladium layer (～3 μm) was deposited on the pre-treated PSS using electroless plating, and the membrane stability was tested at 673–773 K for ～ 200 h. A hydrogen permeation flux of 9.86 × 10^?2 mol m^?2 s^?1 and an H₂/N₂ selectivity of 595 were obtained at 773 K and a transmembrane pressure difference of 20 kPa. The surface and cross-sectional SEM/EDX analysis confirmed that the 8YSZ layer sufficiently prevented the interdiffusion between Pd and PSS elements, such as Fe, Cr and Ni.     

Experimental investigation of PEM fuel cells for a m-CHP system with membrane reformer

An innovative small-scale cogeneration system based on membrane reformer and PEM fuel cells is under development within the FluidCELL project. An experimental campaign has been carried out to characterize the PEM fuel cell and to define the operative conditions when integrated within the system. The hydrogen feeding the PEM is produced by a membrane reactor which in principle can separate pure hydrogen; however, in general, hydrogen purity is around 99.9%–99.99%. The focus of this work is the assessment of the PEM performance under different hydrogen purities featuring actual membrane selectivity and gases build-up by anode off-gas recirculation. Their effects on the cells voltage and local current distribution are measured at different conditions (pressure, humidity, stoichiometry, with and without air bleeding, in flow-through and dead-end operation). In flow-through mode, the cell voltage is relatively insensitive to the presence of inert gases (e.g. ?20 mV with inerts/H₂ from 0 to 20·10^?2 at 0.3 A/cm²), and resistant also to CO (e.g. ?35 mV with inerts/H₂ = 20·10^?2 and CO/H₂ from 0 to 20·10^?6 at 0.3 A/cm²), thanks to the Ru presence in the anode catalyst. Looking at the current density distribution on the cell surface, the most critical areas are the cathode inlet, likely due to insufficient air humidification, and the anode outlet, because of low hydrogen concentration and CO poisoning of the catalyst. Dead-end operation is also investigated using humid or impure hydrogen. In this case relatively small amount of impurities in the hydrogen feed rapidly reduces the cell voltage, requiring frequent purges (e.g. every 30 s with inerts/H₂ = 0.5·10^?2 at 0.3 A/cm²). These experiments set the basis for the management of the PEMFC stack integrated into the m-CHP system based on the FluidCELL concept.     

585 divacancy-defective germanene as a hydrogen separation membrane: A DFT study

As sustainable and clean energy, hydrogen is the most attractive and promising energy source in the future. Membrane separation is attractive due to its high hydrogen separation performance and low energy consumption. Van-der-Waals-corrected density functional theory (DFT) calculations are performed to investigate the hydrogen separation performance of 585 divacancy-defective germanene (585 germanene). It is found that the 585 germanene presents a surmountable energy barrier (0.34 eV) for hydrogen molecule passing through the membrane, and that membrane exhibits extremely high selectivity for H₂ molecules over CO, CO₂, N₂, CH₄ and H₂S molecules in a wide range of temperatures. Meanwhile, the hydrogen permeance of 585 germanene can reach 1.94 × 10^?7 mol s^?1 m^?2 Pa^?1 at the low limit temperature of methane reforming (at 450 K), which is higher than the industrially acceptable gas permeance. With high selectivity and permeance, the 585 germanene is a promising candidate for hydrogen separation.     

Characteristic of a multi-pass membrane separator for hydrogen separation through self-supported PdAg membranes

Dense PdAg membranes have shown immense potential to achieve high hydrogen purity required for proton exchange membrane (PEM) fuel cell. However, high hydrogen recovery and flux at lower transmembrane partial pressure is still a concern. In current study self-supported dense PdAg membranes were used to study the hydrogen recovery in a multi-pass membrane separator. Performance of a single and four collective membranes are tested in a single (without baffle) and multi-pass (with longitudinal baffles) membrane separator. Further, array of membrane configurations were tested experimentally by using longitudinal baffles and placing membranes at different locations. The hydrogen recovery for each configuration was measured experimentally. Experiments were performed using binary gas mixture 50H₂:50N₂ (v/v) at 3 bar pressure, 673 K temperature and gas-hourly space velocity (GHSV) 43 h^?1. The best assembly was further tested with typical methanol reformate gas composition by using simulated gas mixture of 50H₂:30N₂:18CO₂:2CO (v/v) at same operating condition. Numerical simulations were performed by using commercial software ANSYS 14.5 to understand the flow dynamics inside the separator with and without baffle. The results demonstrate that a multi-pass membrane separator enables to control hydrogen partial pressure radially along the length of reactor. This resulted in 33% enhancement in hydrogen recovery with multi-pass in comparison to single pass membrane separator.     

ANFIS modeling of CO2 separation from natural gas using hollow fiber polymeric membrane

The present study is proposed to develop the Adaptive Neuro-Fuzzy Inference System optimized by genetic algorithm to estimate CO₂ value in permeate stream using a hollow fiber polymeric membrane for separation of binary gas containing CO₂ and CH₄ in natural gas. To that end, a number of 65 samples was gathered from the literature. Results indicated that the proposed ANFIS model has great potential with high correlation (R² = 0.9993) and less error (RMSE = 0.0064) for estimation of aforementioned parameter.     

Hydrogen-rich gas production from pyrolysis of wet sludge in situ steam agent

A series of wet sludge samples with different moisture contents were pyrolyzed in situ steam in a bench-scale fixed bed reactor in order to examine the influence of moisture and temperature on product distribution and gas composition. The results demonstrated that inherent moisture in wet sludge had a great effect on the product yield. The pyrolysis of wet sludge (43.38% moisture content) at 800 °C exhibited maximum H₂ yield (7.76 mol kg^?1 dry basis wet sludge) and dry gas yield (0.61 Nm³ kg^?1) and H₂ content of 42.13 vol%. When the moisture exceeded 43.38%, H₂ yield and gas yield both tended to decline. It was also shown that the elevated temperature exhibited a significant influence on gas content increase and tar reduction; at the same time, H₂ yield and H₂ content were increased from 1.83 mol kg^?1 dry basis wet sludge and 16.67 vol% to 9.15 mol kg^?1 dry basis wet sludge and 45.67 vol%, respectively, as temperature increased from 600 °C to 850 °C. LHV of fuel gas varies from 15.49 MJ Nm^?3 to 11.65 MJ Nm^?3 because of decrease in CH₄ and C₂H₄ content as temperature increasing. In conclusion, hydrogen rich gas production by pyrolysis of wet sludge which avoided pre-drying process and utilized in situ steam agent from wet sludge is an economic method.     

Graphite coating on alumina substrate for the fabrication of hydrogen selective membranes

Development of composite membranes is a suitable alternative to improve the hydrogen flux through palladium membranes. The porous substrate should not represent a barrier to gas permeation, but the roughness of its surface should be sufficiently smooth for the deposition of a thin and defect-free metal layer. In this study, the performances of the modification of the outer surface of an asymmetric alumina hollow fibre substrate by the deposition of a graphite layer were evaluated. The roughness of the substrate outer surface was reduced from 120 to 37 nm after graphite coating. After graphite coating, the hydrogen permeance through the composite membrane produced with 2 Pd plating cycles was of 1.02 × 10^?3 mol s^?1 m^?2 kPa^?1 at 450 °C and with infinite H₂/N₂ selectivity. Similar hydrogen permeance was obtained with the composite membrane without graphite coating, also at infinite H₂/N₂ selectivity, but 3 Pd plating cycles were necessary. Thus, graphite coating on asymmetric alumina hollow fibres is a suitable alternative to reduce the required palladium amount to produce hydrogen selective membranes.     

CFD study of heat and mass transfer in ethanol steam reforming in a catalytic membrane reactor

This work shows the analysis of ethanol steam reforming process within a catalytic membrane reactor. A 2-D non-isothermal CFD model was developed using Comsol Multiphysics, based on previous experimentally validated isothermal model. A comprehensive heat and mass transfer study was carried out utilizing the model. Operating conditions such as liquid hourly space velocity (LHSV) (3.77–37.7 h^?1), temperature (673–823 K), reaction side pressure (4–10 bar) and permeate side sweep gas flow pattern were discussed. A temperature gradient along the reactor was observed from the model and a “cold spot” was seen at the reactor entrance area, which is unfavorable for the highly endothermic ethanol steam reforming process. By changing the sweep gas pattern to counter-current, the “cold spot” appears to be smaller with a reduced temperature drop. By studying the individual reaction rates, reverse methane steam reforming (methanation) was observed, caused by the low temperature in the “cold spot”. Optimal operating conditions were found to be under LHSV = 37.7 h^?1 and counter-current sweep gas conditions.     

Biohydrogen purification using a commercial polyimide membrane module: Studying the effects of some process variables

In this work the purification of biohydrogen was attempted in mixed gas measurements using a commercial polyimide membrane module. The impact of several process variables (gas composition, temperature, ratio of retentate and feed flows) on the real separation efficiency was statistically studied applying a 3-level full-factorial experimental design. The results showed that all the factors examined could significantly affect the achievable selectivity and it was observed that the theoretical and real separation factors were remarkably different. It was also found that – in comparison with other commercially available membranes – the module reflected potential for hydrogen enrichment. Considering the design boundaries, the highest H₂/CO₂ gas selectivity (1.62) could be achieved at feed pressure, separation temperature and recovery value of ∼2.2 bar, 55 °C and 0.6, respectively, using a 65 vol% hydrogen/35 vol% carbon-dioxide binary mixture.     

Hydrogen permeation in a palladium membrane tube: Impacts of outlet and vacuum degree

Palladium (Pd) membranes are a crucial device for separating hydrogen and are usually operated at normal pressure on the permeate side with a single outlet. Instead of these common operating conditions, the difference between using a double outlet and a single outlet is studied. Four different vacuum degrees (15–60 kPa) are applied on the permeate side, and the results are compared with the non-vacuum operations. Situations under the vacuum and the effects of temperatures (300–400 °C) on H₂ permeation are discussed. Finally, the influences of different feed gas mixtures (H₂/N_2, H₂/CO_2, and H₂/CO) on the Pd membrane performance are investigated. The results show that there is no difference in H₂ permeation impact the single outlet and the double outlet on the permeate side. When a vacuum is imposed on the permeate side, the H₂ permeation rate and H₂ recovery are efficiently intensified, that is, when the pressure difference is 9 atm, they increase from 73.21 to 84.51% and from 0.0035378 to 0.0040808 mol?s^?1, respectively. Moreover, the H₂ recovery can be improved to up to 68.44% under a vacuum degree of 60 kPa. At a given Reynolds number, an increase in temperature increases the H₂ permeation rate but lowers its recovery, stemming from more H₂ in the feed gas. This study also investigates the feed gas of H₂/N₂ under a vacuum to provide a useful insight into H₂ production and separation from ammonia, and the results are compared with two different feed gases of H₂/CO₂ and H₂/CO mixtures. The results suggest that the impurities (i.e., N₂, CO₂, and CO) have a negative influence on the Pd membrane, which causes the H₂ permeation rate to decrease, and the effect of N₂ is the least significant compared to the other two.     

Ultra-compact microstructured methane steam reformer with integrated Palladium membrane for on-site production of pure hydrogen: Experimental demonstration

A novel metal-based modular microstructured reactor with integrated Pd membrane for hydrogen production by methane steam reforming is presented. Thin Pd foils with a thickness of 12.5 μm were leak-tight integrated with laser welding between microstructured plates. The laser-welded membrane modules showed ideal H₂/N₂ permselectivities between 16,000 and 1000 at 773 K and 6 bar retentate pressure. An additional metal microsieve support coated with an YSZ diffusion barrier layer (DBL) facilitated the operation at temperatures up to 873 K and pressures up to 20 bar pressure difference. The membrane permeability in this configuration is expressed with Q = 1.58E-07*exp(−1460.2/T) mol/(msPa^0.5).     

Preparation of thin Pd membrane on porous stainless steel tubes modified by a two-step method

Thin Pd membranes for hydrogen filtration were deposited on modified porous stainless steel (PSS) tubes using an electroless plating technique. Alumina oxide (Al₂O₃) particles of two different sizes were subsequently used to modify the non-uniform pore distribution and the surface roughness of the PSS tubes. The principle of the modification was to use large Al₂O₃ particles (∼10 μm) to fill larger pores on the surface, and leave the smaller pores intact. Small Al₂O₃ particles (∼1 μm) were then used to further decrease the surface roughness. The detailed manufacturing steps of the Al₂O₃ modification were investigated and optimized to achieve a continuous dense Pd membrane with a minimum thickness of 4.4 μm on the modified PSS tubes. The highest hydrogen permeance of the membrane was 2.94 × 10⁻³ mol/m²-s-kPa^0.5 at 773 K, with a selectivity coefficient (H₂/He) of 1124 under a pressure difference of 800 kPa. In comparison, the thickness and hydrogen permeance of a dense Pd membrane on unmodified PSS tubes were 31.5 μm and 5.97 × 10⁻⁴ mol/m²-s-kPa^0.5, respectively, at 773 K under an 800 kPa pressure difference. The stability of the membranes at high temperatures was also investigated. The hydrogen permeation flux at 773 K was stable during a test period of 500 h. These results demonstrate that the two-step method modifies the surface of PSS tubes in a relatively simple way and results in thin, dense Pd membranes with high hydrogen permeance and good thermal stability.     

NOx reduction by CO over ASC catalysts in a simulated rotary reactor: Effect of reaction conditions

A rotary reactor, separated the NO_x removal process into adsorption stage and reduction stage, was utilized to remove the NO_x from the flue gas. The influences of various reaction conditions on the reactor were tested, i.e., oxygen concentration in the adsorption zone, time ratio of adsorption and reduction, gas hourly space velocity (GHSV) of the reactor, GHSV of the reduction zone and effect of H₂O and SO₂. The results showed that the synthesized ASC catalyst had higher deNO_x efficiency with the increasing of oxygen concentration in flue gas. Meanwhile, the GHSV of the reactor had an obvious influence on NO_x adsorption, and high NO_x adsorption and reduction efficiencies were observed at 10,000 h^?1. The optimal reaction conditions in this research were concluded as follows: oxygen concentration was 8%, time ratio of adsorption and reduction was 60 s: 60 s, GHSV of the adsorption zone was 10,000 h^?1 and GHSV of the reduction zone was 12,000 h^?1. While the water and SO₂ tolerance of catalysts was weak, and the catalysts would be inactivated when exposed to 100 ppm SO₂ in 1.5 h. Free nitrate ions were the main nitrate species on the catalyst surface. In situ DRIFT study showed that a large amount of free nitrate ions was released from the catalyst surface when the reduction time was increased from 30 s to 60 s, and much NO_x was adsorbed on the catalyst surface in the form of free nitrate ions when the oxygen concentration was 8%.