Selective CO methanation over amorphous Ni-Ru-B/ZrO_2 catalyst for hydrogen-rich gas purification

Amorphous Ni-Ru-B/ZrO2 catalysts were prepared by chemical reduction method. The effects of Ni-Ru-B loading and Ru/Ni mole ratio on the catalytic performance for selective CO methanation from reformed fuel were studied, and the catalysts were characterized by BET, ICP, XRD and TPD. The results showed that Ru strongly affected the catalytic activity and selectivity by increasing the thermal stability of amorphous structure, promoting the dispersion of the catalyst particle, and intensifying the CO adsorption. For the catalysts with Ru/Ni mole ratio under 0.15, the CO methanation conversion and selectivity increased significantly with the increasing Ru/Ni mole ratio. Among all the catalysts investigated, the 30 wt% Ni-Ru-B loading amorphous Ni61Ru9B30/ZrO2 catalyst with 0.15 Ru/Ni mole ratio presented the best catalytic performance, over which higher than 99.9% of CO conversion was obtained in the temperature range of 230℃-250℃, and the CO2 conversion was kept under the level of 0.9%.

Ultraselective carbon molecular sieve membrane for hydrogen purification

Hydrogen is a green clean fuel and chemical feedstock. Its separation and purification from hydrogencontaining mixtures is the key step in the production of hydrogen with high purity(>99.99%). In this work, carbon molecular sieve(CMS) membranes with ultrahigh permselectivity for hydrogen purification were fabricated by high-temperature(700–900 ℃) pyrolysis of polymeric precursor of phenolphthaleinbased cardo poly(arylene ether ketone)(PEK-C). The evolution of the microstructural texture and ultramicroporous structure and gas separation performance of the CMS membrane were characterized via TG-MS, FT-IR, XRD, TEM, CO2 sorption analysis and gas permeation measurements. CMS membranes prepared at 700 ℃ exhibited amorphous turbostratic carbon structures and high H2 permeability of 5260 Barrer with H2/CH4, H2/N2 and H2/CO selectivities of 311, 142, 75, respectively. When carbonized at900 ℃, the CMS membrane with ultrahigh H2/CH4 selectivity of 1859 was derived owing to the formation of the dense and ordered carbon structure. CMS membranes with ultrahigh permselectivity exhibit an attractive application prospect in hydrogen purification.

Hydrogen Purification Performance of Pressure Swing Adsorption Based on Cu-BTC/zeolite 5A Layered Bed

A pressure swing adsorption (PSA) hydrogen purification model for the four-component gas (H_(2)/CO_(2)/CH_(4)/CO=73/16/8/3 mol%) in a layered bed packed with Cu-BTC and zeolite 5A was established to achieve better hydrogen purification performance.By comparing its simulation results with the experimental data,the adsorption isotherm model was validated and could be used to accurately describe the adsorption process of the gas mixture on the two adsorbents.The breakthrough curves of the mixed gas on the layered bed were studied to verify the correctness of the established simulation models.Based on the validated model,the performance of the PSA system based on the layered bed was carried out,including the hydrogen purity and recovery.The simulation results show that the hydrogen purification system based on the layered bed model can achieve hydrogen purity of 95.469% and hydrogen recovery of 83.219%.Moreover,a parametric study was carried out and its results show that reductions in feed flow rate and adsorption time result in an increase in hydrogen purity and a decrease in hydrogen recovery.A longer equalization time between the two adsorption beds can simultaneously increase the hydrogen purity and recovery.

Review of Alloy Membranes/Films for Hydrogen Separation or Purification

Hydrogen separation and purification are two important chemical processes in the extensive application of hydrogen energy. Membrane technology has opened up a potential solution to the problems of separation and purification in an energy effective way. Membranes of adequate hydrogen permeability, good thermal and mechanical stability are the key to successful application of membrane technology in hydrogen separation and purification. In this paper, the relative parameters concerning hydrogen permeability, the development of different types of membranes namely: palladium composite membranes; V-based alloy membranes, specific functionality embraced alloy membranes, metal hydride (MH) thin films and fabrications, were reviewed and discussed. Pd-free membranes are found to be the ideal alternatives. Suitable MH thin films with mono- or multi-layer microstructures produced by novel fabrication techniques, is likely to be the promising candidates due to possessing properties distinct from those of bulk materials in membrane form.

High Purity Hydrogen Production by Metal Hydride System:A Parametric Study Based on the Lumped Parameter Model

The simulation of hydrogen purification in a mixture gas of hydrogen/carbon dioxide (H2/CO2) by metal hydride system was reported.The lumped parameter model was developed and validated.The validated model was implemented on the software Matlab/Simulink to simulate the present investigation.The simulation results demonstrate that the purification efficiency depends on the external pressure and the venting time.An increase in the external pressure and enough venting time makes it possible to effectively remove the impurities from the tank during the venting process and allows to desorb pure hydrogen.The impurities are partially removed from the tank for low external pressure and venting time during the venting process and the desorbed hydrogen is contaminated.Other parameters such as the overall heat transfer coefficient,solid material mass,supply pressure,and the ambient temperature influence the purification system in terms of the hydrogen recovery rate.An increase in the overall heat transfer coefficient,solid material mass,and supply pressure improves the hydrogen recovery rate while a decrease in the ambient temperature enhances the recovery rate.

Arrayed Cobalt Phosphide Electrocatalyst Achieves Low Energy Consumption and Persistent H2 Liberation from Anodic Chemical Conversion

Electrochemical reduction of water to hydrogen(H2) offers a promising strategy for production of clean energy,but the design and optimization of electrochemical apparatus present challenges in terms of H2 recovery and energy consumption.Using cobalt phosphide nanoarrays(Co2 P/CoP NAs) as a charge mediator,we effectively separated the H2 and O2 evolution of alkaline water electrolysis in time,thereby achieving a membrane-free pathway for H2 purification.The hierarchical array structure and synergistic optimization of the electronic configuration of metallic Co2 P and metalloid CoP make the Co2 P/CoP NAs high-efficiency bifunctional electrocatalysts for both charge storage and hydrogen evolution.Theoretical investigations revealed that the introduction of Co2 P into CoP leads to a moderate hydrogen adsorption free energy and low water dissociation barrier,which are beneficial for boosting HER activity.Meanwhile,Co2 P/CoP NAs with high capacitance could maintain a cathodic H2 evolution time of 1500 s at 10 mA cm^(-2) driven by a low average voltage of 1.38 V.Alternatively,the energy stored in the mediator could be exhausted via coupling with the anodic oxidation of ammonia,whereby only 0.21 V was required to hold the current for 1188 s.This membrane-free architecture demonstrates the potential for developing hydrogen purification technology at low cost.

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 mem- brane 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 purifica- tion. 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%）.

Effects of supports and combined process on hydrogen purification over nickel supported catalysts

Hydrogen purification must be done to meet the different purposes of hydrogen utilization.In the present work,it is confirmed that the catalyst Ni/CeO2 has the highest activity for total methanation(Total MET) of CO and CO2,and is thus most suitable for hydrogen purification for ammonia synthesis.While,the catalyst Ni/ZrO2 appears the best one for selective methanation of CO(CO-SMET) in the H2-rich gas to produce clean fuel for proton exchange membrane fuel cell(PEMFC).In spite of this,the catalyst Ni/ZrO2 without adding chlorine ions as promoter is not yet capable of removing the CO in the reformate gas to below 10 ppm in a wide reaction temperature range by the way of CO-SMET.Adding chlorine ions as promoter is indeed not favorable for practical application due to its gradual loss in the catalytic reaction as proved in our previous work.Therefore,a step to decrease CO2 concentration(called as de-CO2 step) is suggested to be set prior to the CO-SMET step in this work.It is proved that such combination of de-CO2 step and CO-SMET step is efficient to achieve a deep removal of CO to below 10 ppm with a high selectivity more than 50% in a wide reaction temperature range of 220-280℃over the catalyst Ni/ZrO2 without adding chlorine ions as promoter.The combined process has potential for practical application,at least in the large-scale power plant of PEMFC.

Artificial neural network based optimization of a six-step two-bed pressure swing adsorption system for hydrogen purification

The pressure swing adsorption(PSA)system is widely applied to separate and purify hydrogen from gaseous mixtures.The extended Langmuir equation fitted from the extended Langmuir-Freundlich isotherm has been used to predict the adsorption isothermal of hydrogen and methane on the zeolite 5A adsorbent bed.A six-step two-bed PSA model for hydrogen purification is developed and validated by comparing its simulation results with other works.The effects of the adsorption pressure,the P/F ratio,the adsorption step time and the pressure equalization time on the performance of the hydrogen purification system are studied.A four-step two-bed PSA model is taken into consideration,and the six-step PSA system shows higher about 13%hydrogen recovery than the four-step PSA system.The performance of the vacuum pressure swing adsorption(VPSA)system is compared with that of the PSA system,the VPSA system shows higher hydrogen purity than the PSA system.Based on the validated PSA model,a dataset has been produced to train the artificial neural network(ANN)model.The effects of the number of neurons in the hidden layer and the number of samples used for training ANN model on the predicted performance of ANN model are investigated.Then,the well-trained ANN model with 6 neurons in the hidden layer is applied to predict the performance of the PSA system for hydrogen purification.Multi-objective optimization of hydrogen purification system is performed based on the trained ANN model.The artificial neural network can be considered as a very effective method for predicting and optimizing the performance of the PSA system for hydrogen purification.

Surface composition change of chlorine-doped catalyst Ni(Clx)/CeO2 in methanation reaction

The oxide sample NiO/CeO_2 with feed atomic ratio of Ni/Ce at 40%, prepared by co-precipitation method and calcination at 500 oC for 2 h, was impregnated by aqueous solution of NH_4Cl to dope chlorine ions. After the impregnated samples were dried and calcined at 400 oC for 2 h, the calcined samples NiO（Cl_x）/CeO_2（x=0.1–0.5） were characterized by means of X-ray diffraction（XRD） and temperature programmed reduction（TPR） techniques. It was comfirmed that the doped chlorine ions hindered reduction of Ni^（2＋） ions in the calcined samples, and suppressed adsorption of CO_2 and CO on the reduced sample Ni（Cl_（0.3））/CeO_2. The reduced samples Ni（Cl_x）/CeO_2（x=0.0–0.5） were used as catalysts for selective methanation of CO in H_2-rich gas. When chlorine ions were doped at the feed atomic ratio of Cl/Ce（x） equal to 0.3–0.5, CO in the H_2-rich gas could be removed to below 10 ppm with a high selectivity more than 50% in a wide reaction temperature range of 220–280 oC. However, the selectivity of CO methanation decreased with reaction time in the durability tests over the catalyst Ni（Cl_（0.3））/CeO_2 at the reaction temperature of 260 oC and even at 220 oC. The lowering of the selectivity was found to be related with the surface composition change of the catalyst in the catalytic reaction.