Molecular simulation studies of hydrocarbon and carbon dioxide adsorption on coal

Sorption isotherms of hydrocarbon and carbon dioxide （CO2） provide crucial information for designing processes to sequester CO2 and recover natural gas from unmineable coal beds. Methane （CH4）, ethane （C2H6）, and CO2 adsorption isotherms on dry coal and the temperature effect on their maximum sorption capacity have been studied by performing combined Monte Carlo （MC） and molecular dynamics （MD） simulations at temperatures of 308 and 370 K （35 and 97 ~C） and at pressures up to 10 MPa. Simulation results demonstrate that absolute sorption （expressed as a mass basis） divided by bulk gas density has negligible temperature effect on CH4, C2H6, and CO2 sorption on dry coal when pressure is over 6 MPa. CO2 is more closely packed due to stronger interaction with coal and the stronger interaction between CO2 mole- cules compared, respectively, with the interactions between hydrocarbons and coal and between hydrocarbons. The results of this work suggest that the ＂a＂ constant （pro- portional to TcPc） in the Peng-Robinson equation of state is an important factor affecting the sorption behavior of hydrocarbons. CO2 injection pressures of lower than 8 MPa may be desirable for CH4 recovery and CO2 sequestration. This study provides a quantitative under- standing of the effects of temperature on coal sorptioncapacity for CH4, C2H6, and CO2 from a microscopic perspective.

Catalytic steam methane reforming enhanced by CO_2 capture on CaO based bi-functional compounds

Sorption enhanced steam methane reforming（SE-SMR） was performed to maximize hydrogen production and contemporary remove COfrom the product stream using bi-functional sorbent-catalyst compounds.Samples were tested at two different scales: micro and laboratory. The CaO amount varied in the CaO-CaAlOsorbent system synthesized by wet mixing(CaO content of 100 wt%, 56 wt%, 30 wt%, or 0 wt% and balance of CaAlO) which were upgraded to bi-functional compounds by impregnation of 3 wt% of Ni. Nitrogen adsorption（BET/BJH）, X-Ray Diffraction（XRD）, Temperature-Programmed Reduction（TPR） and Scanning and Transmission Electronic Microscopy（SEM and TEM, respectively） analyses were performed to characterize structural and textural properties and reducibility of the bi-functional materials and evaluate their catalytic behavior. A fixed sorbent composition CaO-CaAlO(56 wt% of CaO and CaAlObalance), was chosen to study the effect of different weight hourly space times（WHST） and CHstream compositions in SE-SMR activity. Impregnated mayenite at both micro and laboratory scales showed stable Hcontent of almost 74%, with CHconversion of 72% similarly to the values reported by the sample containing 30 wt% of CaO in the post-breakthrough.Sample with 30 wt% of CaO showed promisingly behavior, enhancing Hcontent up to almost 94.5%.When the sorption enhanced reaction is performed roughly 89% of CHconversion is achieved, and after the pre-breakthrough, the catalyst worked at the thermodynamic level. During cycling sorption/regeneration experiments, even if COremoval efficiency slightly decreases, CHconversion and Hyield remain stable.

Efficiency analysis of sorption-enhanced method in steam methane reforming process

The sorption-enhanced method can change the thermodynamic equilibrium by absorbing CO_(2).However,it also brings about the problems of high regeneration temperature of adsorbent and large regeneration energy consumption.In order to study the impact of enhanced adsorption methods on the overall energy cost of the system in the hydrogen production process,this paper analyzes and compares steam methane reforming and reactive adsorption-enhanced steam methane reforming with the energy consumption of hydrogen production products as the evaluation index.The results showed that the energy consumption per unit hydrogen production decreased from 276.21 MJ/kmol to 131.51 MJ/kmol,and the decomposition rate of H2O increased by more than 20%after the addition of adsorption enhancement method.It is proved that the advantage of sorption enhanced method on pre-separation of CO_(2)in the product makes up for the disadvantage of energy consumption of adsorbent regeneration.In addition,the ability of the process to obtain H element is improved by the high decomposition rate of H2O,which realizes a more rational distribution of the element.

Quantitative Gas-in-place Comparison of Original and Bitumen-free Lacustrine Shale

Residual bitumen in organic-rich shale of oil windows exists widely, and its effect on the gas storage capacity of shale could be two-fold. Bitumen could occupy and block the nanopores of shale, thereby reducing the gas storage capacity. On the other hand, gas could be dissolved in bitumen in shale gas reservoirs, leading to enhanced gas storage capacity. To quantify the effect of bitumen on the gas-in-place(GIP) estimation of lacustrine organic-rich shale, the micropore characteristics and methane sorption capacity of original and bitumen-free shale from the Triassic Yangchang Formation of the Ordos Basin, combined with the methane dissolution capacity for the isolated bitumen, were analyzed and compared. GIP for the original and bitumen-free shale in the depth range of 500–2500 m was evaluated. The results show that micropores in the shale samples were mainly related to organic matter. Clay mineral-hosted pores contributed slightly to microporosity. Bitumen significantly reduced the micropore surface area and volume of the original shale, with average percentages of 28.09% and 51.26%, respectively. The methane sorption capacity decreased after bitumen removal. When normalized to the original shale mass, the sum of the methane sorption capacity for bitumen-free shale and the methane dissolution capacity for isolated bitumen was similar to the methane sorption capacity of the original shale, indicating that the lack of methane absorbed on bitumen is the main reason for the decrease in methane sorption capacity after bitumen removal. The contribution of absorbed methane on bitumen to sorbed methane in shale could be higher than 36.23%. Dual effects of bitumen on shale GIP were observed. A high content of bitumen(1.12%) increased the GIP of the shale samples, with an average percentage of 23.5% in the depth range of 500–2500 m, while a low content of bitumen(0.06%) decreased the GIP, with an average percentage of 13.6%.

Prediction of sorption enhanced steam methane reforming products from machine learning based soft-sensor models

Carbon dioxide-abated hydrogen can be synthesised via various processes,one of which is sorption enhanced steam methane reforming(SE-SMR),which produces separated streams of high purity H_(2) and CO_(2).Properties of hydrogen and the sorbent material hinder the ability to rapidly upscale SE-SMR,therefore the use of artificial intelligence models is useful in order to assist scale up.Advantages of a data driven soft-sensor model over ther-modynamic simulations,is the ability to obtain real time information dependent on actual process conditions.In this study,two soft sensor models have been developed and used to predict and estimate variables that would otherwise be difficult direct measured.Both artificial neural networks and the random forest models were devel-oped as soft sensor prediction models.They were shown to provide good predictions for gas concentrations in the reformer and regenerator reactors of the SE-SMR process using temperature,pressure,steam to carbon ratio and sorbent to carbon ratio as input process features.Both models were very accurate with high R^(2) values,all above 98%.However,the random forest model was more precise in the predictions,with consistently higher R^(2) values and lower mean absolute error(0.002-0.014)compared to the neural network model(0.005-0.024).