Catalytic activity of cobalt on nanotextured polymer films for hydrogen production

We describe the mechanism of cobalt and ligand binding on nanotextured poly(chloro-p-xylylene) (PPX) films as supports for catalytic release of H₂ from alkaline aqueous solutions of sodium borohydride. Cobalt catalysts are prepared on nanotextured PPX substrates via electroless plating using a Sn-free Pd(II) colloid with adsorbed pyridine ligand as an adhesion promoter. Gas physisorption studies on PPX, using N₂ and CO₂ as probe gases, indicate the presence of micropores (∼1 to 2 nm width) responsible for the adsorption and non-covalent stabilization of pyridine molecules on the nanotextured surface. The strongly adsorbed pyridine molecules promote Co adhesion onto the PPX surface during subsequent electroless deposition, thereby retaining the metal's catalytic activity for H₂ evolution even after multiple reaction cycles. In contrast, conventionally deposited PPX is devoid of any nanotexture and contains fewer micropores capable of stabilizing pyridine adsorption, resulting in poor metallization and catalytic activity for H₂ evolution. We also demonstrate the effect of patterning the PPX substrate as a means to further improve the activity of the Co catalyst to achieve H₂ evolution rates comparable to those obtained using precious metal catalysts.     

Effect of CO and CO2 impurities on performance of direct hydrogen polymer-electrolyte fuel cells

Mechanisms by which trace amounts of CO and CO₂ impurities in fuel may affect the performance of direct hydrogen polymer-electrolyte fuel cell stacks have been investigated. It is found that the available data on CO-related polarization losses for Pt electrodes could be explained on the basis of CO adsorption on bridge sites, if the CO concentration is less than about 100 ppm, together with electrochemical oxidation of adsorbed CO at high overpotentials. The literature data on voltage degradation due to CO₂ is consistent with CO production by the reverse water–gas shift reaction between the gas phase CO₂ and the H₂ adsorbed on active Pt sites. The effect of oxygen crossover and air bleed in “cleaning” of poisoned sites could be modeled by considering competitive oxidation of adsorbed CO and H by gas phase O₂. A model has been developed to determine the buildup of CO and CO₂ impurities due to anode gas recycle. It indicates that depending on H₂ utilization, oxygen crossover and current density, anode gas recycle can enrich the recirculating gas with CO impurity but recycle always leads to buildup of CO₂ in the anode channels. The buildup of CO and CO₂ impurities can be controlled by purging a fraction of the spent anode gas. There is an optimum purge fraction at which the degradation in the stack efficiency is the smallest. At a purge rate higher than the optimum, the stack efficiency is reduced due to excessive loss of H₂ in purge gas. At a purge rate lower than the optimum, the stack efficiency is reduced due to the decrease in cell voltage caused by the excessive buildup of CO and CO₂. It is shown that the poisoning model can be used to determine the limits of CO and CO₂ impurities in fuel H₂ for a specified maximum acceptable degradation in cell voltage and stack efficiency. The impurity limits are functions of operating conditions, such as pressure and temperature, and stack design parameters, such as catalyst loading and membrane thickness.     

Investigation of adsorption properties of geological materials for CO2 storage

The assessment for realistic CO₂‐adsorption capacities of different rocks is important for understanding the processes associated with CO₂ storage. This paper investigates the adsorption characteristics of rocks for CO₂ (limestone, sandstone, marl, claystone, clay, siltstone and metamorphic rock) by using a gravimetric method. The measurements were performed at 21°C with pressures from 1 up to 4 MPa. Sandstone (and clay with sand/sandstone) showed the largest adsorption capacity at 21°C. The highest amount of in situ CO₂ contents in measured samples was 21.4 kg/t. The CO₂‐adsorption capacities were lower than past results in different coal samples. The results indicate that adsorption of CO₂ into rocks may play an important role in storing CO₂ in subsurface rock. Copyright © 2012 John Wiley & Sons, Ltd.     

Hydroxyl aluminium silicate clay for biohydrogen purification by pressure swing adsorption: Physical properties,adsorption isotherm,multicomponent breakthrough curve modelling,and cycle simulation

Hydroxyl aluminium silicate clay (HAS-Clay) is a novel adsorbent in pressure swing adsorption for CO₂ capture (CO₂-PSA) and can also adsorb H₂S. To investigate the performance of HAS-Clay as a CO₂-PSA adsorbent, multicomponent breakthrough curves were determined using experimental measurements and theoretical models, and, based on those results, CO₂-PSA simulations were conducted. The breakthrough curves produced from the theoretical models agreed well with those derived from experiment. CO₂-PSA with HAS-Clay could purify biomass-gasification-derived producer gas of contaminants (carbon dioxide, methane, carbon monoxide, and hydrogen sulfide) with high CO₂ recovery and low energy input. The CO₂ recovery rate of CO₂-PSA with HAS-Clay was 58.4%, and the CO₂ purity was 98.4%. The specific energy demand was 2.83 MJ/kg-CO₂. In addition, the H₂S regenerability of HAS-Clay was investigated. The results show that HAS-Clay retained the ability to adsorb H₂S at a steady-state value of 0.02 mol/kg for the regeneration cycles. Therefore, it is suggested that CO₂-PSA with HAS-Clay is suitable for CO₂ separation from multicomponent gas mixtures.     

不同复合页岩模型内气体竞争吸附特性的分子模拟

构建了高岭石-干酪根IID、蒙脱石-干酪根IID和方解石-干酪根IID三种复合模型,采用巨正则蒙特卡罗方法(GCMC)和分子动力学方法(MD),从分子层面研究了CH4与注采气体(CO2、N2)在复合页岩材料中的吸附情况,分析了不同模型对不同气体的吸附能力.结果 表明:在高岭石-干酪根IID复合模型中三种气体的吸附量为m...     

MOF-5 and activated carbons as adsorbents for gas storage

This paper reports comparatively the capacities of two activated carbons (ACs) and MOF-5 for storing gases. It analyzes, using similar equipments and experimental procedures, the density used to convert gravimetric data to volumetric ones, measuring the density (tap and packing at different pressures). It presents data on porosity, surface area and gas storage (H₂, CH₄ and CO₂) obtained under different temperatures (77 K and RT) and pressures (0.1, 4 and 20 MPa). MOF-5 presents lower volume of narrow micropores than both ACs, making its storage at RT lower, independently of the gas used (H₂, CH₄ and CO₂) and the basis of reporting data (gravimetric or volumetric). For H₂ at 77 K the reliability of the results depends too much on the density used. It is shown that the outstanding volumetric performance of MOF-5, in relation to ACs, is due to the use of an unrealistic high density (crystal density) that, not including the adsorbent inter-particle space, gives an apparently high volumetric gas storage capacity. When a density measured similarly in both types of adsorbents is used (e.g. tap or packing densities) MOF-5 presents, for all gases and conditions studied, lower adsorption capacities on volumetric basis and storage capacities than ACs.     

Adsorption behavior and kinetics of H2S on a potassium-promoted hydrotalcite

Adsorption of H₂S and the influence of steam on its adsorption capacity and kinetics were studied on a commercial potassium-promoted hydrotalcite. The sorbent shows a very high cyclic working capacity for H₂S compared to CO₂ and H₂O, even at lower partial pressures and at different operating temperatures ranging between 300 and 500 °C. The operating temperature does not significantly influence the cyclic working capacity for half-cycle times of 30 min. The adsorption mechanism, however, changes at higher temperatures. At lower temperatures (300 °C) a fast adsorption with a fast approach to steady state was observed. At higher operating temperatures, H₂S reacts with the hydrotalcite structure, forming strongly bonded sulfuric species on the sorbent. When using dry regeneration conditions, the first cycles in cyclic operation at higher temperatures show a significantly higher adsorption of H₂S (especially the first cycle), which cannot be desorbed during regeneration with N₂. After the first fast initial adsorption rate a continuous slow adsorption of H₂S occurs, probably caused by a surface reaction between H₂S and the hydrotalcite structure. This reaction is, however, reversible if steam is used.The adsorption mechanism for H₂S and H₂O was determined using multiple cyclic experiments comparable to previous studies performed for CO₂ and H₂O adsorption. It is evident that the adsorption mechanism developed for CO₂ on the same sorbents is also valid for H₂S, indicating that the developed mechanism is consistent for sour gas adsorption on this type of sorbents. The cyclic working capacity can be significantly increased if steam is used during the regeneration step of the sorbent. The mechanistic model developed for the adsorption of CO₂ and H₂O was successfully validated with more than 160 different TGA experiments. An operating temperature of 400 °C seems to be optimal to achieve a high cyclic working capacity for H₂S, because at higher temperatures the regeneration of the formed sulfuric species seems to be hindered resulting in a significant decrease in the cyclic working capacity.     

CO2-selective membranes for hydrogen purification and the effect of carbon monoxide (CO) on its gas separation performance

Industrial hydrogen production may prefer CO₂-selective membranes because high-pressure H₂ can therefore be produced without additional recompression. In this study, high performance CO₂-selective membranes are fabricated by modifying a polymer–silica hybrid matrix (PSHM) with a low molecular weight poly(ethylene glycol) dimethyl ether (PEGDME). The liquid state of PEGDME and its unique end groups eliminate the crystallization tendency of poly(ethylene glycol) (PEG). The methyl end groups in PEGDME hinder hydrogen bonding between the polymer chains and significantly enhance the gas diffusivity. In pure gas tests, the membrane containing 50 wt% additive shows CO₂ gas permeability and CO₂/H₂ selectivity of 1637 Barrers and 13 at 35 °C, respectively. In order to explore the effect of real industrial conditions, the gas separation performance of the newly developed membranes has been studied extensively using binary (CO₂/H₂) and ternary gas mixtures (CO₂/H₂/carbon monoxide (CO)). Compared to pure gas performance, the second component (H₂) in the binary mixed gas test reduces the CO₂ permeability. The presence of CO in the feed gas stream decreases both CO₂ and H₂ permeability as well as CO₂/H₂ selectivity as it reduces the concentration of CO₂ molecules in the polymer matrix. The mixed gas results affirm the promising applications of the newly developed membranes for H₂ purification.     

A theoretical study of the ability of 2D monolayer Au (111) to activate gas molecules

The adsorption and activation of gas molecules are investigated substantially in solid-gas heterogeneous catalysis. Here we investigated the interaction between gas molecules and unique two-dimensional monolayer Au (111) structure using density functional theory. It is found that CO₂, H₂O, N₂ and CH₄ molecules are weakly adsorbed on the surface with the adsorption energies between ?0.150 and ?0.250 eV due to van der Waals interaction. While CO, NO, NO₂, and NH₃ molecules are adsorbed more stably with the adsorption energies between ?0.300 and ?0.470 eV. Especially, the bond length of CO is stretched by 0.038 Å and the bond angle of NO₂ is obviously enlarged by 10.460°. The activation originates from the rearrangement of molecule orbitals and the orbitals hybridization between the partial orbitals of gas molecules and Au-5d orbitals. The fundamental analyses of adsorption mechanism and electronic properties may provide guidance for the applications of two-dimensional monolayer metal catalysis.PACSnumbers 73.22.-f, 73.61.-r     

Augmented hydrogen adsorption on metal (Mg,Mn) doped α-phase TeO2: A DFT investigation

TeO₂, as a promising gas sensor material, has been extensively studied for its capacity to detect hydrogen with high sensitivity. First-principles calculations were applied to explore the adsorption properties of hydrogen (H₂), carbon dioxide (CO₂), methane (CH₄), and hydrogen sulfide (H₂S) on TeO₂ doped with either Mg or Mn to explore this compound's potential as hydrogen sensors. Hydrogen is more readily adsorbed on pure-TeO₂, Mg–TeO₂ and Mn–TeO₂ than CO₂, CH₄ and H₂S molecules by calculating their adsorption energy and charge transfer; the sequence of adsorption strength is H₂>H₂S > CO₂>CH₄. The hydrogen molecules and pure-TeO₂, Mg–TeO₂ and Mn–TeO₂ form H–O bonds with lengths of 0.98, 0.98 and 0.99 Å, respectively, indicating that chemical adsorption is dominant between them. The adsorption of hydrogen leads to significant changes in the density of states (DOSs) of pure-TeO₂, Mg–TeO₂ and Mn–TeO₂, which may lead to changes in their electrical conductivity. Moreover, the larger diffusion coefficients for hydrogen on the surfaces of pure-TeO₂, Mg–TeO₂ and Mn–TeO₂ relative to other gases indicates that hydrogen diffuses readily in TeO₂-based sensing materials, and the higher gas concentration contributes to improvements in response performance. This finding offers a theoretical basis for experimental explorations of the influence of metal dopants on TeO₂ hydrogen sensing performance.     

Hydrogen generation in crushed rocks saturated by crude oil and water using microwave heating

Fossil-based hydrogen (H₂) production, such as steam methane reforming (SMR), typically occurs at surface facilities using hydrocarbons as a major feedstock. Such approach generates significant amount of byproduct carbon dioxide (CO₂) and requires the costly carbon capture and geological storage. Here we propose a novel approach to generate hydrogen within petroleum reservoirs using the remaining/unrecovered oil and gas. To validate this scientific proof-of-concept, we use microwave (MW) heating to initiate the reactions of crude oil, water, and/or catalysts in crushed rock samples. A maximum of 63% ultimate hydrogen content is obtained in generated gas mixtures, while CO₂ is always less than 1%. Besides hydrocarbon cracking, additional hydrogen is generated by water-gas shift reactions. Water-oil ratios in rocks also affect hydrogen yield, with 1:1 appearing as an optimal ratio. Furthermore, we find that iron catalysts can accelerate reaction rate but has limited effects on ultimate hydrogen yield. Metal minerals in rocks may act as natural catalysts to enhance hydrogen generation. Overall, this work demonstrates the technical feasibility of in-situ hydrogen generation directly from petroleum reservoirs.     

K-doped LaNiO3 perovskite for high-temperature water-gas shift of reformate gas: Role of potassium on suppressing methanation

LaNiO₃ perovskite has been successfully used as a catalyst precursor for high temperature water-gas shift (HT-WGS) reaction of reformate gas to produce additional hydrogen from the hydrocarbon reforming. The Ni⁰ nanoparticles with the particle size of ca. 21 nm obtained after reduction of LaNiO₃ perovskite can effectively suppress CO methanation during HT-WGS reaction using pure CO/H₂O gas. However, for HT-WGS reaction of reformate gas (including CO, H₂O, CO₂ and H₂), LaNiO₃ perovskite exhibits lower catalytic activity with significant CH₄ formation predominantly via CO₂ methanation. In this work, the CO₂ methanation during HT-WGS reaction of reformate gas was suppressed by the addition of potassium onto LaNiO₃ perovskite. This is due to the adsorption of H₂O on the potassium which is located at the interface between La₂O₃ and Ni⁰ nanoparticle (as deduced from XPS and HRTEM results) that forms stable KOH, blocking the methanation of CO₂ adsorbed on the La₂O₃ with H₂ adsorbed on the Ni⁰ nanoparticles. Moreover, the formation of stable KOH also promotes the formation of formate (HCOO) – a key intermediate for WGS reaction over the reduced LaNiO₃ perovskite – even at high reaction temperature by continuously supplying hydroxyl group to react with CO adsorbed on the Ni⁰ nanoparticle, which helps to maintain the catalytic activity for WGS reaction at high reaction temperature.     

Fluid inclusion study of the Kirishima geothermal system, Japan

Gases from fluid inclusions in quartz and anhydrite were analyzed with a quadrupole mass spectrometer and a capacitance manometer. The quartz and anhydrite occur in hydrothermal veins in volcanic and pelitic rocks collected from geothermal wells in the Kirishima area, southwest Japan. The geothermal wells are located in a graben made up of Quaternary volcanic rocks underlain by sedimentary rocks of the Shimanto Group.Results of individual fluid inclusion analyses show that the fluid inclusions comprise mainly H₂O and a variable but small amount of CO₂. CH₄ and other hydrocarbons are also detected in inclusions in a hydrothermal sample from the pelitic Shimanto Group. Peak ratios of CO₂/H₂0 in individual fluid inclusions are variable in some samples. This indicates that there is a difference in gas compositions of the fluid inclusions, and suggests that the inclusions were formed in multistages or trapped heterogeneous boiling fluids.Results of bulk analyses show that the inclusions are mainly composed of H₂O (98–99 mol%) with small amounts of non-condensable gases, mainly C0₂ and N₂, CH₄ and Ar. The proportion of N₂ is about one order of magnitude lower than C0₂, CH₄ is generally two orders of magnitude lower than C0₂ and Ar is just above the detection limit of the mass spectrometer. The gas concentration in the fluid inclusions is much higher than that in the present-day discharge fluids in this area. CO₂/N₂ and C0₂/CH₄ ratios of the fluid inclusions from the volcanic rocks are lower than those of the present-day discharge fluids. CO₂/N₂ and CO₂/CH₄ ratios in residual fluids increase with progressive degassing, because N₂ and CH₄ are released from the residual fluids more easily than CO₂. Thus, the difference in the CO₂/N₂ and CO₂/CH₄ ratios between the fluid inclusions and the present-day discharge fluids in the Kirishima area may be ascribed to the degree of degassing, and the fluid inclusions in the area were probably formed by trapping fluids that were weakly influenced by degassing. P_co2, values calculated from the gas compositions of the fluid inclusions are higher than that of buffer systems involving alteration minerals in the area. This suggests that the fluid inclusions might be trapped fluids which were not in equilibrium with the alteration mineral assemblages, that is, fluids prior to considerable degassing and alteration.     

Post combustion CO2 capture by carbon fibre monolithic adsorbents

As generation of carbon dioxide (CO₂) greenhouse gas is inherent in the combustion of fossil fuels, effective capture of CO₂ from industrial and commercial operations is viewed as an important strategy which has the potential to achieve a significant reduction in atmospheric CO₂ levels. At present, there are three basic capture methods, i.e. post combustion capture, pre-combustion capture and oxy-fuel combustion. In pre-combustion, the fossil fuel is reacted with air or oxygen and is partially oxidized to form CO and H₂. Then it is reacted with steam to produce a mixture of CO₂ and more H₂. The H₂ can be used as fuel and the carbon dioxide is removed before combustion takes place. Oxy-combustion is when oxygen is used for combustion instead of air, which results in a flue gas that consists mainly of pure CO₂ and is potentially suitable for storage. In post combustion capture, CO₂ is captured from the flue gas obtained after the combustion of fossil fuel. The post combustion capture (PCC) method eliminates the need for substantial modifications to existing combustion processes and facilities; hence, it provides a means for near-term CO₂ capture for new and existing stationary fossil fuel-fired power plants.This paper briefly reviews CO₂ capture methods, classifies existing and emerging post combustion CO₂ capture technologies and compares their features. The paper goes on to investigate relevant studies on carbon fibre composite adsorbents for CO₂ capture, and discusses fabrication parameters of the adsorbents and their CO₂ adsorption performance in detail. The paper then addresses possible future system configurations of this process for commercial applications.Finally, while there are many inherent attractive features of flow-through channelled carbon fibre monolithic adsorbents with very high CO₂ adsorption capabilities, further work is required for them to be fully evaluated for their potential for large scale CO₂ capture from fossil fuel-fired power stations.     

Towards autothermal hydrogen production by sorption-enhanced water gas shift and methanol reforming: A thermodynamic analysis

Hydrogen production by the water gas shift reaction (WGS) is equilibrium limited. In the current study, we demonstrate that the overall efficiency of the WGS can be improved by co-feeding methanol and removing CO₂ in situ. The thermodynamics of the water gas shift and methanol reforming/WGS (methanol-to-shift, MtoS) reactions for H₂ production alone and with simultaneous CO₂ adsorption (sorption-enhanced, SEWGS and SEMtoS) were studied using a non-stoichiometric approach based on the minimisation of the Gibbs free energy. A typical composition of the effluent from a steam methane reformer was used for the shift section. The effects of temperature (450–750 K), pressure (5–30 barg), steam and methanol addition, fraction of CO₂ adsorption (0–95%) and energy efficiency of the shift systems have been investigated. Adding methanol to the feed facilitates autothermal operation of the shift unit, with and without CO₂ removal, and enhances significantly the amount of H₂ produced. For a set methanol and CO input, the MtoS and SEMtoS systems show a maximum productivity of H₂ between 523 and 593 K due to the increasing limitation of the exothermic shift reaction while the endothermic methanol steam reforming is no longer limited above 593 K. The heat of adsorption of CO₂ was found to make only a small difference to the H₂ production or the autothermal conditions.     

Hydrogen adsorption on natural and sulphuric acid treated sepiolite and bentonite

In this study, hydrogen (H₂) adsorption on sepiolite and bentonite and those of acid treated forms were studied at 77 K using volumetric apparatus up to 100 kPa. Both clay minerals were treated with 100 ml of 0.5, 1.0, 2.0 and 4.0 M H₂SO₄ solutions at 80 °C for 5 h. Differences in the structures of the sepiolite and bentonite samples before and after the acid treatments were determined by XRD, XRF, TG, DTA and N₂ adsorption methods. The level of H₂ adsorption of original and acid treated sepiolite samples (1.332–2.252 mmol/g) was higher than those of the bentonite samples (0.341–1.003 mmol/g). The variation in the H₂ adsorption capacities during the acid treatment was also discussed.     

Hydrogen storage in carbon fibers activated with supercritical CO2: Models and the importance of porosity

In this work we studied the adsorption of H₂ at 77 K and 0.0–0.12 MPa onto carbon fibers activated with supercritical CO₂ (ACFs) and with different burn-offs (10–53%). The highest amount of H₂ stored was 2.45 wt% in an ACF with a burn-off of 51% at 0.12 MPa. The measured isotherms were analyzed using an equilibrium model derived by analogy with a multiple-site Langmuir-type adsorption model. The different equilibria correspond to adsorption in pores of different sizes. The experimental results fitted a model with two different adsorption sites satisfactorily, allowing such sites to be related to the microporous structure of the ACFs. Thus, a high-energy adsorbent–adsorbate interaction site, associated with very small micropores, accessible only to very small molecules such as H₂, and another lower-energy site associated with larger pores can be proposed. The model also predicts the adsorption behavior under equilibrium conditions at higher pressures, allowing the maximum adsorption capacity of the ACFs to be determined. The results show that the ACFs adsorb most of the H₂ molecules at low equilibrium pressures, and that they become almost saturated at pressures around 1.0 MPa. The maximum H₂ storage capacity in these ACFs lies between 1.50 and 3.15 wt%.     

CO reactive adsorption at low temperature over CuO/CeO2 structured catalytic monolith

CO adsorption on a copper/ceria nanopowder washcoated onto a cordierite monolith has been studied at low temperature by following the time evolution of the outlet concentration of CO and CO₂ on nanometric CuO/CeO₂ catalyst. The effects of adsorption time length, gas phase composition (H₂ or O₂ addition), temperature and contact time were investigated. Results showed that the high surface and the large availability of labile oxygen allows CO oxidation and CO₂ release even at room temperature. Moreover, tests under transient conditions showed that i) interfacial copper/ceria sites re-oxidation can benefit of oxygen transfer from ceria depending on the operating conditions (O₂ partial pressure, temperature, etc.), ii) hydroxyl groups, boosting CO₂ production rate, can be formed over the catalyst surface by reaction with molecular H₂ at temperature above 80 °C, and iii) several CO and CO₂ adsorbed species must be taken into account, covering not only copper but also ceria sites, some of them being spectators in the reaction pathway. Finally a novel strategy for CO removal based on CO trap is proposed.     

Two-stage PSA/VSA to produce H2 with CO2 capture via steam methane reforming (SMR)

A two-stage pressure/vacuum swing adsorption (PSA/VSA) process was proposed to produce high purity H₂ from steam methane reforming (SMR) gas and capture CO₂ from the tail gas of the SMR-H₂-PSA unit. Notably, a ten-bed PSA process with activated carbon and 5A zeolite was designed to produce 99.99+% H₂ with over 85% recovery from the SMR gas (CH₄/CO/CO₂/H₂ = 3.5/0.5/20/76 vol%). Moreover, a three-bed VSA system was constructed to recover CO₂ from the tail gas using silica gel as the adsorbent. CO₂ product with 95% purity and over 90% recovery could be attained. Additionally, the effects of various operating parameters on the process performances were investigated in detail.     

Feasibility and sustainability analyses of carbon dioxide – hydrogen separation via de-sublimation process in comparison with other processes

Hydrogen (H₂) plays a vital role both as a reactant in petrochemical processes and as an energy carrier and storage medium. When produced from carbon-containing feed stocks, such as fossil fuels and biomass, hydrogen is typically produced as a mixture with carbon dioxide (CO₂), and must be subsequently separated by the associated energy, with an invertible energy penalty. In this study, the process for the removal of carbon dioxide from CO₂ - H₂ mixtures by de-sublimation was analysed. This process is particularly relevant to the production of liquid hydrogen (LH₂) at cryogenic temperatures, for which cooling of the H₂ stream is already necessary. The solid – gas equilibrium of CO₂ - H₂ was studied using the Peng-Robinson equation of state which provided a wide range of operating conditions for process simulation. The de-sublimation process was compared with selected conventional separation processes, including amine-based absorption, pressure swing adsorption and membrane separation. In the scenario in which the resulting products, carbon dioxide and hydrogen, were subsequently liquefied for transportation and storage at 10 bar and −46 °C, and 1 bar and −251.8 °C, respectively. The overall energy consumption per kg of CO₂ separated (MJ/kgCO₂₎, was found to follow the order: 8.19–11.21 for monoethanolamine (MEA) absorption; 1.81–8.93 for membrane separation; 1.53–5.69 for pressure swing adsorption; and 0.81–3.35 de-sublimation process. Each process was evaluated and compared on the bases of electricity demand, cooling water usage, high-pressure steam usage, and refrigeration energy requirements. Finally, the advantages and disadvantages were discussed and the feasibility and sustainability of the processes for application in the production of liquid hydrogen were assessed.