Tetra-n-butyl Ammonium Bromide Solution Research Articles

Morphological Study of Tetra-n-Butylammonium Bromide Semi-Clathrate Hydrate in Confined Space

Tetra-n-butylammonium Bromide (TBAB) finds extensive use in diverse applications. An in-depth investigation into the effects of the formation conditions on TBAB hydrate is necessary to optimize the application process. This work focuses on examining the influence of the mass concentration of TBAB solution and the cooling rate on TBAB hydrate formation through optical microscopy and Raman spectroscopy. The TBAB hydrate formation process occurs in a confined space created by an optical sheet with a 0.03 mm deep groove. Four TBAB solutions of 13. 8 wt%, 18 wt%, 32 wt%, and 40 wt% are investigated, and the supercooling required for hydrate nucleation increases with concentration at a cooling rate of 0.5 K/min. Notably, Type A TBAB hydrate preferentially forms in all of the solutions, although type B hydrate is thermodynamically stable in the two dilute solutions. At a larger cooling rate of 2 K/min, two distinct crystal growth patterns are observed: one controlled by mass transfer and the other regulated by heat transfer. Increasing the cooling rate not only alters the optical morphology, but also reduces the supercooling due to a decrease in the Gibbs free energy barrier caused by a larger temperature gradient. This is beneficial for practical applications as it helps to alleviate the supercooling degree.

Experimental investigation on the synergistic influence of tetra-n-butyl ammonium bromide(TBAB) and cyclopentane(CP) in hydrate-based gas separation

To enhance the CO2 separation efficiency of hydrate-based gas separation (HBGS) technology, the kinetic process of hydrate formation from synthesized CH4/CO2/N2 gas mixtures in the presence of cyclopentane (CP) and tetra-n-butyl ammonium bromide (TBAB) and gas separation efficiency were studied at an initial pressure of 7.0 MPa and temperatures ranging from 275.1 to 290.1 K. The crystallographic properties of the mixed hydrates were also evaluated by Raman, powder X-ray diffraction(XRD) and cryo-scanning electron microscop(cryo-SEM). Results showed that the combination of CP and TBAB tended to inhibit the separation efficiency compared with pure CP. The maximum CH4 recovery was 1.37 and the CO2 split ratio was 0.791 when using CP and TBAB solution. The order of CO2 split ratio in the different systems followed the order SDS > CP > TBAB/CP > CP/SDS > TBAB. Meanwhile, the adsorption capacity and gas consumption also decreased with an increase in TBAB concentration. Raman and XRD tests revealed that sI, sII, and semi-clathrate hydrates were found to coexist after hydrate formation and no other types of hydrates was formed. CH4 could only enter the small cages (512) of the hydrate. SEM images showed that the hydrate crystals were ellipsoid-shaped with different sizes and stacked together to form a globular structure, suggesting that the specific surface area of the hydrate crystals enhanced with the increasing of TBAB concentration. These findings can be used to evaluate the feasibility of applying TBAB and CP in HBGS technology.

Experimental study on visualization of TBAB hydrate formation in confined small channels

Hydrate crystals' microscopic characteristics and agglomerating morphologies play an important role in the hydrate reaction equipment's flow assurance and heat transfer. In order to study the formation process of hydrate, experimental quartz tubes with small diameters were selected, and a fully visualized flow loop system was established. The study investigated the effects of supercooling, solution concentration, tube diameter, and flow rate on hydrate blockage time and agglomeration morphology. The results show that under the same supercooling conditions, the density of single crystal hydrate formed in 10 wt%-20 wt% TBAB (Tetra-n-butylammonium bromide) hydrate solution is low, and the crystal front appears needle-like or sword-like, which is conducive to mass and heat transfer. High concentration TBAB solution(30 wt%-40 wt%) can form dense hydrate crystals, and the tip effect was significantly weakened. For low concentration TBAB solution, the increased flow rate can accelerate the formation of new nuclei and inhibit the growth of large crystals. Grout solutions with different particle sizes can be obtained by adjusting the flow rate. It was found that the initial morphology of TBAB hydrate crystals included spherical and cylindrical shapes, and the morphological evolution process of a single hydrate crystal was similar. Finally, a microscopic physical model of the TBAB hydrate growth and aggregation process was established.

CO2 capture enhancement by forming tetra‐n‐butyl ammonium bromide semiclathrate in graphite nanofluids

AbstractIn this work, CO2 capture was experimentally investigated by forming tetra‐n‐butyl ammonium bromide (TBAB) semiclathrate in a new system of TBAB + graphite nanofluids. The experiments were carried out at 3.5 MPa and 277.15 K. Compared to the TBAB solution and the TBAB + sodium dodecyl sulphate (SDS) solution, it was found that the system of TBAB + graphite nanofluids was preferable for CO2 capture, and 0.2 wt.% graphite nanoparticles (GNP) was an optimal concentration for the enhancement of hydrate growth in TBAB + graphite nanofluids. At this GNP concentration, CO2 consumption gained at 0.29 mol% TBAB is greater than that acquired at 0.62 and 2.57 mol% TBAB. CO2 consumption obtained in TBAB + graphite nanofluids is larger than other systems containing GNP. Moreover, the morphologies of TBAB + CO2 semiclathrate formed in TBAB solution, TBAB + SDS solution, and TBAB + graphite nanofluids were presented, and the mechanism of CO2 capture using TBAB semiclathrate formation in graphite nanofluids was presented. Therefore, it is an efficient way to capture CO2 by forming TBAB semiclathrate in graphite nanofluids.

Kinetic study of semiclathrate hydrates formed with CO2 in the presence of tetra-n-butyl ammonium bromide and tetra-n-butyl phosphonium bromide

The kinetics of semiclathrate hydrates formation with CO2 in the presence of tetra-n-butyl ammonium bromide (TBAB), tetra-n-butyl phosphonium bromide (TBPB), and TBAB + TBPB were investigated. The experiments were conducted at the stoichiometric concentration of TBAB hydrate (2.57 mol%) and three subcoolings (ΔT = 6 K, 9 K, and 12 K) with the initial pressure fixed at 2.8 MPa. It was found that adding TBPB into the TBAB solution can promote hydrate nucleation, and this promotion effect at a lower subcooling (ΔT = 6 K) was stronger compared to that at higher subcoolings (ΔT = 9 K and 12 K). The gas consumption obtained in TBAB, TBPB, and TBAB + TBPB solutions decreased with the increase of subcooling, despite the increase of the rate of hydrate growth. At a given subcooling, gas consumption (CO2 uptake) in TBAB + TBPB solutions was greater than that in TBAB and TBPB solutions, indicating that hydrate formation kinetics and the CO2 storage capacity were improved in the TBAB + TBPB solution. The largest gas consumption was obtained at ΔT = 6 K in the TBAB + TBPB solution, which was 28.7% and 17.2% larger than those obtained in TBAB and TBPB solutions, respectively. Therefore, a mixture of TBAB + TBPB is a promising option to improve the kinetics of semiclathrate hydrate formation with CO2.

Application of tetra-n-butyl ammonium bromide semi-clathrate hydrate for CO2 capture from unconventional natural gases

In this study, tetra-n-butyl ammonium bromide (TBAB) semi-clathrate hydrate was employed for CO2 capture from unconventional natural gases exploited by supercritical CO2 injection. The TBAB hydrate formation kinetics and CO2 separation efficiency were studied under different TBAB concentrations and subcoolings using a stirred tank reactor. Optimum experimental conditions were obtained (2.8 MPa, ΔT = 6 K, 2.57 mol% TBAB), and the synergetic effect of sodium dodecyl sulfate (SDS) and TBAB on CO2 separation from CH4 + CO2 was investigated under these conditions. The results indicate that gas consumption and CO2 selectivity declined with the increase of subcooling, and the best CO2 selectivity was obtained at 2.57 mol% TBAB. The kinetics of TBAB hydrate nucleation and growth were promoted when adding SDS into the TBAB solution, but the CO2 separation efficiency was reduced. The CO2 selectivity obtained at 2.57 mol% TBAB was significantly improved as compared to the THF, THF/SDS, and TBPB systems. Therefore, TBAB is a prospective promoter for hydrate-based CO2 capture from CH4 + CO2. Continued efforts are required in the future to increase the gas consumption without sacrificing the CO2 separation efficiency.

Experimental and process simulation of hydrate-based CO2 capture from biogas

This study experimentally investigated the effects of operation conditions for the CO2 capture from biogas by clathrate hydrate formation. The experiments were tested at 3.0 MPa and 278 K in the present of 5.0 wt % tetra-n-butylammonium bromide (TBAB). In addition, the dissociation enthalpies of CH4/CO2 hydrates in TBAB solution was calculated for energy consumption. The hydrate process simulation with Aspen Plus was carried out at the same experimental conditions to simulate the actual hydrate-based CO2 capture (HBCC), and the energy consumption of this process was analyzed. Experimental results show that the CH4 fraction in the residual gas phase increased with the decrease of gas liquid volume ratio (Rv). Rv decreased from 35.93 to 3.61 while the concentration of CH4 in residual gas increased from 80.5 mol % to 92.76 mol %. The CH4 concentration in residual gas phase was enriched from 67.00 mol% to 97.00 mol% by two stages of HBCC. Process simulation results showed that the energy cost was 1.17 kWh/kg CH4. According to the handing capacity of the feed gas, the energy cost was 0.390 kWh/kg biogas, which was lower than that by chemical absorption method. After adjusting the process parameters and increasing exhaust gas energy recovery, the energy consumption was reduced to 0.357 kWh/kg biogas. The energy consumption could be decreased to 0.204–0.223 kWh/kg biogas by using static hydration enhancement technology.

Morphology and kinetic investigation of TBAB/TBPB semiclathrate hydrates formed with a CO2 + CH4 gas mixture

This work presents a morphological and kinetic investigation of tetra-n-butyl ammonium bromide (TBAB) or tetra-n-butyl phosphonium bromide (TBPB) semiclathrate hydrates formed with a CO2 + CH4 gas mixture at the stoichiometric concentration (2.57 mol%). A 3-stage procedure was proposed and employed in the experiments. All experiments were performed at 2.8 MPa and a subcooling of 12 K was used as driving force for hydrate nucleation and growth. It was found that the shapes of hydrate crystals formed in TBPB and TBAB solutions were quite different. Besides, the TBPB semiclathrate hydrate grew laterally at gas/liquid interface and quickly covered the interface while the TBAB semiclathrate hydrate initially formed around the gas/liquid interface and then sank to the reactor bottom. As a consequence, gas uptake and the rate of hydrate growth obtained in TBAB solutions were higher than that in TBPB solutions. It was also found that CO2 content in hydrate phase, CO2 recovery, and separation factor obtained in TBAB solutions were higher than those obtained in TBPB solutions. Therefore, TBAB semiclathrate hydrate formed at the stoichiometric concentration and quiescent conditions will be a promising approach to improve the hydrate based CO2 separation from the CO2 + CH4 gas mixture.

Study on TBAB hydrate nucleating activity of electrode products due to DC voltage application

The effect of the products obtained by applying a direct current (DC) voltage to electrodes on the nucleation of tetra-n‑butyl ammonium bromide (TBAB) hydrate was investigated experimentally. Six kinds of materials were used as electrodes and the products were generated by applying a DC voltage to the electrodes in a TBAB aqueous solution at a normal temperature. The nucleating activities of the products were estimated by measuring the freezing probability of the TBAB aqueous solution containing the products. High probabilities of freezing were obtained for the Zn, Cu, and Ag electrodes. Moreover, the insoluble products were separated from the TBAB solution after a DC voltage was applied to the Zu, Cu, and Ag electrodes. The products were placed in a clear TBAB aqueous solution and the freezing probability of the TBAB solution was measured. The products had a high nucleating activity for TBAB hydrate.

Semi-clathrate hydrate process of methane in porous media-microporous materials of 5A-type zeolites

Porous media can significantly promote the kinetics of hydrate formation by reducing the barrier of physical chemistry, where zeolites are typical microporous minerals. In this paper, the formation process and the reaction kinetics of the methane hydrate were investigated in A-type zeolite with tetrahydrofuran (THF) and tetra-n-butyl ammonium bromide (TBAB) aqueous solution in a long tubular reactor. The results showed that good kinetic characteristics of methane hydrate formation can be achieved with A-type zeolite. At initial pressure of 1.5 MPa and 1.8 MPa at 285.15 K, the aqueous solution of tetrahydrofuran (THF) and tetra-n-butyl ammonium bromide (TBAB) with 5A-type zeolite can form methane hydrate with gaseous methane in 10 h. The temperature raised significantly during the formation process of the system with 5A-type zeolite. Throughout the reaction, there was an obvious temperature rising region which was located in the inlet side of tubular reactor. The gas uptake increased rapidly in the beginning of 100 min and then maintained stable increasing during the hydrate formation. The final gas uptake capacity raised with the reaction pressure but was little affected by the type of promoter. From 1.5 MPa to 1.8 MPa the final gas uptake of hydrate increased 6.48% and 6.15% in the THF and TBAB solution respectively. The reaction rate quickly reached the peak after the reaction began and then rapidly dropped to decays. Simultaneously the average of reaction rate of THF solution was 13.2–30.8% higher than that of TBAB solution when the pressure was 1.5 MPa and 1.8 MPa at the same experimental conditions.

Solubility of Nitrogen Gas in Aqueous Solution of Tetra-n-Butylammonium Bromide

Semiclathrate hydrates are water-based host-guest compounds formed from aqueous solutions of ionic guest substances. These materials can greatly moderate formation pressures and temperatures from canonical gas hydrates. This is a significant advantage for industrial applications such as gas separation and storage. $$\hbox {N}_{2}$$ gas is a major component contained in various flue gases and is usually mixed with $$\hbox {CO}_{2}$$ . Semiclathrate hydrates can separate these gases under moderate thermodynamic conditions. Tetra-n-butylammonium bromide (TBAB) is a widely used ionic guest substance. To develop the application technologies and their theoretical models, solubility data of $$\hbox {N}_{2}$$ gas in TBAB aqueous solutions are required. In this study, we report $$\hbox {N}_{2}$$ gas solubility measured by an absolute gravimetric method for the semiclathrate hydrate formation system of $$\hbox {TBAB} + \hbox {H}_{2}\hbox {O} + \hbox {N}_{2}$$ . The measurement pressures, temperatures and TBAB mass fractions were 3 MPa, 5 MPa and 7 MPa, 292.15 K, 302.15 K and 307.15 K, and 0 (pure water), 0.10, 0.20, 0.32 and 0.40, respectively. The uncertainties were 0.056 MPa, 0.44 K and 0.00012 in mole fraction. Although the technical difficulty lays on measurements of small $$\hbox {N}_{2}$$ gas solubility by the absolute gravimetric method, our data implied the unique gas dissolution property of aqueous TBAB solution depending on the TBAB concentration. The aqueous TBAB solutions with mass fractions of 0.10 and 0.20 had similar $$\hbox {N}_{2}$$ gas solubility as that in pure water. With higher mass fractions, 0.32 and 0.40, the $$\hbox {N}_{2}$$ gas solubility slightly increased from that in pure water, which implies the salting-in effect of TBAB.

Kinetic study of hydrate formation for argon + TBAB + SDS aqueous solution system

In this communication, the effects of initial temperature and pressure, aqueous TBAB (tetra-n-butylammonium bromide) solution concentration, and sodium dodecyl benzene sulfonate (SDS) concentration on the kinetic behaviour of semi-clathrate hydrates of Ar+aqueous TBAB solutions were investigated. Kinetic experiments were performed in a high pressure equilibrium cell with an inner volume of approximately 40cm3 at initial temperatures of (281, 285 and 287.5)K and initial pressures of (6.1, 8.1 and 10.1)MPa. The results indicate that induction time decreases significantly with an increase in the initial pressure. However, the kinetic constant, and consumption of Ar during the semi-clathrate hydrate formation, increases. The same trends were detected with a decrease in the initial temperature, at a constant pressure. In addition, with an increase in the TBAB concentration, from 0.1 to 0.3mass fraction TBAB, the rate of semi-clathrate hydrate nucleation and consumption of Ar, increases during the hydrate formation, while the induction time decreases, significantly. The results therefore show a positive kinetic effect of TBAB on Ar hydrates which indicates that TBAB is a reliable promoter to increase the rate of argon hydrate formation. The results for the addition of SDS (at concentrations of 100, 200ppm) at initial temperatures of 285K and initial pressures of (6.1 and 8.1)MPa indicate that SDS increases the induction time of the semi-clathrate hydrate formation for the system of Ar+0.1mass fraction TBAB+0.9mass fraction water, but there is no systematic trend between induction times and the SDS concentrations for this system.

Semiclathrate-based CO2 capture from fuel gas in the presence of tetra-n-butyl ammonium bromide and silica gel pore structure

Pre-combustion CO2 capture technology was investigated via a hydrate-based gas separation process. Semiclathrate phase equilibria were measured for the simulated fuel gas from the integrated gasification combined cycle (IGCC) consisting of 40mol% CO2 and balanced H2 in the presence of tetra-n-butyl ammonium bromide (TBAB) and porous silica gel particles containing water inside. The basic idea is an extension of our previous work [34], that is, using a porous silica gel structure made it possible to get rid of stirring the content inside the hydrate reactor and ensure the rapid hydrate formation with relatively short induction. TBAB was introduced to confined aqueous solution in silica gel pore structure, having nominal pore diameter of 100nm, as a thermodynamic promoter and formed semiclathrate with the gas mixture under milder temperature and pressure conditions. Compositional analysis of semiclathrate and coexisting gas phases was also performed at various temperatures and TBAB concentrations. The highest CO2 concentration obtained from the dissociated semiclathrate was 94mol% formed at 277.15K and 3.0MPa, with 20wt% TBAB solution in 100nm silica gel. To demonstrate the highly-concentrated CO2 outlet stream from the single-stage semiclathrate reactor, the kinetic study of CO2 distribution through fixed-bed type reactor charged with silica gel particles containing aqueous TBAB solution was also investigated. Utilization of porous silica gel makes it possible to capture higher concentration of CO2 in the semiclathrate phase, but it also reduced the total amount of gas consumed for semiclathrate conversion. However, the use of silica gel particles with TBAB enabled formation of semiclathrate hydrate under milder conditions and unstirred continuous method to a high extent and a high rate.

CO2 Capture from CH4/CO2 Mixture Gas with Tetra-n-butylammonium Bromide Semi-clathrate Hydrate through a Pressure Recovery Method

In this study, CO2 capture from (67.00 mol %) CH4/CO2 mixed gas with tetra-n-butylammonium bromide (TBAB) solution at 281.3 K through a pressure recovery of hydrate separation method were studied. During the experiment, pressure was recovered by TBAB solution injected into the cell to improve the separation efficiencies of CO2, and the effects of the concentration of TBAB solution and the operating conditions was investigated. The results showed that the CH4 concentration in the gas phase could achieve 93.52 mol % with a pressure recovery method at 1.14 MPa and 0.293 mol % TBAB. Under the pressure of 1.14 MPa and 0.1 mol % TBAB, the maximum CO2 separation factor was 52.87 and the CH4 separation and recovery factor was 2.050. The results demonstrated that the pressure recovery method can significant enhance the separation efficiency of hydrate separation. It is an effective method to cut down energy consumption of hydrate-based gas separation.

Unexpected inhibition of CO2 gas hydrate formation in dilute TBAB solutions and the critical role of interfacial water structure

Gas hydrates formed under moderated conditions open up novel approaches to tackling issues related to energy supply, gas separation, and CO2 sequestration. Several additives such as tetra-n-butylammonium bromide (TBAB) have been empirically developed and used to promote gas hydrate formation. Here we report unexpected experimental results which show that TBAB inhibits CO2 gas hydrate formation when used at minuscule concentration. We also used spectroscopic techniques and molecular dynamics simulation to gain further insights and explain the experimental results. They have revealed the critical role of water alignment at the gas-water interface induced by surface adsorption of tetra-n-butylammonium cation (TBA+) which gives rise to the unexpected inhibition of dilute TBAB solution. The water perturbation by TBA+ in the bulk is attributed to the promotion effect of high TBAB concentration on gas hydrate formation. We explain our finding using the concept of activation energy of gas hydrate formation. Our results provide a step toward to mastering the control of gas hydrate formation.

Investigation of CO2 separation from synthesis CO2/CH4 mixture utilizing tetra‐n‐butyl ammonium bromide semi‐hydrate

Semi‐clathrate hydrates of tetra‐n‐butyl ammonium bromide (TBAB) offer a potential solution for separation of CO2 from biogas. In this work, gas hydrate formation from a CO2/CH4 mixture in distilled water with 0.05 g/g (5 wt%) TBAB was examined at 275, 277, and 279 K with pressures of 4000, 5000, and 6000 kPa. The compositional changes of the gas phase were analyzed continuously during the hydrate formation process. The results indicated that no significant induction occurred during hydrate formation. The CO2 separation factor increased with decreasing temperature and increasing pressure. The maximum amount of CO2 gas molar ratio in the residual gas phase was 79.81 mol% at 4000 kPa and 275 K with a gas/liquid volume ratio (Vg/Vl) of 1. TBAB promoted hydrate formation and CO2 separation; however, the CO2 separation factor decreased in a decomposed solution compared with fresh TBAB solution. The experimental results provide a theoretical basis for the use of hydrate‐based gas separation (HBGS) technology in biogas purification.

Volumetric Properties of Tetra-n-butyl ammonium bromide in Aqueous Solutions of Magnesium sulphate in the Temperature Range 298.15 to 318.15K and under the Atmospheric Pressure

ABSTRACTDensity and sound speed measurements have been carried out for the ternary systems consisting of tetra-n-butyl ammonium bromide (TBAB) in 0.1 m aqueous magnesium sulphate heptahydrate (MgSO4.7H2O)-water over the full range of composition from T = 293.15 to 318.15 K by using volumetric method. Using this experimental data, various physical and thermodynamical parameters such as adiabatic compressibility, apparent molal compressibility, apparent molal volume, apparent and limiting partial molar volumes of the electrolytes and ions in these mixtures have been evaluated and split into respective ionic contributions. The results have been discussed in terms of ion–ion and ion–solvent interactions occurring between TBAB and aqueous MgSO4 solutions. Further, structure making/breaking behaviour of MgSO4 has been reported in terms of sign of the partial molar expansibility at infinite dilution.

Study of tetra-n-butylammonium bromide and tetrahydrofuran hydrate formation kinetics as a cold storage material for air conditioning system

In order to utilize hydrate slurry for cold storage in air-conditioning system, the experimental studies on the phase behavior and formation kinetics of tetra-n-butylammonium bromide (TBAB) semiclathrate hydrate, tetrahydrofuran (THF) hydrate and TBAB–THF mixture hydrate have been carried out. By changing the concentrations of TBAB (5–55wt.%), the variations of phase change temperature, equilibrium temperature, sub-cooling driving force, nucleation rate and electrical conductivity measurements have been compared. The results have revealed that the TBAB solution with 40–45wt.% may be a promising cold storage material for air conditioning system because of higher temperature phase change of about 11.2°C and maximum amount of hydrate formed of about 99.8%. In the case of TBAB and THF mixture, which prepared at 0–5.37 mass ratios, the phase change temperature and kinetic parameters depend on the amounts of THF and TBAB into the solution. At the mass ratios higher than 1.0, the above mentioned parameters increase, so that the increase in the TBAB concentration helps to increase the phase change temperature and kinetic parameters.

Phase Transition of Tetra-n-butylammonium Bromide Hydrates Enclosing Krypton

The phase equilibrium conditions for krypton (Kr)–tetra-n-butylammonium bromide (TBAB)–water systems were determined using an isochoric method. The pressure and temperature ranges were (0.06 to 1.0) MPa and (280 to 290) K, respectively, and TBAB solutions had TBAB molar fractions, xTBAB, of 0.0062, 0.0138, 0.0234, and 0.0359. A second order transition of the TBAB hydrate was observed in all the Kr–TBAB–water systems. In the region at lower pressure than the phase transition point, the Kr–TBAB–water systems with low concentration (xTBAB = 0.0062 and 0.0138) and high concentration (xTBAB = 0.0234 and 0.0359) prefer to form TBAB·38H2O and TBAB·26H2O hydrates, respectively. However, a new TBAB hydrate was observed as a stable crystal structure in the higher pressure regions. Raman spectrum of the new TBAB hydrate shows band shapes remarkably similar to that of pure TBAB·38H2O with the crystalline space group Pmma in the frequency ranges of the lattice for C–C stretching, C–H bending, the C–H stretching bands ...

Experiment on the continuous recovery of H2 from hydrogenation plant off-gas via hydrate formation in tetra-n-butyl ammonium bromide solution

Here, an approach toward for continuous H2 recovery from hydrogenation plant off-gas based on hydrate formation in the presence of tetra-n-butyl ammonium bromide (TBAB) is proposed. Firstly, we explored the conditions to form the CH4/H2/TBAB hydrate through pressure search method in the single-stage equilibrium separation experiments toward CH4/H2 mixture. The influence of initial pressure, temperature, and initial gas–liquid volume ratio were systematically optimized in the context of 10 wt% TBAB solution. Then, we conducted the continuous separation experiments of CH4/H2 binary mixture and hydrogenation plant off-gas using a set of laboratory-scale continuous stirred reactor according to the optimized conditions, in which the effects of pressure and liquid flow rate upon continuous separation were further studied. The experimental results that the H2 concentration in the unhydrated gas (the recovered gas) is up to 89 mol% and the yield of H2 recovery is more than 58.68% indicate the efficiency to recover H2 using continuous hydrate separation, which lays the foundation for further industrial application.