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The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.

Anisole is a straw-colored aromatic compound mainly used in making solvents, flavoring agents, perfumes, fuel additives, and in the synthesis industries. Anisole, also known as methoxybenzene, is synthesized from sodium phenoxide or phenol using various methylating agents. The use of dimethyl ether (DME) as an alkylating agent is seldom reported in the literature. Herein, we have synthesized anisole through the O-alkylation process of phenol and DME to obtain zero discharge from this process. The thermodynamic equilibrium for the reaction of phenol and DME is simulated by using Aspen HYSYS (Hyprotech and Systems). The O-alkylation of phenol has been investigated using phosphotungstic acid (PTA) over γ-Al2O3 with appropriate acidity. Active metal loadings of various percentages were studied and the conversion was optimized at 46.57% with a selectivity of 88.22% at a temperature of 280 °C. The liquid products from the continuously stirred reactor were analyzed with liquid G.C. and the conversion and selectivity were calculated. A comparison of the O-alkylation and C-alkylation of phenol at different temperatures, reactant ratios, residence times, and recyclability was explored, as well as the impact of these factors on the yield of the desired anisole. The catalyst was characterized by XRD, BET, HR-TEM, FE-SEM, elemental mapping, XPS, and DRIFT studies.

This paper deals with the proposition of a kinetic model for the direct synthesis of DME via CO2 hydrogenation in view of the necessary optimization of the catalytic system, reactor design, and process strategy. Despite the fact that DME synthesis is typically treated as a mere combination of two separated catalytic steps (i.e., methanol synthesis and methanol dehydration), the model analysis is now proposed by taking into account the improvements related to the process running over a hybrid catalyst in a rational integration of the two catalytic steps, with boundary conditions properly assumed from the thermodynamics of direct DME synthesis. Specifically, the CO2 activation step at the metal–oxide interface in the presence of ZrO2 has been described for the first time through the introduction of an ad hoc mechanism based on solid assumptions from inherent studies in the literature. The kinetic modeling was investigated in a tubular fixed-bed reactor operating from 200 to 260 °C between 1 and 50 bar as a function of a gas hourly space velocity ranging from 2500 to 60,000 NL/kgcat/h, in a stoichiometric CO2/H2 feed mixture of 1:3 v/v. A well-detailed elementary mechanism was used to predict the CO2 conversion rate and identify the key reaction pathways, starting with the analysis of the implicated reactions and corresponding kinetic mechanisms and expressions, and finally estimating the main parameters based on an appropriate modeling of test conditions.

The conceptual design and engineering of an integrated catalytic reactor requires a thorough understanding of the prevailing mechanisms and phenomena to ensure a safe operation while achieving desirable efficiency and product yields. The necessity and importance of these requirements are demonstrated in this investigation in the case of novel membrane-assisted reactors tailored for CO2 hydrogenation. Firstly, a carbon molecular sieve membrane was developed for simultaneous separation of CO2 from a hot post-combustion CO2-rich stream, followed by directing it along a packed-bed of hybrid CuO-ZnO/ZSM5 catalysts to react with hydrogen and produce DiMethyl Ether (DME). The generated water is removed from the catalytic bed by permeation through the membrane which enables reaction equilibrium shift towards more CO2-conversion. Extra process intensification was achieved using a membrane-assisted reactive distillation reactor, where similarly several such parallel membranes were erected inside a catalytic bed to form a reactive-distillation column. This provides the opportunity for a synchronized separation of CO2 and water by a membrane, mixing the educts (i.e., hydrogen and CO2) and controlling the reaction along the catalytic bed while distilling the products (i.e., methanol, water and DME) through the catalyst loaded column. The hybrid catalyst and carbon molecular sieve membrane were developed using the synthesis methods and proved experimentally to be among the most efficient compared to the state-of-the-art. In this context, selective permeation of the membrane and selective catalytic conversion of hybrid catalysts under the targeted operating temperature range of 200–260 °C and 10–20 bar pressure were studied. For the membrane, the obtained high flux of selective CO2-permeation was beyond the Robeson upper bound. Moreover, in the hybrid catalytic structure, a combined methanol and DME yield of 15% was secured. Detailed results of catalyst and membrane synthesis and characterization along with catalyst test and membrane permeation tests are reported in this paper. The performance of various configurations of integrated catalytic and separation systems was studied through an experimentally supported simulation along with the systematic analysis of the conceptual design and operation of such reactive distillation. Focusing on the subnano-/micro-meter scale, the performance of sequential reactions while considering the interaction of the involved catalytic materials on the overall performance of the hybrid catalyst structure was studied. On the same scale, the mechanism of separation through membrane pores was analyzed. Moreover, looking at the micro-/milli-meter scale in the vicinity of the catalyst and membrane, the impacts of equilibrium shift and the in-situ separation of CO2 and steam were analyzed, respectively. Finally, at the macro-scale separation of components, the impacts of established temperature, pressure and concentration profiles along the reactive distillation column were analyzed. The desired characteristics of the integrated membrane reactor at different scales could be identified in this manner.

Due to the complexity of the structure–activity relationship of the CuAl2O4 spinel catalyst, optimization of the catalyst structure is a great challenge. In this paper, three different CuAl2O4 spinel catalysts were prepared by the solid-phase method using copper hydroxide, copper nitrate, and copper oxide as the copper source, respectively, to study the difference in the structure of CuAl2O4 spinel catalysts induced by the raw materials and the catalytic behavior for CO hydrogenation. The structure of CuAl2O4 spinel catalyst was characterized by XRD, BET, SEM, TEM, H2-TPR and XPS. The activity of CO hydrogenation over the CuAl2O4 spinel catalyst without pre-reduction was evaluated in the slurry reactor. The results demonstrated that different copper sources had obvious influence on the CuAl2O4 spinel texture properties, surface enrichment degree, as well as decomposition and reduction ability, which further regulated the ratio of Cu+/Cu0 and thus affected the catalytic performance, especially the alcohol distribution. The CuAl2O4 spinel, employing copper hydroxide as the copper source, showed better selectivity of C2+OH, which was assigned to a higher ratio of Cu+/Cu0, along with larger pore size and pore volume. Moreover, the synergistic effect between Cu0 and γ-Al2O3 improved the selectivity of dimethyl ether.

One of the methods of industrial dimethyl ether production is the catalytic dehydration of methanol. In this research work, methanol dehydration reactor has been modeled using continuous model and its results have been compared with experimental works and Voronoi pore network model. A 1D heterogeneous dispersed plug flow model was utilized to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether. The mass and heat transfer equations are numerically solved for the reactor. The concentration of the reactant and products and also the temperature varies along the reactor, therefore the effectiveness factor would also change in the reactor. We used the the effectiveness factor that was simulated according to the diffusion and reaction in the catalyst pellet as a Voronoi pore network model. Sensitivity analysis was performed to determine the influence of T, P and weight hourly space velocity on performance of the chemical reactor. Acceptable agreement was reached between the measured and the model data. The results showed that the maximum reaction conversion was obtained about 90 % at WHSV = 10 h−1 and T = 560 K, while the inlet temperature (Tinlet) had a greater effect on methanol conversion. In addition, the effect of water in the feed on methanol conversion was quantitatively studied. Also, the deactivation kinetics of γ-Al2O3 heterogeneous-acidic catalyst in methanol to dimethyl ether dehydration process was studied using integral analysis method. Based on independent deactivation kinetics, a second order was found that accurately fitted the experimental conversion time data. The main reaction activation energies and catalyst deactivation energies were 143.1 and −102.1 kJ/mol, respectively.

This work presents results on CO2 hydrogenation to dimethyl ether (DME) over bifunctional catalysts consisting of In2O3, supported on natural clay halloysite nanotubes (HNT), and HNT modified with Al-MCM-41 silica arrays. The catalysts were characterized by TEM, STEM, EDX-mapping, NH3-TPD, XRD, low-temperature nitrogen adsorption, TPO, and H2-TPR techniques. Catalytic properties of In2O3/HNT and In2O3/Al-MCM-41/HNT in the CO2 hydrogenation to DME were investigated in a fixed-bed continuous flow stainless steel reactor at 10–40 atm, in the temperature range of 200–300°C, at GHSV = 12,000 h−1 and molar ratio of H2:CO2 = 3:1. The best catalyst for CO2 hydrogenation was In2O3/Al-MCM-41/HNT that provided DME production rate 0.15 gDME·(gcat·h)−1 with DME selectivity 53% and at 40 bar, GHSV = 12,000 h−1, and T = 250°C. It was shown that In2O3/Al-MCM-41/HNT exhibited stable operation for at least 40 h on stream.

The influence of hafnium metal (Hf) and sulfate ions (SO42−) on the acidic properties of SiO2 mesopores synthesized by a non-hydrothermal method was studied using the following characterization techniques; TG-DTG, XRD, BET, SEM, TEM, EDS, FTIR, n-butylamine titration, FTIR-pyridine, and alcohol dehydration. The incorporation of 3.6% mol of Hf during the silicate synthesis step caused the characteristic structural arrangement of MCM-41 to collapse. However, an increase in the acid strength of the catalyst of up to 315 mV was observed, with Brönsted and Lewis-type acid sites being mostly present therein. Furthermore, the acidity of Hf- and (SO42−) -modified SiO2 in the dehydration of ethanol and methanol was evaluated, resulting in a selectivity towards ethylene and dimethyl ether, respectively. Acid solids have enormous potential to produce important compounds for the chemical industry using alternative routes other than petrochemical processes. They also represent a significant advance for biorefineries.

Various ferrierite zeolites were investigated as catalysts for the dimethyl ether (DME)-to-olefin (DTO) reactions to efficiently synthesize n-butene, such as 1-butene, trans-2-butene, and cis-2-butene except for iso-butene using a fixed-bed flow reactor. Twenty P-loaded ferrierite zeolites with different structural parameters and acidic properties were prepared by the impregnation method by varying the P content and the temperature of air calcination as a pretreatment. The zeolites were characterized by X-ray diffraction (XRD), N2 adsorption-desorption, and NH3 temperature-programmed desorption (NH3-TPD). Micropore surface area, external surface area, total pore volume, micropore volume, and weak and strong acid sites affected the DTO reaction behavior. A high n-butene yield (31.2 C-mol%) was observed, which is higher than the previously reported maximum yield (27.6 C-mol%). Multiple regression analysis showed that micropore surface area and strong acid sites had a high correlation with n-butene yield. Based on our findings, we explained the reaction mechanism for selective n-butene synthesis except for iso-butene in the DTO reaction by the dual cycle model.

The carbonylation of dimethyl ether (DME) to produce methyl acetate (MA) has a promising prospect in industry. Mordenite (MOR) has been widely studied due to its excellent catalytic activity and high MA selectivity; however, its microporous characteristic limits the intracrystalline diffusion that influences the activity and stability. Therefore, it becomes essential to clarify the relationship between catalytic activity and diffusion. In this study, a series of MOR samples with similar Si/Al contents and aspect ratios, but different sizes, were successfully synthesized by adjusting the synthesis parameters (Si/Al contents in gel, aging time, the amount of water, and alkalinity). Based on quantitative analysis of acid properties and catalyst evaluation, both the apparent turnover frequency of MA (TOFMA) and the stability decrease with the increase in particle size. Diffusion parameter measurements and kinetic analysis via zero length column methods show that the intracrystalline diffusion restriction becomes more serious with increasing particle size. The larger the MOR crystals with enhanced mass transfer limitation that undergo lower activity, the higher the selectivity of byproducts, as well as the faster their deactivation.

A series of catalysts based on hybrid intergrowth structure zeolites MFI-MEL, MFI-MTW, and MFI-MCM-41 are studied in the reaction of olefins synthesis from dimethyl ether at atmospheric pressure and a temperature of 340 °C. The total acidity of hybrid zeolite-based catalysts is shown to correlate with their activity. However, the use of zeolite with the structure MFI-MCM-41, which is characterized by a high content of medium acid sites, additionally catalyzes the methanol dehydration reaction, resulting in a decrease in the observed DME conversion. The obtained product distributions are brought into correlation with the texture of catalysts. It is shown that the use of hybrid zeolites does not change the mechanism of reaction, but the structural features of zeolites influence the priority of the competing MTO reactions: high ethylene yield is observed for catalysts with high micropore volume. The topology of the hybrid zeolite has been shown to influence the hydrogen transfer reaction rate, but not to change the isomerizing activity of the catalyst.

In this work, we propose two bifunctional nanocomposite catalysts based on acidic mesostructured γ-Al2O3 and a Cu/ZnO/ZrO2 redox phase. γ-Al2O3 was synthesized by an Evaporation-Induced Self-Assembly (EISA) method using two different templating agents (block copolymers Pluronic P123 and F127) and subsequently functionalized with the redox phase using an impregnation method modified with a self-combustion reaction. These nanocomposite catalysts and their corresponding mesostructured supports were characterized in terms of structural, textural, and morphological features as well as their acidic properties. The bifunctional catalysts were tested for the CO2-to-DME process, and their performances were compared with a physical mixture consisting of the most promising support as a dehydration catalyst together with the most common Cu-based commercial redox catalyst (CZA). The results highlight that the most appropriate Pluronic for the synthesis of γ-Al2O3 is P123; the use of this templating agent allows us to obtain a mesostructure with a smaller pore size and a higher number of acid sites. Furthermore, the corresponding composite catalyst shows a better dispersion of the redox phase and, consequently, a higher CO2 conversion. However, the incorporation of the redox phase into the porous structure of the acidic support (chemical mixing), favoring an intimate contact between the two phases, has detrimental effects on the dehydration performances due to the coverage of the acid sites with the redox nanophase. On the other hand, the strategy involving the physical mixing of the two phases, distinctly preserving the two catalytic functions, assures better performances.

Directly synthesising dimethyl ether (DME) from CO2 hydrogenation is a promising technique for efficiently utilising CO2 as a feedstock to produce clean fuel. The main challenges in this process are the low CO2 conversion and DME selectivity of the catalyst and its deactivation over time due to sintering, aggregation, coke formation, and water adsorption. This study aimed to develop a dual-functional, halloysite nanotube-supported CuZnO-PTA catalyst with a core-shell structure and investigate the effects of the active site mass ratio CuZnO/PTA on CO2 conversion and DME selectivity. A dual-functional core-shell mesopores halloysite nanotube (HNT) catalyst was developed, and both active sites were co-hosted on one support. The co-impregnation method was used to synthesise CuZnO and 12-phosphotungstic acids (PTA) that were then supported by a mesoporous core-shell (HNT). BET surface area, N2 physisorption, FE-SEM, SEM, XRD, H2-TPR, and NH3-TPD of the core-shell catalyst characterised physio-chemical properties of the prepared hybrid catalyst. The experimental results showed that the synthesised CuZn-PTA@HNT core-shell bifunctional catalyst was promising; the CO2 conversion was almost the same for all four catalysts, with an average of 22.17%, while the DME selectivity reached 68.9%. Furthermore, the effect of both active sites on the hybrid catalyst was studied, and the metal Cu wt% mass ratio loading was not significant. In contrast, the PTA acid sites positively affected DME selectivity; they also showed an excellent tolerance towards the water generated in the methanol dehydration reaction. In addition, the effect of the temperature and reusability of the CZ-PTA@HNT catalyst has also been investigated, and the results show that increasing the temperature improves CO2 conversion but decreases DME selectivity. A temperature of less than 305 °C is a good compromise between CO2 conversion and DME selectivity, and the catalyst also showed good stability and continuous activity/stability over five consecutive cycles. In conclusion, this study presents a novel approach of using a core-shell halloysite nanotube-supported CuZnO-PTA catalyst to directly synthesise dimethyl ether (DME) from CO2 hydrogenation which exhibits promising results in terms of CO2 conversion and DME selectivity.

Dimethyl ether as a clean fuel has been attracted in the recent decade. It can be produced in the catalytic reaction of methanol dehydration. Modeling and simulation of the fixed-bed reactor for this process is desired to predict the reactor performance. A Voronoi 3-dimensional pore network model for the reactor is used to study the effect of pore space on the reactor performance. Considering the morphological structure of the pore space is one of the advantages of this model. In this study, pore network modeling was used to consider mass and heat transfer both in the reactor and catalyst scales. The effectiveness factor results for the catalyst scale are used for the reactor simulations and the effect of methanol temperature and concentration on reactor performance is studied. The results indicated that the reduction of flow rate increases reactants residence time in the reactor and consequently increases the amount of conversion. The inlet methanol concentration had a significant influence on the conversion and the methanol concentration in the middle of the reactor increased from 22 to 34 mol/m3 when its purity decreased from 99 to 97%.

The steam reforming of dimethyl ether (SRD) has been proved to be one of the most promising routes for on-site H2 production. However, the two-step consecutive nature of the SRD reaction makes the design of an efficient bifunctional catalyst a challenge. Herein, a series of Cu incorporated into amorphous silica–alumina (Cu–ASA) as integrated bifunctional catalysts for SRD were synthesized by the single-step complex decomposition method, and ammonium carbonate was confirmed to be an effective complex agent for dispersing Cu in ASA. The results indicated that the initial conversion of dimethyl ether and a H2 yield higher than 90% were achieved at 300 °C over the optimal catalyst. More importantly, a slightly decreased SRD performance with increasing time-on-stream was mainly caused by Cu sintering, and the synergetic effect between ASA and Cu played a crucial role in determining the activity, hydrogen yield, and stability of the integrated Cu–ASA bifunctional catalyst for SRD. These findings are helpful to develop a high-performance integrated bifunctional catalyst for the SRD reaction.

The CO2 hydrogenation to dimethyl ether (DME) is a potentially promising process for efficiently utilizing CO2 as a renewable and cheap carbon resource. Currently, the one-step heterogeneous catalytic conversion of CO2 to value-added chemicals exhibits higher efficiency than photocatalytic or electrocatalytic routes. However, typical catalysts for the one-step CO2 hydrogenation to DME still suffer from the deficient space–time yield and stability in industrial demonstrations/applications. In this perspective, the recent development of the one-step CO2 hydrogenation to DME is focused on different catalytic systems by examining the reported experimental results and the reaction mechanism including the catalytic nature of active sites, activation modes and of CO2 molecules under relevant conditions; surface intermediates are comparatively analyzed and discussed. In addition to the more traditional Cu-based, Pd-based, and oxide-derived bifunctional catalysts, a further emphasis is given to the characteristics of the recently emerged In2O3-based bifunctional catalysts for the one-step conversion of CO2 to DME. Moreover, GaN itself, as a bifunctional catalyst, shows over 90% DME selectivity and a reasonably high activity for one-step CO2 hydrogenation, and the direct hydrogenation of CO2 via the unique non-methanol intermediate mechanism is highlighted as an important illustration for exploring new catalytic systems. With these analyses and current understandings, the research directions in the aspects of catalysis and DME economy are suggested for the further development of one-step DME synthesis from CO2 hydrogenation.

Core-shell-type catalysts, which are synthesized by encapsulating the Cu-ZnO-Alumina type methanol synthesis catalyst (CZA) by silicotungstic acid (STA)-incorporated mesoporous alumina, were prepared following a hydrothermal route and tested in DME synthesis from syngas and CO2. Activity tests, which were performed in the pressure range of 30–50 bar, and the temperature range of 200–300 °C, with different feed compositions (CO2/CO/H2: 50/-/50, 40/10/50, 25/25/50, 10/40/50) showed that the best-operating conditions for the highest DME yield were 275 °C and 50 bar. Results proved that the presence of CO2 in the syngas had a positive effect on the DME yield. The total conversion of CO + CO2 increased with an increase in CO2/CO ratio. An overall conversion of CO + CO2 and DME selectivity values were obtained as 65.6% and 73.2%, respectively, with a feed composition of H2/CO2/CO = 50/40/10. Synthesis of methanol using the CZA catalyst from the CO2-containing gas mixtures was also investigated, and the total conversion of CO + CO2 and methanol selectivity values of 32.0% and 83.6%, respectively, were obtained with the H2/CO2/CO = 50/40/10 gas mixture. Results proved that the new STA incorporated core-shell-type bifunctional catalysts were highly promising for the conversion of CO2-containing syngas to DME.

The effect of crystal size of HMOR from micro size to 50 nm, with the apparent similar acid site density, on catalytic performance for the dimethyl ether (DME) carbonylation was investigated. The crystal size of HMOR is sensitive to the deactivation rate of DME carbonylation reaction, and the higher stability around 200 nm can be achieved. The characterization studies reveal that the diffusions of MA product play a key role during the induction and deactivation period in DME carbonylation. These will be helpful for guiding the large-scale synthesis of mordenite zeolites catalysts with high efficiencies for DME carbonylation.

The authors studied the direct conversion of syngas to light paraffins in a dual-bed fixed-bed reactor. A dual-bed catalyst composed of three catalysts, a physically mixed methanol synthesis catalyst (CZA), and a methanol dehydration to dimethyl ether (DME) catalyst (Al2O3(C)) were put in the upper bed for direct conversion of syngas to DME, while the SAPO-34 (SP34-C) zeolite was put in the lower bed for methanol and DME conversion. The effects of the mass ratio of CZA to Al2O3(C), the H2/CO molar ratio, and the space velocity on catalytic performance of syngas to DME were studied in the upper bed. Moreover, a feed gas with a CO/CO2/DME/N2/H2 molar ratio of 9/6/4/5 balanced with H2 was simulated and studied in the lower bed over SP34-C; after optimizing the reaction conditions, the selectivity of light paraffins reached 90.8%, and the selectivity of propane was as high as 76.7%. For the direct conversion of syngas to light paraffins in a dual bed, 88.9% light paraffins selectivity in hydrocarbons was obtained at a CO conversion of 33.4%. This dual-bed strategy offers a potential route for the direct conversion of syngas to valuable chemicals.

The depletion of fossil energy sources and the legislation regarding emission control demand the use of alternative fuels and rapid progression of aftertreatment technologies. The study of dimethyl ether (DME) catalytic oxidation is important in this respect, as DME is a promising clean fuel and at the same time a VOC pollutant present in the tail gases of industrial processes. In the present work, copper ferrite catalysts synthesized via the citrate complexation method have been evaluated in DME oxidation. N2-physisorption, XRD, H2-TPR, and XPS were employed for the characterization of the mixed oxide catalysts. The copper ferrite spinel phase was detected in all samples accompanied by a gradual decrease in the bulk CuO phase upon increase in iron content, with the latter never vanishing completely. The Fe0.67Cu0.33 catalyst exhibited the highest catalytic activity in DME oxidation, attaining approximately a 4-fold higher oxidation rate compared to the respective pure copper and iron oxides. The enhanced catalytic performance was attributed to the higher specific surface area of the catalyst and its enhanced redox properties. Highly dispersed copper species were developed owing to the formation of the spinel phase. DME-TPD/TPSR experiments showed that the surface lattice oxygen of the Fe0.67Cu0.33 catalyst can oxidize preadsorbed DME at a lower temperature than all other catalysts which is in agreement with the H2-TPR findings.

The synthesis of olefins from dimethyl ether (DME) on a hydrothermally treated Mg-HZSM-5/Al2O3 catalyst in artificial synthesis gas atmospheres was studied. The study was carried out on a micropilot unit in a flow mode at 0.1 MPa and 320 °C. The use of synthesis gas with different hydrogen concentration as a diluent did not decrease selectivity for the formation of C2–C4 olefins. The formation of alkanes occurred only in H-transfer reactions without the participation of molecular hydrogen.

FER-type zeolite was recently recognized as good catalyst for DME synthesis via methanol dehydration or one-pot CO2 hydrogenation, in terms of DME selectivity, stability and coke formation. In this research, we investigated the role of crystal size of both FER- and MFI-type zeolites on catalysis of methanol dehydration to DME reaction. The results show that FER-type zeolites, both micro- and nano-sized, exhibit better performances than micro-sized MFI-type zeolite. On the contrary, the application of nano-sized MFI allows to obtain a DME selectivity similar to FER, but with higher DME production rate and a lower coke deposition.

This paper presents comparative data on the selectivity and gasoline fraction composition for commercial catalysts based on Zn- and Pd-modified zeolites with the same MFI structural type, but produced by different manufacturers. The data are obtained in the operation of a two-reactor micropilot unit in a flow circulation mode. The relationship and differences between the character and type of Brønsted acid site were investigated using in situ high-temperature diffuse reflectance IR spectroscopy during annealing of the catalysts in dry argon, hydrogen, and dimethyl ether flows. It was found that catalysts contain organic ammonium cations with different structures of organic substituents, which decompose to give a very strong nitrogen-containing acid site. This site can promote the formation of branched paraffins and light aromatics from dimethyl ether. Under the action of these sites, methanol can be rapidly converted to DME, which is more reactive towards the production of gasoline fraction.

Dimethyl ether (DME) is considered an alternative hydrogen carrier with potential use in fuel cells and automotive and domestic applications. Dimethyl ether hydrolysis to methanol is a thermodynamically limited reaction catalyzed by solid-acid catalysts, mainly Al2O3 and zeolites. Moreover, it is the rate-limiting step of the DME steam reforming reaction, which is employed for the production of hydrogen fuel for fuel cell feeding. In the present study, the performance of WO3/Al2O3 catalysts (0–44% wt. WO3) was tested in DME hydrolysis reaction. The catalysts were characterized by means of N2-physisorption, XRD, Raman spectroscopy, XPS, NH3-TPD and 2,6-di-tert-butylpyridine adsorption experiments. The reaction rate of DME hydrolysis exhibited a volcanic trend as a function of tungsten surface density, while the best-performing catalyst was 37WO3/Al2O3, with a tungsten surface density of 7.4 W/nm2, noting that the theoretical monolayer coverage for the specific system is 4–5 W/nm2. Brønsted acidity was directly associated with the catalytic activity, following the same volcanic trend as a function of tungsten surface density. Blocking of Brønsted acid sites with 2,6-di-tert-butylpyridine led to a dramatic decrease in hydrolysis rates by 40 times, proving that Brønsted acid sites are primarily responsible for the catalytic activity. Thus, the type and strength rather than the concentration of acid sites are the key factors influencing the catalytic activity.

Hybrid kinetic models represent a promising alternative to describe and evaluate the effect of multiple variables in the performance of complex chemical processes, since they combine system knowledge and extrapolability of the (semi-)mechanistic models in a wide range of reaction conditions with the adaptability and fast convergence of data-based approaches (e.g., artificial neural networks—ANNs). For the first time, a hybrid kinetic model for the direct DME synthesis was developed consisting of a reactor model, i.e., balance equations, and an ANN for the reaction kinetics. The accuracy, computational time, interpolation and extrapolation ability of the new hybrid model were compared to those of a lumped and a data-based model with the same validity range, using both simulations and experiments. The convergence of parameter estimation and simulations with the hybrid model is much faster than with the lumped model, and the predictions show a greater degree of accuracy within the models’ validity range. A satisfactory dimension and range extrapolation was reached when the extrapolated variable was included in the knowledge module of the model. This feature is particularly dependent on the network architecture and phenomena covered by the underlying model, and less on the experimental conditions evaluated during model development.

Sector coupling remains a crucial measure to achieve climate change mitigation targets. Hydrogen and Power-to-X (PtX) products are recognized as major levers to allow the boosting of renewable energy capacities and the consequent use of green electrons in different sectors. In this work, the challenges presented by the PtX processes are addressed and different process intensification (PI) strategies and their potential to overcome these challenges are reviewed for ammonia (NH3), dimethyl ether (DME) and oxymethylene dimethyl ethers (OME) as three exemplary, major PtX products. PI approaches in this context offer on the one hand the maximum utilization of valuable renewable feedstock and on the other hand simpler production processes. For the three discussed processes a compelling strategy for efficient and ultimately maintenance-free chemical synthesis is presented by integrating unit operations to overcome thermodynamic limitations, and in best cases eliminate the recycle loops. The proposed intensification processes offer a significant reduction of energy consumption and provide an interesting perspective for the future development of PtX technologies.

Dimethyl ether (DME), derived from methanol, has been issued as an alternative to diesel and LPG. This study will continue the research of an optimized process control design for DME purification plants, specifically the methanol purification process. This way, water can be separated, and the main product, methanol, can be recycled for DME synthesis. A setpoint-based linear model of a methanol–water purification system has been developed with four controlled variables (CV) with objectives to; maintain a separated liquid water stream in the bottom stage (Stage 30) of the distillation column for methanol–water separation at 11.22%, keep the purified liquid methanol at a condenser at 58.81 °C and 49.96% of level, and the last CV is the cooler in the distillate stream, to keep the purified methanol’s top product at 40.75 °C. To complete the model, a first order plus dead time (FOPDT) disturbance model is created against the inlet temperature and flow rate of the feed, the major cause of disturbances in the industry. Using a traditional proportional integral controller connected to each controlled variable, a multi-loop control system is formed with optimization and compared to the disturbance rejection of multivariable model predictive control (MMPC). The final improvement against the feed temperature and flow for CV1, CV2, CV3, and CV4 is shown by, respectively, Integral Absolute Error (IAE) values of 79.49%, 99.90%, 100%, and 99.99% and Integral Square Error (ISE) values of 97.1%, 100%, 99.99%, and 100%.

Hydrogenation of CO2 relative to valuable chemical compounds such as methanol or dimethyl ether (DME) is an attractive route for reducing CO2 emissions in the atmosphere. In the present work, the hydrogenation of CO2 into DME over CuO-In2O3, supported on halloysite nanotubes (HNT) was investigated in the temperature range 200–300 °C at 40 atm. HNT appears to be novel promising support for bifunctional catalysts due to its thermal stability and the presence of acidic sites on its surface. CuO-In2O3/HNT catalysts demonstrate higher CO2 conversion and DME selectivity compared to non-indium CuO/HNT catalysts. The catalysts were investigated by N2 adsorption, X-ray diffraction, hydrogen-temperature programmed reduction and transition electron microscopy. The acid sites were analyzed by temperature programmed desorption of ammonia. It was shown that CuO/HNT was unstable under reaction conditions in contrast to CuO-In2O3/HNT. The best CuO-In2O3/HNT catalyst provided CO2 conversion of 7.6% with 65% DME selectivity under P = 40 atm, T = 250 °C, gas hour space velocity 12,000 h−1 and H2:CO2 = 3:1.

Zeolite catalysts that could allow the efficient synthesis of n-butene, such as 1-butene, trans-2-butene, and cis-2-butene, in the dimethyl ether (DME)-to-olefin (DTO) reaction were investigated using a fixed-bed flow reactor. The zeolites were characterized by N2 adsorption and desorption, X-ray diffraction (XRD), thermogravimetry (TG), and NH3 temperature-programmed desorption (NH3-TPD). A screening of ten available zeolites indicated that the ferrierite zeolite with NH4+ as the cation showed the highest n-butene yield. The effect of the temperature of calcination as a pretreatment method on the catalytic performance was studied using three zeolites with suitable topologies. The calcination temperature significantly affected DME conversion and n-butene yield. The ferrierite zeolite showed the highest n-butene yield at a calcination temperature of 773 K. Multiple regression analysis was performed to determine the correlation between the six values obtained using N2 adsorption/desorption and NH3-TPD analyses, and the n-butene yield. The contribution rate of the strong acid site alone as an explanatory variable was 69.9%; however, the addition of micropore volume was statistically appropriate, leading to an increase in the contribution rate to 76.1%. Insights into the mechanism of n-butene synthesis in the DTO reaction were obtained using these parameters.

Cu-mordenite (Cu-MOR) catalysts with different copper loadings were prepared, characterized and examined in continuous, gas-flow synthesis of methyl acetate (MA) by dimethyl ether (DME) carbonylation. Improved activity and selectivity were observed for Cu-MOR catalysts with up to 1 wt% Cu and X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR) spectroscopy and temperature-programmed reduction with hydrogen (H2-TPR) were used to elucidate the state of copper in the catalysts. Moreover, mesoporous MOR catalysts (RHMs) were prepared by mild stepwise recrystallization with X-ray powder diffraction (XRPD) and ammonia temperature-programmed desorption (NH3-TPD) demonstrating the retained MOR structure and the acid property of the catalysts, respectively. The RHM catalysts showed improved lifetime compared to pristine MOR giving a yield up to 78% MA with 93% selectivity after 5 h on stream (GHSV = 6711 h−1). Under identical reaction conditions, 1 wt% Cu-RHM catalysts had an even higher catalytic activity and durability resulting in a MA yield of 90% with 97% selectivity for 7–8 h of operation as well as a lower coke formation.

Dimethyl ether (DME) is a versatile raw material and an interesting alternative fuel that can be produced by the catalytic direct hydrogenation of CO2. Recently, this process has attracted the attention of the industry due to the environmental benefits of CO2 elimination from the atmosphere and its lower operating costs with respect to the classical, two-step synthesis of DME from syngas (CO + H2). However, due to kinetics and thermodynamic limits, the direct use of CO2 as raw material for DME production requires the development of more effective catalysts. In this context, the objective of this review is to present the latest progress achieved in the synthesis of bifunctional/hybrid catalytic systems for the CO2-to-DME process. For catalyst design, this process is challenging because it should combine metal and acid functionalities in the same catalyst, in a correct ratio and with controlled interaction. The metal catalyst is needed for the activation and transformation of the stable CO2 molecules into methanol, whereas the acid catalyst is needed to dehydrate the methanol into DME. Recent developments in the catalyst design have been discussed and analyzed in this review, presenting the different strategies employed for the preparation of novel bifunctional catalysts (physical/mechanical mixing) and hybrid catalysts (co-precipitation, impregnation, etc.) with improved efficiency toward DME formation. Finally, an outline of future prospects for the research and development of efficient bi-functional/hybrid catalytic systems will be presented.

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Mordenite (H-MOR) catalysts were synthesized by a hydrothermal method, and silver-modified mordenite (Ag-MOR) catalysts were prepared by ion exchange with AgNO3 at different concentrations. The performance of these catalysts in the carbonylation of dimethyl ether (DME) to methyl acetate (MA) was also evaluated. The catalysts were characterized by Ar adsorption/desorption, XRD, ICP-AES, SEM, HRTEM, 27Al NMR, H2-TPR, NH3-TPD, Py-IR, and CO-TPD. According to the characterization results, Ag ion exchange sites were mainly located in the 8-membered ring (8-MR) channels of Ag-MOR; evenly dispersed Ag2O particles were also present. The acid site distribution was changed by the modification of Ag, and the amount of Brønsted acid sites increased in 8-MR and decreased in 12-MR. The CO adsorption performance of the catalyst significantly increased with the modification of Ag. These changes improved the conversion and selectivity of the carbonylation of DME. Over 4Ag-MOR in particular, DME conversion and MA selectivity reached 94% and 100%, respectively.

The climate situation that the planet is experiencing, mainly due to the emission of greenhouse gases, poses great challenges to mitigate it. Since CO2 is the most abundant greenhouse gas, it is essential to reduce its emissions or, failing that, to use it to obtain chemicals of industrial interest. In recent years, much research have focused on the use of CO2 to obtain methanol, which is a raw material for the synthesis of several important chemicals, and dimethyl ether, which is advertised as the cleanest and highest efficiency diesel substitute fuel. Given that the bibliography on these catalytic reactions is already beginning to be extensive, and due to the great variety of catalysts studied by the different research groups, this review aims to expose the most important catalytic characteristics to take into account in the design of silica-based catalysts for the conversion of carbon dioxide to methanol and dimethyl ether.

Combustion characteristics and harmful emissions with emphasized soot emission in the new concept of a biogas-dimethyl ether (DME) hybrid dual-fuel engine were analyzed. The effects of DME content, biogas compositions and diesel injection were examined. At any biogas composition, a rise in DME content in the fuel mixture leads to an increase in indicative engine cycle work (Wi) and NOx but a decrease in CO and soot volume fraction (fv). The effects of DME on Wi and soot volume fraction are more significant for poor biogas than for rich biogas, contrary to its effect tendency on CO and NOx concentrations. With a given operating condition and DME content, the biogas compositions slightly affect the performance and emission of a biogas-DME hybrid dual-fuel engine. At a fixed global equivalence ratio, the reduction of diesel injection leads to an increase in Wi and NOx concentration but a decrease in CO and soot volume fraction. The lower the diesel injection is, the more significant the effects of DME content on the combustion properties and pollutant emissions are. At a given operating condition and the same global equivalence ratio, the biogas-DME PCCI combustion mode is more advantageous than biogas-DME dual-fuel combustion mode. The substitution of diesel pilot ignition by DME pilot ignition in a biogas-DME hybrid dual engine is the optimal solution for both performance improvement and pollution emissions reduction.