Effect of Ni loadings on the activity and coke formation of MgO-modified Ni/Al_2O_3 nanocatalyst in dry reforming of methane

MgO-modified Ni/Al2O3 catalysts with different Ni loadings were prepared and employed in dry reforming of methane （DRM）. The effect of Ni loadings on the activity and coke formation of Ni/MgO-A1203 catalysts were investigated. The synthesized catalysts were characterized by XRD, N2 adsorption-desorption, SEM, TPO and TPR techniques. The obtained results showed that increasing nickel loading decreased the BET surface area and increased the catalytic activity and amount of deposited carbon. In addition, the effect of gas hourly space velocity （GHSV） and feed ratio were studied.

Intrinsic properties of active sites for hydrogen production from alcohols without coke formation

The detailed reaction pathway and coke formation mechanism over Pt/metal oxide nanoparticles during the steam reforming of ethanol （SRE） at 300℃ were studied. The catalysts were prepared by incipient wetness impregnation method and were characterized with CO pulse chemisorption, BET surface measurement, oxygen adsorption, ethanol-TPD, NH3-TPD, and TPO. The SRE activity of the catalysts with steam/ethanol molar ratio of 3/1 was tested using a continuous fixed-bed reactor. Strong interaction between Pt and supports causes lower H2 production temperatures and no C2H4 formation, while weak interaction leads to C2H4 formation and strong bonded CO on Pt particles during ethanol- TPD. H2 production over Pt-based catalysts is mainly resulted from the decomposition and dehydrogenation of ethanol, and decarbonylation of acetaldehyde. Meanwhile, coke can be formed from acetaldehyde, acetone, C2H4 and CO. However, when the interaction between Pt and supports is weak, more coke is formed especially from acetone, C2H4 and CO. When the interaction is strong, no coke formation is observed due to high oxygen storage capacity of the catalyst.

Utilizing bimetallic catalysts to mitigate coke formation in dry reforming of methane

Dry reforming of methane(DRM) involves the conversion of carbon dioxide(CO_(2)) and methane(CH_(4)) into syngas(a mixture of hydrogen, H_(2), and carbon monoxide, CO), which can then be used to produce a wide range of products by means of Fischer–Tropsch synthesis. DRM has gained much attention as a means of mitigating damage from anthropogenic greenhouse gas(GHGs) emissions to the environment and instead utilizing these gases as precursors for value-added chemicals or to synthesize sustainable fuels and chemicals. Carbon deposition or coke formation, a primary cause of catalyst deactivation, has proven to be a major challenge in the development of DRM catalysts. The use of nickel-and cobalt-based catalysts has been extensively explored for DRM for their high activity and low cost but suffer from poor stability due to coke formation that has hindered their commercialization. Numerous articles have reviewed the various aspects of catalyst deactivation and strategies for mitigation, but few has focused on the benefit of bimetallic catalysts for mitigating coke formation. Bimetallic catalysts, often improve the catalytic stability over their monometallic counterparts due to synergistic effects resulting from two metal-tometal interactions. This review will cover DRM literature for various bimetallic catalyst systems, including the effect of supports and promoters, on the mitigation of carbonaceous deactivation.

Influence of catalyst support structure on ethene/decene metathesis and coke formation over WO_3/SiO_2 catalyst

8wt%WO3/SiO2 metathesis （disproportionation） catalysts with different pore structures were prepared by the incipient-wetness-impregnation method. The as-synthesized catalysts were characterized by N2 adsorpfion-desorption, scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-visible diffuse reflectance spectroscopy （DRS） and scanning transmission electron microscopy-high-angle annular dark field （STEM HAADF）. The results of STEM HAADF showed that WO3 species were not uniformly distributed on the SiO2 support. The experimental results of 8wt%WO3/SiO2 performance in ethene/decene metathesis revealed that the catalytic effect of 8wt%WO3/SiO2 catalyst and coke formation over it were closely related to the support pore structure： The 8wt%WO3/SiO2 catalyst with a more complicated pore structure showed better catalytic performance but the coke deposition rate was also faster.

Improvement strategies for Ni-based alcohol steam reforming catalysts

Steam reforming(SR)of fossil methane is already a well-known,documented and established expertise in the industrial sector as it accounts for the vast majority of global hydrogen production.From a sustainable development perspective,hydrogen production by SR of biomass-derived feedstock represents a promising alternative that could help to lower the carbon footprint of the traditional process.In this regard,bio-alcohols such as methanol,ethanol or glycerol are among the attractive candidates that could serve as green hydrogen carriers as they decompose at relatively low temperatures in the presence of water compared to methane,allowing for improved H_(2)yields.However,significant challenges remain regarding the activity and stability of nickel-based catalysts,which are most widely used in alcohol SR processes due to their affordability and ability to break C–C,O–H and C–H bonds,yet are prone to rapid deactivation primarily caused by coke deposition and metal particle sintering.In this state-of-the-art review,a portfolio of strategies to improve the performance of Ni-based catalysts used in alcohol SR processes is unfolded with the intent of pinpointing the critical issues in catalyst development.Close examination of the literature reveals that the efforts tackling these recurring issues can be directed at the active metal,either by tuning Ni dispersion and Ni-support interactions or by targeting synergistic effects in bimetallic systems,while others focus on the support,either by modifying acid-base character,oxygen mobility,or by embedding Ni in specific crystallographic structures.This review provides a very useful tool to orient future work in catalyst development.

Comparison of the activities of binder-added and binder-free Mo/HZSM-5 catalysts in methane dehydroaromatization at 1073 K in periodic CH_4-H_2 switch operation mode

Three industry-supplied, well-shaped Mo/HZSM-5 catalysts, two binder-added and one binder-free, were tested for the first time in methane dehydroaromatization to benzene at 1073 K and 10000 mL/（g·h） in periodic CH4-H2 switch operation mode, and their catalytic performances were compared with those of three self-prepared, binder-free powder Mo/HZSM-5 catalysts. XRD, 27Al NMR, SEM, BET and NH3-TPD characterizations of all the catalysts show that the zeolites in the two binder-added catalysts are comparable to those in the three binder-free powder catalysts in crystallinity, crystal size, micropore volume and Br{／o}nsted acidity. The test results, on the other hand, show that the catalytic performances of the two binder-added catalysts are worse than those of the four binder-free catalysts on both catalyst mass and zeolite mass bases. Then, TPO and BET measurements of all spent samples were conducted to get a deep insight into the negative effects of binder addition, and the results suggest that the binder additives functioned mainly to enhance the polyaromatization of formed aromatics to coke on their external surfaces and consequently lower the catalysts＇ benzene formation activity and selectivity.

The effect of FER zeolite acid sites in methanol-to-dimethyl-ether catalytic dehydration

In this paper, the effect of acidity of zeolites with FER framework was studied in the methanol dehydration to dimethyl ether reaction, by comparing catalysts with different Si/Al ratios(namely 8, 30 and60). The aim of this work was to investigate how the acid sites concentration, strength, distribution and typology(Br?nsted and Lewis) affect methanol conversion, DME selectivity and coke formation. It was found that the aluminium content affects slightly acid sites strength whilst a relevant effect on acid sites concentration and distribution(Br?nsted/Lewis) was observed as 24% of Lewis sites were found on Alrichest samples, whilst less than 10% of Lewis acid sites were observed on FER at higher Si/Al ratio. All the investigated catalyst samples showed a selectivity toward DME always greater than 0.9 and samples with the lowest Si/Al ratio exhibit the best performances in terms of methanol conversion, approaching the theoretical equilibrium value(around 0.85) at temperatures below 200 °C. Turnover-frequency analysis suggests that this result seems to be related not only to the higher amount of acid sites but also that the presence of Lewis acid sites may play a significant role in converting methanol. On the other hand, the presence of Lewis acid sites, combined with a high acidity, promote the formation of by-products(mainly methane) and coke deposition during the reaction. As final evidence, all the investigated catalysts exhibit very high resistance to deactivation by coke deposition, over 60 h continuous test, and a GC–MS analysis of the coke deposited on the catalyst surface reveals tetra-methyl benzene as main component.

Syngas production from chemical looping reforming of ethanol over iron-based oxygen carriers: Theoretical analysis and experimental investigation

Chemical looping reforming(CLR)is a recent trend for syngas production,which has several merits compared to the conventional manner.One of the most important issues for CLR is to find low-cost material as oxygen carriers,so iron is a promising candidate.This paper contributes to testing the thermodynamic ability of iron-based oxygen carrier for chemical looping reforming of ethanol(CLRE).Iron thermodynamically investigated in temperature 100–1300℃and excess oxygen number(φ)0–4.It was found that the temperature andφhave an apparent effect on the gaseous composition produced from the process.Increases in temperature within the range of 100–1300℃enhanced syngas generated and reduced coke formation and CH4.Whereas,increasedφ,particularly at higher temperatures,had also enhanced syngas production as well as reduced coke formation.However,increasingφfor values beyond one had decreased syngas and not significantly reduced coke deposition.Moreover,an experimental investigation was carried out in a fixed bed reactor for more in-depth verification of iron ability as an oxygen carrier through using magnetite ore(mainly Fe3O4).It found that the effect of temperature on syngas production was consistent with that calculated thermodynamically,as syngas increased with raising the temperature through the CLRE.

Studies on accelerated deactivation of ruthenium-promoted alumina-supported alkalized cobalt Fischer-Tropsch synthesis catalyst

Accelerated deactivation of ruthenium-promoted alumina-supported alkalized cobalt （K-Ru-Co/γ-Al 2 O 3 ） Fischer-Tropsch （FT） synthesis catalyst along the catalytic bed over 120 h of time-on-stream （TOS） was investigated. Catalytic bed was divided into three parts and structural changes of the spent catalysts collected from each catalytic bed after FT synthesis were studied using different techniques. Rapid deactivation was observed during the reaction due to high reaction temperature and low feed flow rates. The physico-chemical properties of the catalyst charged in the Bed #1 of the reactor did not change significantly. Interaction of cobalt with alumina and the formation of CoAl 2 O 4 increased along the catalytic bed. Reducibility percentage decreased by 4.5%, 7.5% and 12.9% for the catalysts in the Beds #1, #2 and #3, respectively. Dispersion decreased by 8.8%, 14.4% and 26.6% for the catalysts in the Beds #1, #2 and #3, respectively. Particle diameter increased by 0.6%, 2.4% and 10.4% for the catalysts in the Beds #1, #2 and #3, respectively, suggesting higher rate of sintering at the last catalytic bed. The amount of coke at the last catalytic bed was significantly higher than those of Beds #1 and #2.

Regeneration of C_4H_(10) dry reforming catalyst by nonthermal plasma

Carbon deposition via coke formation is one of the critical problems causing catalyst deactivation during the reforming of hydrocarbons. An effort was made to regenerate the catalyst （Ni/γ-alumina） by oxidation methods. Two approaches were carded out for the regeneration of the deactivated catalyst. The first one involves the plasma treatment of the deactivated catalyst in the presence of dry air over a temperature range of 300-500℃, while the second one only the thermal treatment in the same temperature range. The performance of the regenerated catalyst was evaluated in terms of C4H10 and CO2 conversions and the physicochemical characteristics were examined using a surface area analyzer, an elemental analyzer, scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. It was observed that the carbon deposit （coke） on the catalyst was about 9.89 wt% after reforming C4H10 for 5 h at 540℃. The simple thermal treatment at 400 ℃ reduced carbon content to 6.59 wt% whereas it was decreased to 3.25 wt% by the plasma and heat combination. The specific surface area was fully restored to the original state by the plasma-assisted regeneration at 500℃. As far as the catalytic activity is concerned, the fresh and regenerated catalysts exhibited similar C4H10 and CO2 conversion efficiencies.

Oil oxidation in the whole temperature regions during oil reservoir air injection and development methods

The oil oxidation characteristics of the whole temperature regions from 30 ℃ to 600 ℃ during oil reservoir air injection were revealed by experiments. The whole oil oxidation temperature regions were divided into four different parts: dissolving and inflation region, low temperature oxidation region, medium temperature oxidation region and high temperature oxidation region. The reaction mechanisms of different regions were explained. Based on the oil oxidation characteristics and filed tests results, light oil reservoirs air injection development methods were divided into two types: oxygen-reducing air flooding and air flooding;heavy oil reservoirs air injection in-situ combustion development methods were divided into two types: medium temperature in-situ combustion and high temperature in-situ combustion. When the reservoir temperature is lower than 120 ℃, oxygen-reducing air flooding should be used for light oil reservoir development. When the reservoir temperature is higher than 120 ℃, air flooding method should be used for light oil reservoir development. For a normal heavy oil reservoir, when the combustion front temperature is lower than 400 ℃, the development method is medium temperature in-situ combustion. For a heavy oil reservoir with high oil resin and asphalting contents, when the combustion front temperature is higher than 450 ℃, the development method at this condition is high temperature in-situ combustion. Ten years field tests of air injection carried out by PetroChina proved that air has advantages in technical, economical and gas source aspects compared with other gas agents for oilfield gas injection development. Air injection development can be used in low/super-low permeability light oil reservoirs, medium and high permeability light oil reservoirs and heavy oil reservoirs. Air is a very promising gas flooding agent.

Production of Synthesis Gases from Ethanol Steam Reforming Process

In this study, the production of synthesis gases has been purposed under between 250oC - 700oC and 1 - 2 bars pressures. The research was conducted over a commercial BASF catalyst and a laboratory prepared catalyst. The catalyst has a content of different substances including basically NiO/Al2O3 and some additionals (Ca, Mg, Cr, Si). The experimental measurements were carried out within a recently developed experimental equipment which can be operated up to 1200o and 1 to 3 bars pressures. The study was conducted over a commercial BASF catalyst and a laboratory prepared catalyst under different ethanol/water ratios, temperatures, and catalyst loads. Under the condition when ethanol/water ratios were decreased from 1/2 to 1/10, it was observed that hydrogen ratios increased in exit gas composition of the reactor. With increments in catalyst loads from 1 to 5 grammes, hydrogen ratios in exit gas composition gradually increased. Reaction of ethanol-steam reforming started nearly at 300oC, and when temperature increments continued further up to 700oC, hydrogen yields in exit gas compositions of the reactor increased significantly to a range of 70% - 80%. In the case of using commercial BASF catalyst, hydrogen ratios in exit gas composition were found slightly higher than laboratory prepared catalyst. According to our observations, life time of laboratory prepared catalyst was found higher than the commercial BASF catalyst. In this study which kinetic measurements were applied, some kinetic parameters of ethanol-steam reaction were calculated. The mean activation energy of ethanol consumptions at 573oK - 973oK was found as 26.87 kJ/mol, approximately. All kinetic measurements were analyzed with a first order reaction rate model. In this study, some diffusion limitations existed, however, overall reaction was chemically controlled.

Enhancing both selectivity and coking-resistance of a single-atom Pd1/C3N4 catalyst for acetylene hydrogenation

Selective hydrogenation is an important industrial catalytic process in chemical upgrading, where Pd-based catalysts are widely used because of their high hydrogenation activities. However, poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns. In this work, atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride （g-C3N4） using atomic layer deposition. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy （HAADF-STEM） confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle （NP） formation. During selective hydrogenation of acetylene in excess ethylene, the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/Al2O3 and Pd/SiO2 catalysts. In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement. More impressively, the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance. Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.

Process,reactor and catalyst design:Towards application of direct conversion of methane to aromatics under nonoxidative conditions

The Mo/HZSM-5 catalyzed,non-oxidative methane dehydroaromatization reaction provides a promising direct approach for production of benzene as well as naphthalene from CH4 resources and therefore its early industrial application is highly desired.A simplified methane dehydroaromatization process that consists of only one reactor unit and two product separation units is presented,and the factors that could significantly affect the process efficiency are quantitatively analyzed.While efficiently separating and recycling up to 70vol%unreacted CH4 from the stream out of condensable aromatics separation unit might become the main problem in maximizing the process efficiency,increasing the operating temperature as high as possible of the CH4 converter in the reactor unit and raising the system operation pressure to a level somewhat higher than one atmosphere should help maximize the process performance.At process-required high reaction temperatures,however,Mo/HZSM-5 catalyst suffers from vary rapid deactivation due to serious coke formation.Therefore,it becomes necessary to employ a reactor system that enables continuous and simultaneous regeneration of deactivated catalyst so as to maintain the catalytic activity and stability of catalyst over a sufficiently long operation period.Nineteen years of sustained R&D efforts of the author’s team have led to a few applicable technologies related to preparation of a fluidizable binder-free Mo/HZSM-5 catalyst for use in fluidized bed reactors,regeneration of deactivated Mo/HZSM-5 catalyst using H_(2),and design and operation of a dual-bed circulating fluidized bed reactor system for continuous processing of the Mo/HZSM-5 catalyzed methane dehydroaromatization reaction.Operated at 1073 K and under a continuous regeneration mode,an in-house developed binder-free 6%Mo/HZSM-5 catalyst has proven to be capable of providing a stable benzene yield of approximately 13%over a cumulative period of 1800 min.Nevertheless,minimizing the catalyst deactivation by coking and developing a highly effective coke-removal and catalyst regeneration approach have still remained two important issues to be addressed in realization of early application of the Mo/HZSM-5 catalyzed methane dehydroaromatization reaction.While the key to a practical solution to these challenging issues lies in designing an advanced Mo/HZSM-5 catalyst with improved coking resistance and H_(2)-regeneration activity,effective approaches to the design of such a catalyst are presented and discussed based on four possible coke formation routes.In the end,developing a pressurized pilot-scale dual-bed type of circulating fluidized bed reactor system that is capable of providing a yearly production of benzene of approximately 35 tons and naphthalene of 5 tons is visualized to make demonstration of the industrial applicability of the Mo/HZSM-5 catalyzed methane dehydroaromatization reaction.