scholarly journals Heteropolyacid Salt Catalysts for Methanol Conversion to Hydrocarbons and Dimethyl Ether: Effect of Reaction Temperature

Catalysts ◽  
2019 ◽  
Vol 9 (4) ◽  
pp. 320 ◽  
Author(s):  
Yuehong Yu ◽  
Daoming Sun ◽  
Shuanjin Wang ◽  
Min Xiao ◽  
Luyi Sun ◽  
...  
Keyword(s):  
Copper Ions ◽  
Strong Acid ◽  
Methanol Conversion ◽  
Acid Sites ◽  
Light Olefins ◽  
Acid Salt ◽  
Silicotungstic Acid ◽  
Different Temperatures ◽  
Light Olefins Selectivity ◽  
Strong Acid Sites

Phosphotungstic and silicotungstic acid salt catalysts (CuPW, CuSiW, FePW, FeSiW) were synthesized by substitution of protons with ferric and copper ions through a simple replacement reaction. The structure and thermal stability were characterized by IR, XRD and TG, and the salts showed a keggin structure and a thermal tolerance near 450 °C. Temperature programmed reactions indicated that the four catalysts showed similar trends in the change of methanol conversion, DME selectivity, and light olefins selectivity at 100–400 °C. Copper salt catalysts showed a 100% DME selectivity at temperatures ranging from 100–250 °C, while FeSiW and FePW catalysts had a 100% DME selectivity near 250 °C. Moreover, the heteropolyacid salt catalysts also produced a certain number of light olefins at the temperature ranging from 250–350 °C, and the CuSiW catalyst exhibited the highest ethylene and propylene selectivity of 44%. In the stability test evaluated at 200 °C, the catalysts showed different tendencies during the induction period and the same trends during the reduction period for the methanol conversion to DME, due to the differences in the strengths of the strong acid sites. Finally, the silicotungstic acid salt catalysts showed the longest lifetime of 120 h, much longer than the heteropolyacids. This approach provides an effective way to synthesize hydrocarbons through methanol, especially DME, at different temperatures using one catalyst.

Reaction Characteristic of MeAPSO-34 (Me=Mn, Co) Catalysts for Olefins Production from Dimethyl Ether

2012 ◽  
Vol 550-553 ◽  
pp. 416-419
Author(s):  
Young Ho Kim ◽  
Su Gyung Lee ◽  
Eun Jee Kang ◽  
Hyo Sub Kim ◽  
Chu Sik Park
Keyword(s):  
Dimethyl Ether ◽  
Strong Acid ◽  
Acid Sites ◽  
Coke Deposition ◽  
Light Olefins ◽  
Co Catalysts ◽  
Strong Acid Sites ◽  
Reaction Characteristic ◽  
Catalyst Lifetime

In DME to olefins (DTO) reaction, SAPO-34 catalyst with CHA structure is well known to be one of the catalysts with good performance. However, the SAPO-34 catalyst is easily deactivated due to coke deposition during DTO reaction. In this study, MeAPSO-34 catalysts (Me=Mn, Co) were prepared for the increase of the catalyst lifetime and their properties have been characterized by XRD and SEM. The DTO reaction was carried out over the MeAPSO-34 catalysts, and the results were compared with the SAPO-34 catalyst. The lifetime of MeAPSO-34 catalysts with high DME conversion and selectivity of light olefins was prolonged than that of the SAPO-34 catalyst. It may be concluded that the decrease of strong acid sites, which were responsible for the formation of coke, affect on the lifetime of the MeAPSO-34 catalysts. In addition, the CoAPSO-34 catalyst with a Co additive showed the best performance in terms of the catalytic lifetime and the selectivity to light olefins.

Preparation of Phosphorus Modified HZSM-5 Zeolite Catalysts and their Catalytic Performances of Methanol to Olefins

2014 ◽  
Vol 875-877 ◽  
pp. 295-299
Author(s):  
Shu Xun Tian ◽  
Sheng Fu Ji ◽  
Qi Sun
Keyword(s):  
Phosphorus Content ◽  
Strong Acid ◽  
Weight Percent ◽  
Acid Sites ◽  
Zeolite Catalysts ◽  
Light Olefins ◽  
Microporous Structure ◽  
Phosphorous Content ◽  
Propylene Yield ◽  
Strong Acid Sites

To improve the selectivity of light olefins, Phosphorous modified ZSM-5 zeolites catalysts with different phosphorous content were prepared by impregnation and were used in the conversion of methanol to olefins. The properties of acidity and microporous structure of the phosphorous modified ZSM-5 zeolites were investigated by XRD, N2-adsorption and desorption, and NH3-TPD. The highest propylene yield (50.82%) was observed over the H-ZSM-5 modified with the phosphorus content at 9% (weight percent). The selectivity of propylene depended strongly on the phosphorus content in the zeolites; The enhancement of propylene selectivity with increasing phosphorous content was attributed to reduction of strong acid sites on the H-ZSM-5. Modification of the ZSM-5 zeolites with phosphorous also changes the microporous structure.

scholarly journals Facile and Rapid Synthesis of Durable SSZ-13 Catalyst using Choline Chloride Template for Methanol-to-Olefins Reaction

Catalysts ◽  
2021 ◽  
Vol 11 (10) ◽  
pp. 1250
Author(s):  
Xiongchao Lin ◽  
Sasha Yang ◽  
Xiaojia Li ◽  
Caihong Wang ◽  
Yonggang Wang
Keyword(s):  
Choline Chloride ◽  
Strong Acid ◽  
Methanol Conversion ◽  
Catalytic Performance ◽  
Acid Sites ◽  
Weak Acid ◽  
Rapid Synthesis ◽  
Light Olefin ◽  
Mto Reaction ◽  
Strong Acid Sites

In the current study, a facile and rapid synthesis approach for a SSZ-13 catalyst using choline chloride (CC) as a template was proposed, and the catalytic performance for the methanol-to-olefins (MTO) reaction was examined. With a proper amount of CC addition (i.e., m(CC)/m(SiO2)=0.14), uniform and homogeneously distributed cubic SSZ-13 crystals were obtained within 4 h with lower aggregation. The synthesized catalyst demonstrated excellent porous features with a total specific surface area and mesopore volume of 641.71 m2·g−1 and 0.04 cm3·g−1, respectively. The optimized strong and weak acid sites on SSZ-13 were obtained by regulating the m(CC)/m(SiO2) ratio. The less strong acid sites and a larger amount of weak acid sites in the synthesized catalyst were conducive to the catalytic performance of the MTO reaction under a lower reaction temperature (450 °C). The appropriate acidity and well-developed pore structure of synthesized SSZ-13 could also slow down the carbon deposition rate and, thus, significantly improve the catalytic lifetime of the catalyst. The methanol conversion rate and initial selectivity of light olefin using the synthesized catalyst could maintain over 95% and 50%, respectively, and a lifetime of 172 min was achieved. Although the low olefin selectivity of the synthesized SSZ-13 catalyst was slightly lower than that of the purchased one, its desirable features were thought to have good potential for industrial application.

scholarly journals Control of zeolite microenvironment for propene synthesis from methanol

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Longfei Lin ◽  
Mengtian Fan ◽  
Alena M. Sheveleva ◽  
Xue Han ◽  
Zhimou Tang ◽  
...  
Keyword(s):  
Active Sites ◽  
Inelastic Neutron Scattering ◽  
Sustainable Manufacturing ◽  
Methanol Conversion ◽  
Acid Sites ◽  
Light Olefins ◽  
Carbon Bond ◽  
X Ray ◽  
Carbon Carbon Bond ◽  
Catalytic Stability

AbstractOptimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

Reaction Mechanism for CCl2F2 Catalytic Decomposition over MoO3/ZrO2

2013 ◽  
Vol 295-298 ◽  
pp. 326-330 ◽  
Author(s):  
Tian Cheng Liu ◽  
Yu Jiao Guo ◽  
Ping Ning ◽  
Ming Long Yuan
Keyword(s):  
Reaction Mechanism ◽  
Main Product ◽  
Solid Acid ◽  
Fixed Bed ◽  
Catalytic Decomposition ◽  
Strong Acid ◽  
Acid Sites ◽  
Fixed Bed Reactor ◽  
Surface Intermediate ◽  
Strong Acid Sites

Catalytic hydrolysis decomposition of dichlorodifluoromethane (CCl2F2) in the presence of water vapor and oxygen was studied over a series of solid acids using a fixed-bed reactor. Solid acid MoO3/ZrO2 displayed the highest activity, over which the conversion of CCl2F2 reached 100 % at 250 °C. CO2 was the main-product and the selectivity to CClF3 remained lower than 28.0 %. CO was not detected as by-product. The decomposition activity depended on the calcination temperature and the ZrO2 content. The activity of solid acid MoO3/ZrO2 correlates well with its specific surface area and the amount of medium-strong acid sites on the surface. To explain the reaction mechanism for CCl2F2 catalytic decomposition over MoO3/ZrO2, a surface intermediate, Osurface-CF2-Osurface is proposed.

Generation and Identification of Strong Acid Sites in AlMCM-41 Prepared by Gel Equilibrium Adjustment Method

1997 ◽  
Vol 26 (7) ◽  
pp. 637-638 ◽  
Author(s):  
K. Ramesh Reddy ◽  
Nobuyuki Araki ◽  
Miki Niwa
Keyword(s):  
Strong Acid ◽  
Acid Sites ◽  
Adjustment Method ◽  
Strong Acid Sites

scholarly journals Controlled direct synthesis of single- to multiple-layer MWW zeolite

2020 ◽  
Author(s):  
Jie-Qiong Chen ◽  
Yu-Zhao Li ◽  
Qing-Qing Hao ◽  
Huiyong Chen ◽  
Zhao-Tie Liu ◽  
...  
Keyword(s):  
Large Scale ◽  
Direct Synthesis ◽  
Single Layer ◽  
Strong Acid ◽  
Acid Sites ◽  
Synthesis Conditions ◽  
Alkylation Of Benzene ◽  
Controlled Structure ◽  
Strong Acid Sites ◽  
Mww Zeolite

ABSTRACT The minimized diffusion limitation and completely exposed strong acid sites of the ultrathin zeolites make it an industrially important catalyst especially for converting bulky molecules. However, the structure-controlled and large-scale synthesis of the material is still a challenge. In this work, the direct synthesis of the single-layer MWW zeolite was demonstrated by using hexamethyleneimine and amphiphilic organosilane as structure-directing agents. Characterization results confirmed the formation of the single-layer MWW zeolite with high crystallinity and excellent thermal/hydrothermal stability. The formation mechanism was rigorously revealed as the balanced rates between the nucleation/growth of the MWW nanocrystals and the incorporation of the organosilane into the MWW unit cell, which is further supported by the formation of MWW nanosheets with tunable thickness via simply changing synthesis conditions. The commercially available reagents, well-controlled structure and the high catalytic stability for the alkylation of benzene with 1-dodecene make it an industrially important catalyst.

scholarly journals Effect of support acidity during selective hydrogenolysis of glycerol over supported palladium–ruthenium catalysts

2020 ◽  
Vol 378 (2176) ◽  
pp. 20200055
Author(s):  
Susana Guadix-Montero ◽  
Alba Santos-Hernandez ◽  
Andrea Folli ◽  
Meenakshisundaram Sankar
Keyword(s):  
Catalytic Activity ◽  
Supported Catalysts ◽  
Bond Cleavage ◽  
Strong Acid ◽  
Acid Sites ◽  
Ruthenium Catalysts ◽  
Impregnation Method ◽  
Selective Hydrogenolysis ◽  
Strong Acid Sites ◽  
Effect Of Support

We report the role of the acidity of support during the selectivity hydrogenolysis of glycerol over supported bimetallic palladium–ruthenium (PdRu) catalysts. The PdRu nanoparticles were supported on a series of metal oxides and zeolitic supports via the modified impregnation method and tested for the liquid-phase hydrogenolysis of glycerol using gaseous hydrogen. The relative acid site densities of selected catalysts were determined by ammonia temperature-programmed desorption and pyridine desorption experiments. Based on these studies, we report a direct correlation between the catalytic activity (conversion and 1,2 propane diol yield) and two different acid sites (strong acid sites and very strong acid sites). Besides zeolite-supported catalysts, TiO 2 supported PdRu nanoparticles exhibit moderate catalytic activity; however, this catalyst shows high selectivity for the desired C–O bond cleavage to produce C3 products over the undesired C–C bond cleavage to produce < C3 products. This article is part of a discussion meeting issue ‘Science to enable the circular economy’.

Effect of autotransformation on the layer charge of smectites determined by the alkylammonium method

Clay Minerals ◽  
1997 ◽  
Vol 32 (4) ◽  
pp. 623-632 ◽  
Author(s):  
M. Janek ◽  
P. Komadel ◽  
G. Lagaly
Keyword(s):  
Aqueous Dispersion ◽  
Strong Acid ◽  
Acid Sites ◽  
Weak Acid ◽  
Layer Charge ◽  
Exchange Method ◽  
Density Distributions ◽  
Titration Curves ◽  
The Mean ◽  
Strong Acid Sites

AbstractHydrogen-forms of <2 µm fractions of six bentonites of various Fe contents were prepared by H+→OH-→H+ ion exchange using resins. Potentiometric titration curves revealed that the number of strong acid sites varied and accounted for 60-95% of the total acidity in the freshly prepared H-forms. The number of strong acid sites decreased and that of the weak acid sites increased on ageing. The process of autotransformation in aqueous dispersion at 90~ was completed within four days. Layer-charge distributions of all samples were inhomogeneous with layer charges from 0.25-0.39 Eq/unit O10(OH)2. Oxalate pretreatment of the samples resulted in changes in the layer-charge distribution due to the removal of readily soluble phases which may have blocked exchange sites. After autotransformation, the alkylammonium exchange method revealed inhomogeneous charge density distributions; the fraction of layers of the highest charge decreased. Comparison of total CEC obtained from potentiometric curves and interlamellar CEC calculated from the mean layer charge confirmed attack of protons from particle edges. However, for several samples the structural attack may also occur from the interlayer space. Autotransformation of the Hsmectites decreased the mean layer charge. Protons probably attack the Mg(O,OH)6 octahedra preferentially during the autotransformation.

scholarly journals Catalytic Rapid Pyrolysis ofQuercus variabilisover Nanoporous Catalysts

2015 ◽  
Vol 2015 ◽  
pp. 1-6 ◽  
Author(s):  
Hyeon Koo Kang ◽  
In-Gu Lee ◽  
Kyong-Hwan Lee ◽  
Beom-Sik Kim ◽  
Tae Su Jo ◽  
...  
Keyword(s):  
Oil Quality ◽  
Strong Acid ◽  
Abundant Species ◽  
Acid Sites ◽  
Weak Acid ◽  
Nanoporous Materials ◽  
Bio Oil ◽  
Strong Acid Sites ◽  
Rapid Pyrolysis ◽  
Mcm 41

Catalytic rapid pyrolysis ofQuercus variabilis, a Korean native tree species, was carried out using Py-GC/MS. Mesoporous MFI, which has both nanopores and micropores, and three nanoporous materials, Al-MCM-41, Al-SBA-15, andγ-Al2O3, were used as the catalyst. The acid sites of mesoporous MFI were strong Brønsted acid sites, whereas those of nanoporous materials were mostly weak acid sites. The composition of the product bio-oil varied greatly depending on the acid characteristics of the catalyst used. Phenolics were the most abundant species in the bio-oil, followed by acids and furanics, obtained over Al-MCM-41 or Al-SBA-15 with weak acid sites, whereas aromatics were the most abundant species produced over mesoporous MFI with strong acid sites, followed by phenolics. Aromatics, phenolics, and furanics are all important chemicals contributing to the improvement of bio-oil quality.

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