scholarly journals Dimethyl Ether to Olefins over Modified ZSM-5 Based Catalysts Stabilized by Hydrothermal Treatment

Catalysts ◽  
2019 ◽  
Vol 9 (5) ◽  
pp. 485 ◽  
Author(s):  
Maria Magomedova ◽  
Ekaterina Galanova ◽  
Ilya Davidov ◽  
Mikhail Afokin ◽  
Anton Maximov

The reaction of dimethyl ether to olefin over HZSM-5/Al2O3 catalysts modified by Zr and Mg and stabilized by hydrothermal treatment has been studied. Regardless of the introduction method and the nature of the metal, the dependence of the key products selectivity on X(DME) over hydrothermally treated steady-state catalysts does not change, and the experimental points are described by the same curves. Metal introduction and the corresponding changes in the acid sites distribution do not change the ratio of main reaction rates, only the absolute values of the formation rate of the products are changed. Zr doping leads to the greatest activity in the DME conversion due to an equable decrease in the total acidity of the sample. On the other hand, the Mg-modified sample has a higher amount of weak acid sites, which reduces activity. At low DME conversion, methanol is one of the primary reaction products which formed from DME simultaneously with propylene in alkene cycle. At high DME conversion, the methanol acts as a main reagent which leads to ethylene formation in the arene cycle. Based on the results, the role of the metal in the reaction chemistry is considered and the mechanism of product formation from DME over steady-state catalyst is proposed, which describes both the participation of DME and the methanol produced.

2019 ◽  
Vol 19 (4) ◽  
pp. 307-315
Author(s):  
N. G. Grigoryeva ◽  
D. V. Serebrennikov ◽  
S. V. Bubennov ◽  
B. I. Kutepov

Oligomerization of pent-1-ene is an effective process for synthesis of high-quality environmentally friendly fuel components. Catalytic properties of H-zeolites FAU, OFF, MOR, ВЕА, MTW and MFI were studied for synthesis of pentene oligomers in an autoclave at 110–200 °C. The wide-pore structure of H-Y and H-Beta (18) zeolites and the high concentration of acid sites were established to cause the high oligomerization activity to obtain 97–100 % yields of oligomers. Oligomers obtained over these catalysts comprised, depending on the reaction conditions, 30–73 % dimers, 25–50 % trimers and 2–14 % oligomers with more than three monomer units (n > 3). Fine-pore zeolites (H-ZSM-5) and zeolites with one-dimensional channel systems (H-OFF, H-MOR, H-ZSM-12) were less active to oligomerization of pent-1-ene, decenes being the main reaction products.


1990 ◽  
Vol 270 (1) ◽  
pp. 251-256 ◽  
Author(s):  
M Claeyssens ◽  
H van Tilbeurgh ◽  
J P Kamerling ◽  
J Berg ◽  
M Vrsanska ◽  
...  

Endoglucanase I from the filamentous fungus Trichoderma reesei catalyses hydrolysis and glycosyl-transfer reactions of cello-oligosaccharides. Initial bond-cleaving frequencies determined with 1-3H-labelled cello-oligosaccharides proved to be substrate-concentration-dependent. Using chromophoric glycosides and analysing the reaction products by h.p.l.c., kinetic data are obtained and, as typical for an endo-type depolymerase, apparent hydrolytic parameters (kcat., kcat./Km) increase steadily as a function of the number of glucose residues. At high substrate concentrations, and for both free cellodextrins and their aromatic glycosides, complex patterns (transfer reactions) are, however, evident. In contrast with the corresponding lactosides and 1-thiocellobiosides, and in conflict with the expected specificity, aromatic 1-O-beta-cellobiosides are apparently hydrolysed at both scissile bonds, yielding the glucoside as one of the main reaction products. Its formation rate is clearly non-hyperbolically related to the substrate concentration and, since the rate of D-glucose formation is substantially lower, strong indications for dismutation reactions (self-transfer) are again obtained. Evidence for transfer reactions catalysed by endoglucanase I further results from experiments using different acceptor and donor substrates. A main transfer product accumulating in a digest containing a chromophoric 1-thioxyloside was isolated and its structure elucidated by proton n.m.r. spectrometry (500 MHz). The beta 1-4 configuration of the newly formed bond was proved.


2020 ◽  
Vol 6 (11) ◽  
pp. 31-39
Author(s):  
R. Brovko ◽  
L. Mushinskii ◽  
V. Doluda

Zeolite deactivation during the methanol transformation into hydrocarbons is a complex chemical process that includes reversible and irreversible degradation of active sites. The irreversible deactivation of the catalyst is associated with the degradation of active sites during long-term functioning of the zeolite under high-temperature exposure conditions of to water vapor as one of the main reaction products. The carbon deposits formation on the catalyst surface is the main cause of reversible deactivation. The formation of carbon can occur both in the cavities of the zeolites channels, which usually leads to a change in the selectivity of the process for light hydrocarbons, and at the junctions of the channels, which leads to pores blockage and a decrease in the activity of the catalyst. In addition, carbon deposition can occur directly on the active site of the zeolite, which also reduces the activity of the catalyst. The study of the synthesized catalytic systems deactivation rate to process time correlation was carried out in a tubular reactor installation of continuous operation, consisting of a reactor for producing dimethyl ether and a reactor for transformation of dimethyl ether into hydrocarbons. Determination of the kinetic regularities of the deactivation process of zeolite H-ZSM-5 makes it possible to adequately describe the actual course of the catalytic transformation of methanol into hydrocarbons. As a result of solving the differential equations of catalyst deactivation by numerical methods, the values of the preexponential factors and activation energies were obtained. Base on the values of the preexponential factors and activation energies, the methanol into hydrocarbons conditions range optimal for the catalytic transformation was determined, providing the minimum rate of catalyst deactivation, Ptotal = 1 Bar, W (methanol) = 2.3 kg (methanol) / (kg (cat) × h), t = 330–360 °C, which correlates with the results of the literature data on the transformation of methanol into zeolite of the H-ZSM-5 type.


2013 ◽  
Vol 2013 ◽  
pp. 1-9 ◽  
Author(s):  
Hyo-Sub Kim ◽  
Su-Gyung Lee ◽  
Young-Ho Kim ◽  
Dong-Hee Lee ◽  
Jin-Bae Lee ◽  
...  

Transition metal (Mn, Fe, or Ni) incorporated SAPO-34 (MeAPSO-34) nanocatalysts were synthesized using a hydrothermal method to improve the catalytic lifetime in the conversion of dimethyl ether to light olefins (DTO). The structures of the synthesized catalysts were characterized using several methods including XRD, SEM, BET,29Si-MAS NMR, and NH3-TPD techniques. Although the structure of the MeAPSO-34 catalysts was similar to that of the SAPO-34 catalyst, the amount of weak acid sites in all MeAPSO-34 catalysts was markedly increased and accompanied by differences in crystallinity and structural arrangement. The amount of weak acid sites decreased in the following order: NiAPSO-34 > FeAPSO-34 > MnAPSO-34 > SAPO-34 catalyst. The MeAPSO-34 catalysts, when used in the DTO reaction, maintained DME conversion above 90% for a longer time than the SAPO-34 catalyst, while also maintaining the total selectivity above 95% for light olefins. In addition, the NiAPSO-34 catalyst showed the longest catalytic lifetime; the lifetime was extended approximately 2-fold relative to the SAPO-34 catalyst. Therefore, the increase in the catalytic lifetime is related to the amount of weak acidic sites, and these sites are increased in number by incorporating transition metals into the SAPO-34 catalyst.


1996 ◽  
Vol 61 (8) ◽  
pp. 1115-1130 ◽  
Author(s):  
Jiří Čejka ◽  
Naděžda Žilková ◽  
Blanka Wichterlová

Kinetic study of toluene and benzene alkylation with isopropyl alcohol on alumo- and ferrisilicates of MFI structure has shown that the alkylation activity does not follow the acidity (both the number and strength of bridging OH groups) of these molecular sieves. The rate of the overall reaction is controlled by the desorption/transport rate of bulky, strongly adsorbed cymenes and cumene. A higher concentration of n-propyltoluenes compared to n-propylbenzene, both undesired reaction products, formed via a bimolecular isomerization of isopropyl aromate with benzene or toluene, was due to the higher reactivity of isopropyltoluene with toluene in comparison with that of cumene with benzene. It is concluded that ferrisilicates of MFI structure possessing low strength acid sites appear to be promising catalysts for achieving both a high isopropyl- and para-selectivity in toluene alkylation to p-cymene.


Author(s):  
Ning-Ning Cheng ◽  
Zi-Liang Li ◽  
Hong-Chao Lan ◽  
Wen-Long Xu ◽  
Wen-Jing Jiang ◽  
...  

2020 ◽  
Vol 75 (4) ◽  
pp. 285-291
Author(s):  
Jiao-Nan Yuan ◽  
Hai-Chao Ren ◽  
Yong-Kai Wei ◽  
Wei-Sen Xu ◽  
Guang-Fu Ji ◽  
...  

AbstractMicroscopic electron properties of α-hexahydro-1,3,5-trinitro-1,3,5-triazine (α-RDX) with different shock wave velocities have been investigated based on molecular dynamics together with multi-scale shock technique. The studied shock wave velocities are 8, 9 and 10 km ⋅ s−1. It has been said that the shock sensitivity and reaction initiation of explosives are closely relevant with their microscopic electron properties. The reactions, including the reaction products, which are counted from the trajectory during the simulations are analysed first. The results showed that the number of the products strictly rely on shock wave velocities. The reaction rates and decomposition rates are also studied, which showed the differences between the different shock velocities. The results of electron properties show that α-RDX is a wide-gap insulator in the ground state and the metallisation conditions of shocked RDX are determined, which are lower than under-static high pressure.


2015 ◽  
Vol 1769 ◽  
Author(s):  
C.E. Velasquez ◽  
M. A. F. Veloso ◽  
A. L. Costa ◽  
C. Pereira

ABSTRACTThe displacement per atom (dpa) has been a specific issue to evaluate the damage in the first wall of the Tokamak. Two different first wall materials were evaluated. In this study, MCNP5 code was used to obtain the neutron flux, the energy deposition and the main reaction rates, on the inboard and outboard first wall. The damage calculations were performed by the SPECTER code using the neutronic parameters obtained by MCNP5. The Tokamak reactor modeled has similar dimensions to the ITER. Tungsten and beryllium alloys were simulated on the outboard first wall. The results indicate which material has a higher resistance to be damage and dpa values for the analyzed material.


2014 ◽  
Vol 633-634 ◽  
pp. 545-549
Author(s):  
Hong Li Xiao ◽  
Lan Zhang Chong ◽  
Fei Li Hang ◽  
Wang Yong

In this paper, the nonlinear dynamic system of microbe continuous fermentation products 1,3-propanediol (1,3-PD) is rewritten by improving the specific cellular growth rate, specific substrate consumption rate and specific product formation rate. Firstly, under the condition of substrate glycol excess and active trans-membrane transport, according to the dynamic behavior the fermentation process, we consider the glycerol and 1,3–PD concentration within the cell, and improve the specific cellular growth rate, specific substrate consumption rate and specific product formation rate, then rewrite the dynamic system of microbial continuous fermentation process. Secondly, taking the dynamic system as main constraint condition, we establish the parameter identification model and prove the existence of the optimal solution. Lastly, the numerical results calculated by particle swarm algorithm show that the improved model is suitable for describe the dynamic behavior of 1,3-PD, but is not accurate enough for by-products.


1999 ◽  
Vol 2 (03) ◽  
pp. 271-280 ◽  
Author(s):  
Ekrem Kasap ◽  
Kun Huang ◽  
Than Shwe ◽  
Dan Georgi

Summary The formation-rate-analysis (FRASM) technique is introduced. The technique is based on the calculated formation rate by correcting the piston rate with fluid compressibility. A geometric factor is used to account for irregular flow geometry caused by probe drawdown. The technique focuses on the flow from formation, is applicable to both drawdown and buildup data simultaneously, does not require long buildup periods, and can be implemented with a multilinear regression, from which near-wellbore permeability, p * and formation fluid compressibility are readily determined. The field data applications indicate that FRA is much less amenable to data quality because it utilizes the entire data set. Introduction A wireline formation test (WFT) is initiated when a probe from the tool is set against the formation. A measured volume of fluid is then withdrawn from the formation through the probe. The test continues with a buildup period until pressure in the tool reaches formation pressure. WFTs provide formation fluid samples and produce high-precision vertical pressure profiles, which, in turn, can be used to identify formation fluid types and locate fluid contacts. Wireline formation testing is much faster compared with the regular pressure transient testing. Total drawdown time for a formation test is just a few seconds and buildup times vary from less than a second (for permeability of hundreds of millidarcy) to half a minute (for permeability of less than 0.1 md), depending on system volume, drawdown rate, and formation permeability. Because WFT tested volume can be small (a few cubic centimeters), the details of reservoir heterogeneity on a fine scale are given with better spatial resolution than is possible with conventional pressure transient tests. Furthermore, WFTs may be preferable to laboratory core permeability measurements since WFTs are conducted at in-situ reservoir stress and temperature. Various conventional analysis techniques are used in the industry. Spherical-flow analysis utilizes early-time buildup data and usually gives permeability that is within an order of magnitude of the true permeability. For p* determination, cylindrical-flow analysis is preferred because it focuses on late-time buildup data. However, both the cylindrical- and spherical-flow analyses have their drawbacks. Early-time data in spherical-flow analysis results in erroneous p* estimation. Late-time data are obtained after long testing times, especially in low-permeability formations; however, long testing periods are not desirable because of potential tool "sticking" problems. Even after extended testing times, the cylindrical-flow period may not occur or may not be detectable on WFTs. When it does occur, permeability estimates derived from the cylindrical-flow period may be incorrect and their validity is difficult to judge. New concepts and analysis techniques, combined with 3-D numerical studies, have recently been reported in the literature.1–7 Three-dimensional numerical simulation studies1–6 have contributed to the diagnosis of WFT-related problems and the improved analysis of WFT data. The experimental studies7 showed that the geometric factor concept is valid for unsteady state probe pressure tests. This study presents the FRA technique8 that can be applied to the entire WFT where a plot for both drawdown and buildup periods renders straight lines with identical slopes. Numerical simulation studies were used to generate data to test both the conventional and the FRA techniques. The numerical simulation data are ideally suited for such studies because the correct answer is known (e.g., the input data). The new technique and the conventional analysis techniques are also applied to the field data and the results are compared. We first review the theory of conventional analysis techniques, then present the FRA technique for combined drawdown and buildup data. A discussion of the numerical results and the field data applications are followed by the conclusions. Analysis Techniques It has been industry practice to use three conventional techniques, i.e., pseudo-steady-state drawdown (PSSDD), spherical and cylindrical-flow analyses, to calculate permeability and p* Conventional Techniques Pseudo-Steady-State Drawdown (PSSDD). When drawdown data are analyzed, it is assumed that late in the drawdown period the pressure drop stabilizes and the system approaches to a pseudo-steady state when the formation flow rate is equal to the drawdown rate. PSSDD permeability is calculated from Darcy's equation with the stabilized (maximum) pressure drop and the flowrate resulting from the piston withdrawal:9–11 $$k {d}=1754.5\left({q\mu \over r {i}\Delta p {{\rm max}}}\right),\eqno ({\rm 1})$$where kd=PSSDD permeability, md. The other parameters are given in Nomenclature.


Sign in / Sign up

Export Citation Format

Share Document