Life Time Improvement of Hierarchically Structured SAPO-34 Nanocatalyst in MTO Reaction via Applying Clinoptilolite, Investigating of Composite Design via RSM

Author(s):  
Reza Yazdanpanah ◽  
Eshagh Moradiyan ◽  
Rouein Halladj ◽  
Sima Askari

Aim and Objective: The research focuses on recent progress in the production of light olefins. Hence, the common catalyst of the reaction (SAPO-34) deactivates quickly because of coke formation, we reorganized the mechanism combining SAPO-34 with a natural zeolite in order to delay the deactivation time. Materials and Methods: The synthesis of nanocomposite catalyst was conducted hydrothermally using experimental design. Firstly, Clinoptilolite was modified using nitric acid in order to achieve nano scaled material. Then, the initial gel of the SAPO-34 was prepared using DEA, aluminum isopropoxide, phosphoric acid and TEOS as the organic template, sources of Aluminum, Phosphor, and Silicate, respectively. Finally, the modified zeolite was combined with SAPO-34's gel. Results: 20 different catalysts due to D-Optimal design were synthesized and the nanocomposite with 50 weight percent of SAPO-34, 4 hours Crystallization and early Clinoptilolite precipitation showed the highest relative crystallinity, partly high BET surface area and hierarchical structure. Conclusion: Different analysis illustrated the existence of both components. The most important property alteration of nanocomposite was the increment of pore mean diameters and reduction in pore volumes in comparison with free SAPO-34. Due to low price of Clinoptilolite, the new catalyst develops the economy of the process. Using this composite, according to formation of multi-sized pores located hierarchically on the surface of the catalyst and increased surface area, significant amounts of Ethylene and Propylene, in comparison with free SAPO-34, were produced, as well as deactivation time that was improved.

Catalysts ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 16 ◽  
Author(s):  
Yuehong Yu ◽  
Jiaxiang Qin ◽  
Min Xiao ◽  
Shuanjin Wang ◽  
Dongmei Han ◽  
...  

Introducing mesopores into the channels and cages of conventional micropores CHA (Chabazite) topological structure SAPO-34 molecular sieves can effectively improve mass transport, retard coke deposition rate and enhance the catalytic performance for methanol to olefins (MTO) reaction, especially lifetime and olefins selectivity. In order to overcome the intrinsic diffusion limitation, a novel CO2-based polyurea copolymer with affluent amine group, ether segment and carbonyl group has been firstly applied to the synthesis of SAPO-34 zeolite under hydrothermal conditions. The as-synthesized micro-mesoporosity SAPO-34 molecular sieve catalysts show heterogeneous size distribution mesopores and exhibit slightly decrease of BET surface area due to the formation of defects and voids. Meanwhile, the catalysts exhibit superior catalytic performance in the MTO reaction with more than twice prolonged catalytic lifespan and improvement of selectivity for light olefins compared with conventional microporous SAPO-34. The methodology provides a new way to synthesize and control the structure of SAPO-34 catalysts.


2014 ◽  
Vol 926-930 ◽  
pp. 32-35
Author(s):  
Shu Qin Zheng ◽  
Shao Ren ◽  
Jian Ce Zhang ◽  
Wei Zhu

A novel Y zeolite-containing composite material was prepared via in situ crystallization with sepiolite and catalyst residue as starting materials, of which the BET surface area is up to 582 m2/g, the pore volume is 0.43 cm3/g, the relative crystallinity is as high as 55.7 %, the surface is smooth and regular, and Y zeolite particles are in the range of 0.4-1.0 mirons, the composite contains large number Y zeolite with more meso-macro porous structure.The alkalinity in reaction medium has a pronounced effect on the relative crystallinity of Y zeolite.


2019 ◽  
Vol 15 (28) ◽  
pp. 85-96
Author(s):  
Aída Luz Villa Holguín ◽  
Carlos Fernando Imbachí Gamba

Hierarchical zeolites were synthesized by two methodologies, following desilication procedures of commercial zeolites. Starting from USY zeolite (Zeolyst CBV720,Si/Al=15), the effect of the amount of CTAB in the desilication media and the hydrothermal treatment time on the synthesized materials were analyzed.The results showed that the surfactant amount has a higher influence on relative crystallinity (%RC) and textural properties of the materials than synthesis time. All the samples showed a lower BET surface area compared with the starting zeolite, although mesopore surface area increased from 210.33 to 467.30 m2/g in the case of Z720-75sample. In the case of USY zeolite withSi/Al=2.6 (ZeolystCBV500),a previous dealumination with H4EDTA and anacid washingwith Na2H2EDTAsteps were included.It was found that the micropore and the mesopore surface areasincreased 13.96% and 11.23%, respectively, compared with the parent zeolite; furthermore, the %RC was 99% after treatmentprocedures.


2010 ◽  
Vol 1279 ◽  
Author(s):  
Liping Ye ◽  
Fahai Cao ◽  
Weiyong Ying ◽  
Dingye Fang ◽  
Qiwen Sun

AbstractThe effect of different combinations of a new tri-templating agent TEAOH/DEA/TEA, namely tetraethyl ammonium hydroxide (TEAOH)/diethylamine (DEA)/triethylamine (TEA), on the catalytic performance of SAPO-34 was investigated in MTO conversion. It was found that SAPO-34 and SAPO-5 are competing phases at TEA concentrations higher than 40 %. Pure SAPO-34 with high crystallinity, large BET surface area and small crystal size (0.8~1.4μm) was obtained at a low TEA concentrations. The combination of TEAOH/DEA/TEA strongly governed the acidity of crystals. TEAOH:DEA:TEA=0.67:0.67:0.67 gave an economical catalyst active in MTO reaction with 100 % methanol conversion, 89.39 % ethylene and propylene selectivity, a longest lifetime and a high coke capability of 24.2 wt %.


Catalysts ◽  
2022 ◽  
Vol 12 (1) ◽  
pp. 95
Author(s):  
Chu-Chin Hsieh ◽  
Jyong-Sian Tsai ◽  
Hwo-Shuenn Sheu ◽  
Jen-Ray Chang

V2O5/NaY-SiO2 adsorbents were prepared by soaking up vanadium oxalate precursors into pellet NaY-SiO2. The NaY-SiO2 supports were prepared from NaY-SiO2 dough followed by extrusion and calcination at 450 °C. Ethanol was used as a model adsorbate to test the performance of the adsorbents. The regeneration efficacy, defined as the ratio of the adsorption capacity of a regenerated adsorbent to that of the fresh adsorbent, was investigated through the dynamics of fixed-bed adsorption (breakthrough curve). TPO, DSC, and FT-IR were used to characterize carbonaceous species on the adsorbents; meanwhile, synchrotron XRPD, XAS, and the N2 isotherm were used to characterize the zeolite, vanadia structure, and surface area, respectively. The results indicated that in low temperature (300 °C) regeneration, adsorption sites covered by alkylated aromatic coke formed during regeneration, causing adsorbent deactivation. In contrast, during regeneration at a high temperature (450 °C), the deactivation was caused by the destruction of the NaY framework concomitant with channel blockage, as suggested by the BET surface area combined with Rietvelt XRPD refinement results. In addition, the appearance of V-O-V contribution in the EXAFS spectra indicated the aggregation of isolated VO4, which led to a decrease in the combustion rate of the carbonaceous species deposited on the adsorbents. For regeneration at 350 and 400 °C, only trace coke formation and minor structural destruction were observed. Long-term life tests indicated that regeneration at 400 °C presents a higher maintenance of stability.


In this paper, easy, rapid and cheap synthetic method was described for florfenicol-silver nanocomposite by sonochemical method. Florfenicol-silver nanocomposite was characterized based on three classes namely index, identification and morphology class. Index characterization was carried out by zeta sizing, BET surface area and zeta potential. Identification characterization was performed using X-ray diffraction (XRD) and Raman spectrometry. Morphology characterization was done utilizing transmission electron microscope (TEM), scanning electron microscope (SEM) and atomic force microscope (AFM). Characterization results showed zeta sizing of florfenicol was 30.44nm, while florfenicol-silver nanocomposite was 33.5 nm with zeta potential -14.1 and -18, respectively. BET surface area was found to be 13.3, 73.2 and 103.69 m2/g for florfenicol, silver nanoparticles and florfenicol-silver nanocomposite respectively. XRD and Raman charts confirmed the formation of florfenicol-silver nanocomposite without any contamination. TEM, SEM and AFM spectral data illustrated spherical to sub spherical shape of silver nanoparticles on cubic to sheet shape of florfenicol with size less than 50 nm. Antimicrobial activity was screened where the average zone of inhibitions caused by the prepared nanocomposite were 28.3 mm, 24 mm, 27.3 mm and 24 mm compared to 17.7 mm, 16 mm, 18.7 mm and 13.3 mm of the native drug and 13 mm, 10 mm, 14.3 mm and 15 mm of the used positive reference standards against E. coli, Salmonella typhymurium, Staphylococcus aureus and Staph.aureus MRSA respectively.


Processes ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 1238
Author(s):  
Garven M. Huntley ◽  
Rudy L. Luck ◽  
Michael E. Mullins ◽  
Nick K. Newberry

Four naturally occurring zeolites were examined to verify their assignments as chabazites AZLB-Ca and AZLB-Na (Bowie, Arizona) and clinoptilolites NM-Ca (Winston, New Mexico) and NV-Na (Ash Meadows, Nevada). Based on powder X-ray diffraction, NM-Ca was discovered to be mostly quartz with some clinoptilolite residues. Treatment with concentrated HCl (12.1 M) acid resulted in AZLB-Ca and AZLB-Na, the chabazite-like species, becoming amorphous, as confirmed by powder X-ray diffraction. In contrast, NM-Ca and NV-Na, which are clinoptilolite-like species, withstood boiling in concentrated HCl acid. This treatment removes calcium, magnesium, sodium, potassium, aluminum, and iron atoms or ions from the framework while leaving the silicon framework intact as confirmed via X-ray fluorescence and diffraction. SEM images on calcined and HCl treated NV-Na were obtained. BET surface area analysis confirmed an increase in surface area for the two zeolites after treatment, NM-Ca 20.0(1) to 111(4) m2/g and NV-Na 19.0(4) to 158(7) m2/g. 29Si and 27Al MAS NMR were performed on the natural and treated NV-Na zeolite, and the data for the natural NV-Na zeolite suggested a Si:Al ratio of 4.33 similar to that determined by X-Ray fluorescence of 4.55. Removal of lead ions from solution decreased from the native NM-Ca, 0.27(14), NV-Na, 1.50(17) meq/g compared to the modified zeolites, 30 min HCl treated NM-Ca 0.06(9) and NV-Na, 0.41(23) meq/g, and also decreased upon K+ ion pretreatment in the HCl modified zeolites.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Yoottapong Klinthongchai ◽  
Seeroong Prichanont ◽  
Piyasan Praserthdam ◽  
Bunjerd Jongsomjit

AbstractMesocellular foam carbon (MCF-C) is one the captivating materials for using in gas phase dehydrogenation of ethanol. Extraordinary, enlarge pore size, high surface area, high acidity, and spherical shape with interconnected pore for high diffusion. In contrary, the occurrence of the coke is a majority causes for inhibiting the active sites on catalyst surface. Thus, this study aims to investigate the occurrence of the coke to optimize the higher catalytic activity, and also to avoid the coke formation. The MCF-C was synthesized and investigated using various techniques. MCF-C was spent in gas-phase dehydrogenation of ethanol under mild conditions. The deactivation of catalyst was investigated toward different conditions. Effects of reaction condition including different reaction temperatures of 300, 350, and 400 °C on the deactivation behaviors were determined. The results indicated that the operating temperature at 400 °C significantly retained the lowest change of ethanol conversion, which favored in the higher temperature. After running reaction, the physical properties as pore size, surface area, and pore volume of spent catalysts were decreased owing to the coke formation, which possibly blocked the pore that directly affected to the difficult diffusion of reactant and caused to be lower in catalytic activity. Furthermore, a slight decrease in either acidity or basicity was observed owing to consumption of reactant at surface of catalyst or chemical change on surface caused by coke formation. Therefore, it can remarkably choose the suitable operating temperature to avoid deactivation of catalyst, and then optimize the ethanol conversion or yield of acetaldehyde.


Polymers ◽  
2021 ◽  
Vol 13 (14) ◽  
pp. 2275
Author(s):  
Arafat Toghan ◽  
Mohamed Gouda ◽  
Kamal Shalabi ◽  
Hany M. Abd El-Lateef

Converting low-cost bio-plant residuals into high-value reusable nanomaterials such as microcrystalline cellulose is an important technological and environmental challenge. In this report, nanocrystalline cellulose (NCC) was prepared by acid hydrolysis of macrocrystalline cellulose (CEL). The newly synthesized nanomaterials were fully characterized using spectroscopic and microscopic techniques including FE-SEM, FT-IR, TEM, Raman spectroscopy, and BET surface area. Morphological portrayal showed the rod-shaped structure for NCC with an average diameter of 10–25 nm in thickness as well as length 100–200 nm. The BET surface area of pure CEL and NCC was found to be 10.41 and 27 m2/g, respectively. The comparative protection capacity of natural polymers CEL and NCC towards improving the SS316 alloy corrosion resistance has been assessed during the acid pickling process by electrochemical (OCP, PDP, and EIS), and weight loss (WL) measurements. The outcomes attained from the various empirical methods were matched and exhibited that the protective efficacy of these polymers augmented with the upsurge in dose in this order CEL (93.1%) < NCC (96.3%). The examined polymers display mixed-corrosion inhibition type features by hindering the active centers on the metal interface, and their adsorption followed the Langmuir isotherm model. Surface morphology analyses by SEM reinforced the adsorption of polymers on the metal substrate. The Density Functional Theory (DFT) parameters were intended and exhibited the anti-corrosive characteristics of CEL and NCC polymers. A Monte Carlo (MC) simulation study revealed that CEL and NCC polymers are resolutely adsorbed on the SS316 alloy surface and forming a powerful adsorbed protective layer.


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