Search results for: clinoptilolite zeolite
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 142

Search results for: clinoptilolite zeolite

52 Heterogeneous Catalytic Hydroesterification of Soybean Oil to Develop a Biodiesel Formation

Authors: O. Mowla, E. Kennedy, M. Stockenhuber

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Finding alternative renewable resources of energy has attracted the attentions in consequence of limitation of the traditional fossil fuel resources, increasing of crude oil price and environmental concern over greenhouse gas emissions. Biodiesel (or Fatty Acid Methyl Esters (FAME)), an alternative energy source, is synthesised from renewable sources such as vegetable oils and animal fats and can be produced from waste oils. FAME can be produced via hydroesterification of oils. The process involves two stages. In the first stage of this process, fatty acids and glycerol are being obtained by hydrolysis of the feed stock oil. In the second stage, the recovered fatty acids are then esterified with an alcohol to methyl esters. The presence of a catalyst accelerates the rate of the hydroesterification reaction of oils. The overarching aim of this study is to find the effect of using zeolite as a catalyst in the heterogeneous hydroesterification of soybean oil. Both stages of the catalytic hydroesterification of soybean oil had been conducted at atmospheric and high-pressure conditions using reflux glass reactor and Parr reactor, respectively. The effect of operating parameters such as temperature and reaction time on the overall yield of biodiesel formation was also investigated.

Keywords: biodiesel, heterogeneous catalytic hydroesterification, soybean oil, zeolite

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51 A Study on the Performance Improvement of Zeolite Catalyst for Endothermic Reaction

Authors: Min Chang Shin, Byung Hun Jeong, Jeong Sik Han, Jung Hoon Park

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In modern times, as flight speeds have increased due to improvements in aircraft and missile engine performance, thermal loads have also increased. Because of the friction heat of air flow with high speed on the surface of the vehicle, it is not easy to cool the superheat of the vehicle by the simple air cooling method. For this reason, a cooling method through endothermic heat is attracting attention by using a fuel that causes an endothermic reaction in a high-speed vehicle. There are two main ways of cooling the fuel through the endothermic reaction. The first is physical heat absorption. When the temperature rises, there is a sensible heat that accompanies it. The second is the heat of reaction corresponding to the chemical heat absorption, which absorbs heat during the fuel decomposes. Generally, since the decomposition reaction of the fuel proceeds at a high temperature, it does not achieve a great efficiency in cooling the high-speed flight body. However, when the catalyst is used, decomposition proceeds at a low temperature thereby increasing the cooling efficiency. However, when the catalyst is used as a powder, the catalyst enters the engine and damages the engine or the catalyst can deteriorate the performance due to the sintering. On the other hand, when used in the form of pellets, catalyst loss can be prevented. However, since the specific surface of pellet is small, the efficiency of the catalyst is low. And it can interfere with the flow of fuel, resulting in pressure loss and problems with fuel injection. In this study, we tried to maximize the performance of the catalyst by preparing a hollow fiber type pellet for zeolite ZSM-5, which has a higher amount of heat absorption, than other conventional pellets. The hollow fiber type pellet was prepared by phase inversion method. The hollow fiber type pellet has a finger-like pore and sponge-like pore. So it has a higher specific surface area than conventional pellets. The crystal structure of the prepared ZSM-5 catalyst was confirmed by XRD, and the characteristics of the catalyst were analyzed by TPD/TPR device. This study was conducted as part of the Basic Research Project (Pure-17-20) of Defense Acquisition Program Administration.

Keywords: catalyst, endothermic reaction, high-speed vehicle cooling, zeolite, ZSM-5

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50 Batch and Dynamic Investigations on Magnesium Separation by Ion Exchange Adsorption: Performance and Cost Evaluation

Authors: Mohamed H. Sorour, Hayam F. Shaalan, Heba A. Hani, Eman S. Sayed

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Ion exchange adsorption has a long standing history of success for seawater softening and selective ion removal from saline sources. Strong, weak and mixed types ion exchange systems could be designed and optimized for target separation. In this paper, different types of adsorbents comprising zeolite 13X and kaolin, in addition to, poly acrylate/zeolite (AZ), poly acrylate/kaolin (AK) and stand-alone poly acrylate (A) hydrogel types were prepared via microwave (M) and ultrasonic (U) irradiation techniques. They were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The developed adsorbents were evaluated on bench scale level and based on assessment results, a composite bed has been formulated for performance evaluation in pilot scale column investigations. Owing to the hydrogel nature of the partially crosslinked poly acrylate, the developed adsorbents manifested a swelling capacity of about 50 g/g. The pilot trials have been carried out using magnesium enriched Red Seawater to simulate Red Seawater desalination brine. Batch studies indicated varying uptake efficiencies, where Mg adsorption decreases according to the following prepared hydrogel types AU>AM>AKM>AKU>AZM>AZU, being 108, 107, 78, 69, 66 and 63 mg/g, respectively. Composite bed adsorbent tested in the up-flow mode column studies indicated good performance for Mg uptake. For an operating cycle of 12 h, the maximum uptake during the loading cycle approached 92.5-100 mg/g, which is comparable to the performance of some commercial resins. Different regenerants have been explored to maximize regeneration and minimize the quantity of regenerants including 15% NaCl, 0.1 M HCl and sodium carbonate. Best results were obtained by acidified sodium chloride solution. In conclusion, developed cation exchange adsorbents comprising clay or zeolite support indicated adequate performance for Mg recovery under saline environment. Column design operated at the up-flow mode (approaching expanded bed) is appropriate for such type of separation. Preliminary cost indicators for Mg recovery via ion exchange have been developed and analyzed.

Keywords: batch and dynamic magnesium separation, seawater, polyacrylate hydrogel, cost evaluation

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49 Effect of Synthesis Parameters on Crystal Size and Perfection of Mordenite and Analcime

Authors: Zehui Du, Chaiwat Prapainainar, Paisan Kongkachuichay, Paweena Prapainainar

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The aim of this work was to obtain small crystalline size and high crystallinity of mordenites and analcimes, by modifying the aging time, agitation, water content, crystallization temperature and crystallization time. Two different hydrothermal methods were studied. Both methods used Na2SiO3 as the silica source, NaAlO2 as the aluminum source, and NaOH as the alkali source. The first method used HMI as the template while the second method did not use the template. Mordenite crystals with spherical shape and bimodal in size of about 1 and 5 µm were obtained from the first method using conditions of 24 hr aging time, 170°C and 24 hr crystallization. Modernites with high crystallinity were formed using agitation system in the crystallization process. It was also found that the aging time of 2 hr and 24 hr did not much affect the formation of mordenite crystals. Analcime crystals were formed in spherical shape and facet on surface with the size between 13-15 µm by the second method using the conditions of 30 minutes aging time, 170°C and 24 hr crystallization without calcination. By increasing water content, the crystallization process was slowed down and resulted in smaller analcime crystals. Larger size of analcime crystals were observed when the samples were calcined at 300°C and 580°C. Higher calcination temperature led to higher crystal growth and resulted in larger crystal size. Finally, mordenite and analcime was used as fillers in zeolite/Nafion composite membrane to solve the fuel cross over problem in direct alcohol fuel cell.

Keywords: analcime, hydrothermal synthesis, mordenite, zeolite

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48 Fabrication of Zeolite Modified Cu Doped ZnO Films and Their Response towards Nitrogen Monoxide

Authors: Irmak Karaduman, Tugba Corlu, Sezin Galioglu, Burcu Akata, M. Ali Yildirim, Aytunç Ateş, Selim Acar

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Breath analysis represents a promising non-invasive, fast and cost-effective alternative to well-established diagnostic and monitoring techniques such as blood analysis, endoscopy, ultrasonic and tomographic monitoring. Portable, non-invasive, and low-cost breath analysis devices are becoming increasingly desirable for monitoring different diseases, especially asthma. Beacuse of this, NO gas sensing at low concentrations has attracted progressive attention for clinical analysis in asthma. Recently, nanomaterials based sensors are considered to be a promising clinical and laboratory diagnostic tool, because its large surface–to–volume ratio, controllable structure, easily tailored chemical and physical properties, which bring high sensitivity, fast dynamic processand even the increasing specificity. Among various nanomaterials, semiconducting metal oxides are extensively studied gas-sensing materials and are potential sensing elements for breathanalyzer due to their high sensitivity, simple design, low cost and good stability.The sensitivities of metal oxide semiconductor gas sensors can be enhanced by adding noble metals. Doping contents, distribution, and size of metallic or metal oxide catalysts are key parameters for enhancing gas selectivity as well as sensitivity. By manufacturing doping MOS structures, it is possible to develop more efficient sensor sensing layers. Zeolites are perhaps the most widely employed group of silicon-based nanoporous solids. Their well-defined pores of sub nanometric size have earned them the name of molecular sieves, meaning that operation in the size exclusion regime is possible by selecting, among over 170 structures available, the zeolite whose pores allow the pass of the desired molecule, while keeping larger molecules outside.In fact it is selective adsorption, rather than molecular sieving, the mechanism that explains most of the successful gas separations achieved with zeolite membranes. In view of their molecular sieving and selective adsorption properties, it is not surprising that zeolites have found use in a number of works dealing with gas sensing devices. In this study, the Cu doped ZnO nanostructure film was produced by SILAR method and investigated the NO gas sensing properties. To obtain the selectivity of the sample, the gases including CO,NH3,H2 and CH4 were detected to compare with NO. The maximum response is obtained at 85 C for 20 ppb NO gas. The sensor shows high response to NO gas. However, acceptable responses are calculated for CO and NH3 gases. Therefore, there are no responses obtain for H2 and CH4 gases. Enhanced to selectivity, Cu doped ZnO nanostructure film was coated with zeolite A thin film. It is found that the sample possess an acceptable response towards NO hardly respond to CO, NH3, H2 and CH4 at room temperature. This difference in the response can be expressed in terms of differences in the molecular structure, the dipole moment, strength of the electrostatic interaction and the dielectric constant. The as-synthesized thin film is considered to be one of the extremely promising candidate materials in electronic nose applications. This work is supported by The Scientific and Technological Research Council of Turkey (TUBİTAK) under Project No, 115M658 and Gazi University Scientific Research Fund under project no 05/2016-21.

Keywords: Cu doped ZnO, electrical characterization, gas sensing, zeolite

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47 Mordenite as Catalyst Support for Complete Volatile Organic Compounds Oxidation

Authors: Yuri A. Kalvachev, Totka D. Todorova

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Zeolite mordenite has been investigated as a transition metal support for the preparation of efficient catalysts in the oxidation of volatile organic compounds (VOCs). The highly crystalline mordenite samples were treated with hydrofluoric acid and ammonium fluoride to get hierarchical material with secondary porosity. The obtained supports by this method have a high active surface area, good diffusion properties and prevent the extraction of metal components during catalytic reactions. The active metal phases platinum and copper were loaded by impregnation on both mordenite materials (parent and acid treated counterparts). Monometalic Pt and Cu, and bimetallic Pt/Cu catalysts were obtained. The metal phases were fine dispersed as nanoparticles on the functional porous materials. The catalysts synthesized in this way were investigated in the reaction of complete oxidation of propane and benzene. Platinum, copper and platinum/copper were loaded and there catalytic activity was investigated and compared. All samples are characterized by X-ray diffraction analysis, nitrogen adsorption, scanning electron microscopy (SEM), X-ray photoelectron measurements (XPS) and temperature programed reduction (TPR). The catalytic activity of the samples obtained is investigated in the reaction of complete oxidation of propane and benzene by using of Gas Chromatography (GC). The oxidation of three organic molecules was investigated—methane, propane and benzene. The activity of metal loaded mordenite catalysts for methane oxidation is almost the same for parent and treated mordenite as a support. For bigger molecules as propane and benzene, the activity of catalysts based on treated mordenite is higher than those based on parent zeolite.

Keywords: metal loaded catalysts, mordenite, VOCs oxidation, zeolites

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46 High Temperature and High Pressure Purification of Hydrogen from Syngas Using Metal Organic Framework Adsorbent

Authors: Samira Rostom, Robert Symonds, Robin W. Hughes

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Hydrogen is considered as one of the most important clean and renewable energy carriers for a sustainable energy future. However, its efficient and cost-effective purification remains challenging. This paper presents the potential of using metal–organic frameworks (MOFs) in combination with pressure swing adsorption (PSA) technology for syngas based H2 purification. PSA process analysis is done considering high pressure and elevated temperature process conditions, it reduces the demand for off-gas recycle to the fuel reactor and simultaneously permits higher desorption pressure, thereby reducing the parasitic load on the hydrogen compressor. The elevated pressure and temperature adsorption we present here is beneficial to minimizing overall process heating and cooling demand compared to existing processes. Here, we report the comparative performance of zeolite-5A, Cu-BTC, and the mix of zeolite-5A/Cu-BTC for H2 purification from syngas typical of those exiting water-gas-shift reactors. The MOFs were synthesized hydrothermally and then mixed systematically at different weight ratios to find the optimum composition based on the adsorption performance. The formation of different compounds were characterized by XRD, N2 adsorption and desorption, SEM, FT-IR, TG, and water vapor adsorption technologies. Single-component adsorption isotherms of CO2, CO, CH4, N2, and H2 over single materials and composites were measured at elevated pressures and different temperatures to determine their equilibrium adsorption capacity. The examination of the stability and regeneration performance of metal–organic frameworks was carried out using a gravimetric system at temperature ranges of 25-150℃ for a pressure range of 0-30 bar. The studies of adsorption/desorption on the MOFs showed selective adsorption of CO2, CH4, CO, and N2 over H2. Overall, the findings of this study suggest that the Ni-MOF-74/Cu-BTC composites are promising candidates for industrial H2 purification processes.

Keywords: MOF, H2 purification, high T, PSA

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45 Development and Characterization of Cobalt Metal Loaded ZSM-5 and H-ZSM-5 Catalyst for Fischer -Tropsch Synthesis

Authors: Shashank Bahri, Divyanshu Arya, Rajni Jain, Sreedevi Upadhyayula

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Petroleum products can be obtained from syngas catalytic conversion using Fischer Tropsch Reaction. The liquid fuels obtained from FTS are sulphur and nitrogen free and thus may easily meet the increasing stringent environment regulations. In the present work we have synthesized Meso porous ZSM-5 supported catalyst. Meso structure were created in H-ZSM-5 crystallites by demetalation via subsequent base and acid treatment. Desilication through base treatment provides H-ZSM-5 with pore size and volumes similar to amorphous SiO2 (Conventional Carrier). Modifying the zeolite texture and surface chemistry by Desilication and acid washing alters its accessibility and interactions with metal phase and consequently the CO adsorption behavior and hydrocarbon product distribution. Increasing the mesoporosity via desilication provides the micro porous zeolite with essential surface area to support optimally sized metal crystallites. This improves the metal dispersion and hence improve the activity of the catalyst. Transition metal (Co) was loaded using wet impregnation method. Synthesized catalysts were characterized by Infrared Spectroscopy, Powdered X-Ray Diffraction, Scanning Electron Microscopy (SEM), BET Method analytical techniques. Acidity of the catalyst which plays an important role in FTS reaction was measured by DRIFT setup pyridine adsorption instead of NH3 Temperature Programmed Desorption. The major difference is that, Pyridine Adsorption can distinguish between Lewis acidity and Bronsted Acidity, thus giving their relative strengths in the catalyst sample, whereas TPD gives total acidity including Lewis and Bronsted ones.

Keywords: mesopourus, fischer tropsch reaction, pyridine adsorrption, drift study

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44 Impact of Soot on NH3-SCR, NH3 Oxidation and NH3 TPD over Cu/SSZ-13 Zeolite

Authors: Lidija Trandafilovic, Kirsten Leistner, Marie Stenfeldt, Louise Olsson

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Ammonia Selective Catalytic Reduction (NH3 SCR), is one of the most efficient post combustion abatement technologies for removing NOx from diesel engines. In order to remove soot, diesel particulate filters (DPF) are used. Recently, SCR coated filters have been introduced, which captures soot and simultaneously is active for ammonia SCR. There are large advantages with using SCR coated filters, such as decreased volume and also better light off characteristics, since both the SCR function as well as filter function is close to the engine. The objective of this work was to examine the effect of soot, produced using an engine bench, on Cu/SSZ-13 catalysts. The impact of soot on Cu/SSZ-13 in standard SCR, NH3 oxidation, NH3 temperature programmed desorption (TPD), as well as soot oxidation (with and without water) was examined using flow reactor measurements. In all experiments, prior to the soot loading, the fresh activity of Cu/SSZ-13 was recorded with stepwise increasing the temperature from 100°C till 600°C. Thereafter, the sample was loaded with soot and the experiment was repeated in the temperature range from 100°C till 700°C. The amount of CO and CO2 produced in each experiment is used to calculate the soot oxidized at each steady state temperature. The soot oxidized during the heating to next temperature step is included, e.g. the CO+CO2 produced when increasing the temperature to 600°C is added to the 600°C step. The influence of the two factors seem to be of the most importance to soot oxidation: ammonia and water. The influence of water on soot oxidation shift the maximum of CO2 and CO production towards lower temperatures, thus water increases the soot oxidation. Moreover, when adding ammonia to the system it is clear that the soot oxidation is lowered in the presence of ammonia, resulting in larger integrated COx at 500°C for O2+H2O, while opposite results at 600 °C was received where more was oxidised for O2+H2O+NH3 case. To conclude the presence of ammonia reduces the soot oxidation, which is in line with the ammonia TPD results where we found ammonia storage on the soot. Interestingly, during ammonia SCR conditions the activity for soot oxidation is regained at 500°C. At this high temperature the SCR zone is very short, thus the majority of the catalyst is not exposed to ammonia and therefore the inhibition effect of ammonia is not observed.

Keywords: NH3-SCR, Cu/SSZ-13, soot, zeolite

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43 Wound Healing Dressing and Some Composites Such as Zeolite, TiO2, Chitosan and PLGA as New Alternative for Melanoma Therapy: A Review

Authors: L. B. Naves, L. Almeida

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The development of Drugs Delivery System (DDS), has been wildly investigated in the last decades. In this paper, first a general overview of traditional and modern wound dressing is presented. This is followed by a review of what scientist have done in the medical environment, focusing the possibility to develop a new alternative for DDS through transdermal pathway, aiming to treat melanoma skin cancer.

Keywords: cancer therapy, dressing polymers, melanoma, wound healing

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42 Synthesis of Belite Cements at Low Temperature from Silica Fume and Natural Commercial Zeolite

Authors: Tatiana L. Avalos-Rendon, Elias A. Pasten Chelala, Carlos J. Mendoza EScobedo, Ignacio A. Figueroa, Victor H. Lara, Luis M. Palacios-Romero

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The cement industry is facing cost increments in energy supply, requirements for reduction of CO₂, and insufficient supply of raw materials of good quality. According to all these environmental issues, cement industry must change its consumption patterns and reduce CO₂ emissions to the atmosphere. This can be achieved by generating environmental consciousness, which encourages the use of industrial by-products and/or recycling for the production of cement, as well as alternate, environment-friendly methods of synthesis which reduce CO₂. Calcination is the conventional method for the obtainment of Portland cement clinker. This method consists of grinding and mixing of raw materials (limestone, clay, etc.) in an adequate dosage. Resulting mix has a clinkerization temperature of 1450 °C so that the formation of the main component occur: alite (Ca₃SiO₅, C₃S). Considering that the energy required to produce C₃S is 1810 kJ kg -1, calcination method for the obtainment of clinker represents two major disadvantages: long thermal treatment and elevated temperatures of synthesis, both of which cause high emissions of carbon dioxide (CO₂) to the atmosphere. Belite Portland clinker is characterized by having a low content of calcium oxide (CaO), causing the presence of alite to diminish and favoring the formation of belite (β-Ca₂SiO₄, C₂S), so production of clinker requires a reduced energy consumption (1350 kJ kg-1), releasing less CO₂ to the atmosphere. Conventionally, β-Ca₂SiO₄ is synthetized by the calcination of calcium carbonate (CaCO₃) and silicon dioxide (SiO₂) through the reaction in solid state at temperatures greater than 1300 °C. Resulting belite shows low hydraulic reactivity. Therefore, this study concerns a new simple modified combustion method for the synthesis of two belite cements at low temperatures (1000 °C). Silica fume, as subproduct of metallurgic industry and commercial natural zeolite were utilized as raw materials. These are considered low-cost materials and were utilized with no additional purification process. Belite cements properties were characterized by XRD, SEM, EDS and BET techniques. Hydration capacity of belite cements was calculated while the mechanical strength was determined in ordinary Portland cement specimens (PC) with a 10% partial replacement of the belite cements obtained. Results showed belite cements presented relatively high surface áreas, at early ages mechanical strengths similar to those of alite cement and comparable to strengths of belite cements obtained by different synthesis methods. Cements obtained in this work present good hydraulic reactivity properties.

Keywords: belite, silica fume, zeolite, hydraulic reactivity

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41 Synthesis, Characterization, and Catalytic Application of Modified Hierarchical Zeolites

Authors: A. Feliczak Guzik, I. Nowak

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Zeolites, classified as microporous materials, are a large group of crystalline aluminosilicate materials commonly used in the chemical industry. These materials are characterized by large specific surface area, high adsorption capacity, hydrothermal and thermal stability. However, the micropores present in them impose strong mass transfer limitations, resulting in low catalytic performance. Consequently, mesoporous (hierarchical) zeolites have attracted considerable attention from researchers. These materials possess additional porosity in the mesopore size region (2-50 nm according to IUPAC). Mesoporous zeolites, based on commercial MFI-type zeolites modified with silver, were synthesized as follows: 0.5 g of zeolite was dispersed in a mixture containing CTABr (template), water, ethanol, and ammonia under ultrasound for 30 min at 65°C. The silicon source, which was tetraethyl orthosilicate, was then added and stirred for 4 h. After this time, silver(I) nitrate was added. In a further step, the whole mixture was filtered and washed with water: ethanol mixture. The template was removed by calcination at 550°C for 5h. All the materials obtained were characterized by the following techniques: X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption/desorption isotherms, FTIR spectroscopy. X-ray diffraction and low-temperature nitrogen adsorption/desorption isotherms revealed additional secondary porosity. Moreover, the structure of the commercial zeolite was preserved during most of the material syntheses. The aforementioned materials were used in the epoxidation reaction of cyclohexene using conventional heating and microwave radiation heating. The composition of the reaction mixture was analyzed every 1 h by gas chromatography. As a result, about 60% conversion of cyclohexene and high selectivity to the desired reaction products i.e., 1,2-epoxy cyclohexane and 1,2-cyclohexane diol, were obtained.

Keywords: catalytic application, characterization, epoxidation, hierarchical zeolites, synthesis

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40 New Approach for Melanoma Skin Cancer Controled Releasing Drugs for Neutron Capture Therapy: A Review

Authors: Lucas Bernardes Naves, Luis Almeida

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The paper includes a review concerning the use of some composites including poly(lactide-co-glycolide) (PGLA), zeolite and Gadopentetic acid (Gd-DTPA) loaded chitosan nanoparticles (Gd-nanoCPs) in order to establish a new alternative for the treatment of Melanoma Skin Cancer. The main goal of this paper it to make a review of what scientist have done in the last few years, as well as to propose a less invasive therapy for skin cancer, by using Hydrocolloid, based on PLGA coated with Gd-nanoCPs for Neutron Capture Therapy.

Keywords: cancer therapy, dressing polymers, melanoma, wound healing

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39 Quantum Chemical Investigation of Hydrogen Isotopes Adsorption on Metal Ion Functionalized Linde Type A and Faujasite Type Zeolites

Authors: Gayathri Devi V, Aravamudan Kannan, Amit Sircar

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In the inner fuel cycle system of a nuclear fusion reactor, the Hydrogen Isotopes Removal System (HIRS) plays a pivoted role. It enables the effective extraction of the hydrogen isotopes from the breeder purge gas which helps to maintain the tritium breeding ratio and sustain the fusion reaction. One of the components of HIRS, Cryogenic Molecular Sieve Bed (CMSB) columns with zeolites adsorbents are considered for the physisorption of hydrogen isotopes at 1 bar and 77 K. Even though zeolites have good thermal stability and reduced activation properties making them ideal for use in nuclear reactor applications, their modest capacity for hydrogen isotopes adsorption is a cause of concern. In order to enhance the adsorbent capacity in an informed manner, it is helpful to understand the adsorption phenomena at the quantum electronic structure level. Physicochemical modifications of the adsorbent material enhances the adsorption capacity through the incorporation of active sites. This may be accomplished through the incorporation of suitable metal ions in the zeolite framework. In this work, molecular hydrogen isotopes adsorption on the active sites of functionalized zeolites are investigated in detail using Density Functional Theory (DFT) study. This involves the utilization of hybrid Generalized Gradient Approximation (GGA) with dispersion correction to account for the exchange and correlation functional of DFT. The electronic energies, adsorption enthalpy, adsorption free energy, Highest Occupied Molecular Orbital (HOMO), Lowest Unoccupied Molecular Orbital (LUMO) energies are computed on the stable 8T zeolite clusters as well as the periodic structure functionalized with different active sites. The characteristics of the dihydrogen bond with the active metal sites and the isotopic effects are also studied in detail. Validation studies with DFT will also be presented for adsorption of hydrogen on metal ion functionalized zeolites. The ab-inito screening analysis gave insights regarding the mechanism of hydrogen interaction with the zeolites under study and also the effect of the metal ion on adsorption. This detailed study provides guidelines for selection of the appropriate metal ions that may be incorporated in the zeolites framework for effective adsorption of hydrogen isotopes in the HIRS.

Keywords: adsorption enthalpy, functionalized zeolites, hydrogen isotopes, nuclear fusion, physisorption

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38 Synthesis of Nanoparticle Mordenite Zeolite for Dimethyl Ether Carbonylation

Authors: Zhang Haitao

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The different size of nanoparticle mordenite zeolites were prepared by adding different soft template during hydrothermal process for carbonylation of dimethyl ether (DME) to methyl acetate (MA). The catalysts were characterized by X-ray diffraction, Ar adsorption-desorption, high-resolution transmission electron microscopy, NH3-temperature programmed desorption, scanning electron microscopy and Thermogravimetric. The characterization results confirmed that mordenite zeolites with small nanoparticle showed more strong acid sites which was the active site for carbonylation thus promoting conversion of DME and MA selectivity. Furthermore, the nanoparticle mordenite had increased the mass transfer efficiency which could suppress the formation of coke.

Keywords: nanoparticle mordenite, carbonylation, dimethyl ether, methyl acetate

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37 Hierarchical Zeolites as Catalysts for Cyclohexene Epoxidation Reactions

Authors: Agnieszka Feliczak-Guzik, Paulina Szczyglewska, Izabela Nowak

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A catalyst-assisted oxidation reaction is one of the key reactions exploited by various industries. Their conductivity yields essential compounds and intermediates, such as alcohols, epoxides, aldehydes, ketones, and organic acids. Researchers are devoting more and more attention to developing active and selective materials that find application in many catalytic reactions, such as cyclohexene epoxidation. This reaction yields 1,2-epoxycyclohexane and 1,2-diols as the main products. These compounds are widely used as intermediates in the perfume industry and synthesizing drugs and lubricants. Hence, our research aimed to use hierarchical zeolites modified with transition metal ions, e.g., Nb, V, and Ta, in the epoxidation reaction of cyclohexene using microwaveheating. Hierarchical zeolites are materials with secondary porosity, mainly in the mesoporous range, compared to microporous zeolites. In the course of the research, materials based on two commercial zeolites, with Faujasite (FAU) and Zeolite Socony Mobil-5 (ZSM-5) structures, were synthesized and characterized by various techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and low-temperature nitrogen adsorption/desorption isotherms. The materials obtained were then used in a cyclohexene epoxidation reaction, which was carried out as follows: catalyst (0.02 g), cyclohexene (0.1 cm3), acetonitrile (5 cm3) and dihydrogen peroxide (0.085 cm3) were placed in a suitable glass reaction vessel with a magnetic stirrer inside in a microwave reactor. Reactions were carried out at 45° C for 6 h (samples were taken every 1 h). The reaction mixtures were filtered to separate the liquid products from the solid catalyst and then transferred to 1.5 cm3 vials for chromatographic analysis. The test techniques confirmed the acquisition of additional secondary porosity while preserving the structure of the commercial zeolite (XRD and low-temperature nitrogen adsorption/desorption isotherms). The results of the activity of the hierarchical catalyst modified with niobium in the cyclohexene epoxidation reaction indicate that the conversion of cyclohexene, after 6 h of running the process, is about 70%. As the main product of the reaction, 2-cyclohexanediol was obtained (selectivity > 80%). In addition to the mentioned product, adipic acid, cyclohexanol, cyclohex-2-en-1-one, and 1,2-epoxycyclohexane were also obtained. Furthermore, in a blank test, no cyclohexene conversion was obtained after 6 h of reaction. Acknowledgments The work was carried out within the project “Advanced biocomposites for tomorrow’s economy BIOG-NET,” funded by the Foundation for Polish Science from the European Regional Development Fund (POIR.04.04.00-00-1792/18-00.

Keywords: epoxidation, oxidation reactions, hierarchical zeolites, synthesis

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36 Removal of Nitenpyram from Farmland Runoff by an Integrated Ecological Ditches with Constructed Wetland System

Authors: Dan Qu, Dezhi Sun, Benhang Li

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The removal of Nitenpyram from farmland runoff by an integrated eco-ditches and constructed wetland system was investigated in the case of different HRT. Experimental results show that the removal of COD, N and P was not influenced by the Nitenpyram. When the HRT was 2.5 d, 2 d, and 1 d, the Nitenpyram removal efficiency could reach 100%, 100% and 84%, respectively. The removal efficiency in the ecological ditches was about 38%-40% in the case of different HRT, while that in the constructed wetland was influenced by the HRT variation. The optimum HRT for Nitenpyram and pollutants removal was 2 d. The substrate zeolite with soil and hollow brick layer enabled higher Nitenpyram removal rates, probably due to the cooperative phenomenon of plant uptake and microbiological deterioration as well as the adsorption by the substrate.

Keywords: ecological ditch, vertical flow constructed wetland, hydraulic retention time, Nitenpyram

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35 Investigation of Modified Microporous Materials for Environmental Depollution

Authors: Souhila Bendenia, Chahrazed Bendenia, Hanaa Merad-Dib, Sarra Merabet, Samia Moulebhar, Sid Ahmed Khantar

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Today, environmental pollution is a major concernworldwide, threateninghumanhealth. Various techniques have been used, includingdegradation, filtration, advancedoxidationprocesses, ion exchange, membrane processes, and adsorption. The latter is one of the mostsuitablemethods, usinghighly efficient materials. In this study, NaX zeolite was modified with Cu or Ni at various rates. Following ion exchange, the samples were characterized by XRD, BET and SEM/EDX. After characterization, the exchanged zeolites were used for adsorption of various pollutants as CO2. Different thermodynamic parameters were studied such as Qst. XRD results show that the most intense peaks characteristic of 13X persist after the exchange reaction for all samples. The SEM images of our samples have uniform and regular crystal shapes. The results show that ion exhange with Cu or Ni affect the textural properties of X zeolites and prove that the exchange zeolites can be used as an adsorbent for depollution.

Keywords: X zeolites (NaX), ion exchange, characterization, adsorption

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34 Usy-Cui Zeolite: An Efficient and Reusable Catalyst for Derivatives Indole Synthesis

Authors: Hassina Harkat, Samiha Taybe, Salima Loucif, Valérie Beneteau, Patrick Pale

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Indole and its derivatives have attracted great interest because of their importance in the synthetic organic and medicinal chemistry. They are widely used as anti hypertension, anti tubercular, anticancer activity, antiviral, Alzheimer's disease, antioxidant properties, and free radical induced lipid peroxidation. Many drugs and natural products contain indole moiety, such as the vinca alkaloids, fungal metabolites and marine natural products. Generally applicable synthetic methods for indole moiety involve ring closure to form the pyrrole. Indole derivatives can also be accessed by further functionalization of the indole nucleus. Therefore we report a mild and efficient protocol for the synthesis of analogues of indole catalyzed via zeolithe USY doped with CuI under solvent-free conditions.

Keywords: indole, zeolithe, USY-CuI, heterogeneous catalysis

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33 Phenols and Manganese Removal from Landfill Leachate and Municipal Waste Water Using the Constructed Wetland

Authors: Amin Mojiri, Lou Ziyang

Abstract:

Constructed wetland (CW) is a reasonable method to treat waste water. Current study was carried out to co-treat landfill leachate and domestic waste water using a CW system. Typha domingensis was transplanted to CW, which encloses two substrate layers of adsorbents named ZELIAC and zeolite. Response surface methodology and central composite design were employed to evaluate experimental data. Contact time (h) and leachate to waste water mixing ratio (%; v/v) were selected as independent factors. Phenols and manganese removal were selected as dependent responses. At optimum contact time (48.7 h) and leachate to waste water mixing ratio (20.0%), removal efficiencies of phenols and manganese removal efficiencies were 90.5%, and 89.4%, respectively.

Keywords: constructed wetland, Manganese, phenols, Thypha domingensis

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32 Silver Nanoparticles Impregnated Zeolitic Composites: Effect of the Silver Loading on Adsorption of Mercury (II)

Authors: Zhandos Tauanov, Dhawal Shah, Grigorios Itskos, Vasileios Inglezakis

Abstract:

Removal of mercury (II) from aqueous phase is of utmost importance, as it is highly toxic and hazardous to the environment and human health. One way of removal of mercury (II) ions from aqueous solutions is by using adsorbents derived from coal fly ash (CFA), such as synthetic zeolites. In this work, we present the hydrothermal production of synthetic zeolites from CFA with conversion rate of 75%. In order to produce silver containing nanocomposites, synthetic zeolites are subsequently impregnated with various amounts of silver nanoparticles, from 0.2 to 2wt.%. All produced zeolites and parent materials are characterized by XRD, XRF, BET, SEM, and TEM to obtain morphological and microstructural data. Moreover, mercury (II) ions removal from aqueous solutions with initial concentration of 10 ppm is studied. According to results, zeolites and Ag-nanocomposites demonstrate much higher removal than parent CFA (up to 98%). In addition to this, we could observe a distinct adsorption behavior depending on the loading of Ag NPs in nanocomposites. A possible reaction mechanism for both zeolites and Ag-nanocomposites is discussed.

Keywords: coal fly ash, mercury (II) removal, nanocomposites, silver nanoparticles, synthetic zeolite

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31 Cellulose Supported Heterogeneous Pd(II) Catalyst for Synthesis of Biaryls

Authors: Talat Baran

Abstract:

The Suzuki C(sp2)-C(sp2) coupling reaction is considered to be one of the best ways for the synthesis of biaryl compounds. There are many studies reporting the catalytic performance of palladium catalyst in Suzuki coupling reactions. Natural biopolymer (such as zeolite, carbon, silica, and chitosan) supporting catalysts have been lately attracted interest because of their low-cost, nontoxicity, and eco-friendliness. One of the most important natural biopolymer is cellulose, which is widely considered as an eco-friendly biopolymer due to its biodegradable, non-toxic and renewable nature. In this study, (1) cellulose supported Pd(II) catalyst was synthesized (2) its chemical structure was characterized by FT-IR, SEM/EDAX, XRD, TG-DTG, ICP-OES techniques (3) to investigate the performance of the catalyst in Suzuki coupling reactions by using microwave irradiation technique (4) reusability of the catalyst was done under optimum conditions. This cellulose supported Pd(II) catalyst exhibited high selectivity and efficiency in Suzuki coupling reactions under mild conditions (50°C). High TON and TOF values were recorded for the catalyst. Also, the reusability tests showed the catalysts could be used for several times in consequence of reusability tests.

Keywords: palladium, cellulose, Schiff base, reusability

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30 The Key Role of Yttrium Oxide on Devitrification Resilience of Barium Gallo-germanate Glasses: Physicochemical Properties and Crystallization Study

Authors: Samar Aoujia, Théo Guérineaub, Rayan Zaitera, Evelyne Fargina, Younès Messaddeqb, Thierry Cardinala

Abstract:

Two barium gallo-germanate glass series were elaborated to investigate the effect of the yttrium introduction on the glass physicochemical properties and crystallization behavior. One to twenty mol% of YO3/2 were either added into the glass matrix or substituted for gallium oxide. The glass structure was studied by Raman spectroscopy, and the thermal, optical, thermo-mechanical and physical properties are examined. The introduction of yttrium ions in both glass series increases the glass transition temperature, crystallization temperature, softening temperature, coefficient of linear thermal expansion and density. Through differential scanning calorimetry and X-ray diffraction analyses, it was found that competition occurs between the gallo-germanate zeolite-type phase and the yttrium-containing phase. From 13 mol% of YO3/2, the yttrium introduction impedes the formation of surface crystallization in these glasses.

Keywords: photonic, heavy-metal oxide, glass, crystallization

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29 Effect of Evaporator Temperature on the Performance of Water Desalination/Refrigeration Adsorption System Using AQSOA-ZO2

Authors: Peter G. Youssef, Saad M. Mahmoud, Raya K. AL-Dadah

Abstract:

Many water desalination technologies have been developed but in general they are energy intensive and have high cost and adverse environmental impact. Recently, adsorption technology for water desalination has been investigated showing the potential of using low temperature waste heat (50-85oC) thus reducing energy consumption and CO2 emissions. This work mathematically compares the performance of an adsorption cycle that produces two useful effects namely, fresh water and cooling using two different adsorbents, silica-gel and an advanced zeolite material AQSOA-ZO2, produced by Mitsubishi plastics. It was found that at low chilled water temperatures, typically below 20oC, the AQSOA-Z02 is more efficient than silica-gel as the cycle can produce 5.8 m3 of fresh water per day and 50.1 Rton of cooling per tonne of AQSOA-ZO2. Above 20oC silica-gel is still better as the cycle production reaches 8.4 m3 per day and 62.4 Rton per tonne of silica-gel. These results show the potential of using the AQSOA-Z02 at low chilled water temperature for water desalination and cooling applications.

Keywords: adsorption, desalination, refrigeration, seawater

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28 Analysis of Sulphur-Oxidizing Bacteria Attack on Concrete Based on Waste Materials

Authors: A. Eštoková, M. Kovalčíková, A. Luptáková, A. Sičáková, M. Ondová

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Concrete durability as an important engineering property of concrete, determining the service life of concrete structures very significantly, can be threatened and even lost due to the interactions of concrete with external environment. Bio-corrosion process caused by presence and activities of microorganisms producing sulphuric acid is a special type of sulphate deterioration of concrete materials. The effects of sulphur-oxidizing bacteria Acidithiobacillus thiooxidans on various concrete samples, based on silica fume and zeolite, were investigated in laboratory during 180 days. A laboratory study was conducted to compare the performance of concrete samples in terms of the concrete deterioration influenced by the leaching of calcium and silicon compounds from the cement matrix. The changes in the elemental concentrations of calcium and silicon in both solid samples and liquid leachates were measured by using X – ray fluorescence method. Experimental studies confirmed the silica fume based concrete samples were found out to have the best performance in terms of both silicon and calcium ions leaching.

Keywords: biocorrosion, concrete, leaching, bacteria

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27 Synthesis of Green Fuel Additive from Waste Bio-Glycerol

Authors: Ala’a H. Al-Muhtaseb, Farrukh Jamil, Lamya Al-Haj, Mohab Al-Hinai

Abstract:

Bio-glycerol is considered as high boiling polar triol and immiscible with fossil fuel fractions due to which it is transformed into its respective ketals and acetals which help to improve the quality of diesel emitting less amount of aldehydes and carbon monoxide. Solketal visual appearance is transparent and it is odorless organic liquid used as fuel additive for diesel to improve its cold flow properties. Condensation of bio-glycerol with bio-acetone in presence of beta zeolite has been done for synthesizing solketal. It was observed that glycerol conversion and selectivity of solketal was largely effected by temperature, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. At the optimum conditions, the bio-glycerol conversion and solketal yield were about 94.26% and 94.21wt% respectively. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: bio-acetone, bio-glycerol, acetylation, solketal

Procedia PDF Downloads 239
26 Synthesis of Oxygenated Fuel Additive from Bio-Glycerol

Authors: Farrukh Jamil, Ala'a H. Al-Muhtaseb, Lamya Al-Haj, Mohab A. Al-Hinai

Abstract:

Glycerol is considered as high boiling polar triol and immiscible with fossil fuel fractions due to which it is transformed into its respective ketals and acetals which help to improve the quality of diesel emitting less amount of aldehydes and carbon monoxide. Solketal visual appearance is transparent, and it is odorless organic liquid used as a fuel additive for diesel to improve its cold flow properties. Condensation of bio-glycerol with bio-acetone in presence of beta zeolite has been done for synthesizing solketal. It was observed that glycerol conversion and selectivity of solketal was largely effected by temperature, as it increases from 40 ºC to 60 ºC the conversion of glycerol rises from 80.04 % to 94.26 % and selectivity of solketal from 80.0 % to 94.21 % but further increase in temperature to 100 ºC glycerol conversion reduced to 93.06 % and solketal selectivity to 92.08 %. At the optimum conditions, the bio-glycerol conversion and solketal yield were about 94.26% and 94.21wt% respectively. This process offers an attractive route for converting bio-glycerol, the main by-product of biodiesel to solketal with bio-acetone; a value-added green product with potential industrial applications as a valuable green fuel additive or combustion promoter for gasoline/diesel engines.

Keywords: bio-glycerol, catalyst, green additive, biomass

Procedia PDF Downloads 215
25 Soil Mixed Constructed Permeable Reactive Barrier for Groundwater Remediation: Field Observation

Authors: Ziyda Abunada

Abstract:

In-situ remediation of contaminated land with deep mixing can deliver a multi-technique remedial strategy. A field trail includes permeable reactive barrier (PRB) took place at a severely contaminated site in Yorkshire to the north of the UK through the SMiRT (Soil Mix Remediation Technology) project in May 2011. SMiRT involved the execution of the largest research field trials in the UK to provide field validation. Innovative modified bentonite materials in combination with zeolite and organoclay were used to construct six different walls of a hexagonal PRB. Field monitoring, testing and site cores were collected from the PRB twice: once 2 months after the construction and again in March 2014 (almost 34 months later).This paper presents an overview of the results of the PRB materials’ relative performance with some initial 3-year time-related assessment. Results from the monitoring program and the site cores are presented. Some good correlations are seen together with some clear difference among the materials’ efficiency. These preliminary observations represent a potential for further investigations and highlighted the main lessons learned in a filed scale.

Keywords: in-situ remediation, groundwater, permeable reactive barrier, site cores

Procedia PDF Downloads 178
24 Numerical Analysis of Heat and Mass Transfer in an Adsorbent Bed for Different Working Pairs

Authors: N. Allouache, O. Rahli

Abstract:

Solar radiation is by far the largest and the most world’s abundant, clean, and permanent energy source. In recent years, many promising technologies have been developed to harness the sun's energy. These technologies help in environmental protection, economizing energy, and sustainable development, which are the major issues of the world. One of these important technologies is the solar refrigerating machines that make use of either absorption or adsorption technologies. In this present work, the adsorbent bed is modelized and optimized using different working pairs, such as zeolite-water, silica gel-water, activated carbon-ammonia, calcium chlorid-ammonia, activated carbon fiber- methanol and activated carbon AC35-methanol. The results show that the enhancement of the heat and mass transfer depends on the properties of the working pair; the performances of the adsorption cycle are essentially influenced by the choice of the adsorbent-adsorbate pair. The system can operate successfully for optimal parameters such as the evaporator, condenser, and generating temperatures. The activated carbon is the best adsorbent due to its high surface area and micropore volume.

Keywords: adsorbent bed, heat and mass transfer, numerical analysis, working pairs

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23 Impact of Zn/Cr Ratio on ZnCrOx-SAPO-34 Bifunctional Catalyst for Direct Conversion of Syngas to Light Olefins

Authors: Yuxuan Huang, Weixin Qian, Hongfang Ma, Haitao Zhang, Weiyong Ying

Abstract:

Light olefins are important building blocks for chemical industry. Direct conversion of syngas to light olefins has been investigated for decades. Meanwhile, the limit for light olefins selectivity described by Anderson-Schulz-Flory (ASF) distribution model is still a great challenge to conventional Fischer-Tropsch synthesis. The emerging strategy called oxide-zeolite concept (OX-ZEO) is a promising way to get rid of this limit. ZnCrOx was prepared by co-precipitation method and (NH4)2CO3 was used as precipitant. SAPO-34 was prepared by hydrothermal synthesis, and Tetraethylammonium hydroxide (TEAOH) was used as template, while silica sol, pseudo-boehmite, and phosphoric acid were Al, Si and P source, respectively. The bifunctional catalyst was prepared by mechanical mixing of ZnCrOx and SAPO-34. Catalytic reactions were carried out under H2/CO=2, 380 ℃, 1 MPa and 6000 mL·gcat-1·h-1 in a fixed-bed reactor with a quartz lining. Catalysts were characterized by XRD, N2 adsorption-desorption, NH3-TPD, H2-TPR, and CO-TPD. The addition of Al as structure promoter enhances CO conversion and selectivity to light olefins. Zn/Cr ratio, which decides the active component content and chemisorption property of the catalyst, influences CO conversion and selectivity to light olefins at the same time. C2-4= distribution of 86% among hydrocarbons at CO conversion of 14% was reached when Zn/Cr=1.5.

Keywords: light olefins, OX-ZEO, Syngas, ZnCrOₓ

Procedia PDF Downloads 151