Search results for: zeolites

Authors: Jeeranun Neaungjumnong, Sasikarn Yairit, Sudarat Pattanapaiboonkul, Pramoch Rangsunvigit, Santi Kulprathipanja

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Crystallization has been used for the separation of chloronitrobenzene or CNBs, which are isomeric substances (o-, mand p-CNB) and important intermediates in chemical productions. Effects of feed composition on the crystallization of m- and p-CNB was first studied. The results conform to the binary phase diagram of m- and p-CNB. After that, effects of FAU zeolites (NaX, CaX, BaX, NaY and CaY) above the eutectic composition (63.5 and 65.0 wt% m-CNB in the feed) was also investigated. The results showed that the FAU zeolites significantly affected the precipitates, the composition of which was shifted from being rich in m-CNB to rich in p-CNB. Effects of the number of FAU zeolites on the precipitate composition was then studied. The results revealed that the precipitates from the lower number of the zeolites had higher p-CNB purity than those from the higher number of zeolite.

Keywords: Chloronitrobenzenes, crystallization, separation, eutectic

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Authors: Esma Gizem Daskiran, Mehmet Mustafa Daskiran

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This paper investigates the effectiveness of two natural zeolites in reducing expansion of concrete due to alkali-silica reaction. These natural zeolites have different reactive silica content. Three aggregates; two natural sands and one crushed stone aggregate were used while preparing mortar bars in accordance with accelerated mortar bar test method, ASTM C1260. Performances of natural zeolites are compared by examining the expansions due to alkali silica reaction. Natural zeolites added to the mixtures at 10% and 20% replacement levels by weight of cement. Natural zeolite with high reactive silica content had better performance on reducing expansions due to ASR. In this research, using high reactive zeolite at 20% replacement levels was effective in mitigating expansions.

Keywords: Alkali silica reaction, natural zeolite, durability, expansion.

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Authors: V. Golubeva, A. Korableva, O. Anischenko, A. Nemova, N. Yegorushina, L. Kustov, G. Kapustin, U.S.Rohatgi

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The implementation of Super-Ultra Low Emission Vehicle standards requires more efficient exhaust gas purification. To increase the efficiency of exhaust gas purification, an the adsorbent capable of holding hydrocarbons up to 250-300 ОС should be developed. The possibility to design such adsorbents by modification of zeolites of mordenite type, ZSM-5 and NaY, using different metals cations has been studied. It has been shown that introducing Cr, Cs, Zn, Ni, Co, Li, Mn in zeolites results in modification of the toluene TPD and toluene sorption capacity. 5%LiZSM-5 zeolite exhibits the most attractive TPD curve, with toluene desorption temperature ranging from 250 to 350ОС. The sorption capacity of 5%Li-ZSM-5 is 0.4 mmol/g. NaY zeolite has the highest sorption capacity, up to 2 mmol/g, and holds toluene up to 350ОС, but at 120ОС toluene desorption starts, which is not desirable, since the adsorbent of cold start hydrocarbons should retain them until 250-300ОС. Therefore 5%LiZSM-5 zeolite was found to be the most promising to control the cold-start hydrocarbon emissions among the samples studied.

Keywords: Hydrocarbon emission control, adsorbents, zeolites, temperature-programmed desorption.

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Authors: Alireza Behvandi, Somayeh Tourani

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High pressure adsorption of carbon dioxide on zeolite 13X was investigated in the pressure range (0 to 4) Mpa and temperatures 298, 308 and 323K. The data fitting is accomplished with the Toth, UNILAN, Dubinin-Astakhov and virial adsorption models which are generally used for micro porous adsorbents such as zeolites. Comparison with experimental data from the literature indicated that the virial model would best determine results. These results may be partly attributed to the flexibility of the virial model which can accommodate as many constants as the data warrants.

Keywords: adsorption models, zeolite, carbon dioxide

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Authors: E. Vejmelková, M. Ondráček, R. Černý

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Mechanical and water transport properties of high performance concrete (HPC) containing natural zeolite as partial replacement of Portland cement are studied. Experimental results show that in the investigated mixes the use of natural zeolite leads to an increase of porosity, decrease of compressive strength and increase of moisture diffusivity and water vapor diffusion coefficient, as compared with the reference HPC. However, for the replacement level up to 20% of the mass of Portland cement the concretes still maintain their high performance character and exhibit acceptable water transport properties. Therefore, natural zeolite can be considered an environmental friendly binder with a potential to replace a part of Portland cement in concrete in building industry.

Keywords: Natural zeolites, high-performance concrete; hydric properties, mechanical properties

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Authors: Shahryar Aftabi, Saeed Fathi, Mohammad H. Aminfar

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It is well known that cemented sand is one of the best approaches for soil stabilization. In some cases, a blend of sand, cement and other pozzolan materials such as zeolite, nano-particles and fiber can be widely (commercially) available and be effectively used in soil stabilization, especially in road construction. In this research, we investigate the effects of CaO which is based on the geotechnical characteristics of zeolite composition with sandy silt soil. Zeolites have low amount of CaO in their structures, that is, varying from 3% to 10%, and by removing the cement paste, we want to investigate the effect of zeolite pozzolan without any activator on soil samples strength. In this research, experiments are concentrated on various weight percentages of zeolite in the soil to examine the effect of the zeolite on drainage shear strength and California Bearing Ratio (CBR) both with and without curing. The study also investigates their liquid limit and plastic limit behavior and makes a comparative result by using Feng's and Wroth-Wood's methods in fall cone (cone penetrometer) device; in the final the SEM images have been presented. The results show that by increasing the percentage of zeolite in without-curing samples, the fine zeolite particles increase some soil's strength, but in the curing-state we can see a relatively higher strength toward without-curing state, since the zeolites have no plastic behavior, the pozzolanic property of zeolites plays a much higher role than cementing properties. Indeed, it is better to combine zeolite particle with activator material such as cement or lime to gain better results.

Keywords: CBR, direct shear, fall-cone, sandy-silt, SEM, zeolite.

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Authors: Kolay P. K., Singh H.

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The coal utilization in thermal power plants in Malaysia has increased significantly which produces an enormous amount of coal combustion by-product (CCBP) or coal ash and poses severe disposal problem. As each coal ash is distinct, this study presents the geochemistry of the coal ash, in particular fly ash, produced from the combustion of local coal from Kuching Sarawak, Malaysia. The geochemical composition of the ash showed a high amount of silica, alumina, iron oxides and alkalies which was found to be a convenient starting material for the hydrothermal synthesis of zeolites with the higher Na₂O percentage being a positive factor for its alkaline activation; while the mineral phases are mainly quartz, mullite, calcium oxide, silica, and iron oxide hydrate. The geochemical changes upon alkali activation that can be predicted in a similar type of ash have been described in this paper. The result shows that this particular ash has a good potential for a high value industrial product like zeolites upon alkali activation.

Keywords: Coal ash, chemical composition, mineralogical composition, alkali activation, SEM.

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Authors: Abu S.M. Junaid, Wei Wang, Christopher Street, Moshfiqur Rahman, Matt Gersbach, Sarah Zhou, William McCaffrey, Steven M. Kuznicki

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Oilsands bitumen is an extremely important source of energy for North America. However, due to the presence of large molecules such as asphaltenes, the density and viscosity of the bitumen recovered from these sands are much higher than those of conventional crude oil. As a result the extracted bitumen has to be diluted with expensive solvents, or thermochemically upgraded in large, capital-intensive conventional upgrading facilities prior to pipeline transport. This study demonstrates that globally abundant natural zeolites such as clinoptilolite from Saint Clouds, New Mexico and Ca-chabazite from Bowie, Arizona can be used as very effective reagents for cracking and visbreaking of oilsands bitumen. Natural zeolite cracked oilsands bitumen products are highly recoverable (up to ~ 83%) using light hydrocarbons such as pentane, which indicates substantial conversion of heavier fractions to lighter components. The resultant liquid products are much less viscous, and have lighter product distribution compared to those produced from pure thermal treatment. These natural minerals impart similar effect on industrially extracted Athabasca bitumen.

Keywords: Natural Zeolites, Oilsands Bitumen, Cracking, Viscosity Reduction, Upgrading.

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Authors: Yi-Jie Lin, Jyh-Cherng Chen

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The fly ash of waste incineration processes is usually hazardous and the disposal or reuse of waste incineration fly ash is difficult. In this study, the waste incineration fly ash was converted to useful zeolites by the alkali fusion and hydrothermal synthesis method. The influence of different operating conditions (the ratio of Si/Al, the ratio of hydrolysis liquid to solid, and hydrothermal time) was investigated to seek the optimum operating conditions for the synthesis of zeolite from waste incineration fly ash. The results showed that concentrations of heavy metals in the leachate of Toxicity Characteristic Leaching Procedure (TCLP) were all lower than the regulatory limits except lead. The optimum operating conditions for the synthesis of zeolite from waste incineration fly ash by the alkali fusion and hydrothermal synthesis method were Si/Al=40, NaOH/ash=1.5, alkali fusion at 400 ^oC for 40 min, hydrolysis with Liquid to Solid ratio (L/S)= 200 at 105 ^oC for 24 h, and hydrothermal synthesis at 105 ^oC for 24 h. The specific surface area of fly ash could be significantly increased from 8.59 m²/g to 651.51 m²/g (synthesized zeolite). The influence of different operating conditions on the synthesis of zeolite from waste incineration fly ash followed the sequence of Si/Al ratio > hydrothermal time > hydrolysis L/S ratio. The synthesized zeolites can be reused as good adsorbents to control the air or wastewater pollutants. The purpose of fly ash detoxification, reduction and waste recycling/reuse is achieved successfully.

Keywords: Alkali fusion, hydrothermal, fly ash, zeolite.

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Authors: D. Mowla, N. Rasti, P. Keshavarz

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Reduction of fossil fuels sources, increasing of pollution gases emission, and global warming effects increase the demand of renewable fuels. One of the main candidates of alternative fuels is biodiesel. Biodiesel limits greenhouse gas effects due to the closed CO₂ cycle. Biodiesel has more biodegradability, lower combustion emissions such as CO, SO_x, HC, PM and lower toxicity than petro diesel. However, biodiesel has high production cost due to high price of plant oils as raw material. So, the utilization of waste cooking oils (WCOs) as feedstock, due to their low price and disposal problems reduce biodiesel production cost. In this study, production of biodiesel by transesterification of methanol and WCO using modified sodic potassic (SP) clinoptilolite zeolite and sodic potassic calcic (SPC) clinoptilolite zeolite as heterogeneous catalysts have been investigated. These natural clinoptilolite zeolites were modified by KOH solution to increase the site activity. The optimum biodiesel yields for SP clinoptilolite and SPC clinoptilolite were 95.8% and 94.8%, respectively. Produced biodiesel were analyzed and compared with petro diesel and ASTM limits. The properties of produced biodiesel confirm well with ASTM limits. The density, kinematic viscosity, cetane index, flash point, cloud point, and pour point of produced biodiesel were all higher than petro diesel but its acid value was lower than petro diesel. Finally, the reusability and regeneration of catalysts were investigated. The results indicated that the spent zeolites cannot be reused directly for the transesterification, but they can be regenerated easily and can obtain high activity.

Keywords: Biodiesel, renewable fuel, transesterification, waste cooking oil.

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Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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Catalytic cracking of butene to propylene was carried out in a continuous-flow fixed-bed reactor over HZSM-5 catalysts modified by nickel and phosphorus. The structure and acidity of catalysts were measured by N₂ adsorption, NH₃-TPD and XPS. The results revealed that surface area and strong acid sites both decreased with increasing phosphorus loadings. The increment of phosphorus loadings reduced the butene conversion but enhanced the propylene selectivity and catalyst stability.

Keywords: Butene, catalytic cracking, HZSM-5, modification.

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Authors: Andrew P. Hurt, George J. Vine, Samantha E. Booth, Nichola J. Coleman

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Silver-exchanged zeolites and clays are used in polymer composites to confer broad-spectrum antimicrobial properties on a range of functional materials. Tobermorite is a layer lattice mineral whose potential as a carrier for Ag+ ions in antibacterial composites has not yet been investigated. Accordingly, in this study, synthetic tobermorite was ion-exchanged with 10 wt% silver ions and the resulting material was incorporated into a composite film with chitosan. Chitosan is a biocompatible, biodegradable derivative of chitin, a polysaccharide obtained from the shells of crustaceans. The solvent-cast Ag+-exchanged tobermorite-chitosan films were found to exhibit antimicrobial action against Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa.

Keywords: Antimicrobial, chitosan, silver, tobermorite.

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Authors: Jianwen Li, Hongfang Ma, Weixin Qian, Haitao Zhang, Weiyong Ying

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Methanol-to-propylene conversion was carried out in a continuous-flow fixed-bed reactor over nano-sized HZSM-5 zeolites. The HZSM-5 catalysts were synthesized with different Si/Al ratio and silicon sources, and treated with NaOH. The structural property, morphology, and acidity of catalysts were measured by XRD, N₂ adsorption, FE-SEM, TEM, and NH₃-TPD. The results indicate that the increment of Si/Al ratio decreased the acidity of catalysts and then improved propylene selectivity, while silicon sources had slight impact on the acidity but affected the product distribution. The desilication after alkali treatment could increase intracrystalline mesopores and enhance propylene selectivity.

Keywords: Alkali treatment, HZSM-5, methanol-to-propylene, synthesis condition.

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Authors: Jianwen Li, Hongfang Ma, Haitao Zhang, Qiwen Sun, Weiyong Ying

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HZSM-5 zeolites modified by iron and phosphorus were applied in catalytic cracking of butene. N2 adsorption and NH3-TPD were employed to measure the structure and acidity of catalysts. The results indicate that increasing phosphorus loading decreased surface area, pore volume and strong acidity of catalysts. The addition of phosphorus significantly decreased butene conversion and promoted propylene selectivity. The catalytic performance of catalyst was strongly dependent on the reaction conditions. Appropriate reaction conditions could suppress side reactions and enhance propylene selectivity.

Keywords: Butene catalytic cracking, HZSM-5, modification, reaction conditions.

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Authors: Tunchanok Nitipan, Siriporn Jongpatiwut, Thirasak Rirksomboon, Boonyarach Kitiyanan, Tivaporn Apphakvan

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In this study, the conversion of n-pentane to aromatics is investigated on HZSM-5 zeolites modified by Ga ion-exchange and silylation using tetraethyl orthosilicate (TEOS) via chemical liquid deposition (CLD). The effect of SiO2/Al2O3 ratios of HZSM-5 was also studied. Parameters in preparing catalysts i.e. TEOS loading and cycles of deposition were varied to obtain the optimal condition for enhancing p-xylene selectivity. The highest p-xylene selectivity 99.7% was achieved when the amount of TEOS was 20 vol.%.The catalysts were characterized by TPD, TPO, XRF, and BET. Results show that the conversion of n-pentane was influenced remarkably by the SiO2/Al2O3 ratios of HZSM-5. The highest p-xylene selectivity 99.7% was achieved when the amount of TEOS was 20 vol.%. And cycles of deposition greatly improves HZSM-5 shape-selectivity.

Keywords: Aromatization, Chemical Liquid Deposition (CLD), p-Xylene, ZSM-5 Zeolite

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Authors: P.P. Diale, S.S.L. Mkhize, E. Muzenda, J. Zimba

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For more than 120 years, gold mining formed the backbone the South Africa-s economy. The consequence of mine closure was observed in large-scale land degradation and widespread pollution of surface water and groundwater. This paper investigates the feasibility of using natural zeolite in removing heavy metals contaminating the Wonderfonteinspruit Catchment Area (WCA), a water stream with high levels of heavy metals and radionuclide pollution. Batch experiments were conducted to study the adsorption behavior of natural zeolite with respect to Fe2+, Mn2+, Ni2+, and Zn2+. The data was analysed using the Langmuir and Freudlich isotherms. Langmuir was found to correlate the adsorption of Fe2+, Mn2+, Ni2+, and Zn2+ better, with the adsorption capacity of 11.9 mg/g, 1.2 mg/g, 1.3 mg/g, and 14.7 mg/g, respectively. Two kinetic models namely, pseudo-first order and pseudo second order were also tested to fit the data. Pseudo-second order equation was found to be the best fit for the adsorption of heavy metals by natural zeolite. Zeolite functionalization with humic acid increased its uptake ability.

Keywords: gold-mining, natural zeolites, water pollution, WestRand.

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Authors: Rana Th. A. Al-Rubaye, Burcin Atilgan, Richard J. Holmes, Arthur A. Garforth

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Structured catalysts formed from the growth of zeolites on substrates is an area of increasing interest due to the increased efficiency of the catalytic process, and the ability to provide superior heat transfer and thermal conductivity for both exothermic and endothermic processes. However, the generation of structured catalysts represents a significant challenge when balancing the relationship variables between materials properties and catalytic performance, with the Na2O, H2O and Al2O3 gel composition paying a significant role in this dynamic, thereby affecting the both the type and range of application. The structured catalyst films generated as part of this investigation have been characterised using a range of techniques, including X-ray diffraction (XRD), Electron microscopy (SEM), Energy Dispersive X-ray analysis (EDX) and Thermogravimetric Analysis (TGA), with the transition from oxide-on-alloy wires to hydrothermally synthesised uniformly zeolite coated surfaces being demonstrated using both SEM and XRD. The robustness of the coatings has been ascertained by subjecting these to thermal cycling (ambient to 550oC), with the results indicating that the synthesis time and gel compositions have a crucial effect on the quality of zeolite growth on the FeCrAlloy wires. Finally, the activity of the structured catalyst was verified by a series of comparison experiments with standard zeolite Y catalysts in powdered pelleted forms.

Keywords: FeCrAlloy, Structured catalyst, and Zeolite Y.

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Authors: Ali Zaker, Zhi Chen

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Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.

Keywords: Activated char, bio-oil, catalytic pyrolysis, HZSM5, sewage sludge.

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