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1.
ACS Omega ; 8(36): 32775-32783, 2023 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-37720756

RESUMO

The aim of this research was to examine the effect of strontium content in the MgAlO catalyst for the catalytic ethanol reaction on the product distribution. The structure of the catalysts and the actual amount of strontium on the catalysts were verified using XRD and ICP techniques, respectively. The acid and basic strength characteristics of catalysts were examined using NH3-TPD and CO2-TPD techniques, respectively. The strontium content was found to influence the textural properties and the acidic and basic characteristics of the catalysts, leading to differences in product selectivity and ethanol conversion. The MgAlO catalyst with 1.9 wt % strontium provided the maximum ethylene and butanol selectivity, probably due to the presence of appropriate medium acidic and strong basic sites. All catalysts can efficiently produce ethylene by a dehydration reaction and acetaldehyde by a dehydrogenation reaction. Acetaldehyde selectivity was dominant with increased strontium loading.

2.
ACS Omega ; 7(29): 25783-25797, 2022 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-35910179

RESUMO

The deterioration behaviors of Cu/ZnO/Al2O3 (CZA) catalysts upon different Cu contents were elucidated. The fresh and spent catalysts after being used in CO and CO2 hydrogenation at 250 °C under atmospheric pressure were properly characterized using various techniques including X-ray powder diffraction, X-ray photoelectron spectroscopy, and temperature-programmed reduction for the changes of metal sites, while the textural and chemical properties and carbon deposition on spent CZA catalysts were analyzed by N2 physisorption, energy-dispersive X-ray spectroscopy, and temperature-programmed oxidation. During the hydrogenation reaction for both CO and CO2, the unstable Cu0 site on the spent CZA catalyst having a low Cu loading (sCZA-L) was oxidized to CuO and the aggregation of metal crystallite sites (Cu-ZnO and ZnO) was observed. Moreover, the amount of carbon deposition on sCZA-L (ca. >2%) is higher than the spent CZA catalyst having a high Cu loading (sCZA-H, ca. <0.5%). These phenomena led to a decrease in the surface area and the blockage of active sites. These findings can be determined on the catalytic deactivation and the obvious decrease in the catalytic activity of the CZA catalyst having a low Cu content (CZA-L, Cu:Zn = 0.8).

3.
Chemosphere ; 301: 134579, 2022 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-35413367

RESUMO

Hydrogen sulfide (H2S) is a critical problem for biogas applications, such as electricity and heat generation, or the production of different chemical compounds, due to corrosion and toxic effluent gases. The selective catalytic oxidation of H2S to S is the most promising way to eliminate H2S from biogas due to the lack of effluents, therefore can be considered a green technology. The most extensively used catalysts for H2S selective oxidation can be classified in two groups: metal oxide-based catalysts, including vanadium and iron oxides, and carbon-based catalysts. Numerous studies have been devoted to studying their different catalytic performances. For industrial applications, the most suitable catalysts should be less sensitive to the operating parameters like the temperature, O2/H2S ratio, and H2O content. More specifically, for metal oxides and carbon-based catalysts, the temperature and O2/H2S ratio have a similar effect on the conversion and selectivity, but carbon-based catalysts are less sensitive to water in all operating conditions.


Assuntos
Sulfeto de Hidrogênio , Biocombustíveis , Carbono , Catálise , Sulfeto de Hidrogênio/química , Oxirredução , Óxidos , Enxofre/química
4.
J Oleo Sci ; 71(1): 141-149, 2022 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-34880152

RESUMO

The MgAlO catalyst was obtained from thermal decomposition of the MgAl-LDH catalyst having Mg/Al molar ratio of 5. The catalytic Guerbet reaction of ethanol was investigated to determine the effect of WHSV and nitrogen flow rate on butanol production and product distribution. It was performed in a fixed-bed microreactor under continuous flow of vaporized ethanol mixed with N2. The MgAlO catalyst had high total basic sites and high total acid sites that were crucial for ethanol Guerbet reaction. The MgAlO catalyst showed the highest butanol selectivity at 300℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 3,600 mL/h, and the highest butanol yield at 400℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 900 mL/h. It can be summarized that in order to enhance the butanol yield, the low WHSV is preferred to increase the contact time of ethanol and catalyst under moderate temperature.


Assuntos
Alumínio/química , Butanóis/síntese química , Etanol/química , Hidróxidos/química , Magnésio/química , Biocombustíveis , Catálise , Temperatura Alta , Nitrogênio/química , Volatilização
5.
ACS Omega ; 6(30): 19911-19923, 2021 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-34368578

RESUMO

This study aims to convert ethanol to higher value-added products, particularly diethyl ether and ethylene using the catalytic dehydration of ethanol. Hence, the gas-phase dehydration of ethanol over Al2O3-HAP catalysts as such and modified by addition of palladium (Pd) in a microreactor was evaluated. The commercial Al2O3-HAP catalyst was first prepared by the physical mixing method, and then, the optimal ratio of the Al2O3-HAP catalyst (2:8 by wt %) was impregnated with Pd to develop a new functional catalyst to alter surface acidity. Based on the results, the combination of Al2O3 and HAP catalysts generated significant quantities of weak acid sites which demonstrates an enhancement in catalytic activity. In addition, Pd modification in the optimal composition ratio of the Al2O3-HAP catalyst extremely increased the amount of weak acid sites as well as weak acid density due to the synergistic effect between the Pd and Al2O3-HAP catalyst that are supposed to suggest the active sites in the reaction. Among all catalysts, the Al20-HAP80-Pd catalyst displayed brilliant catalytic performance in the course of diethyl ether yield (ca. 51.0%) at a reaction temperature of 350 °C and ethylene yield (ca. 75.0%) at a reaction temperature of 400 °C having an outstanding stability under time-on-stream for 10 h. This is recognized to the combination of the effects of weak acid sites (Lewis acidity), small amount of strong acid sites, and structural characteristics of the catalytic materials used.

6.
Heliyon ; 7(7): e07682, 2021 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-34386633

RESUMO

The ternary Cu/ZnO/Al2O3 (CZA) catalysts having different Cu loading were prepared by the co-precipitation method. Then, they were used in CO and CO2 hydrogenation to produce methanol under atmospheric pressure at 250 °C. The high Cu loading CZA catalyst (CZA-H) resulted in the enhancement of structural features and textural properties (e.g., BET surface area and the crystallite size of copper species). Furthermore, the conversion of CO and CO2 over CZA-H catalyst was apparently higher than that of the CZA-L (low Cu loading) catalyst. The major product of CO hydrogenation obtained from both catalysts was methanol, whereas in CO2 hydrogenation, the main product was CO. Deactivation of catalysts was also crucial during CO and CO2 hydrogenation. Therefore, the spent catalysts were determined to identify the nature of carbon formation. It revealed that amorphous and graphitic cokes were present. These cokes have different mechanisms in the elimination from the surface leading to influencing the deactivation process. The spent CZA-L was found to have higher carbon content, which was around 2.3% and 3.1% for CO and CO2 hydrogenation, respectively. Besides the amorphous coke, the graphitic coke was also observed in CZA-L after time on stream for 5 h.

7.
Sci Rep ; 11(1): 11683, 2021 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-34083667

RESUMO

Mesocellular 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.

8.
Molecules ; 25(18)2020 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-32899569

RESUMO

The porous carbon (bacterial cellulose (BC)-activated carbon (AC)(BA)) prepared via two-step activation of bacterial nanocellulose by treatments with potassium hydroxide (KOH) and then phosphoric acid (H3PO4) solutions showed superior adsorption properties and effective performance as catalyst support. BC-AC(BA) had an open and interconnected multi-porous structure, consisting of micropores (0.23 cm3/g), mesopores (0.26 cm3/g), and macropores (4.40 cm3/g). The BET surface area and porosity were 833 m2/g and 91.2%, respectively. The methylene blue adsorption test demonstrated that BC-AC(BA) was superior in its mass transfer rate and adsorption capacities. Moreover, BC-AC(BA) modified by H3PO4 treatment showed a significant enhancement of catalytic performance for dehydration of ethanol. At the reaction temperature of 250-400 °C, 30P/BC-AC(BA) gave ethanol conversion at 88.4-100%, with ethylene selectivity of 82.6-100%, whereas, high selectivity for diethyl ether (DEE) at 75.2%, at ethanol conversion of 60.1%, was obtained at the reaction temperature of 200 °C.


Assuntos
Bactérias/química , Celulose/química , Carvão Vegetal/química , Nanopartículas/química , Adsorção , Catálise , Etanol/química , Cinética , Nitrogênio/química , Espectroscopia Fotoeletrônica , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Difração de Raios X
9.
Sci Rep ; 10(1): 13643, 2020 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-32788643

RESUMO

The Na-ZSM-5 catalysts (SiO2/Al2O3 molar ratio = 20, 35, and 50) were prepared by rapid crystallization method to investigate their performance in butene cracking reaction. The XRD, XRF, NH3-TPD, FT-IR, TPO, UV-Vis, and 1H, 27Al, 29Si MAS NMR techniques were used to identify the physical and chemical properties of Na-ZSM-5 catalysts. The silanol group (Si-OH) was the main acid site of Na-ZSM-5, and it was proposed to be the active site for the butene cracking reaction. The butene conversion and coke formation were associated with the abundance of silanol groups over the Na-ZSM-5 catalyst. The dealumination, resulting in the deformation of tetrahedral framework aluminum species was a key factor for Na-ZSM-5 catalyst deactivation, because of the Si-O-Al bond breaking and formation of Si-O-Si bond. The stability of the Si-O-Al bond was linked to the molar number of sodium since the Na atom interacts with the Si-O-Al bond to form Si-ONa-Al structure, which enhances the stability of the silanol group. Therefore, the Si-ONa-Al in zeolite framework was an essential structure to retain the catalyst stability during the reaction. The Na-ZSM-5 with the lowest SiO2/Al2O3 molar ratio showed the best performance in this study resulting the highest propylene yield and catalyst stability.

10.
J Oleo Sci ; 69(5): 503-515, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32378552

RESUMO

In the present work, the palladium (Pd) modification and supporting effect of W/TiO2 catalysts on catalytic ethanol dehydration to ethylene and diethyl ether were investigated. The Pd modification with different sequence of Pd and W impregnation on the catalysts was prepared by the incipient wetness impregnation technique. The catalyst characterization and activity testing revealed that the different sequence during impregnation influenced the physicochemical properties and ethanol conversion of catalyst. The differences in structure and surface properties were investigated by XRD, BET, SEM, EDX, XPS and NH3-TPD. Upon the reaction temperature between 200 to 400°C, it was found that the conversion increased with increasing of temperature for all catalysts. The Pd incorporated into catalysts enhanced the ethanol conversion depending on the sequence of impregnation. At low temperature (ca. 200 to 300°C), diethyl ether is a major product and the Pd modification over W/TiO2 catalyst resulted in increased diethyl ether yield. This is because an increase of ethanol conversion was obtained with Pd modification, while diethyl ether selectivity did not change. This can be attributed to the higher amount of weak acids sites present after Pd modification into catalyst. Among all catalysts, the PdW/TiO2 catalyst (coimpregnation) achieved the highest diethyl ether yield of 41.4% at 300℃. At high temperature (ca. 350 to 400°C), ethylene is the major product. The W/Pd/TiO2 catalyst (with sequential impregnation of Pd on TiO2 followed by W) exhibited the highest ethylene yield of 68.1% at 400°C. It can be concluded that the modification of Pd onto W/TiO2 upon different sequence of Pd and W impregnation can improve the diethyl ether and ethylene yield in catalytic ethanol dehydration.


Assuntos
Etanol/química , Éter/química , Etilenos/química , Paládio/química , Titânio/química , Tungstênio/química , Catálise , Fenômenos Químicos , Hidrólise , Temperatura
11.
J Hazard Mater ; 384: 121161, 2020 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-31629599

RESUMO

Mesoporous ZSM-5 (MFI) zeolite was synthesized by using bacterial cellulose-derived activated carbon (BC-AC500) with a high surface area as a hard template. Different ratios of BC-AC500 and zeolite precursor gel were prepared in a Teflon-lined autoclave and crystallized at 180 °C for 48 h in a rotating oven. The physicochemical properties of the samples were characterized by x-ray diffraction (XRD), scanning/transmission electron microscopies (SEM/TEM), and N2 physisorption techniques. It was found that the mesoporous ZSM-5 zeolites have a specific surface area of 184-190 m2/g, a high mesopore volume of 0.120-0.956 ml/g and a wide pore size distribution ranging from 5 to 100 nm with a maximum at approximately 25.3 nm. The successfully made mesoporous ZSM-5 was tested as an adsorbent for formaldehyde adsorption in batch mode. The mesoporous ZSM-5 zeolite made from bacterial cellulose-derived activated carbon showed significantly faster adsorption kinetics than conventional ZSM-5 (0.0081 vs. 0.0007 g/mg min, respectively). The prepared material has an adsorption capacity of 98 mg/g and is highly reusable. The reported mesoporous ZSM-5 zeolites can be deployed for the rapid removal of toxic organics from wastewater when urgently needed, e.g., under breakthrough conditions.


Assuntos
Formaldeído/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Zeolitas/química , Adsorção , Bactérias , Carbono , Celulose
12.
Sci Rep ; 9(1): 19738, 2019 Dec 24.
Artigo em Inglês | MEDLINE | ID: mdl-31875002

RESUMO

The high ethylene selectivity exhibited on the zirconia-activated-carbon bi-support catalyst is investigated by experiment and density functional theory-based (DFT) analysis. This bi-support catalyst systems prepared by the physical mixing method for the tungsten catalyst show a significant increase in ethylene selectivity up to 90% compared to the zirconia single support system (~58%) during the ethanol dehydration reaction. Besides, the optimal percent weight ratio of zirconia to activated carbon, which results in the highest ethanol conversion is 50:50. The DFT-based analysis is used to investigate high ethylene selectivity in the bi-support system. It shows that the WO5/zirconia is the most stable model for the zirconia single-support tungsten catalyst represented by the zirconia (101) facet of the tetrahedral phase. The carbon atoms were added to the WO5/zirconia to model the tungsten catalyst on the bi-support system. The Bader charge analysis is carried out to determine the electron transfer in the catalyst. The bonding between ethylene and the WO5 active site on the catalyst is weakened when the system is bi-support, where the added carbon atoms on the catalyst in the ZrO2 region decrease the ethylene adsorption energy. Thus, the desorption and the selectivity of ethylene are promoted. The decrease in adsorption energy can be explained via the analysis of the projected density of states (PDOS) profiles of atom involving the adsorption. It was found that the added carbon in the ZrO2 region induces the electron transfer from the ethylene molecule to the surface, especially to the ZrO2 region. The depletion of the electron around the ethylene molecule weakens the bonds, thus, promote desorption. Hence, the advantages of using the bi-support system in the tungsten catalyst are that the catalyst exhibit (1) high conversion due to the zirconia support and (2) high ethylene selectivity due to the added carbon promoting the desorption of ethylene via the induction of electron from an ethylene molecule to surface.

13.
Heliyon ; 5(8): e02324, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31463407

RESUMO

This research investigated pyrolysis as a potential method to manage plastic waste in Sichang Island, Thailand. Pyrolysis was chosen to convert waste plastic into fuel oil using Al-Si catalysts derived from cogon grass. The study consisted of three stages. The first stage determined the composition of the waste plastics found in Sichang Island. High-density polyethylene (48%) comprised the highest proportion of the waste plastics, followed by low-density polyethylene (22%), polyethylene terephthalate (13%), polypropylene (10%), and polystyrene (7%). In the second stage, the Al-Si catalysts were prepared from cogon grass (Imperata cylindrica (L.) Beauv) by treating it with acid and calcination. The optimum conditions to extract silica from cogon grass through acid treatment were heating at 700 °C for 2 h, which yielded 97.7% of amorphous silica with a surface area of 172 m2/g and a pore volume of 0.43 cc/g. This amorphous silica was combined with an aluminum precursor to form Al-Si catalysts with 20-80 wt% of Al-Si. The results showed that the surface area of the catalyst increased with increasing aluminum content. The optimum ratio was 60 wt% of Al-Si with a surface area of 200 m2/g. In the final stage, the catalytic properties of the previously prepared Al-Si catalysts in the pyrolysis of waste plastics were evaluated. The catalyst enhanced the plastic cracking process and the oil yield while decreasing the reaction time. The optimum ratio of 60% Al-Si to 10% waste plastic provided the maximum oil yield of 93.11% and the minimum reaction time of 20 min. The results showed that catalytic cracking with 60% Al-Si contributed to a high quantity of oil yield, similar to using a commercial Al-Si catalyst. The results of this research will be applied as an alternative method of recycling plastic for sustainable waste management in Sichang Island.

14.
J Oleo Sci ; 68(7): 679-687, 2019 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-31178468

RESUMO

Hydrotalcite or Mg-Al LDHs were synthesized by co-precipitation method. The Mg-Al mixed oxide was then derived by calcination of hydrotalcite at 450°C. The metal modified catalysts (Mo/Mg-Al and V/Mg-Al) were prepared by incipient wetness impregnation method. The obtained catalysts were characterized by several useful techniques and tested the reactivity for dehydrogenation and oxidative dehydrogenation of ethanol (gas-phase) to produce acetaldehyde. The catalytic reactions were performed at temperature range from 200 to 400°C for both non-oxidative and oxidative atmospheres. The results showed that the vanadium-modified hydrotalcite (V/Mg-Al) exhibited the highest ethanol conversion (34.3%) and acetaldehyde yield (15.5%) at 400℃ in the non-oxidative atmosphere. For the oxidative dehydrogenation of ethanol, the V/Mg-Al catalyst showed the highest activity at 400°C giving the ethanol conversion and acetaldehyde yield of 73.7% and 29.5%, respectively. This result probably related to the highest base density of V/Mg-Al catalyst (6.13 µmol CO2/m2) measured by CO2-TPD. The catalytic activity of Mg-Al catalyst and metal modified catalyst slightly decreased upon time-on-stream test for 10 h on oxidative dehydrogenation of ethanol due to carbon deposition.


Assuntos
Compostos de Alumínio/química , Hidróxido de Alumínio/química , Etanol/química , Compostos de Magnésio/química , Hidróxido de Magnésio/química , Molibdênio/química , Vanádio/química , Compostos de Alumínio/síntese química , Hidróxido de Alumínio/síntese química , Carbono , Catálise , Precipitação Química , Temperatura Alta , Hidrogenação , Compostos de Magnésio/síntese química , Hidróxido de Magnésio/síntese química , Oxirredução
15.
J Oleo Sci ; 68(1): 95-102, 2019 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-30542011

RESUMO

Oxidative dehydrogenation of ethanol to acetaldehyde over Mg-Al layered double hydroxides (LDH) and their differently calcined derivative catalysts was investigated in this study. The Mg-Al catalysts were synthesized via co-precipitation method and calcined at different temperatures at 450°C, 600°C and 900°C. It revealed that the calcination temperature affected the physicochemical properties and the catalytic activity of these catalysts toward the oxidative dehydrogenation of ethanol. It was found that ethanol conversion increased with increasing reaction temperature from 200 to 400°C, whereas acetaldehyde selectivity decreased. At low reaction temperature (200-300°C), the non-calcined catalyst (Mg-Al-000) showed the highest ethanol conversion, which can be attributed to the hydroxyl groups on surface having acetaldehyde as a major product. The calcination process led to formation of mixed oxide phase in Mg-Al catalysts as proven by the XRD and FT-IR results. The catalyst calcined at 450°C (Mg-Al-450) exhibited the highest basicity as measured by the CO2-TPD with ethanol conversion of 45.8% and acetaldehyde yield of 29.7% at 350°C.


Assuntos
Acetaldeído/síntese química , Hidróxido de Alumínio/química , Etanol/química , Hidróxido de Magnésio/química , Catálise , Modelos Químicos , Oxirredução , Porosidade , Temperatura
16.
J Oleo Sci ; 67(8): 1005-1014, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-30068826

RESUMO

This study aims to investigate the production of ethylene and diethyl ether from ethanol via catalytic dehydration using Si- and Al-based catalysts with Pd modification. First, six catalysts including H-beta zeolite (HBZ), mixed phases of γ-χ-Al2O3 (M-Al) and γ-Al2O3 (G-Al) with and without Pd modification (0.5 wt%) were prepared. The catalytic dehydration of vaporized ethanol at temperature ranging from 200 to 400°C was performed over the catalysts. For ethylene production, the most promising catalyst is HBZ (giving ethylene yield of ca. 99% at 400°C), whereas Pd modification has no significant effect on ethylene production. Considering the production of diethyl ether, it is produced at lower temperature (ca. 250°C) than that of ethylene. The most active catalyst to produce diethyl ether is HBZ with Pd modification (giving diethyl ether yield of ca. 48% at 250°C). Thus, increased diethyl ether yield can be achieved with Pd modification at low temperature for the HBZ catalyst. Other catalysts such as M-Al and G-Al can also produce significant amounts of ethylene. To elucidate the effect of Pd modification on these catalysts, different characterization techniques such as nitrogen physisorption (BET and BJH methods), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and ammonia temperature-programmed desorption were performed and further discussed in more detail.


Assuntos
Compostos de Alumínio/química , Etanol/química , Éter/síntese química , Etilenos/síntese química , Paládio/química , Compostos de Silício/química , Catálise , Química Orgânica/métodos , Dessecação , Temperatura , Volatilização
17.
J Oleo Sci ; 67(2): 235-243, 2018 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-29367488

RESUMO

The present work deals with the catalytic performance of SBA-15 supported catalysts in the gas phase catalytic dehydration of ethanol in the temperature range of 200 to 400°C. The SBA-15 support was incorporated on a zirconium (Zr) and bimetal of zirconium and lanthanum (Zr-La) prepared by sol-gel (SG) and hydrothermal (HT) methods. The catalysts were characterized by means of N2 physisorption, SEM/EDX, and NH3-TPD. The experimental results demonstrated that the Zr-La/SBA-15-HT exhibited the highest catalytic activity. Ethanol conversion and ethylene selectivity were found to increase with increased reaction temperature. The best catalytic results were achieved for Zr-La/SBA-15-HT indicating values of ethanol conversion and ethylene yield of ca. 84% and 80%, respectively at 400°C. The most important parameter influencing their catalytic properties appears to be the interaction between metal and support depending on different methods. The metal dispersion inside the siliceous matrix of SBA-15 has a direct influence on their surface acidity. Meanwhile, the performance of these SBA-15 supported catalysts in ethanol dehydration is also related with the alteration of surface acidity caused by the introduction of Zr and Zr-La.


Assuntos
Química Orgânica/métodos , Etanol/química , Etilenos/síntese química , Dióxido de Silício/química , Catálise , Dessecação , Lantânio/química , Temperatura , Zircônio/química
18.
J Oleo Sci ; 66(12): 1355-1364, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29199209

RESUMO

Montmorillonite clay (MMT) is one of materials that can be "green material" due to its environmental safety. In this work, acid-activated MMT catalysts were prepared for the dehydration reaction of ethanol. To be the green process, the reaction with bioethanol was also studied. Ethanol concentrations in feed were varied in the range of 10-99.95 wt%. Moreover, the concentrations of hydrochloric acid activated MMT were investigated in range of 0.05-4 M. From the experiment, it reveals that different acid concentrations to activate MMT affect the catalytic activity of catalysts. The 0.3 M of HCl activated MMT exhibits the highest activity (under the best condition of 30 ml HCl aging for 1 h) with the Si/Al ratio of 7.4. It can reach the ethanol conversion and ethylene selectivity up to 95% and 98% at reaction temperature of 400°C, respectively. For the several ethanol feed concentrations, it does not remarkably affect in ethanol conversion. However, it has some different effect on ethylene selectivity between lower and higher reaction temperatures. It was found that at lower temperature reaction, ethylene selectivity is high due to the behavior of water in feed. In addition, the 0.3 M-MMT can be carried out under the hydrothermal effect.


Assuntos
Bentonita/química , Dessecação , Etanol/química , Etilenos , Ácido Clorídrico/química , Catálise , Éter/química , Temperatura
19.
J Oleo Sci ; 66(9): 1029-1039, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-28867758

RESUMO

The study is aimed to investigate the combination of nanocrystalline γ- and χ- alumina that displays the attractive chemical and physical properties for the catalytic dehydration of ethanol. The correlation between the acid density and ethanol conversion was observed. The high acid density apparently results in high catalytic activity, especially for the equally mixed γ- and χ- phase alumina (G50C50). In order to obtain a better understanding on how different catalysts would affect the ethylene yield, one of the most powerful techniques such as X-ray photoelectron spectroscopy (XPS) was performed. Hence, the different O 1s surface atoms can be identified and divided into three types including lattice oxygen (O, 530.7 eV), surface hydroxyl (OH, 532.1 eV) and lattice water (H2O, 532.9 eV). It was remarkably found that the large amount of O 1s surface atoms in lattice water can result in increased ethylene yield. In summary, the appearance of metastable χ-alumina structure exhibited better catalytic activity and ethylene yield than γ- alumina. Thus, the introduction of metastable χ- alumina structure into γ- alumina enhanced catalytic activity and ethylene yield. As the result, it was found that the G50C50 catalyst exhibits the ethylene yield (80%) at the lowest reaction temperature ca. 250°C among other catalysts.


Assuntos
Óxido de Alumínio/química , Etanol/química , Etilenos/síntese química , Nanopartículas/química , Catálise , Desidratação , Hidróxidos , Oxigênio , Espectroscopia Fotoeletrônica , Temperatura , Água
20.
J Oleo Sci ; 66(2): 199-207, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-28154350

RESUMO

In the present study, the catalytic dehydration of ethanol over H-beta zeolite (HBZ) catalyst with ruthenium (Ru-HBZ) and platinum (Pt-HBZ) modification was investigated. Upon the reaction temperature between 200 and 400°C, it revealed that ethanol conversion and ethylene selectivity increased with increasing temperature for both Ru and Pt modification. At lower temperature (200 to 250°C), diethyl ether (DEE) was the major product. It was found that Ru and Pt modification on HBZ catalyst can result in increased DEE yield at low reaction temperature due to increased ethanol conversion without a significant change in DEE selectivity. By comparing the DEE yield of all catalysts in this study, the Ru-HBZ catalyst apparently exhibited the highest DEE yield (ca. 47%) at 250°C. However, at temperature from 350 to 400°C, the effect of Ru and Pt was less pronounced on ethylene yield. With various characterization techniques, the effects of Ru and Pt modification on HBZ catalyst were elucidated. It revealed that Ru and Pt were present in the highly dispersed forms and well distributed in the catalyst granules. It appeared that the weak acid sites measured by NH3 temperature-programmed desorption technique also decreased with Ru and Pt promotion. Thus, the increased DEE yields with the Ru and Pt modification can be attributed to the presence of optimal weak acid sites leading to increased intrinsic activity of the catalysts. It can be concluded that the modification of Ru and Pt on HBZ catalyst can improve the DEE yields by ca. 10%.


Assuntos
Etanol/química , Éter/síntese química , Platina/química , Rutênio/química , Zeolitas/química , Catálise , Desidratação , Éter/química , Tamanho da Partícula , Propriedades de Superfície
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