Resin Amberlyst Research Articles

Efficient conversion of glucose into 5-hydroxymethylfurfural using a bifunctional Fe3+ modified Amberlyst-15 catalyst

In this study, a series of Fe3+ modified Amberlyst-15 resins (Fe/AR) were prepared and used as environmentally friendly bifunctional catalysts for the conversion of glucose to 5-hydroxymethylfurfural (HMF).

Dimerization of iso-butene on sodium exchanged Amberlyst-15 resins

This work reports a new technical approach for the production of aviation gasoline through the catalytic dimerization of iso-butene on sodium exchanged Amberlyst-15 resins (20–40 mesh) in the absence of selectivity-enhancing components at T = 50 °C, P = 2 MPa and LHSV of 2 h−1. The dimers selectivity could be significantly improved by effectively controlling the acid capacity of resins via Na+ exchange. When the acid capacity of the catalyst was controlled to <2.45 mmol/g, the 2,4,4-trimethylpentenecontent in C8 olefins reached ~100%. It was also confirmed that the sodium exchanged resins have longer lifetime than Amberlyst-15 resins.

Esterification Reaction Kinetics Using Ion Exchange Resin Catalyst by Pseudo-Homogenous and Eley-Ridel Models

This work deals with kinetics and chemical equilibrium studies of esterification reaction of ethanol with acetic acid. The esterification reaction was catalyzed by an acidic ion exchange resin (Amberlyst-15) using a batch stirred tank reactor. The pseudo-homogenous and Eley-Rideal models were successfully fitted with experimental data. At first, Eley-Rideal model was examined for heterogeneous esterification of acetic acid and ethanol. The pseudo-homogenous model was investigated with a power-law model. The apparent reaction order was determined to be (0.88) for Ethanol and (0.92) for acetic acid with a correlation coefficient (R2) of 0.981 and 0.988, respectively. The reaction order was determined to be 4.1087x10-3 L0.8/(mol0.8.min) with R2 of 0.954. The adsorption constants of acetic acid and ethanol were calculated as 0.023 and 0.044 L/mol, respectively and the lumped reaction constant were determined to be 5*10-4 L2/gcat.mol.min. The results of the reaction kinetic study show that the high acetic acid/ethanol molar ratio was favored. The maximum conversion of 70 % was obtained at 70°C for acetic acid/ethanol molar ratio of 4.

Organic–Inorganic Composites Based on Gel-Type Sulfonic Resin KU-2-8 and Zirconia: Acid and Catalytic Properties in the Etherification Reaction of iso-Butylene with Ethanol

Although acid and catalytic properties of the sulfonic resins and zirconia are well-characterized, a little is known about their composites, particularly about the KU-2-8-ZrO2 composites, in which KU-2-8 is a commercial gel-type sulfonic resin. In this article, the acidity of the KU-2-8-ZrO2 composites has been studied by the ammonia quasi-equilibrium thermo-desorption technique and their catalytic characteristics in etherification of isobutylene with ethanol were defined. The KU-2-8-ZrO2 productivity in this reaction was found to be an order of magnitude higher compared to KU-2-8 and several times higher compared to the commercial macroporous sulfonic resin Amberlyst 15. A high productivity of the KU-2-8-ZrO2 composites is achieved by the improved accessibility of the sulfonic resin acid sites for reagents. The composites do not swell in the polar medium and show high resistance to osmotic shock. The KU-2-8-ZrO2 composites with 70–80 wt % of KU-2-8 were found promising for industrial applications.

Efficient hydrolysis of hemicellulose to furfural by novel superacid SO4H-functionalized ionic liquids

Novel superacid SO4H-functionalized ionic liquids (SFILs) were designed and prepared in this work. The catalytic activities of SFILs were evaluated in xylan hydrolysis and xylose dehydration to produce furfural. Combined with the results of acid strength of SFILs characterized by solid-state 31P MAS NMR, it was found that the catalytic performance of SFILs was positively correlated to their acid strength. The superacid SFIL [Ch-SO4H][CF3SO3] displayed the best catalytic performance with more than 80% yield of furfural, and it was also obviously superior to usual SO3H-functionalized acidic ILs, mineral liquid acids, and acidic resin Amberlyst-15 catalysts in catalytic activity under optimized conditions. In addition, the superacid SFIL [Ch-SO4H][CF3SO3] could be easily separated from reaction system and reused at least five times without obvious decrease.

Upgrading of pyrolysis biofuel via esterification of acetic acid with benzyl alcohol catalyzed by Brønsted acidic ionic liquid functionalized ethyl-bridged organosilica hollow nanospheres

Catalytic esterification of acetic acid with high boiling point benzyl alcohol is a primary goal to decrease oxygen content and acidity of crude pyrolysis biofuels before their further refining steps; meanwhile, the produced benzyl acetate is a value-added chemical building. In the search for efficient and recyclable solid acids for the above process, Brønsted acidic ionic liquid functionalized ethyl-bridged organosilica hollow nanospheres, [C3Im][SO3CF3]-Si(Et)Si HNSs (C3 = PrSO3H, Im = imidazolium cation), are demonstrated via co-condensation route followed by quaternary ammonization and anion exchange. The [C3Im][SO3CF3]-Si(Et)Si HNSs with nanometer size, hollow interior, opening and permeable thin shell as well as large BET surface area are successfully applied in esterification of acetic acid with benzyl alcohol in toluene as a simulated pyrolysis biofuel, and influence of reaction temperature, benzyl alcohol-to-acetic acid molar ratio and water content on the catalytic activity and selectivity are evaluated. The [C3Im][SO3CF3]-Si(Et)Si HNSs exhibit significantly high catalytic activity and selectivity in target reaction, outperforming Amberlyst-15 resin and HY zeolite; moreover, morphological characteristics, textural properties and surface hydrophobicity impact the esterification activity. The [C3Im][SO3CF3]-Si(Et)Si HNSs also exhibit good catalytic stability and reusability, and leaching of acid sites as well as changes of chemical structure and morphology of the nanohybrids are hardly observed after the reaction.

The Catalytic Activity of Amberlyst A-21 to Disproportionation of Trichlorosilane at Critical Temperatures

Catalytic properties of anion-exchange resin Amberlyst A-21 in gas-phase disproportionation of trichlorosilane (TCS) at resine critical temperature (up to 423 K) were studied for the first time. The thermodesorprtion followed by pyrolysis were used to establish thermal destruction of Amberlyst A-21 undergoes to form methyl chloride and of the spherical matrix at above 423 K. When Amberlyst A-21 operated at 333–423 K, the apparent activation energy of TCS disproportionation was 37.12 kJ/mol, and the reaction rate constant 0.80 s –1 (at 423 K). Three-month testing of the resin for TCS disproportionation at 423 K demonstrated the stabile catalytic activity.

Synthesis of jet fuel additive with cyclopentanone

Abstract A new route was developed for the synthesis of renewable decalin with cyclopentanone which can be derived from lignocellulose. It was found that 1,2,3,4,5,6,7,8-octahydronaphthalene could be selectively produced by the hydrogenation/dehydration/rearrangement of [1,1′-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed catalyst system. Among the investigated catalysts, the Ru/C and Amberlyst-15 resin exhibited the highest activities for the hydrogenation of [1,1′-bi(cyclopentylidene)]-2-one to [1,1′-bi(cyclopentan)]-2-ol and the dehydration/rearrangement of [1,1′-bi(cyclopentan)]-2-ol to 1,2,3,4,5,6,7,8-octahydronaphthalene, respectively. Using Ru/C and Amberlyst-15 resin as the first bed and the second bed catalysts, 1,2,3,4,5,6,7,8-octahydronaphthalene was directly produced in high carbon yield (83.7%) under mild conditions (393 K, 1 MPa). After being hydrogenated, the 1,2,3,4,5,6,7,8-octahydronaphthalene was converted to decalin which can be used as additive to improve the thermal stability and volumetric heat value of jet fuel.

The Hydroloysis of ammonia borane by using Amberlyst-15 supported catalysts for hydrogen generation

Resin catalysts have the advantage of having various properties and long lifetime due to their ability to be regenerated easily, which makes them attractive supports. In this paper, a comparative study was conducted to optimize the dehydrogenation reaction condition using two different types of support materials: alumina (Al2O3), and Amberlyst-15 and to improve the catalytic activity as well as preparing an efficient and low-cost system for practical application, ruthenium metal catalyst was incorporated on Amberlyst-15 resin (a sulfonic acid type based upon a styrene-divinylbenzene copolymer) to release H2 via hydrolytic dehydrogenation of ammonia borane. Using ruthenium (Ru) catalysts based on Amberlyst-15 support material and comparing the results with Al2O3 as the common supporting material is considered to be studied for the first time. The effect of temperature (20–50 °C), the initial ammonia borane concentration (0.05–0.5 %wt), and catalyst amount (0.2–0.5 g) on the produced H2 yield was also investigated. Ru@Amberlyst-15 nanoparticle was discovered to be an effective catalyst for hydrogen evolution via the hydrolysis of ammonia borane with a turnover frequency value (TOF) of 343.3 min−1, while Ru@Al2O3 yielded a TOF of 87.5 min−1 at the room temperature. Therefore, it can be concluded that the Amberlyst-15 supporting effect on ruthenium metal leads an increase in the hydrogen production rate.

Efficient Production of N-Butyl Levulinate Fuel Additive from Levulinic Acid Using Amorphous Carbon Enriched with Oxygenated Groups

The aim of this study was to develop an effective carbonaceous solid acid for synthesizing green fuel additive through esterification of lignocellulose-derived levulinic acid (LA) and n-butanol. Two different sulfonated carbons were prepared from glucose-derived amorphous carbon (GC400) and commercial active carbon (AC400). They were contrastively studied by a series of characterizations (N2 adsorption, X-ray diffraction, elemental analysis, transmission electron microscopy, Fourier transform infrared spectroscopy and NH3 temperature programmed desorption). The results indicated that GC400 possessed stronger acidity and higher –SO3H density than AC400, and the amorphous structure qualified GC400 for good swelling capacity in the reaction solution. Assessment experiments showed that GC400 displayed remarkably higher catalytic efficiency than AC400 and other typical solid acids (HZSM-5, Hβ, Amberlyst-15 and Nafion-212 resin). Up to 90.5% conversion of LA and 100% selectivity of n-butyl levulinate could be obtained on GC400 under the optimal reaction conditions. The sulfonated carbon retained 92% of its original catalytic activity even after five cycles.

Bio-propylene glycol as value-added product from Epicerol® process

The production of chemicals from bio-based feedstocks is an emerging field of research in both industrial and academic communities. Here we present the synthesis of propylene glycol through catalytic hydrogenolysis of glycidol, obtained using a side-stream from the bio-based epichlorohydrin production plant, over Pd/C catalyst. In particular, we show the prominent effect of the acidic resin Amberlyst-15 in the selective and quantitative conversion of glycidol that permits to reach a TOF value of 162h−1. Propylene glycol is obtained with high yields and selectivity (> 99%) in only 1h under mild reaction conditions. The effect of solvent is also investigated giving interesting results on the reaction selectivity. The catalytic system (Pd/C + Amberlyst-15) shows a good recyclability also after seven reaction cycles reaching high performances in term of conversion and selectivity. This allowed minimizing the amount of waste and enhancing the efficiency of the whole system.

Counter-Ion Effect on the Thermodynamics of Cr(III) Exchange by Macroporous Amberlyst-15

Abstract In the present study, we have investigated the counter-ion effect on the thermodynamics of Cr(III) sorption by macroporous resin Amberlyst-15. The exchange reaction was studied as a function of concentration of Cr(III) and nature of counter-ions at different temperatures. It was observed that nature of counter-ions have a profound effect on the exchange of Cr(III) ions. The selectivity of Amberlyst-15 towards metal ion sorption follows the order univalent&gt;divalent&gt; trivalent forms. This trend can be associated to the electrostatic interaction of ions with the functional sites of the resin. The equilibrium pH values (pHeq) were observed to decrease with Cr3+/H+ exchange whereas an increase in pHeq was detected during the exchange of Cr3+/Li+, Cr3+/Na+, Cr3+/Ca2+ and Cr3+/Al3+. Different adsorption models such as Dubinin–Radushkevich (D–R) and Langmuir were employed to analyze the sorption data. The maximum exchange capacities (X m ) and binding energy constants (K b ) values were determined by using the Langmuir model. The values of both ΔHo and ΔSo were found positive inferring that the exchange process is endothermic accompanied by the dehydration of Cr(III) ions. The thermodynamic parameters revealed that the mechanism of Cr(III) sorption for all the counter ions is entropy driven ion exchange.

Effect of Acid Site Localization in Sulfonic Resin Amberlyst 15 on its Catalytic Properties in Ethyl tert-butyl Ether Synthesis

The role of the localization of acid sites in macroporous sulfonic resin Amberlyst 15 in the synthesis of ethyl tert-butyl ether was investigated. By partial blockage of the acid sites by Na+ cations it was established that internal acid sites are primarily active in the reaction while a side reaction with the formation of tert-butanol takes place at the external acid sites.

Reaction Process of Resin-Catalyzed Methyl Formate Hydrolysis in Biphasic Continuous Flow

In the frame of process development for the generation of chemical energy carriers, we studied the synthesis of methanol and formic acid from methyl formate hydrolysis in a continuous-flow millireactor. The aim was to establish the link between kinetics and phase behavior in the biphasic liquid regime. Reaction performance using the acidic ion-exchange resin Amberlyst 15 as catalyst was examined at various operating conditions such as space velocity, catalyst particle size, temperature, and initial reactant ratio. Results revealed substantially higher yields without mass transfer impediment with feed compositions exceeding methyl formate saturation in water. The simultaneous decrease in methyl formate and increase in polar product concentrations sufficed to bring the initially biphasic mixture to a homogeneous system as confirmed by thermodynamic UNIFAC equilibrium calculations. The separate analysis of effluent liquid phases unveiled a quasi-homogeneous catalytic process rooted in an aqueous layer at the...

Catalytic etherification of bioglycerol with bioethanol over H-Beta, H-Y and H-MOR zeolites

Etherification of glycerol with ethanol, both from renewable resources, was studied over heterogeneous catalysts (zeolites of the type BEA, MOR and FAU) and ion-exchange resin Amberlyst 35. The best results were obtained with zeolite H-Beta (CP 814 Q) with the ratio Si/Al=25. The conversion of glycerol at the temperature of 200°C was 51,7% at mono-ethyl ethers selectivity of 62% and di-+tri-ethyl ether selectivity of 37,7%. The conversion of glycerol, which was obtained by purification of glycerol phase from MERO production (methyl esters of acids from rape-seed oil), at the same conditions was 50,8%, selectivity to mono-ethers was 71,8% and to di-+tri- ethers 28,1%. Ethers of glycerol have utilization as oxygenate additives to fuels and have positive effect on decreasing particulate matters and carbonyl compounds in exhaust gases.

Etherification of Glycerol with Propylene or 1-Butene for Fuel Additives.

The etherification of glycerol with propylene over acidic heterogeneous catalysts, Amberlyst-15, S100, and S200 resins, produced mono-propyl glycerol ethers (MPGEs), 1,3-di- and 1,2-di-propyl glycerol ethers (DPGEs), and tri-propyl glycerol ether (TPGE). The propylation of glycerol over Amberlyst-15 yielded only TPGE. The glycerol etherification with 1-butene over Amberlyst-15 and S200 resins produced 1-mono-, 2-mono-, 1,2-di-, and 1,3-di-butyl glycerol ethers (1-MBGE, 2-MBGE, 1,2-DBGE, and 1,3-DBGE). The use of Amberlyst-15 resulted in the propylation and butylation of glycerol with higher yields than those obtained from the S100 and S200 resins. The PGEs, TPGE, and BGEs were evaluated as cold flow improvers and octane boosters. These alkyl glycerol ethers can reduce the cloud point of blended palm biodiesels with diesel. They can increase the research octane number and the motor octane number of gasoline.

Esterification of Mixed Carboxylic-fatty Anhydrides Using Amberlyst-15 as Heterogeneous Catalyst.

The article deals with the use of mixed anhydrides for the synthesis of fatty esters. Both aliphatic and aromatic acids are involved, indicating different behaviors according to the chain length of the aliphatic acid. We describe a novel and efficient method for the synthesis of fatty esters by the esterification reaction of primary, secondary and tertiary alcohols with mixed carboxylic-palmitic anhydrides using resin Amberlyst-15 as heterogeneous acid catalyst. Influence of various reaction parameters such as molar ratio (anhydride/alcohol), catalyst amount, type of alcohol and type of mixed anhydride were studied to optimize the conditions for maximum yield. Among tested anhydrides we quote mainly the 4-chlorobenzoic palmitic anhydride because it was both reactive and selective for the preparation of palmitic acid ester. This anhydride gave a good yield of palmitic ester.

ESTERIFICATION OF RENEWABLE LEVULINIC ACID TO LEVULINATE ESTERS USING AMBERLYST-15 AS A SOLID ACID CATALYST

Levulinic acid (LA) is a versatile biomass-derived building block as it can be used for the synthesis of organic chemicals as alternative to the depleting fossil fuel resources. Levulinate esters, obtained from catalytic esterification of LA with alcohol, can be used in many applications such as fragrance and fuel additives. In this study, ion-exchange resins Amberlyst-15 was employed as solid acid catalyst for esterification of LA with methanol for methyl levulinate (ML) production. The effect of reaction time, catalyst loading, and molar ratio of LA to methanol, was investigated on LA esterification to ML at the reflux condition. The optimum ML yield of 82% was obtained from reaction conducted at reflux temperature for 5h, using 30% of Amberlyst-15 loading, and 1:20 of LA to methanol molar ratio. The reusability of Amberlyst-15 for ML production was examined for five successive reactions. In addition, Amberlyst-15 catalyst, employed in the esterification of LA with ethanol and 1-butanol for ethyl levulinate (EL) and butyl levulinate (BL), respectively, registered good performance. Yields of 71% and 55% have been obtained for EL and BL, respectively. Amberlyst-15 is a promising solid acid catalyst for production of biomass derived levulinate esters at mild process conditions.

Theory and Practice of Alkyl Phenol Synthesis. tert-Octylphenols

Liquid-phase alkylation of phenol with diisobutylenes was studied in the presence of ion-exchange resin Amberlyst 36 Dry. Thermodynamic characteristics were calculated for the reactions that occur in a reaction system. Kinetics of the alkylation process was studied. The conditions of selective synthesis were recommended for 4-tert-octylphenol. Recommendations on the use of obtained data were given.

Ion exchange separation for recovery of monosaccharides, organic acids and phenolic compounds from hydrolysates of lignocellulosic biomass

Abstract This paper describes two effective ion exchange chromatography processes to separate and recover monosaccharides, organic acids and phenolic compounds from two kinds of hydrothermal liquefaction (HTL) hydrolysates derived under different temperatures. Anion exchange resin Amberlyst A21 (OH − ) and cation exchange resin Amberlite IR-120 (Na + ) were selected to separate synthetic solution and real hydrolystes by column chromatography. The results showed that glucose and acetic acid could be successfully separated by anion resin with purities of 87% and 98%, respectively. Acetic acid and phenol could be recovered by cation resin with purities up to 97% and 81%. In separation processes of real HTL hydrolysates, monosaccharides and organic acids in hydrolysate derived from low-temperature HTL were separated by anion exchange resin with recoveries of about 80% and 90%, respectively. Phenolic compounds in high-temperature HTL hydrolysate were recovered by cation exchange resin with recovery of about 70%.