Chawalit Ngamcharussrivichai

Adsorption characteristics of haloacetonitriles on functionalized silica-based porous materials in aqueous solution.

The effect of the surface functional group on the removal and mechanism of dichloroacetonitrile (DCAN) adsorption over silica-based porous materials was evaluated in comparison with powdered activated carbon (PAC). Hexagonal mesoporous silicate (HMS) was synthesized and functionalized by three different types of organosilanes (3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and n-octyldimethysilane). Adsorption kinetics and isotherm models were used to determine the adsorption mechanism. The selective adsorption of five haloacetonitriles (HANs) in the single and mixed solute systems was also studied. The experiments revealed that the surface functional groups of the adsorbents largely affected the DCAN adsorption capacities. 3-Mercaptopropyl-grafted HMS had a high DCAN adsorption capacity compared to PAC. The adsorption mechanism is believed to occur via an ion-dipole electrostatic interaction in which water interference is inevitable at low concentrations of DCAN. In addition, the adsorption of DCAN strongly depended on the pH of the solution as this related to the charge density of the adsorbents. The selective adsorption of the five HANs over PAC was not observed, while the molecular structure of different HANs obviously influenced the adsorption capacity and selectivity over 3-mercaptopropyl-grafted HMS.

Effects of crystalline structures and surface functional groups on the adsorption of haloacetic acids by inorganic materials.

The effects of the crystalline structure and surface functional groups of porous inorganic materials on the adsorption of dichloroacetic acid (DCAA) were evaluated by using hexagonal mesoporous silicates (HMS), two surface functional group (3-aminopropyltriethoxy- and 3-mercaptopropyl-) modified HMSs, faujasite Y zeolite and activated alumina as adsorbents, and compared with powdered activated carbon (PAC). Selective adsorption of HAA(5) group was studied by comparing single and multiple-solute solution, including effect of common electrolytes in tap water. Adsorption capacities were significantly affected by the crystalline structure. Hydrogen bonding is suggested to be the most important attractive force. Decreasing the pH lower than the pH(zpc) increased the DCAA adsorption capacities of these adsorbents due to electrostatic interaction and hydrogen bonding caused by protonation of the hydronium ion. Adsorption capacities of HAA(5) on HMS did not relate to molecular structure of HAA(5). Common electrolytes did not affect the adsorption capacities and selectivity of HMS for HAA5, while they affected those of PAC.

Selective adsorption mechanisms of antilipidemic and non-steroidal anti-inflammatory drug residues on functionalized silica-based porous materials in a mixed solute

The selective adsorption mechanisms of naproxen (NAP), acetaminophen (ACT), and clofibric acid (CFA) on silica-based porous materials were examined by single and mixed-batch adsorption. Effects of the types and densities of surface functional groups on adsorption capacities were determined, including the role of hydrophobic and hydrophilic dissolved organic matters (DOMs). Hexagonal mesoporous silica (HMS), superparamagnetic HMS (HMS-SP) and SBA-15 were functionalized and applied as adsorbents. Compared with powdered activated carbon (PAC), amine-functionalized HMS had a better adsorption capacity for CFA, but PAC possessed a higher adsorption capacity for the other pharmaceuticals than HMS and its two derivatives. In contrast to PAC, the adsorption capacity of the mesoporous silicas varied with the solution pH, being highest at pH 5. Electrostatic interactions and hydrogen bonding were found to be the main mechanisms. Increase in grafted amine group density on silica surfaces can enhance the CFA adsorption capacity. Further, hydrophilic DOM can decrease CFA adsorption capacities on amino-grafted adsorbents by adsorption site competition, while hydrophobic DOM can interfere with CFA adsorption by the interaction between hydrophobic DOM and CFA. Finally, in a competitive adsorption study, the adsorption capacity of hydrophilic adsorbents for acidic pharmaceuticals varied with their pKa values.

Adsorption of ciprofloxacin on surface functionalized superparamagnetic porous silicas

AbstractThe effect of surface functional groups 3-aminopropyltriethoxy- and 4-(triethoxysilyl)-butyronitrile-, 3-mercaptopropyltriethoxy-, phenyltrimethoxy-, and n-octyl-dimethoxychloro- grafted superparamagnetic particles coated with hexagonal mesoporous silicas (HMS-SPs) on the adsorption of ciprofloxacin (CIP) was evaluated. CIP adsorption followed the pseudo-second-order kinetic model, and intraparticle diffusion was suggested to be the rate-controlling step. Higher CIP adsorption capacities revealed on the hydrophobicity of the adsorbents, however, the phenyltrimethoxy group had the highest adsorption capacity due to the interaction of electron-donor acceptors. The adsorption capacities strongly depended on an electrostatic interaction, with the exception of the phenytrimethoxy group. The presence of tannic acid (TA) could increase the adsorption capacity of CIP on adsorbent surfaces by multilayer adsorption between a positively charged amine group of CIP and negatively charged TA.

Removal of haloacetonitriles in aqueous solution through adsolubilization process by polymerizable surfactant-modified mesoporous silica

To investigate the adsorption properties and mechanisms of haloacetonitriles (HANs), large-pore SBA-15 mesoporous silica (SBA-CHX) was synthesized using cyclohexane as a swelling agent, and the surface was modified with polymerizable gemini surfactant (PG). The structure and textural properties of the synthesized adsorbents were characterized. PG surfactant coverage on the surface and the degree of polymerization were confirmed with FT-IR analysis. Adsorption experiments were performed under batch conditions to evaluate the influence of the contact time, adsorption isotherms, the effect of the pH solution, and the selective adsorption of five haloacetonitriles (HAN(5)) in individual-solute and mixed-solute solutions and surfactant leaching studies. The results indicated that the hydrophobic HANs were efficiently adsorbed onto PG surfactant-modified SBA-CHX. The selective adsorption mechanisms involved a more complex interplay between the organic partition, surface adsorption (i.e., ion-dipole electrostatic interactions) and hydrophobic interaction that depended upon the adsorbent and adsorbate characteristics. An increased degree of halogen substitution in the HAN molecule significantly affected the adsorption capacity and selectivity by the organic partition. Polymerization of the polymerizable surfactant increased the stability of the adsorbed surfactant on the adsorbent surface.

Al2O3-supported Mixed Ca and Zn Compounds Prepared from Waste Seashells for Synthesis of Palm Fatty Acid Methyl Esters

Waste mixed seashells of Perna viridis, Anadara granosa, Amusium pleuronectes, and Meretrix meretrix, as abundant, low-cost, and nontoxic calcium sources, were used as renewable raw materials in the preparation of a heterogeneous base catalyst for the transesterification of palm oil in refluxed methanol. The new mixed metal compound catalyst was prepared by mixing the calcined seashells with Zn(NO3)2 and Al2O3 in an acidic aqueous solution, followed by calcination at 500°C (ZSA-500). The ZSA-500 catalyst exhibited an enhanced surface area, dispersion, and total basicity compared to the parent calcined seashells. The fatty acid methyl ester (FAME) yield attained over ZSA-500 was 99 wt.% and dropped by 3% after five repetitive uses when the reaction was performed for 3 h at 60°C and ambient pressure with 10 wt.% catalyst and a methanol:oil molar ratio of 30:1. Structural and thermal analysis indicated that the active phases of ZSA-500 had a high stability against the glycerol adsorption as well as the phase transformation to calcium glyceroxides (Ca(C3H7O3)2).

Effects of KF Loading on Mg-Al Mixed Oxides for the Selective Synthesis of Trimethylolpropane Triesters

A series of Mg–Al hydrotalcites (HTCs) calcined at different temperatures were evaluated for their suitability as solid base catalysts for the selective synthesis of trimethylolpropane triesters (TMPTEs) via transesterification of trimethylolpropane (TMP) with a mixture of C8–C10 fatty acid methyl esters (FAMEs). The effect of potassium fluoride (KF) loading of the calcined HTCs on the physicochemical and catalytic properties of the materials attained was ascertained. Using a 5 wt% catalyst loading and a FAME:TMP molar ratio of 3.5:1 at 170°C for 8 h, the Mg–Al mixed oxide obtained by calcining HTC at 500°C (HTC-500) gave the highest TMPTE selectivity and FAME conversion. Impregnating HTC-500 with 10 wt% KF (KF/HTC-500) generated strongly basic KMgF3, KOH, K2O, and coordinatively unsaturated F− sites. The FAME conversion and TMPTE yield obtained over different HTC and KF/HTC-500 catalysts depended on their total basicity, where a basic strength of 15 < H_ < 18.4 was required for optimal TMPTE selectivity. The KF/HTC-500 calcined at 500°C was the most suitable catalyst and showed a superior performance to NaOCH3, a common homogeneous base for the polyol ester production.

Adsorption of single and mixed haloacetonitriles on silica-based porous materials: Mechanisms and effects of porous structures

Adsorption mechanisms and the role of different porous and crystalline structures on the removal of five haloacetonitriles (HANs) over hexagonal mesoporous silica (HMS), titanium substituted mesoporous silica (Ti-HMS), rod-shaped SBA-15 and microporous zeolite NaY were investigated. In addition, the effect of pH on adsorption mechanism and selective adsorption of five HANs individually and in an equimolar mixed solution were evaluated. The results indicated that the intraparticle diffusion rate constants of the mesoporous adsorbents were higher than that of the microporous NaY. In single solute, the order of adsorption preference (highest to lowest) was mono-HANs > di-HANs > tri-HAN. However, in mixed solute, the large molecular weight of the tri-HAN and di-HANs are more easily adsorbed than the smaller molecular weight mono-HANs. Except for SBA-15, the order of adsorption capacities in mixed HANs solute was not different compared to that observed for the single HAN solute, which might be caused by the higher accessibility to the active sites due to larger pore size. The ion-dipole electrostatic interaction was likely to be the main adsorption mechanism, and was favored at high pH values due to the high negative surface charge density of the adsorbent. The molecular structure of the HANs and hydrophilic/hydrophobic nature affected the adsorption capacities and their selective adsorption from mixed solutes.

Preparation of sulfonic acid-containing rubbers from natural rubber vulcanizates

In this work, a series of sulfonic acid-containing rubbers were prepared by aqueous phase oxidation of natural rubber vulcanizates in the presence of hydrogen peroxide (H2O2) and formic acid (HCOOH). The starting vulcanizates were neatly prepared via an efficient vulcanization (EV) system by varying mass ratio of N-cyclohexyl-2-benzothiazole sulfonamide (CBS), as an accelerator, to sulfur. The oxidation conditions were controlled at the molar ratio of H2O2: HCOOH = 1:1, the concentration of H2O2 = 15 wt.%, the temperature = 50 °C, and the reaction time = 3 h. The rubber materials before and after the oxidation were characterized for their physicochemical properties by using Fourier transform infrared spectroscopy, bomb calorimetry, acid-base titration and swelling measurements. The results indicated the presence of sulfonic acid group in the oxidized rubbers, generated by the oxidative cleaves of sulfide crosslinks in the rubber vulcanizates. The oxidation decreased the sulfur content of the rubber in which the level of sulfur loss was determined by the CBS/sulfur ratio. Moreover, the acidity of the oxidized products was correlated with the amount of sulfur remaining.

Degradation of Poly(methyl methacrylate) over Zeolites in a Batch Reactor

Thermal degradation is an attractive way to eliminate poly(methyl methacrylate) (PMMA) waste to which high temperatures are applied in the absence of oxygen. However, the process is not selective, resulting in a complex composition of products. Catalytic degradation over zeolites provides an effective route to selectively convert PMMA into desired products at lower temperatures, since zeolites have high acidity and shape-selectivity. In this work, the degradation of PMMA over various zeolites, including ZSM-5, BETA and USY, has been investigated in a batch reactor as a feasibility study to recover methyl methacrylate (MMA) as well as other valuable chemicals. The results showed that PMMA can be completely degraded at 300 oC and MMA was recovered as light oil. With increasing the degradation time, PMMA was converted over zeolites into more gaseous and light oil products, while the thermal degradation gave higher portion of heavy oil. From GC-MS analysis of light oil, MMA was found as the main product, co-existing with methyl 2-methyl propionate and methyl 2-methyl butyrate both of which can be used as synthetic fragrance.