Feruloylated Products from Coconut Oil and Shea Butter

The synthesis of feruloylated coconut oil and feruloylated shea butter were demonstrated in 0.5-L scale, shaken, batch reactions. Ethyl ferulate and the vegetable oil/fat were combined in a 1.0:1.3 mol ratio in the presence of Candida antartica lipase B immobilized on an acrylic resin (Novozym 435) at 60 °C. The transesterification of ethyl ferulate with coconut oil and shea butter reached equilibrium conversions, after 22 days, of 63 and 70%, respectively, with the shea butter transesterifications producing a white precipitate not observed in the coconut oil transesterifications. The faster transesterification rates, equilibrium conversions and white precipitate were shown to result from di- and monoacylglycerols (DAG and MAG) present in the shea butter. The transesterification of ethyl ferulate and coconut oil was also tested in a continuous, enzymatic, packed-bed bioreactor using Novozym 435 at 60 °C to produce feruloylated coconut oil at rates of 0.5–0.9 kg/day over 4.5 months. The feruloylated coconut oil acylglycerol species were identified by LC–MS analysis of transesterification reactions of ethyl ferulate with medium chain triacylglycerol (TAG) standards, C8–C14. The feruloylated vegetable oils possessed an ultra violet (UV) absorbing λ _max 328 nm, making them good UVAII absorbers, as defined by the U.S. Food and Drug Administration. The feruloylated coconut oil possessed a 17.5% higher absorption capacity than feruloylated shea butter on a per weight basis. All the feruloylated vegetable oils possessed rapid antioxidant capacity (50% reduction of initial radical concentration <5 min) at the concentrations tested, 0.5–2.5 mM. Feruloylated coconut oil possessed chemical and physical characteristics that suggested it would be fungible for feruloylated soybean oil in current retail formulations.     

Adsorption isotherms of pigments from alkali-refined vegetable oils with clay minerals

Adsorption isotherms of pigments from alkali-refined oils (rapeseed, soybean, wheatgerm, safflower, corn, cottonseed and sunflower) were measured to investigate the applicability of the Langmuir and Freundlich equations and to elucidate the adsorption characteristics of pigments on sepiolites and standard activated clay. The Freundlich equation was more applicable to the experimental adsorption isotherms. The equilibrium amount adsorbed, acidity, pore size distribution and inflection of the Freundlich isotherms could be explained by assuming that pigments were adsorbed on the stronger acid sites in smaller pores at low concentration, and then in the larger ones when the concentration increased. The amount adsorbed increased with a rise in adsorption temperatures from 70 to 110°C, and the heat of adsorption was below 10 kcal/mol. The results indicate that pigments were physically adsorbed on the acid sites activated at higher adsorption temperatures.     

Vapor phase adsorption of trichloroethane using organically modified montmorillonite

The vapor of 1,1,1-trichloroethane (TCA) was adsorbed to organically modified montmorillonite (organoclay). Hexadecyltrimethylammonium (HDTMA) was used to modify the surface of the clay and three types of organoclays with different HDTMA loadings were prepared. In adsorption experiments, the three types of organoclays, along with the non-modified (washed) clay were used. TCA was adsorbed from gaseous phase (nitrogen) by using a fixed adsorption bed. The adsorption breakthrough curves and the adsorption isotherms were determined at three different temperatures (24, 34, and 44 °C). The adsorption data were modeled with the Langmuir and BET isotherm equations. It was found that the isotherms of non-modified clay exhibited a favorable Type I behavior, which implies that the adsorption capacity is strongly dependent on vapor concentration at low concentration ranges. In regards to the organoclays, isotherms showed a marginally favorable Type II behavior with a reduced adsorption capacity at low concentrations, and exhibited a linear increase at elevated vapor concentrations. The temperature effect on the adsorption capacities of non-modified clay and organoclays exhibited different patterns. Desorption of TCA from clays was also performed by using pure nitrogen. The desorption rate constant k was in the order of 10^?4 min^?1 for all types of clay.     

An infrared spectroscopy study of lipid adsorption from hexane onto an acid-activated bleaching clay

The mode of adsorption of oleic acid (OA) (0.05 M), triglyceride (TG) (0.05 M) and phosphatidylcholine (PC) (0.5 mM) from hexane solution onto 0.5 g of an acid-activated bleaching clay was investigated using diffuse reflectance Fourier transform infrared spectroscopy. OA was mostly weakly adsorbed by bound water, with some OA adsorbed to silanol sites through carboxyl carbonyl groups. TG was hydrogen- bonded to surface silanol groups through ester carbonyl groups. The CH₂ stretches indicated that TG was oriented perpendicular or at an angle to the surface. PC phosphate groups were bound by the surface moisture with little interaction with silanol groups. The adsorption mechanism of these lipids contrasts with the adsorption of carotenoid and chlorophyll under the same conditions. These pigments are bound by chemisorption, with catalytic modification often occurring before adsorption.     

Formation and characteristics of cationic-polymer/bentonite complexes as adsorbents for dyes

The adsorption of cationic polymer, i.e., epicholorohydrin-dimethylamine polyamine (EPI-DMA), on bentonite particles was investigated under various conditions of bulk polymer concentration, pH, inorganic salts, and temperature. The resulting high adsorption rate and alkaline solution (pH = 7–11) effect indicated a strong electrostatic interaction between the clay particles and EPI-DMA molecules. Addition of salt can also influence the adsorption of EPI-DMA onto bentonite by affecting the clay particle sizes, the polymer zeta potential and etc. The Freundlich and Langmuir isotherm models were employed and fit the experimental data well in the low EPI-DMA concentration range 0.5–5.0 mg L^− 1. The enthalpy implied by the temperature dependence of adsorption of EPI-DMA on bentonite is 7.93 kJ mol^− 1, suggesting that neither coordination exchange nor chemical bond forces exit in this system. In addition, at high temperatures, larger amounts of EPI-DMA were adsorbed by bentonite, which indicated that increased entropy in the dissolved EPI-DMA molecules contributes to adsorption. The X-ray diffraction (XRD) analysis showed that besides the EPI-DMA molecules intercalated between the layers of bentonite, excess polymer molecules were adsorbed onto polymer loops protruding from the surface of the complex. The TGA and corresponding DSC plots demonstrated that the EPI-DMA polymer had intercalated into the clay layers and thus the EPI-DMA/bentonite was more hydrophobic than natural bentonite. With the addition of EPI-DMA polymer, the negatively charged clay particles increased to a net positive charge and the capacity for dye removal also went up with increasing polymer contents in EPI-DMA/bentonite complexes.     

Uptake of Ni(II) Ions from Aqueous Solution by Kaolinite and Montmorillonite: Influence of Acid Activation of the Clays

Abstract

Kaolinite and montmorillonite were treated with 0.25 M H₂SO₄ and the acid activated clays along with the parent clays were tested for their uptake capacity for Ni(II) ions from aqueous solution. The batch adsorption experiments were conducted under a set of variables (concentration of Ni(II) ion, amount of clay, pH, time and temperature of interaction). Increasing pH favored Ni(II) uptake till the ions were precipitated as the insoluble hydroxides at pH > 8.0. The uptake was rapid up to 40 min and equilibrium was obtained within 180 min. The kinetics of the process was evaluated by subjecting the results to a number of models like the pseudo-first order, second order, Elovich equation, liquid film diffusion, and intra-particle diffusion and it was found that the data more closely resembled a second order process. The experimental data conformed to both Langmuir and Freundlich isotherms showing that the interactions were mostly chemical in nature. The clays had reasonable monolayer adsorption capacity of 10.4, 11.9, 28.4, and 29.5 mg g^?1 for kaolinite, acid activated kaolinite, montmorillonite, and acid-activated montmorillonite respectively. Montmorillonite had much better adsorption capacity than kaolinite and the acid activation boosted the adsorption capacity of both kaolinite and montmorillonite. The interactions were exothermic in nature, accompanied by decrease in both entropy and Gibbs energy. The results have established good potentiality for kaolinite, montmorillonite and their acid-activated forms to take up and separate Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Adsorption Isotherms for Bleaching Soybean Oil with Activated Attapulgite

Activated attapulgite was characterized and used as bleaching clay (adsorbent) for soybean oil. Adsorption isotherms for bleaching soybean oil were determined to investigate the applicability of the Langmuir and Freundlich equations and to elucidate the adsorption characteristics of oil on activated attapulgite. The Freundlich model was found to provide a better fit with the experimental data than the Langmuir model. The larger Freundlich constant, K _F at higher temperature indicated more effective adsorption. The heat evolved for oil bleaching increased as the levels of activated attapulgite increased from 0.5 to 3%, due to the increase in adsorptive sites with increasing attapulgite levels as well as multilayer adsorption driven by van der Waals’ forces at smaller amounts of adsorbents. There are enough adsorptive sites with 3% attapulgite to adsorb the pigments associated with soybean oil bleaching. The amount of attapulgite has no effect on ΔH _a when it is >3%, and ΔH _a is about 32 kJ/mol.     

Enhanced fluoride removal from water by non-thermal plasma modified CeO2/Mg–Fe layered double hydroxides

A novel fast and efficient adsorbent based on lamellar compound namely CeO₂/Mg–Fe layered double hydroxide composite has been designed for fluoride removal from water. In order to improve fluoride removal efficiency, non-thermal plasma (NTP) was used to modify the surface state of composites. The prepared composites were characterized by powder X-ray diffraction, thermogravimetric analysis and surface area analyzer. Adsorption equilibrium and kinetics of fluoride on NTP modified composites were investigated. Experimental results indicated that the adsorption capacity was enhanced with NTP surface modification. The maximum adsorption capacity has been found to be 38.7–60.4 mg/g. The kinetic data of adsorption were found to best fit the pseudo-second-order model, while the equilibrium data were found to be well described by Langmuir model. In order to understand the mechanism of adsorption, thermodynamic parameters such as ΔG^θ, ΔS^θ and E_a were calculated. After NTP treatment, the ΔS^θ increased from − 34.7 J/mol·K to − 0.770 J/mol·K, the E_a decreased from 78.8 kJ/mol to 58.9 kJ/mol and the ΔG^θ (25 °C) decreased from − 2.62 kJ/mol to − 3.14 kJ/mol. These values indicate that the fluoride adsorption on NTP modified composites was improved.     

Adsorption and desorption of m-xylene vapor on organically modified montmorillonite

m-Xylene vapor was adsorbed to organically modified montmorillonite (organoclay). Hexadecyltrimethylammonium (HDTMA) was used to modify the surface of the clay. In adsorption experiments, the organoclay, along with the non-modified (washed) clay, was used. m-Xylene was adsorbed from a gaseous phase by using a fixed adsorption bed. The adsorption breakthrough curves and the adsorption isotherms were determined at three different temperatures (24, 34, and 44 °C). The adsorption data were modeled with the BET isotherm equation. It was found that the adsorption isotherms of washed clay exhibited a favorable Type I behavior, which implies that the adsorption capacity is strongly dependent on vapor concentration at low concentration ranges. In regards to the organoclay, isotherms showed a marginally favorable Type II behavior with a reduced adsorption capacity at low concentrations, and exhibited a linear increase at elevated vapor concentrations. The adsorption capacity of both washed clay and organoclay obviously decreased with the temperature. The desorption of m-xylene from the clays was also performed by using pure nitrogen, and the desorption rate constant k was on the order of 10⁻⁵ min⁻¹ for all types of clay.     

Dynamic analysis of adsorption equilibrium and rate parameters of reactants and products in MTBE,ETBE and TAME production

Adsorption equilibrium constants of ethanol, methanol, isobutylene, isoamylenes (2M2B, 2M1B), MTBE and TAME on Amberlyst 15 catalyst were evaluated from the packed bed moment technique. Adsorption equilibrium constants of alcohols were found to be two orders of magnitude greater than the adsorption equilibrium constants of i-olefins and the corresponding tertiary ethers. However, their apparent heat of adsorption values are quite low (-6,7 kJ/mol and ?8.3 kJ/mol for methanol and ethanol, respectively). Among the i-olefins, isobutylene gave the highest adsorption equilibrium constant and the heat of adsorption (-54.2 kJ/mol The adsorption equilibrium constant of 2M2B on a catalyst, which was pretreated with ethanol, was about three times greater than the corresponding value obtained on fresh catalyst. Second moment analysis indicated that diffusion resistance in both macropores and microspheres of the catalyst are equally significant.     

Regeneration and Reutilization of Oil-Laden Spent Bleaching Clay via in Situ Transesterification and Calcination

Landfill bound waste from the oil palm industry, spent bleaching clay (SBC) containing significant amounts of adsorbed crude palm oil (CPO) has the potential to be used for biodiesel production. In this study, SBC was subjected to ultrasound-aided in situ transesterification with a co-solvent to convert the oil into methyl esters (biodiesel). Optimized reaction conditions used were 5.4 wt% KOH, methanol to oil mass ratio of 5.9:1 and 1:1 mass ratio of co-solvent (petroleum ether or ethyl methyl ketone) to SBC. The remaining bleaching clay was calcined at 500 °C for 30 min and reutilized for bleaching. Absence of –CH absorption peaks in the FTIR and TGA-FTIR analysis of regenerated clays shows the regeneration efficiency of the method. In situ transesterification and heat regeneration helped to restore pores without adversely affecting the clay structure. The use of ethyl methyl ketone (EMK) as the co-solvent in the in situ transesterification process produced clay with better bleaching qualities.     

离子交换树脂吸附苯酚的性能研究

研究了717强碱阴离子交换树脂对苯酚的吸附性能。结果表明,在pH=10~13时,吸附能力最好。等温吸附符合Freundlich和Langmuir经验式。在293~313 K条件下,苯酚吸附量为220~260 mg/g的吸附焓变为-13.69~-12.02 kJ/mol,吸附自由能变为-7.02~-7.21 kJ/mol,吸附熵变为-22.76~-15.37 J/(K.mol)。吸附动力学符合Lagergren准二级速率方程,吸附速率常数为8.5×10-4~2.74×10-3g/(mg.min),吸附活化能为44.1 kJ/mol。303 K下其静态累积饱和吸附容量为399.8 mg/g(4.253 mmol/g)。用0.05 mol/L HCl溶液能定量洗脱苯酚,洗脱率达99%。     

Uptake-curves for the determination of diffusion coefficients and sorption equilibria for n-alkanes on zeolites

Sorption capacities and diffusion coefficients were measured for n-alkanes on a 5A-zeolite and ZSM-5 with a gravimetric setup. Significant heat effects were observed during the experimental determination of diffusion coefficients, which complicate the interpretation and the analysis of the experimental Uptake-curves. This effect depends significantly of the sorption rate, heat of adsorption and dissipation of heat. Taking into account these heat effects, reliable transport coefficients can be extracted. These agree well with diffusion coefficients obtained from other techniques, like PFG–NMR or ZLC. With the carbon chain-length the measured diffusivities decrease from 1.6 × 10⁻¹² to 0.5 × 10⁻¹² m²/s for propane to n-hexane for 5A-zeolite at 473 K. For n-butane and n-hexane values about 8 × 10⁻¹¹ and 4.6 × 10⁻¹¹ m²/s on MFI-type zeolites at 303 K are measured.From the equilibrium data, heats of adsorption were calculated and compared with literature data. The heat of adsorption for 5A-zeolite changes with the carbon chain-length from 32 to 44 kJ/mol for n-butane to n-octane, respectively. The heats of adsorption of alkanes on ZSM-5 were 60 kJ/mol for n-butane and 57 kJ/mol for hexane. Due to different adsorption sites in MFI-type zeolites two heats of adsorption were calculated for each alkane.     

Thermodynamics of the process of adsorption of aliphatic amidpolyamine on cellulose

The subject of this research is the thermodynamics of the adsorption equilibrium of three types of bleached pulp in water solutions of aliphatic amidpolyamine—Lamid-1, (L-1) in concentrations from 0.03 to 0.50 g/L in a temperature interval of 0–60°C and the influence of pH of the environment on the adsorption process. It was established that with the increase of temperature the quantity of adsorbed L-1 decreases. The values of the heat of adsorption are negative, do not depend on the quantity of adsorbed L-1, and are of the order 111.7–14.7 kJ/mol. The values of the entropy of the entropy of adsorption are also negative and are of the order of 76.8 ÷ 84.5 J/mol?K. Adsorption equilibrium is described by ther adsorption isotherm of Langmuir. Optimum pH for lower concentrations of the solution is from 5 to 7. When the concentrations of the solution are higher (C ≧ 0.15 g/L) the process can also take place very satisfactorily in an alkaline environment.     

Adsorption of chromate and molybdate by cetylpyridinium bentonite

Bentonite was modified with cetylpyridinium bromide (CPBr) and investigated by elemental analysis, IR, X-ray diffraction, thermogravimetric analysis, specific surface area (BET) and electrokinetic mobility measurements. The surfactant was adsorbed on the montmorillonite in a bilayer structure. The organo-bentonite removed the oxyanions of Cr(VI) and Mo(VI) from aqueous solutions. The adsorption followed a pseudo-second-order kinetics and adsorption capacities of 0.7 and 1.4 mmol/g for Cr(VI) and Mo(VI) were recorded. E_a = 5.34 and 14.50 kJ/mol for the adsorption of Cr(VI) and Mo(VI) indicated an ion exchange mechanism. The standard free energy values (ΔG°) of − 2.11 and − 3.40 kJ/mol for Cr(VI) and Mo(VI) indicated a spontaneous adsorption process. Column studies showed the suitability of the organo-bentonite for operation in continuous flow systems.     

β-Carotene adsorption on acid-activated montmorillonite

The adsorption of β-carotene from solution in benzene on acid-activated Canakkale montmorillonite of Turkey has been investigated. The adsorption isotherm had two steps. The first step was of the Langmuir type, and the isosteric heat of adsorption corresponding to this step was equal to −193.514 kJ/mol. The decrease in the total number of acid sites of the clay surface was determined to be 0.45×10⁻⁴ mol/g clay by nonaqueous titration with diethylamine. The phenomenon seems to be mainly a chemisorption stemming from the interaction of β-carotene with acid sites. Also, the activated clay acts as an oxidation catalyst on the β-carotene left in the solution.     

活性炭对不锈钢酸洗废水中Cr3+和Fe3+的吸附特性

对颗粒活性炭吸附不锈钢酸洗废水中的Cr3+和Fe3+进行了研究. 结果表明,活性炭对Cr3+的饱和吸附量为4.546 mg/g,对Fe3+的饱和吸附量为40.76 mg/g,吸附平衡时间分别为90和60 min. 对吸附过程进行准一级、准二级动力学模型拟合,发现准二级模型拟合较好. 活性炭对Cr3+的吸附基本符合Langmuir和Freundlich等温吸附模型,而对Fe3+的吸附与BET吸附模型拟合较好,吸附Cr3+, Fe3+的活化能Ea分别为37.19和51.01 kJ/mol. 活性炭对Cr3+的吸附以化学吸附为主,而物理吸附则主导对Fe3+的吸附.     

Effect of temperature on the removal of lead(II) by adsorption on China clay and wollastonite

The removal of Pb(II) from aqueous solution by adsorption on china clay and wollastonite is an attractive process. The amount of Pb(II) removed by adsorption is highly dependent on the temperature of the adsorbate solution and favours low temperature. The equilibrium times were noted, i.e. 90 min for china clay and 120 min for wollastonite. The various rate parameters of the adsorption process have been determined at different temperatures. The activation energies were determined and found to be ?5.345 kJ mol^?1 and ?8.730 kJ mol^?1 for Pb(II)-china clay and Pb(II)-wollastonite systems, respectively. The adsorption isotherm was measured experimentally at various temperatures. The negative values of enthalpy change (ΔH = ?77.95 kJ mol^?1 and ?16.40 kJ mol^?1 for china clay and wollastonite, respectively) indicate the exothermic nature of the adsorption processes for both systems. The isosteric heats of the adsorption process have been determined at various surface coverages of the adsorbents used. The various thermodynamic parameters have been calculated to elucidate the mechanism involved in the adsorption process.     

Study of the behavior of adsorbing CS2 by activated carbon

The adsorption of carbon disulfide on one raw and three modified activated carbon samples at different temperatures from 303 K to 333 K and the thermodynamics of adsorption have been investigated using a vacuum adsorption apparatus. The amounts of carbon disulfide adsorbed by three modified carbon samples are all larger than that of the raw one. It is found that organic amine is more effective than KOH as active ingredient for modification of activated carbon. The Freundlich equation is found to be the best model to fit the isotherm data for the four carbon samples at different temperatures studied.The isosteric heats of adsorption on the four carbon samples, derived from the adsorption isotherms using the Clapeyron equation, decrease with increase of surface loading. The heat of adsorption lies between 17.7 and 51.4 kJ/mol, where the carbon sample modified with KOH and ethylenediamine has the highest value with the exception of the case of high surface coverage (> 3.5 mmol/g). It is also found that the choice of adsorption isotherm has a significant influence on the values of isosteric heat of adsorption calculated. The isosteric heats of adsorption at zero surface loadings for the four carbon samples are 53.93, 53.87, 45.17 and 65.54 kJ/mol respectively and the carbon sample modified with KOH and ethylenediamine has the highest value. Analysis of the thermodynamic data shows the mobility of adsorbed carbon disulfide increases with increase of surface loading in all cases. The observed entropy change associated with the adsorption is higher than the theoretical value for the mobile adsorption but lower than the theoretical value for the localized adsorption in all cases except the carbon sample modified with KOH and ethylenediamine at higher surface coverage (> 4 mmol/g). The observed entropy change also decreases with increase of surface loading in all cases.     

Equilibrium modeling for the adsorption of methylene blue from aqueous solutions on activated clay minerals

This work reports the application of an activated clay mineral as adsorbent for the removal of a basic dye, methylene blue (MB), from aqueous solutions. The thermal treatment at 300 °C for 2 h and the acid activation with nitric acid of 0.5 mol/dm³ under reflux conditions improve the adsorption capacity of the raw clay mineral. A maximum of 500 mg/g of MB at equilibrium is achieved. Equilibrium data are mathematically modelled using the Freundlich, Langmuir and Toth isotherm adsorption models.