Sulfonation Process Research Articles

The Production of Surfactant Anionic Methyl Ester Sulfonate (MES) from Virgin Coconut Oil (VCO) with Ultrasound-Assisted

Virgine coconut oil (VCO) is a vegetable oil that has many ingredients that can be used, one of the highest ingredients is lauric acid about 41-51%. It can be used to synthesis of surfactants, which is the surfactant anionic methyl ester sulfonate (MES). However, time of transesterification and sulfonation needed is very long in the conventional process. Because of that, some researchers have proved that ultrasound-assisted can accelerate and increase the yield because ultrasound can directly cavitation that help the rupture mechanism of matrix cells. In the sulfonation process, methyl ester is reacted with sodium bisulfite (NaHSO3) with several predetermined variables. After being reacted, the mixture of methyl ester and NaHSO3 used a separating funnel and then purified using 50% of methanol, then evaporated and neutralized using 20% of NaOH. The measured quantities include yield, density, viscosity, surface tension, FT-IR analysis and Gas Chromatography-Mass Spectrometry (GC-MS) analysis. In transesterification, the optimum conditions were obtained in 1:6 of mole ratio in 3 minutes, the yield of 90%. In sulfonation, the optimum conditions were obtained in temperature at 65°C in 30 minutes. With the resulting viscosity of 4,04 cSt, the yield is 98%, and the surface tension is 32,028 dyne/cm.

The influence of the amount of catalyst on the degree of sulfonation in the sulfonation process on waste-based Styrofoam (polystyrene) into Poly-(Styrene Sulfonic Acid)

This study aims to determine the influence of the amount of Ag2SO4 silver sulfate catalyst and amount of time on the degree of sulfonation in waste-based Styrofoam (polystyrene) into Poly-Styrene Sulfonic Acid (PSSA). The method used is sulfonation with sulfuric acid H2SO4 as a sulfonating agent. Based on the research, the sulfonation reaction was successfully carried out, which was shown by the functional group in the FTIR test and the highest degree of sulfonation achieved was 67.6%, which come from variation amount of 2% Ag2SO4 catalyst and 25 minutes of reaction time.

Yeast-based biodiesel production using sulfonated carbon-based solid acid catalyst by an integrated biorefinery of durian peel waste

An integrated biorefinery concept for yeast-based biodiesel production using durian peel (DP) as a feedstock was developed. After dilute acid hydrolysis, DP hydrolysate (DPH) and DP solid fraction (DPSF) hydrolysis residues were generated. Yeast lipid was produced from undetoxified DPH by Rhodotorula mucilaginosa KKUSY14. DPSF was subjected to a one-step sulfonation process to prepare a solid catalyst (DPSF-SO3H) and was characterized using FTIR, XRD, and FE-SEM analysis. DPSF-SO3H catalyst exhibited good catalytic activity for yeast-based biodiesel (FAME) production from wet cell of KKUSY14 grown in DPH by direct transesterification. FAME yields of 81.57% and 78.73% were reached, respectively, for microwave and conventional heating. The fuel properties of FAME were in accordance with the ASTM and EN standards. Based on the higher heating value of FAME produced, an energy output of about 32.44–34.90 MJ/kg was estimated. The proposed bio-refinery concept led to the production of 101.2 kg yeast biomass, 16.0 kg yeast lipid, 717 kg DPSF-SO3H catalyst, 79.7–82.6 kg FAME, and 70.4 kg yeast residues from 1000 kg of DP waste. This model clearly provides economic benefits by creating value-added products and eliminating any waste streams.

Effect of same chloromethylation and sulfonation process on the ion exchange membranes in terms of polymer types and ionic properties

Ionic membranes are known as dense membranes in which ions have transferred according to the desired purpose under an electrical current. In this study, sulfonation and chloromethylation processes were applied to different polymers and exchangers during the production phase of anion and cation exchange membranes. The results showed that the polysulfone-based anion and cation exchange membrane exhibited the lowest resistance of 0.268 Ω cm-2 and 0.71 Ω cm-2, the highest ion exchange capacities of 3.74 and 3.41 meq/g, and also the highest ionic conductivities of 28.3 and 10.76 mS/cm, respectively. On the other hand, the tensile strengths were measured for polystyrene-based anion exchange and poly(butadiene-co-styrene)-based cation exchange membranes 507 and 626.15 MPa. Although polystyrene and poly(butadiene-co-styrene) exhibited good results in terms of tensile strength, polysulfone-based AEM and CEM were the best in terms of ionic properties such as ion separation, permeability, and resistance. In addition, chloromethylation method with the mixture of formaldehyde and HCl has improved the resistance, ion exchange capacity, and ionic conductivity properties of AEMs compared to other chloromethylation methods.

Synthesis and Initial Evaluation of Solid Acid Catalyst Derived from Spent Coffee Grounds for the Esterification of Oleic Acid and Methanol

Spent coffee grounds (SCGs) were utilized in the synthesis of a solid acid catalyst (SAC) through a carbonization–sulfonation process performed at low temperatures (350–500 °C for carbonization and 50–150 °C for sulfonation) and short processing times (1–10 h). The best SAC from the process was able to convert more than 90% of oleic acid to methyl oleate during esterification with methanol (10 mol OA/mol methanol, 80 °C, 7 h, 10%w/w catalyst loading). It was obtained by carbonizing SCG at 400 °C for 2 h and then sulfonating the biochar at 100 °C for 1 h. The reusability tests performed in 4 cycles at the same esterification conditions reveal loss of activity of about 70% of its original state, corresponding to a decrease in total acid and sulfonic acid densities from 4.22 and 3.36 mmol H+/g to 1.33 and 1.16 mmol H+/g, respectively. This process is a considerable improvement from that reported in previous works, having no activating agents in the carbonization process and with significantly shorter times for processing.

Mathematical Modeling of Poly[styrene-co-(ethylene glycol dimethacrylate)] Sulfonation

The production of sulfonated resins is of great interest to be applied in different industrial processes such as esterification, etherification, biodiesel production and water treatment. Mathematical models play an important role in process control and optimization, through prediction of process variables and adjustment of parameters. Currently mathematical models for resin sulfonation processes are still scarce in literature. In the present study, mathematical tools were used to build a model that is able to describe the sulfonation process of poly[styrene-co-(ethylene glycol dimethacrylate)] particles. The diffusion and rate coefficients were estimated through comparison between the model and the experimental data and presented coherent values. An average activation energy of 170 kJ/mol was obtained for the sulfonation reaction. The results revealed that, for the conditions studied herein, the process is diffusion-controlled and can be represented by the shrinking core model, considering irreversible pseudo-first order reaction for sulfuric acid.

Полиэлектролитный герметик для топливных элементов на основе привитых фторсополимеров

The preparation of grafted copolymers for electrochemical devices by chemical grafting copolymerization of acrylic acid and α-, β-, β-trifluorostyrene to a film fluorinated copolymer of hexafluoropropylene with vinylidene fluoride is described. The grafted copolymers contained carboxyl groups and the sulfonation process was carried out for additional introduction of ionic sulfo- groups. The optimal conditions for the process have been determined, which make possible to obtain grafted copolymers with a wide range of electrochemical and physical-mechanical properties. The resulting products in the form of ion-conducting membranes can be used as part of current sources and other electrochemical devices and have a specific volumetric electrical resistance of 0.46—1.41 Ohm.m, exchange capacity 1.45—1.62 meq / g, moisture content 25—62%, breaking stress 0.82—1.08 MPa.

Modification and Optimization of Rice Husk Ash Bio-Filler in Sulfonated Polyimide Membrane for Direct Methanol Fuel Cell

Direct methanol fuel cell (DMFC) is a very high potential renewable and sustainable energy for portable devices as it has very high energy density and more environmentally friendly. Adding filler into the membrane matrix had reported in improved performance of the DMFC. However, addition of filler will lead to the decrease of the ion exchange capacity of the membrane, which will in turn reduce the fuel cell performance. Hence, this work studies the modification of rice husk ash via sulfonation process and the effect of the synthesis parameter of novel sulfonated polyimides/sulfonated rice husk ash (SPI/sRHA) composite membrane towards fuel cell performance where filler sRHA had been synthesized via the mixing reaction between rice husk ash (RHA) with chloroform and chlorosulfonic acid. The composition of filler in membranes was optimized with different synthesis parameters such as different types of filler used, loading of filler in membrane and membrane annealing temperature. Investigation of the effects for these three parameters on the physicochemical properties of the composite membranes produced was carried out using response surface methodology (RSM) approach to optimize the synthesis parameters of the composite membrane. The fillers and composite membranes were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller (BET) analysis and transmission electron microscopy. Different synthesis parameters had shown different influences on the physicochemical properties of the composite membranes and consequently, gave different passive fuel cell performances of DMFCs too. The optimized membrane (S-12-sR) showed enhanced physicochemical performance as well as the passive single cell performance as compared to pure SPI and Nafion 117 membranes. The water uptake, proton conductivity and IEC that had been achieved by the optimized membrane were 90.97%, 0.1891 S cm−1 and 0.2608 mmol g−1 respectively. The maximum power density of the passive DMFC was improved from 8.1 mW cm−2 to 16.4 mW cm−2 under ambient conditions.

MODIFYING WASTE POLYSTYRENE TO ION EXCHANGE MATERIAL: OPTIMIZING THE SULFONATION PROCESS AND COLUMN STUDY FOR THE REMOVAL OF Cr3+

The incredible growth of plastic waste is a major concern for the whole society in recent years. The accumulation of plastic waste has badly effects on wildlife, habitat, and humans. Plastics that act as pollutants are categorized into different sizes, from micro to macro. Disposable plastic waste was collected at the bakery shop and removed the residue food by tap water and NaOH 1M to remove residual food. This study focuses on modify waste plastic by sulfuric acid to bind the sulfonated function group on the structure of the polystyrene chain at room temperature. The sulfonated product was used for removing heavy metal ion in water with the mechanism of the ion exchange process. The prepared ion exchange material was characterized by FTIR and SEM to ensure that the sulfonation process has happened. The chromium (III) ion removal by modified ion exchange product in continuous mode was affected by an operational parameter such as the bed height of sulfonated material. The Yoon-Nelson and Thomas model were used to analyze the experimental result and the model parameters were evaluated. From this result, it can be concluded that with the increasing amount of sulfonated waste polystyrene, exchange capacity, and the time required for a 50% adsorbate breakthrough was higher.

Dielectric properties of sulfonated poly(ether ether ketone) (SPEEK) electrolytes with 1-ethyl-3-methylimidazolium tetrafluoroborate salt: Ionic liquid-based conduction pathways

In this study, dielectric properties of sulfonated poly(ether ether ketone) (SPEEK) solid polymer electrolytes (SPEs) containing room-temperature molten salt, 1-ethyl-3-methylimidazolium tetrafluoroborate were investigated. Additionally, the effects of ionic liquid (IL) addition on the thermomechanical properties and the micro-structure of composite electrolytes (SPEEK-30 × 1IM and SPEEK-30 × 2IM) were studied. The characteristics of the SPEs were investigated by FTIR, SEM, TGA, DSC and DMA measurements. FTIR analysis confirmed the success of the sulfonation process and IL/sulfonated polymer interactions. IL addition caused changes in the crystalline structure and surface morphology of the SPEs. It was observed that SPEEK-30 × 1IM and SPEEK-30 × 2IM electrolytes have lower glass transition temperatures (Tg) and crystallinity than that of pure SPEEK-30. Due to the amorphous character formed by IL, proton conduction paths in which ILs exhibit enhanced conductivity have been formed. Among the composite electrolytes, SPEEK-30 × 2IM demonstrated an ionic conductivity (5.45 × 10−4 Scm-1) more than 20 times higher than SPEEK-30.

Preparation of a Sulfonic‐Acid‐Type Ordered Mesoporous Carbon Solid Acid via Hydrothermal Synthesis for the Transesterification of Waste Frying Oil

AbstractHydrothermal carbonisation was used to synthesise hydrothermally ordered mesoporous carbon (HOMC), employing sucrose as the carbon source, a P123 block copolymer as the surfactant and tetraethyl orthosilicate as the silicon source. A high‐density sulfonic‐acid‐based solid acid catalyst (HOMC‐SO3H) was subsequently prepared via low‐temperature sulfonation of the HOMC with concentrated sulfuric acid. Transmission electron microscopy and small‐angle X‐ray diffraction analyses showed that both the HOMC and HOMC‐SO3H exhibited an ordered mesoporous structure. The N2 Brunauer‐Emmett‐Teller surface areas of the HOMC and HOMC‐SO3H were determined to be 112 and 87 m2/g, respectively, and the average pore sizes were 11.0 and 15.1 nm, respectively. X‐ray photoelectron spectroscopy data confirmed that −SO3H groups were successfully introduced onto the HOMC surface by the sulfonation process, and a surface acid concentration of 5.9 mmol/g HOMC‐SO3H was determined by acid‐base titration. The HOMC‐SO3H was applied to the transesterification of waste frying oil with methanol and a fatty acid methyl ester yield of 95 % was obtained after a 5 h reaction at 180 °C.

Magnetic biochar derived from waste palm kernel shell for biodiesel production via sulfonation

Due to its environment-friendly and replenishable characteristics, biodiesel has the potential to substitute fossil fuels as an alternative source of energy. Although biodiesel has many benefits to offer, manufacturing biodiesel on an industrial scale is uneconomical as a high cost of feedstock is required. A novel sulfonated and magnetic catalyst synthesised from a palm kernel shell (PMB-SO3H) was first introduced in this study for methyl ester or biodiesel production to reduce capital costs. The wasted palm kernel shell (PKS) biochar impregnated with ferrite Fe3O4 was synthesised with concentrated sulphuric acid through the sulfonation process. The SEM, EDX, FTIR, VSM and TGA characterization of the catalysts were presented. Then, the optimisation of biodiesel synthesis was catalysed by PMB-SO3H via the Response Surface Methodology (RSM). It was found that the maximum biodiesel yield of 90.2% was achieved under these optimum operating conditions: 65 °C, 102 min, methanol to oil ratio of 13:1 and the catalyst loading of 3.66 wt%. Overall, PMB-SO3H demonstrated acceptable catalysing capability on its first cycle, which subsequently showed a reduction of the reusability performance after 4 cycles. An important practical implication is that PMB-SO3H can be established as a promising heterogeneous catalyst by incorporating an iron layer which can substantially improve the catalyst separation performance in biodiesel production.

Melt synthesis of sulfonated EPDM ionomers in batch and continuous processes

AbstractZinc‐neutralized sulfonated EPDM ionomers (Zn‐SEPDM) were prepared by batch and continuous melt sulfonation processes, and the ionomer products were compared with ionomers synthesized by sulfonation of EPDM in homogeneous solution. The efficiency of a batch melt sulfonation using an intensive mixer as a reactor was comparable to that of the solution sulfonation process, but the efficiency of the melt sulfonation in a twin‐screw extruder was considerably lower, which was thought to be a consequence of a relatively short reaction residence time due to limitations of the equipment. Melt neutralization was not complete, which produced a dark colored product. However, the incomplete neutralization and the color of the product did not affect the mechanical properties of the melt sulfonated ionomers, which were comparable to those of ionomers made by conventional solution sulfonation. The metal sulfonate concentration alone determined the mechanical properties of the ionomer. Melt sulfonation of Zn‐SEPDM ionomers by batch or continuous melt processes appears to be a practical alternative to solution sulfonation, but further optimization of the melt sulfonation processes is needed to ensure uniform sulfonation and complete neutralization.

Strategies to Reduce Biofilm Formation in PEEK Materials Applied to Implant Dentistry-A Comprehensive Review.

Polyether-ether-ketone (PEEK) has emerged in Implant Dentistry with a series of short-time applications and as a promising material to substitute definitive dental implants. Several strategies have been investigated to diminish biofilm formation on the PEEK surface aiming to decrease the possibility of related infections. Therefore, a comprehensive review was carried out in order to compare PEEK with materials widely used nowadays in Implant Dentistry, such as titanium and zirconia, placing emphasis on studies investigating its ability to grant or prevent biofilm formation. Most studies failed to reveal significant antimicrobial activity in pure PEEK, while several studies described new strategies to reduce biofilm formation and bacterial colonization on this material. Those include the PEEK sulfonation process, incorporation of therapeutic and bioactive agents in PEEK matrix or on PEEK surface, PEEK coatings and incorporation of reinforcement agents, in order to produce nanocomposites or blends. The two most analyzed surface properties were contact angle and roughness, while the most studied bacteria were Escherichia coli and Staphylococcus aureus. Despite PEEK’s susceptibility to biofilm formation, a great number of strategies discussed in this study were able to improve its antibiofilm and antimicrobial properties.

Improving water flux and salt rejection by a tradeoff between hydrophilicity and hydrophobicity of sublayer in TFC FO membrane

This paper presents a novel approach using sulfonated polyethersulfone/zeolitic imidazolate framework (SPES/ZIF-8) porous nanocomposite substrate to enhance the salt rejection and water flux of forward osmosis (FO) membrane. The effect of SPES/ZIF-8 substrate on FO membrane properties containing morphologies, hydrophilicity, water permeability and salt rejection were investigated and completely discussed. Based on the obtained results, the selectivity and permeability of thin-film nanocomposite (TFN) FO membranes can be improved simultaneously through adjusting the both hydrophilic and hydrophobic characteristics. But these two results, is achieved in two different processes and with reverse impacts. After the sulfonation process and using the more hydrophilic polymer (SPES) instead of the neat PES, the porosity and consequently the water flux was increased. Because of more hydrophilicity of SPES which reduces the cross-linking degree of the corresponding polyamide (PA) layer, the salt rejection was reduced. In contrast, after the incorporation of ZIF-8 into the SPES substrate, the salt rejection was increased due to the hydrophobic nature of these nanoparticles (NPs). In terms of both salt rejection and water flux, the sulfonated TFN membrane with 0.5% ZIF-8 NPs (TFN-S0.5 membrane) showed the improved results comparing with the bare Thin-film composite (TFC) membrane. Furthermore, the best result for the ratio of reverse salt flux to water flux (Js/Jw) as the selectivity parameter, was about 0.16 g/L using 10 mM and 2 M NaCl solutions as the feed solution (FS) and the draw solution (DS), respectively, in the FO experiment. Also, the structural parameter (S) which is believed to have a strong relationship with the internal concentration polarization (ICP), was decreased to 0.39 nm as the best result, after modification of FO membrane.

Facile preparation of sulfonated biochar for highly efficient removal of toxic Pb(II) and Cd(II) from wastewater

Biochar is deemed as the ideal material for the effective removal of heavy metals in wastewater treatment. Herein, we developed a facile one-step solvothermal method for the preparation of sulfonated biochar (SBC) from Axonopus compressus under a low-temperature condition. FTIR and XPS analysis demonstrate that plenty of –OH, –COOH and –SO3H moieties are generated on the surface of SBC during the sulfonation process. Due to high electronegativity and strong complexation of these moieties, SBC can rapidly adsorb Pb(II) and Cd(II) with capacities of 191.07 and 85.76 mg/g respectively within 5 min. SBC can be reused for 5 cycles with a negligible loss of adsorption capacity. In addition, different biomass-based biochars are prepared under the identical experimental conditions, and they are successfully applied in the treatments of Pb(II) and Cd(II). The satisfying results indicate that one-step low-temperature sulfonation could be a universal method, and various types of biomass waste could be the abundant, effective, economical material source for the treatment of environmental heavy metal pollution in future.

Synthesis and characterization of sulphonic acid ligand immobilized Aminopropyl silanetriol copolymer and evaluation of its Bovine serum albumin adsorption efficiency

Abstract An adsorbent Stearyl Alcohol (SA) - grafted- epichlorohydrin (E) -grafted- aminoproypyl silanetriol (APST) was synthesized, functionalized with sulfonic acid by sulfonation process [(SA-g-E)-g-APST/ SO3H]. The characterization of the adsorbent material was done using FTIR, XRD, SEM and TGA analyses. Adsorption behaviour of bovine serum albumin (BSA) was investigated using batch adsorption experiments. Adsorption efficiency was found to be extreme at pH 4.5. Kinetic studies revealed the suitability of pseudo-second-order model and adsorption equilibrium was attained within 3 h. On studying the rate limiting step, film diffusion process proved to be the best fit. Considering different isotherms, Sips isotherm model proved to be the best acceptable with a maximum adsorption capacity of 35.12 mg/g at 303 K. The favorability of the adsorption process was studied by calculating the separation factor (RL) and the results were found to be positive. Thermodynamic studies pronounce the spontaneous nature of adsorption, having maximum entropy in the system. Revival studies were done using 0.1 M Na2CO3 as the desorbing agent. The desorption experiment was carried out for over six cycles - showed the repeatability and regeneration capability of the adsorbent.

From waste disposal to valuable material: Sulfonating polystyrene waste for heavy metal removal

The conversion of waste into reusable materials has been a focus of many researchers in recent years. Polystyrene waste converted into a cation exchange resin and used as absorbent of cadmium, copper and zinc had been concerned. In this study, the feasibility of sulfonating polystyrene waste was investigated by using sulfuric acid to form sulfonated functional groups on the polystyrene matrix and further used for heavy metal ions removal from wastewater. The modified ion exchange materials were characterized by FTIR, SEM, EDS, XRD and TGA. Batch mode experiments of heavy metal ion exchange were conducted to determine the kinetic parameters. The adsorption of zinc, copper and cadmium by the sulfonated polystyrene fitted with both the Langmuir and the Freundlich isotherm model; the maximum adsorption capacities were 4.09 mg Zn2+/g, 4.58 mg Cu2+/g and 4.04 mg Cd2+/g, respectively. Moreover, fixed-bed adsorption was investigated. When the flow rate decreased, the initial concentration, and the mass of sulfonated polystyrene increased, the adsorption capacity was observed to increase. A maximum adsorption capacity of 10.6 mg Zn2+/g was achieved at the influent concentration of 70 mg/L, sulfonated polystyrene mass of 30 g, and flow rate of 8.33 mL/min when operating with real zinc electroplating wastewater. The kinetic Thomas and Yoon-Nelson models well described the adsorption of Zn2+, Cu2+, and Cd2+ in continuous mode, with R2 value higher than 90 %. From these results, it can be concluded that this sulfonation process of polystyrene waste can be technically and environmentally feasible method for sustainable development.

Conversion of biochar to sulfonated solid acid catalysts for spiramycin hydrolysis: Insights into the sulfonation process

Biochar has been recognized as a sustainable platform for developing functional materials including catalysts. This work demonstrated a method of converting biochar to sulfonated solid-acid catalysts, and the effectiveness of the catalysts for spiramycin hydrolysis was examined. Two biochar samples (H and X) were sulfonated with three reagents (concentrated H2SO4, ClSO3H and p-toluenesulfonic acid (TsOH)) under hydrothermal, simple heating, ambient temperature, and CHCl3-assisted treatments. The effect of elemental compositions and structural characteristics of the feeding materials (H and X) on the acidic properties of the sulfonated biochars were investigated. The results showed that the sulfonation ability of the three reagents was in the order of ClSO3H > H2SO4 > TsOH, while hydrothermal treatment provided the highest total acidity, and largest amount of acidic groups (e.g., SO3H, COOH and Ar-OH). Biochar X with higher O/C and N contents, and less graphitic features showed superior acidic properties than biochar H under all the employed treatments. The hydrolytic efficiencies of the sulfonated biochars under 200 W of microwave irradiation increased with increasing total acidity, and the amount of SO3H and COOH groups. After sulfonation, the O/C of biochars increased, while H/C decreased, and the aromatic and graphitic features did not change. The electromagnetic energy absorbed by the sulfonated biochars did not notably contribute to spiramycin hydrolysis. Thus, this work demonstrated an effective and promising method for maneuvering biochar-based functional solid-acid catalysts for antibiotic remediation in contaminated water.

Fluorescent conjugated microporous polymer (CMP) derived sensor array for multiple Organic/Inorganic contaminants detection

The development of fluorescent sensors for highly sensitive detection of multiple environmental contaminants is highly promising, but still remains to be a challenge up to date. In this work, we provide a highly water-dispersible sulfonated conjugated microporous polymers (S-CMP) based fluorescent sensor array that can be used for high-throughput detection of multiple organic/inorganic contaminants. This S-CMP was synthesized via a two-step process, including a Pd-catalyzed coupling reaction and a sulfonation process. It is differentiated twelve metal ions using principal component analysis (PCA) on the basis of distinguished fluorescent responses of the sensor array on metal ions. Moreover, it is also identified a series of or;1;ganic solvents by this S-CMP-based sensor by virtue of its unique fluorescence-emitting and color response. This work opens up the design of sulfonate-grafted CMP in environmental pollution detection and expands the application scope of CMP.