Hydrogen-rich gas production via supercritical water gasification (SCWG) of oily sludge over waste tire-derived activated carbon impregnated with Ni: Characterization and optimization of activated carbon production.

In this study, the production of activated carbon (AC) through the chemical activation of waste tire (WT) using H3PO4 and KOH for H2 production by SCWG of oily sludge (OS) donated by Persian Gulf Star Oil Company was investigated. H3PO4 was the best activating agent based on some pretests results, and then the synthesis of AC was optimized using Response Surface Methodology. Based on BET surface area of synthesized ACs, thirty combinations of the four variables namely; activation temperature (350-550 °C); activation time (1-4 h); H3PO4 to WT ratio (1-3 w.w-1); and H3PO4 concentration (20-40 wt%) were optimized. CHNS, TGA, FE-SEM, and EDS-mapping analyses were used to characterize the AC and catalyst synthesized in optimum condition (activation temperature: 450 °C; activation time: 2.5 h; H3PO4 to WT ratio: 2 w.w-1; and H3PO4 concentration: 40 wt%), which presented a surface area of 170 m2 g-1. Finally, Ni was impregnated on the optimized AC with different loadings (5-15 wt%) to evaluate its performance in H2 production by SCWG of OS. Although H2 yield in catalytic experiments was higher than that observed in non-catalytic experiment, results showed that the maximum H2 selectivity was 66% in SCWG of OS using AC impregnated with 10 wt% Ni.

Modeling and Experimental Investigation of Sulfurous Compounds Removal from Gas Condensate through Ultrasound-Assisted Oxidative Desulfurization Method.

This study employed an ultrasound-assisted oxidative desulfurization process (UAOD) to investigate the degradation of three sulfurous compounds in the synthetic gas condensate. Various parameters, including oxidizers (hydrogen peroxide, sodium peroxide, potassium superoxide), promoters (formic acid, acetic acid), catalysts (phosphotungstic acid, ferrous(II) sulfate, zirconium dioxide, vanadium pentoxide, aluminum oxide γ, copper(II) oxide), and phase transfer agents (isobutanol, tetraoctylammonium bromide, and tetra-n-butylammonium fluoride), were examined to identify the optimal combination for reducing sulfurous compounds in the UAOD process. The influence of the extraction stage and reactor vessel material on the desulfurization efficiency was also investigated. Results revealed that hydrogen peroxide, formic acid, phosphotungstic acid, and isobutyl alcohol were the most effective oxidizers, promoters, catalysts, and phase transfer agents, respectively. Response surface methodology was used to determine the optimal conditions by evaluating different concentrations of these reagents within specific ranges. The study considered ranges such as 10-70 vol % of hydrogen peroxide, 5-70 vol % of formic acid, 1-30 wt % of phosphotungstic acid, 1-30 vol % of isobutanol, and 5-40 min of ultrasonic ripple time. Empirical models were developed for each sulfurous compound type, providing optimal conditions for sulfur removal with an error margin of less than 0.1%. The validity of the suggested models was confirmed through an industrial data analysis. Additionally, it was observed that increasing the number of extraction stages improved desulfurization efficiency, and using a stainless-steel reactor vessel was more suitable than using a glass vessel.

Hydrogen sulfide removal from normal heptane using zinc oxide, silicon dioxide and zeolite 13X: adsorption capacity, kinetics, selectivity, breakthrough and regeneration.

This article focuses on the H2S adsorption from normal heptane (nC7) as synthetic natural gas liquids (NGL) using ZnO, SiO2 and zeolite 13X in static mode. Results of the isotherm and kinetics of the investigated adsorbents for H2S adsorption under ambient condition showed that ZnO had the highest H2S adsorption capacity between 260 and 700 mgH2S.g-1 in the initial concentration range of 2500 and 7500 ppmH2S with an equilibrium time of less than 30 minutes. Additionally, the ZnO selectivity was greater than 3.16. In continued, H2S removal from nC7 with ZnO was examined in dynamic mode. The H2S breakthrough time for ZnO reduced from 210 to 25 minutes as weight hourly space velocity (WHSV) was increased from 5 to 20 h-1 at 30 bar. Also, the breakthrough time at 30 bar was about 2.5 times greater than that at atmospheric pressure. Furthermore, H2S/CO2 mixture (i.e., 1000 ppmH2S + 1000 ppmCO2) caused the H2S breakthrough time to increase approximately by 1.11-fold. Alternatively, the ZnO regeneration conditions with hot stagnant air were optimized at different initial H2S concentrations (1000 ~ 3000 ppmH2S) using the Box-Behnken design. For instance, ZnO contaminated with 1000 ppmH2S was regenerated with an efficiency of more than 98 % for 160 minutes at 285 °C.

Insight into the application of supercritical water oxidation for dichlorvos degradation: experimental and simulation aspects.

Dichlorvos or 2,2-dichlorovinyl dimethyl phosphate (DDVP) (C4H7Cl2O4P) is a chlorinated organophosphorus pesticide, which is frequently detected in agricultural wastewater. Herein, a batch reactor was used to carry out the supercritical water oxidation (SCWO) of a synthetic wastewater containing dichlorvos as a very hazardous agricultural pollutant. To do so, the impact of four operating parameters including dichlorvos concentration (100-500 ppm), oxidant coefficient (0.7-2), temperature (300-500°C) and time (0-100 s) on dichlorvos removal was optimized by the response surface method (RSM). According to the obtained results, at optimal conditions (i.e. initial concentration of dichlorvos 107.5 ppm, oxidation ratio 1.9234, temperature 419.9°C and time 79.94 s), as an index for dichlorvos removal, the chemical oxygen demand (COD) was found to be about 96.34%. Also, the results of high-performance liquid chromatography test showed that dichloroacetaldehyde (C2CL2H2O) and dichloroacetic acid (C2CL2H2O2) were created as intermediate substances during the dichlorvos degradation. Further, the molecular dynamics simulation was performed using ReaxFF force field to show the reaction path and products obtained in each step of the dichlorvos removal. Finally, as an indication, the simulation results indicated a good coordination with the experimental results.

Kinetic Study on Nannochloropsis Oculata's Lipid Extraction Using Supercritical CO2 and n-Hexane for Biodiesel Production.

Biodiesel as a renewable fuel has attracted increasing attention in recent years. Microalgae biomass is becoming an attractive raw material for producing biodiesel using supercritical CO2 (SC-CO2) as a safe and environmentally friendly technique with high efficiency for lipid extraction. In this study, the lipid of Nannochloropsis oculata was extracted under different conditions of SC-CO2 to assess the kinetics of supercritical fluid extraction. The effective parameters on lipid extraction, including temperature, pressure, and the existence of n-hexane as a co-solvent, were investigated. The results show that an increase in temperature at low or high pressures causes the kinetic constant of lipid extraction to decrease or increase, respectively. Also, an increase in pressure causes the kinetic constant of lipid extraction to increase at low or high temperatures. The most yield and the most kinetic constant value during extraction with pure CO2 are about 0.262 [g extracted lipid/g microalgal biomass] and 0.062 min-1, respectively, at the highest pressure and temperature (i.e., 550 bar and 75 °C). Using SC-CO2 laced with n-hexane increases both the final yield and the rate of lipid extraction. Also, it improves the quality of the biodiesel fuel through the extraction of unsaturated fatty acids with a concentration of almost two times more than saturated fatty acids. Additionally, results reveal that the effect of adding n-hexane to CO2 in lipid extraction would be more efficient by increasing the temperature and lowering the pressure.

Treatment of methyldiethanolamine wastewater using subcritical and supercritical water oxidation: parameters study, process optimization and degradation mechanism.

In this examination, sub/supercritical water oxidation (SCWO) in a batch reactor was employed to degrade methyldiethanolamine (MDEA). To do so, the impact of different operating parameters including temperature (300-500 °C), time (0-100 s), initial MDEA concentration (1000-4000 ppm), oxidant coefficient (0.7-2), and pH (7.3-9.5) on MDEA degradation was separately and together investigated. Subsequently, the response surface method (RSM) was applied to optimize the operating condition of MDEA degradation. Based on the obtained results, a maximum amount of 97.4% MDEA degradation was achieved at the initial MDEA concentration of 1095 ppm in optimal condition (i.e., oxidant coefficient: 1.913, temperature: 472 °C and residence time: about 17 s). Furthermore, according to the HPLC analysis, there was a negligible amounts of formic acid (CH2O2) and nitrous acid (HNO2) in the solution at the end of MDEA removal experiment. Eventually, the mechanism of MDEA degradation was acquired using molecular dynamics simulation (MDS), which had an acceptable coordination with the experimental results. In this way, the MDS results revealed that the presence of CH2O2 and HNO2 compounds in the products was related to the degradation of MDEA and their production as by-products during the SCWO experiments.

Determination of Swelling Behavior and Mechanical and Thermal Resistance of Acrylamide-Acrylic Acid Copolymers under High Pressures and Temperatures.

Unwanted water production is a serious problem accompanying oil extraction especially in oil-fractured reservoirs. An effective approach to tackle this issue is to utilize gels as a blockage agent. In this paper, an effective series of preformed particle gels (PPGs) was synthesized by a free radical copolymerization of acrylamide and acrylic acid [poly(AAm-co-AA)] copolymers. The key factors of synthesis experiments, gelation time, drying behavior, swelling capacity (in CaCl2·2H2O, MgCl2·6H2O, BaCl2·2H2O, KCl, NaCl, and LiCl saline solutions with 200,000 ppm concentration and pH from 3 to 8), and mechanical and thermal resistance of the synthesized PPGs (with a homemade apparatus) were elucidated. Laboratory results revealed that the prepared PPG sample 1 (9.65 mole ratio of AAm/AA and 6 mol % of MBA) would be a good candidate for controlling water in oil and gas reservoirs with a salinity, pressure, and temperature of up to 200,000 ppm, 300 bar, and 170 °C, respectively, and pH values ranging from 3 up to 8.

Environmentally friendly acetic acid/steam explosion/supercritical carbon dioxide system for the pre-treatment of wheat straw.

It is well established that pretreatment of lignocellulosic biomass is required to achieve an effective enzymatic saccharification process. At the present time, most of the touted pre-treatment technologies would cause environmental pollution and unsustainable water use for the pretreated material prior to enzymatic saccharification. To address these shortcomings, the pretreatment technology which combines the supercritical CO2, SC-CO2 (a green solvent), acetic acid, and steam explosion was used to assess the pretreatment of wheat straw for enzymatic saccharification. The effects of solvent concentration, impregnation temperature and time, pre-treatment time, and temperature, as well as SC-CO2 pressure, contact time, and temperature, were evaluated. The results identified that at the optimum SC-CO2 pressure of 18 MPa, the highest amount of reducing sugars (RS) was produced from the cellulosic pulp using Acetic acid/Steam/SC-CO2 at 200 °C for 30 min, a value 20% more than the pulp produced with the Water/Steam/SC-CO2. The effectiveness of the pretreatment process was attributed not only to delignification and defibrillation but also to the exposure of the cellulose structure evidenced from the proportion of the ß-glycosidic linkages as shown by FTIR. Passing SC-CO2 after the pretreatment reduces the amounts of fermentation inhibitors and eliminates the use of wash water.

Formation of ultrafine deferasirox particles via rapid expansion of supercritical solution (RESS process) using Taguchi approach.

The poor water solubility of many drugs is a challenge in pharmaceutical research. Recently, there have been great interests in finding environmentally friendly methods producing fine particles of pharmaceutical products for applications in pharmaceutical engineering. A promising method to improve the bioavailability of pharmaceutical agents is the rapid expansion of supercritical solutions. Deferasirox (DFS), a tridentate chelator, requires two molecules for iron (III) coordination. The bioavailability (the percentage of the drug absorbed compared to its initial dosage) is limited by this insolubility. The effect of four different RESS parameters including, extraction temperature (308-318K), extraction pressure (140-200 bar), effective nozzle diameter (500-1200 µm), with and without cosolvents were investigated on the size and morphology of the precipitated particles of deferasirox based on Taguchi design. The results show great reduction in the size of the precipitated particles of deferasirox (50 nm-5 µm) via RESS process compared with the original particles of deferasirox (5-500 µm).