An efficient and clean oxidative bromination reaction of phenol catalyzed by ammonium salt of heteropoly acids supported on silica

An efficient and eco-friendly oxidative bromination reaction of phenol has been achieved by treatment with KBr–H₂O₂ in the presence of a catalytic amount ammonium salt of molybdophosphoric acid or phosphotungstic acid that supported on silica, which were synthesized by sol–gel method. The physicochemical characterization indicated that supported catalysts still retained its Keggin type and the particles were well dispersed onto the surface of silica support. The evaluated results of liquid phase bromination of phenol showed that these catalysts exhibited high catalytic oxybromination activity and high para substituted selectivity, and good stability was also observed after recycling three times. Meanwhile, no highly toxic and corrosive materials were used and formed in the reaction process, which makes this process environmentally benign. The influences of the reaction time, catalyst amount and solvent on oxidative bromination reaction were also investigated.     

Feasibility of honeycomb monolith supported sugar catalyst to produce biodiesel from palm fatty acid distillate (PFAD)

Carbon coated monolith was prepared by sucrose solution 65 wt.% via dip-coating method. Sulfonation of incomplete carbonized carbon coated monolith was carried out in order to synthesize solid acid catalyst. The textural structure characteristics of the solid acid catalyst demonstrated a low surface area and pore volume. Palm fatty acid distillate (PFAD), a by-product of palm oil refineries, was utilized as oil source in biodiesel production. The esterification reaction subjected to different reaction conditions was performed by using the sulfonated carbon coated monolith as heterogeneous catalyst. The sulfonation process had been performed by using vapour of concentrated H₂SO₄ that was much easier and efficient than liquid phase sulfonation. Total acidity value of carbon coated monolith was measured for unsulfonated sample (0.5 mmol/g) and sulfonated sample (4.2 mmol/g). The effect of methanol/oil ratio, catalyst amount and reaction time were examined. The maximum methyl ester content was 89% at the optimum condition, i.e. methanol/oil molar ratio (15:1), catalyst amount (2.5 wt.% with respect to PFAD), reaction time (240 min) and temperature 80 °C. The sugar catalyst supported on the honeycomb monolith showed comparable reactivity compared with the sugar catalyst powder. However, the catalyst reusability studies showed decrease in FFA% conversion from 95.3% to 68.8% after four cycles as well as the total acidity of catalyst dropped from the value 4.2 to 3.1 mmol/g during these cycles. This might be likely due to the leaching out of SO₃H group from the sulfonated carbon coated monolith surface. The leaching of active species reached a plateau state after fourth cycle.     

Thermal hazard evaluation for iso-octanol nitration with mixed acid

2-Ethylhexyl nitrate (2-EHN), an important additive to diesel fuel, is produced from the nitration of iso-octanol with HNO₃–H₂SO₄ mixed acid. In this study, the differential scanning calorimeter (DSC), accelerating rate calorimeter (ARC) and reaction calorimeter were used to analyze the thermal stability of 2-EHN and the thermal hazard of iso-octanol nitration. Four samples with different ratios of 2-EHN to mixed acid were tested using DSC. The results indicated that more mixed acid could catalyze the decomposition of 2-EHN. Three samples were tested using ARC and the results showed that sample 4 contained the lowest onset temperatures, T_D8 and T_D24. This shows that there is a higher probability of triggering the decomposition of the product 2-EHN from the iso-octanol nitration process. This conclusion was verified using RC1e tests at different temperatures. The RC1e experiments also indicated that the overall heat generation of these reactions was considerably large despite the high yields of the nitration process at 45 °C and 55 °C. This heat generation makes these semi-batch processes difficult to control, especially on a pilot or plant scale. Based on the maximum temperature of the synthesis reaction (MTSR) corrected by the yield, the only acceptable semi-batch process is the nitration reaction at 10 °C.     

Dilute Acid Hydrolysis of Cellulose and Cellulosic Bio-Waste Using a Microwave Reactor System

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175°C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175°C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k₁ = 0.0813 s⁻¹; k₂ = 0.0075 s⁻¹, which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent ‘hot spot’ formation within the reactor, which would have cause localised degradation of glucose.     

Synthesis of Bio-Diesel and Bio-Lubricant by Transesterification of Vegetable Oil with Lower and Higher Alcohols Over Heteropolyacids Supported by Clay (K-10)

The use of different lower and higher alcohols viz; methanol, ethanol, n-propanol and n-octanol, for the synthesis of methyl, ethyl, propyl and octyl fatty acid esters by transesterification of vegetable oil (triglycerides) with respective alcohols also known as ‘Bio-diesel’ and ‘Bio-lubricants’ was studied in detail. The reactions were carried out in a batch process. The activity with different supports like clay (K-10), activated carbon, ZSM-5, H-beta and TS-1 were compared. The superacids (heteropolyacids, HPA) viz; Dodeca-Tungstophosphoric acid [H₃PO₄·12 WO₃·xH₂O] (TPA) and Dodeca-Molybdo phosphoric acid ammonium salt hydrate [H₁₂Mo₁₂N_3-O₄₀P + aq] (DMAA) was used to increase the acidity and so the activity by loading on the most active support viz; clay (K-10). These HPA loaded on clay as a catalyst was used for the following study: effect of percent HPA loading on clay, effect of different vegetable oils, effect of different alcohols on the triglyceride conversion based on glycerol formation and selectivity based on alkyl esters formation. The data is compared at the best-optimized identical set of operating reaction conditions: 170 °C, 170 rpm, catalyst loading: 5% (w/w of reaction mixture), molar ratio (oil: alcohol): 1:15 and time on stream of 8 h. The generated data is also evaluated based on the reported one.     

Refinery wastewater degradation with titanium dioxide,zinc oxide,and hydrogen peroxide in a photocatalytic reactor

This paper presents the photo-catalytic degradation of real refinery wastewater from National Refinery Limited (NRL) in Karachi, Pakistan, using TiO₂, ZnO, and H₂O₂. The pretreatment of the refinery effluent was carried out on site and pretreated samples were tested at 32–37 °C in a stirrer bath reactor by using ultra-violet photo oxidation process. The degradation of wastewater was measured as a change in initial chemical oxygen demand (COD) and with time. Optimal conditions were obtained for catalyst type, and pH. The titanium dioxide proved to be very effective catalysts in photo-catalytic degradation of real refinery wastewater. The maximum degradation achieved was 40.68% by using TiO₂ at 37 °C and pH of 4, within 120 min of irradiations. When TiO₂ was combined with H₂O₂ the degradation decreased to 25.35%. A higher reaction rate was found for titanium dioxide. The results indicate that for real refinery wastewater, TiO₂ is comparatively more effective than ZnO and H₂O₂. The experiments indicated that first-order kinetics can successfully describe the photo-catalytic reaction. The ANOVA results for the model showed satisfactory and reasonable adjustment of the second-order regression model with the experimental data. The ANOVA results also showed that pH is significant than reaction time and catalyst dosage of TiO₂; and in case of ZnO, reaction time is significant than pH and catalyst dosage. This study proves that real refinery wastewater reacts differently than synthetic refinery wastewater, oil field produced water or oil water industrial effluent.     

Biodiesel production from waste oil feedstocks by solid acid catalysis

Biodiesel is a non-toxic and biodegradable substitute for petroleum-based diesel. However, it is impractical to use refined edible oils to produce biodiesel due to its high cost and priority for food products, especially in China, while waste oils with high free fatty acids (FFAs) can be considered as the raw materials. In the present work, a solid acid catalyst comprising SO₄²⁻/TiO₂–SiO₂ was prepared, characterized and studied for its activity for the production of biodiesel from several low cost feedstocks with high FFAs. The solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterification and transesterification. The influence of reaction parameters was studied, and the optimized reaction parameters are reaction temperature 200 °C, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The catalyst showed good stability. A continuous process for biodiesel production from cheap raw feedstocks was proposed, and a 10,000-tonnes/year biodiesel production demonstration plant has been built.     

Process safety aspects in water-gas-shift (WGS) membrane reactors used for pure hydrogen production

The syngas produced by coal gasification processes can be utilized in Pd-based water-gas-shift membrane reactors for the production of pure H₂. Pd/alloy composite membrane reactors exhibit comparative advantages over traditional packed bed reactors such as simultaneous reaction/separation in one compact unit and increased reaction yields. Furthermore, the development of comprehensive process intensification strategies could further enhance membrane reactor performance resulting in a substantially smaller and functional, inherently safer, environmentally friendlier and more energy efficient process.A systematic non-isothermal modeling framework under both steady state and dynamic/transient conditions for a catalytic high temperature water-gas shift reaction in a Pd-based membrane reactor has been developed to characterize the dynamic behavior of the process system at various operating conditions from a process safety standpoint. In particular, various reaction conditions as well as key process variables such as feed temperature and flow rate, catalyst loading, driving force for H₂ permeation are considered as they are critically related to various safety aspects in the operation of a Pd-based membrane reactor. Within the proposed framework, process parameters and operating conditions which may induce hazards and compromise process safety are identified, analyzed and characterized. Finally, the proposed approach is evaluated through detailed simulation studies in an illustrative case study involving a real Pd-based membrane reactor used for pure hydrogen production and separation that exhibits complex behavior over a wide operating regime.     

混酸中甲苯半间歇硝化过程的危险性研究

为了解甲苯在混酸中硝化的危险性,用差示扫描量热法(DSC)测试甲苯、混酸及一硝基甲苯的热分解情况,用反应量热仪(RC1e)研究搅拌速度、温度及硝酸过用率3因素对目的反应的影响。结果表明,混酸分解温度最低,而当目的反应的3因素出现异常,以及反应过程中发生冷却失效时,均可导致硝化反应体系不稳定,此时若不停止加料,并采取措施,易引起混酸的分解,进一步可引起一硝基甲苯的分解,导致严重后果。     

苯和甲苯硝化及磺化反应热危险性分级研究

首先介绍了化工工艺热安全性的内涵,并从反应过程热危险性分析的方法学出发,介绍间隙、半间歇化学反应工艺热危险性分级研究的总体思路及方法。然后,围绕甲苯和苯的硝化、磺化反应,用全自动反应量热仪(RC1e)和加速度量热仪(ARC)测定其反应过程的绝热温升(△Tad)、目标反应所能达到的最高温度(TM)、分解反应最大速率到达时间(θD)等参数。运用风险评价指数矩阵法(方法1)和基于失控过程温度参数的热危险评估法(方法2)分别对其硝化和磺化反应过程的热危险性进行了分级评估。结果表明,这两种方法具有良好的一致性;给定工艺条件下甲苯和苯的一段硝化反应过程的热危险度等级较低;而磺化反应的热危险较高。尽管这两种方法还有一定的局限性,但对于间歇、半间歇合成工艺的本质安全化设计、工艺热危险性的评估具有重要的参考价值和实用意义。     

Recycling of valuable chemicals through the catalytic decomposition of phenol tar in cumene process

The base catalyst LZ-2, which was the mixture of CaO and Na–NaOH/Al₂O₃·3H₂O, was chosen for the decomposition of phenol tar to generate valuable chemicals. The selectivity of LZ-2 for dimethyl phenyl carbinol, α-methyl styrene dimer and cumenyl phenol was 100%, 100% and 98%, respectively. Under the optimum operating conditions of catalyst 2.5 wt%, operating temperature 603.15 K and decomposition time 3.5 h, decomposition ratios of cumenyl phenol and dimethyl phenyl carbinol were 98.7% and 99.97%, respectively. In addition, the experimental repeatability demonstrated that the total yield of valuable chemicals still reached 90.1% after the catalyst being used five times. Mass and energy balance indicated that the catalytic decomposition was a high potential for the recycling of chemicals from phenol tar.     

Sucrose-derived catalytic biodiesel synthesis from low cost palm fatty acid distillate

The current homogeneous acid catalyst for biodiesel product however, would lead to formation of many undesirable by-products that make the post treatment of the biodiesel to be difficult and costly. Thus, sucrose-derived solid acid catalyst was developed in the present study which aims to improve the esterification process and reduce the generation of waste. The physicochemical properties of the synthesized catalysts were studied by various techniques such as, BET surface area, X-ray diffraction (XRD), temperature programmed desorption of NH₃ (TPD-NH₃), scanning electron microscopy (SEM). Response surface methodology (RSM) with central composite design (CCD) is used to determine the optimum parameters for the catalytic reaction. The experimental results showed that the catalyst exhibited good catalytic activity in the transesterification of PFAD, providing maximum biodiesel yield of 94% at optimum parameters. The better catalytic activity of the aforementioned catalyst in the biodiesel reaction could be attributed to the presence of optimal number of catalytically active acid site density on its surface.     

The influence of ClO− and acidity in the reaction between H2O2 and CuCl2

The potentially explosive reaction of hydrogen peroxide (H₂O₂) and copper chloride (CuCl₂) was investigated. Pressure tests revealed that the reaction was strongly temperature - dependent and can easily undergo runaway reaction. Nevertheless, there was only a slight pressure increase at the low temperatures studied or when using low concentrations of CuCl₂. Under the conditions generating the slight pressure increase, hypochlorite anions (ClO⁻) are generated and the acidity increases. As the reaction reaches completion, ClO⁻ disappears, and the acidity decreases. Interestingly, the addition of phosphate buffer to maintain the weakly acid conditions led to a runaway reaction, and the use of basic ClO⁻ promoted the exothermic reaction. Based on the results, acidity has a strong impact on the reaction behaviour.     

Reaction mechanism and process safety assessment of acid-catalyzed synthesis of tert-butyl peracetate

Esterification during the synthesis of tert-butyl peracetate (TBPA) is highly exothermic. Since peroxides (tert-butyl hydroperoxide TBHP and TBPA) are intrinsically thermosensitive, this synthesis process is potentially dangerous. In this work, the exothermic process and mechanism of TBPA synthesis using acetic anhydride (Ac₂O) and TBHP under the catalysis of sulphuric acid (H₂SO₄) were clarified by calorimetry, infrared spectroscopy, and high-performance liquid chromatography. To substantially alleviate the thermal risk of the reaction, and to feasibly select appropriate synthesis conditions for ensuring the process safety of the synthesized products, several sets of isothermal and isoperibol experiments were performed using calorimetry. The intermediates formed and concentration changes during the reaction were monitored using in-situ Fourier-transform infrared spectroscopy. Differential scanning calorimetry and adiabatic calorimetry were used to assess the thermal hazard of the materials during the synthesis process. The reaction mechanism was verified using density functional theory calculations. The results revealed that a controlled increase in exothermicity could be achieved by adding aqueous TBHP to Ac₂O in semi-batch experiments in isothermal mode, and accordingly, the highest yield was 95.71%. Experiments combined with theoretical calculations revealed that the primary exothermic event was the TBPA formation reaction, and the removal of a large amount of water from TBHP prior to this is favourable for the reaction. The criticality classes of this reaction were of Grade 2.     

Feasibility study of decomposing methane with hydroxyl radicals

Coal-mine gas disaster is one of the most serious coal-mine disasters in China. The main component of coal-mine gas, methane is chemically stable and very difficult to be degraded by conventional methods. Hydroxyl radical (OH), due to strong oxidizing ability and high electro-negativity, is the primary degradation source of atmospheric methane. In the present study, methane degradation using hydroxyl radicals generated by Fenton’s reagent, Fe²⁺/H₂O₂, has been carried out in the self-designed bubbling reactor. The effects of H₂O₂ concentration, dosage of FeSO₄·7H₂O and initial pH value on methane removal efficiency were investigated respectively. It has been found that the optimal reaction conditions were 100 mM of hydrogen peroxide, 2.00 mM of ferrous ion and initial pH value of 2.5. Under optimal conditions, the removal efficiency of methane reached 25% after 30 min. The preliminary experimental results unambiguously demonstrate that the degradation of methane using hydroxyl radicals generated by Fenton’s reagent is feasible.     

Use of advance oxidation process to improve the biodegradability of olive oil mill effluents

In this study, recalcitrant total phenol (TPh) and organic matter removal were investigated at olive mill wastewater (OMW) in sequential Coagulation and Fenton system. This study focused on different operational parameters such as pH, H₂O₂, and Fe²⁺ dosages, and [Fe²⁺]/[H₂O₂] ratios. The optimum conditions were determined as; pH = 3; [Fe²⁺] = 2.5 g/L; [Fe²⁺]/[H₂O₂] = 2.5. A higher treatment efficiency was achieved at sequential Coagulation and Fenton system (COD, 65.5%) and TPh, 87.2%), compared to coagulation process (COD, 51.4%; total organic carbon (TOC), 38.6% and total nitrogen (TN) 52.1%). This study demonstrated that the Coagulation and Fenton process has a potential for efficient removal of phenolic pollutants from wastewater.     

Essential hazard and process safety assessment of para-toluene sulfonic acid through calorimetry and advanced thermokinetics

Para-toluene sulfonic acid is a typical intermediary for the synthesis of pharmaceuticals, pesticides, and dyes and is a catalyst for organic synthesis. The consumption of para-toluene sulfonic acid used in organic synthesis has increased substantially. The toluene sulfonation process is the central path for synthesizing para-toluene sulfonic acid in China. However, the process has risks and has resulted in numerous disasters. This study utilized a reaction calorimeter 1 to reproduce the commercial toluene sulfonation process in a laboratory. The para-toluene sulfonic acid product was examined with an accelerating rate calorimeter and through differential scanning calorimetry. Both differential and integral isoconversional methods were used to determine the thermal stability of and appropriate thermokinetic models for para-toluene sulfonic acid. The safety parameters of para-toluene sulfonic acid were estimated. The research findings can be used for optimization of the toluene sulfonation process and for safe handling of para-toluene sulfonic acid.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.     

Modeling and optimization of a sono-assisted photocatalytic water treatment process via central composite design methodology

This work focuses on modeling and optimization of a sono-assisted photocatalytic decolorization process of a model pollutant, azo dye C.I. direct red 16 (DR16). In the process, a high temperature thermal decomposition nano synthesized titanium dioxide (TD-TiO₂) was applied as photocatalyst. Central composite design (CCD) methodology was used for designing the experiments, modeling and optimization of the process. A quadratic model was established to describe dependency of the decolorization efficiency (DE), as the model response, to some effective operational parameters, i.e. the catalyst dosage, pH and the dye initial concentration. The ANOVA analysis confirmed that all of the variables have significant influence on the model response. Under the established optimum conditions, 92.4% DE was achieved after 45 min; however, to access desirable mineralization efficiency, the process should be continued up to 120 min. All withdrawn samples from the reaction media during the process showed no antibacterial activity, which indicates safety of the treated effluent for disposal into the environment. Also studies showed that the process proceeds via two parallel branches of photolysis and photocatalysis, where propagation of the ultrasonic waves into the reaction media plays a vital promoting role on the latter branch.     

Disintegration of waste activated sludge by different applications of Fenton process

Oxidative disintegration of municipal waste activated sludge (WAS) using conventional Fenton (Fe²⁺ + H₂O₂, CFP) and Fenton type (Fe⁰ + H₂O₂, FTP) processes was investigated and compared in terms of the efficiency of sludge disintegration and enhancement of anaerobic biodegradability. The influences of different operational variables namely sludge pH, initial concentration of Fe²⁺ or Fe⁰, and H₂O₂ were studied in detail. The optimum conditions have been found as catalyst iron dosage = 4 g/kg TS, H₂O₂ dosage = 40 g/kg TS and pH = 3 within 1 h oxidation period for both CFP and FTP. Kinetics studies were performed under optimal conditions. It was determined that the sludge disintegration was happened in two stages by both processes: rapid and subsequent slow disintegration stages and rapid sludge disintegration stage can be described by a zero-order kinetic model. The effects of oxidative sludge disintegration under the optimum conditions on anaerobic digestion were experienced with biochemical methane potential (BMP) assay in batch anaerobic reactors. Total methane production in the CFP and FTP pre-treated reactors increased by 26.9% and 38.0%, relative to the untreated reactor (digested the raw WAS). Furthermore, the total chemical oxygen demand reductions in the pre-treated reactors were improved as well.