Biodiesel Production from Waste Cooking Oil by Enzymatic Catalysis Process

Biodiesel is an excellent option for reducing dependence on fossil fuels with environmental advantages by reducing hazardous emissions. The enzymatic transesterification has attracted the attention of researchers in the last decade and the advantages of enzymatic catalysis show that the production of biodiesel by this route has good potential, mainly because it is friendly environment. For biodiesel, production process by enzyme catalysis is chosen the response surface methodology. It is an experimental strategy to find the best operating conditions oftransesterification reaction to improve the biodiesel quality. The Process has three variables： temperature, molar ratio oil-alcohol and catalyst quantity. The process was monitored by GC-FID （gas chromatography with flame ionization detector）. The yield of the transesterification reaction by enzymatic catalysis decreases with increasing temperature, and may be due to inactivation of the enzyme by denaturation at temperatures above 50 ℃. The second-order design used was the ＂CDC （central design composition）＂ which produced a maximum yield of 95.5% in the transesterification reaction by enzymatic catalysis obtained at a temperature of 45 ℃, molar ratio methanol：oil of 8：1 and a catalyst loading of 8% wt.     

Transesterification Reaction of Waste Cooking Oil and Chicken Fat by Homogeneous Catalysis

In the last years, biodiesel production has been on a steady increase due to it is renewable and biodegradable fuel. The process to obtain biodiesel can be carried out using different raw materials. It is conlmonly performed by transesterification reaction of vegetable oils with methanol and using a homogeneous or heterogeneous catalyst. This work seeks to compare the results produced in transesterification of wasted cooking oil and chicken fat by homogeneous catalysis with NaOH. Due to in each case triglyceride comes from different raw materials, operation conditions differ slightly, which is more evident in the values used for the temperature. For chicken fat was used temperature variations between 35 ℃ and 55 ℃, varying catalyst in percentages between 0.3% and 0.7% with a molar ratio 6：1 in all cases and a reaction time of I h. Likewise, the conditions used in the tmnsesterification process of waste cooking oil were temperature between 50 ℃ and 60 ℃ with a molar ratio 6/1 and 9/1 for alcohol and oil, and catalyst percentage between 0.5% and 0.7% by weight. The yields obtained were between 78% and 94%, or 83% and 95%, for chicken fat and wasted cooking oil, respectively.     

Optimization of safflower oil transesterification using the Taguchi approach

Biodiesel is an alternative renewable fuel which is produced by using biomass resources. Its physicochemical properties are close to those of the petroleum diesel fuel. This study highlights biodiesel production from safflower seed oil. The main aim of this experimental work is to optimize the process parameters, namely the methanolto-oil molar ratio, catalyst concentration, reaction time and reaction temperature for biodiesel production. The Taguchi robust design approach was used with an L9 orthogonal array to analyze the influence of process factors on performance parameters. The results showed that the optimum yield of biodiesel was 93.8% with viscosity 5.60 c St, with a methanol-to-oil molar ratio of 4:1, catalyst concentration of 1.5 wt%, reaction time of 90 min and reaction temperature of 60 ℃. The catalyst concentration was found to be the most influencing parameter which contributed 51.1% and 50.8% of the total effect on the yield of biodiesel, Y_1, and viscosity of biodiesel, Y_2, respectively.     

Biodiesel Production from Waste Edible Oils and Grease Containing Free Fatty Acids

Till now, most part of the biodiesel is produced from the refined vegetable oils using methanol as feedstock in the presence of an alkali catalyst. However, large amount of waste edible oils and grease are available. The difficulty with alkali-catalyzed esterification of these oils is that they often contain large amount of free fatty acids （FFA）, polymers and decomposition products. These free fatty acids can quickly react with the alkali catalyst to produce soaps that inhibit the separation of the ester and glycerine. An esterification and transesterification process is developed to convert the high FFA oil to its monoesters, The first step, the acidcatalyzed esterification with glycerine and these FFA reduces the FFA content of the oil and grease to less than 3%, and then an azeotropic distillation solvent is used to remove the water. The major factors affecting the conversion efficiency of the process such as glycerol to free fatty acid molar ratio, catalyst amount, reaction temperature and reaction duration are analyzed, The second step, alkali-catalyzed transesterificatiou process converts the products of the first step to its monoesters and glycerol, and then the glycerol is recycled for utilization in the first step. Technical indicators of the biodiesel product can meet the ASTM 6751 standard.     

Heating of heavy oil by circulating hot water in closed double casing in ultra-deep wells

In heavy oil production,the loss of energy to ambient surroundings decreases the temperature of the heavy oil flowing upwards in a vertical wellbore,which increases the oil viscosity and the oil may not flow normally in the wellbore.Therefore,it is necessary to lower the heavy oil viscosity by heating methods to allow it to be lifted easily.Heating of heavy oil in an oil well is achieved by circulating hot water in annuli in the well(tubing-casing annulus,casing-casing annulus).In this paper,based on heat transfer principles and fluid flow theory,a model is developed for produced fluids and hot water flowing in a vertical wellbore.The temperature and pressure of produced fluids and hot water in the wellbore are calculated and the effect of hot water on heavy oil temperature is analyzed.Calculated results show that the hot water circulating in the annuli may effectively heat the heavy oil in the tubing,so as to significantly reduce both oil viscosity and resistance to oil flow.     

Modeling of Liquid-Liquid Extraction Process for Glycerol Purification from Biodiesel Production

This paper shows some generalities about the glycerin byproduct obtained from biodiesel production process, presents an analysis of the ternary equilibrium between methanol, water and glycerol, and shows the influence that temperature has on the balance. This phase diagram illustrates ternary equilibrium at 10, 20 and 50 ℃, keeping the pressure constant at 1 atm （atmosphere） to standardize the analysis. The purpose of it is to establish the best temperature for the purification of glycerol by liquid-liquid extraction method under the ＂extraction in several stages cross flow＂ taking an initial mixture of glycerol with composition 15 wt.% water, 25 wt.% methanol and 60 wt.% glycerol. Water was used as liquid-liquid extraction solvent in order to remove as much methanol as possible from the initial solution due to the existence of a zone of insolubility between the glycerol and water in the ternary equilibrium. By this reason, two solutions are obtained, one consisting of water and methanol containing a trace of glycerin and the other consisting of water, glycerine and traces of methanol, which contain only 4.62% of the total methanol which enter in the process of liquid-liquid extraction, with 60.62% of the total glycerol, which is sent to a fractional distillation process to purify glycerin up to 98% by weight.     

Fuel properties and emission characteristics of biodiesel produced from unused algae grown in India

The high price of different biodiesels and the need for many of their raw ingredients as food materials are the main constraints to be overcome when seeking the best potential alternative fuels to petro-diesel. Apart from that, some properties like high density, viscosity and acid value along with low cloud and pour points preclude their use in compression ignition(CI) engines as these properties can cause serious damage to the parts of the engine and reduce engine life. In this experiment, biodiesel was produced from the oil of unused algae by a two-step ‘acid esterification followed by transesterification' procedure. Taguchi's method was applied to design the experiment, and a L25 orthogonal array was prepared to optimize the biodiesel production procedure. The optimized conditions for transesterification were: methanol to oil molar ratio of 6:1, catalyst(KOH) concentration of 2.5 wt%, reaction time of 90 min and reaction temperature of 50 ℃,achieving a biodiesel production of 89.7% with free fatty acid content of 0.25%. It was found that the CI engine emitted less CO, CO_2 and hydrocarbon and higher NO_x using algal biodiesel than that using petro-diesel. All properties of the algal biodiesel were within the limit of ASTM standards.     

Production Optimization of Biodiesel from Frying Oil Waste to Reduce the Environmental Impacts

The objective of this study was to reduce the environmental impacts of used frying oil waste through the production of biodiesel. A 22 factorial planning has been used to evaluate the influences of alcohol/oil and reaction time on the biodiesel production yield. The optimal condition to produce the biodiesel has been found by use of the response surface methodology and analysis of variance to obtain the fitting model. This study was conducted in Campinas city, Brazil, where were collected the waste oil. An analysis of ecological cost also has been developed. Cooking oils collected from Campinas homes were mixed with ethanol in planned proportions （1：9, 1：7 and 1：5） and were transesterified at 60 ℃ and planned reaction times （30, 60 or 90 min）, in order to obtain biodiesel, using 0.1% NaOH as a catalyst. The results of the physical-chemical analyses demonstrated that the biodiesels obtained possessed characteristics close to those required by Brazilian standards. This fuel could be used in fleets of buses, trucks and machines, or even sold to fuel distributors, which results in a solving between US$0.8 and US$4.5 millions. Thus, Campinas would gain environmental credits and become a sustainable city.     

正庚烷催化裂解生产低碳烯烃的影响因素探索

The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.     

Development and Commercial Application of RFCC Catalyst for Reducing Sulfur Content in Gasoline

The sulfur-reducing functional component the Lewis acid-base pair compound and associated active zeolite component were developed to prepare the RFCC catalyst DOS for reducing sulfur content in gasoline. The results of catalyst evaluation have revealed that the Lewis acid-base pair compound developed hereby could enhance the conversion of macromolecular sulfur compounds by the catalyst to promote the proceeding of desulfurization reactions, and the synergetic action of the selected zeolite and the Lewis acid-base pair compound could definitely reduce the olefins and sulfur contents in gasoline. The heavy oil conversion capability of the catalyst DOS thus developed was higher coupled with an enhanced resistance to heavy metals contamination to reduce the sulfur content in gasoline by over 20%. The commercial application of this catalyst at the SINOPEC Jiujiang Branch Company has revealed that compared to the GRV-C catalyst the oil slurry yield obtained by the catalyst DOS was reduced along with an improved coke selectivity, an increased total liquid yield, and a decreased olefin content in gasoline. The ratio of sulfur in gasoline/sulfur in feed oil could be reduced by 20.3 m%.     

Production of biodiesel from unused algal biomass in Punjab, India

Biodiesel from inedible sources has become prominent in last few decades. But it is economically incompatible with petroleum diesel. At the same time, both petro-diesel and biodiesels are concerned with environmental pollution, global warming, etc. Algae, on the other hand, utilize CO2 for their growth and can minimize some sort of pollution level and results in carbon credit for a country. In Punjab, India, algae are seen to grow in many water bodies. But all those are taken away and dumped in vats. Some of this huge biomass was used for production of biodiesel in this work. Extraction of oil from algae was conducted by using Soxtherm(solvent extraction). An amount of 9 wt% of algal oil was extracted by comparatively costly hexane, whereas 8% extraction was done by cheaper acetone. In the transesterification reaction, molar ratio(methanol: oil) of 6:1, catalyst(KOH) concentration of 3 wt%, reaction temperature of 60 °C, 60 min reaction time and a settling time of 2.5 h were found to be optimum conditions to get maximum ester with minimum free fatty acid content and viscosity. A statistical analysis for the transesterification procedure also showed a methanol-to-oil molar ratio of 6:1 and catalyst concentration of 3 wt% to be the optimum. Characterization of biodiesel was done and compared with ASTM/BIS standards. Most important properties of biodiesel ester like viscosity(3.12 c St or 3.12 mm2/s), cloud and pour point(-1 and-6 °C, respectively), flash and fire point(153 and 158 °C), carbon residue content(0.03%), acid number(0.36 mg of KOH/gm) were within the range of concerned standards.     

CFD simulation on the gasification of asphalt water slurry in an entrained flow gasifier

Gasification technology is suggested to utilize asphalt particles, which are produced in the heavy oil deep separation process of using coupled low temperature separation of solvent and post extraction residue. In this work, the asphalt particles were first slurried with water and then gasified to produce synthesis gas. The gasification process of asphalt water slurry in an entrained flow gasifier was simulated using a three-dimensional computational fluid dynamics （CFD） model based on an Eulerian- Lagrangian method. The trajectories and residence time of asphalt particles, and the reaction rates, gas species distribution, temperature field and carbon conversion in the entrained flow gasifier were obtained. The predicted results indicated that the asphalt water slurry was a good feedstock for gasification. Moreover, the effects of particle size, oxygen equivalence ratio, and mass content of asphalt particles on the gasification performance of asphalt water slurry were investigated. These results are helpful for industrial application of asphalt water slurry gasification technology.     

Improving reservoir volumetric estimations in petroleum resource assessment using discovery process models

The reservoir volumetric approach represents a widely accepted, but flawed method of petroleum play resource calculation. In this paper, we propose a combination of techniques that can improve the applicability and quality of the resource estimation. These techniques include： 1） the use of the Multivariate Discovery Process model （MDP） to derive unbiased distribution parameters of reservoir volumetric variables and to reveal correlations among the variables; 2） the use of the Geo-anchored method to estimate simultaneously the number of oil and gas pools in the same play; and 3） the crossvalidation of assessment results from different methods. These techniques are illustrated by using an example of crude oil and natural gas resource assessment of the Sverdrup Basin, Canadian Archipelago. The example shows that when direct volumetric measurements of the untested prospects are not available, the MDP model can help derive unbiased estimates of the distribution parameters by using information from the discovered oil and gas accumulations. It also shows that an estimation of the number of oil and gas accumulations and associated size ranges from a discovery process model can provide an alternative and efficient approach when inadequate geological data hinder the estimation. Cross-examination of assessment results derived using different methods allows one to focus on and analyze the causes for the major differences, thus providing a more reliable assessment outcome.     

An experimental and numerical study of chemically enhanced water alternating gas injection

In this work, an experimental study combined with numerical simulation was conducted to investigate the potential of chemically enhanced water alternating gas(CWAG) injection as a new enhanced oil recovery method.The unique feature of this new method is that it uses alkaline, surfactant, and polymer additives as a chemical slug which is injected during the water alternating gas(WAG) process to reduce the interfacial tension(IFT) and simultaneously improve the mobility ratio. In essence, the proposed CWAG process involves a combination of chemical flooding and immiscible carbon dioxide(CO2)injection and helps in IFT reduction, water blocking reduction, mobility control, oil swelling, and oil viscosity reduction due to CO2 dissolution. Its performance was compared with the conventional immiscible water alternating gas(I-WAG) flooding. Oil recovery utilizing CWAG was better by 26 % of the remaining oil in place after waterflooding compared to the recovery using WAG conducted under similar conditions. The coreflood data(cumulative oil and water production) were history matched via a commercial simulator by adjusting the relative permeability curves and assigning the values of the rock and fluid properties such as porosity, permeability, and the experimentally determined IFT data. History matching of the coreflood model helped us optimize the experiments and was useful in determining the importance of the parameters influencing sweep efficiency in the CWAG process. The effectiveness of the CWAG process in providing enhancement of displacement efficiency is evident in the oil recovery and pressure response observed in the coreflood. The results of sensitivity analysis on CWAG slug patterns show that the alkaline–surfactant–polymer injection is more beneficial after CO2 slug injection due to oil swelling and viscosity reduction. The CO2 slug size analysis shows that there is an optimum CO2 slug size,around 25 % pore volume which leads to a maximum oil recovery in the CWAG process. This study shows that the ultralow IFT system, i.e., IFT equaling 10-2or 10-3m N/m, is a very important parameter in CWAG process since the water blocking effect can be minimized.     

A generalized set of correlations for plus fraction characterization

The importance of accurate determination of the critical properties of plus fractions in prediction of phase behaviour of hydrocarbon mixtures by equations of state is well known in the petroleum industry. It has been stated in various papers (Elsharkawy, 2001) that using the plus fraction as a single group in equation of state calculations reduces the accuracy of the results. However in this work it has been shown that using the proper values of critical temperature and pressure for the plus fraction group can estimate the properties of hydrocarbon mixtures, and they are accurate enough to be used in reservoir engineering and enhanced oil recovery calculations. In this paper, a new method is proposed for calculating the critical properties of plus fractions of petroleum fluids. One can use this method either in predicting critical pressure and temperature of single carbon numbers (SCNs) after the splitting process or in predicting critical pressure and temperature of the plus fraction as a single group. A comparison study is performed against Riazi-Daubert correlation (Riazi and Daubert, 1987) and Sancet correlations (Sancet, 2007) for 25 oil samples taken from 14 fields from southwest Iran. The results indicate the superiority of the proposed method to the Riazi-Daubert and Sancet correlations.     

The Method for Avoidance of Palladium/Carbon Catalyst Poisoning and Its Commercial Application

After utilizing an improved method for adding a non-precious promoter to the precious Pd/C catalyst during hydrogenation of benzoic acid, a new understanding concerning regeneration of deactivated Pd/C catalyst has been obtained, and an improved process has emerged. The improved process can avoid the conventional technical shortcomings related with hydrogenation of benzoic acid such as the quick decline of catalyst activity in a relatively short period of time and low palladium recovery from the spent catalyst. Furthermore, according to this process, cyclohexane carboxylic acid （CCA） can be produced Pavorably in a commercial scale at a high selectivity and product yield with a extended catalyst life.     

Boiling Point Distribution of Hydrocarbon Types in Diesel Using Solid-Phase Extraction Followed by GC/FID-EIMS

In this paper, a method was established to determine the boiling point distribution of hydrocarbon types in diesel. The diesel sample was separated into the saturate and aromatic fractions by means of solid-phase extraction （SPE）, and each fraction was analyzed by GC/FID-EIMS. According to the relationship between boiling point and retention time of n-paraffins in the chromatogram, the percentages of saturates and aromatics at each temperature interval were calculated. According to the average mass spectra of the saturate and aromatic fractions at each temperature interval, the hydrocarbon types of the sample were identified through summation of characteristic mass fragments. Using this method, the changes in composition of diesel during hydrotreating process were studied. The results showed that hydrogenation of aromatics is the main reaction during the hydrotreating process. The more rings the aromatics have, the easier the hydrogenation reactions would take place. The aromatics were converted into cycloparaffins via the hydrogenation and saturation process, leading to an increase in low boiling point fractions in the hydrotreated oil.     

活性膨润土在甲苯叔丁基化中的应用

tert-Butylation of toluene with tert-butanol used as the alkylating agent was investigated over the activated bentonite and HY zeolite used as the catalyst.The influences of various butylation reaction parameters,including the toluene/tert-butanol ratio,the reaction temperature,and the space velocity were discussed.The optimal results were obtained at a reaction temperature of 180 ℃,a space velocity of 4 h-1,and a mole ratio of toluene to tert-butanol equating to 2.The structure and acidic properties of catalyst were characterized by the BET method and the Fourier transform infrared (FTIR) spectroscopy.Compared with the HY zeolite,the activated bentonite possessed high activity for toluene conversion and high para-selectivity because it had larger pore diameter,smaller micropore surface area and higher ratio of total Lewis acids to total Br nsted acids.     

Hybrid connectionist model determines CO_2–oil swelling factor

In-depth understanding of interactions between crude oil and CO_2 provides insight into the CO_2-based enhanced oil recovery(EOR) process design and simulation. When CO_2 contacts crude oil, the dissolution process takes place. This phenomenon results in the oil swelling, which depends on the temperature, pressure, and composition of the oil. The residual oil saturation in a CO_2-based EOR process is inversely proportional to the oil swelling factor. Hence, it is important to estimate this influential parameter with high precision. The current study suggests the predictive model based on the least-squares support vector machine(LS-SVM) to calculate the CO_2–oil swelling factor. A genetic algorithm is used to optimize hyperparameters(у and б~2) of the LS-SVM model. This model showed a high coefficient of determination(R~2= 0.9953) and a low value for the mean-squared error(MSE = 0.0003) based on the available experimental data while estimating the CO_2–oil swelling factor. It was found that LS-SVM is a straightforward and accurate method to determine the CO_2–oil swelling factor with negligible uncertainty. This method can be incorporated in commercial reservoir simulators to include the effect of the CO_2–oil swelling factor when adequate experimental data are not available.     

Wild melon: a novel non-edible feedstock for bioenergy

In the present research work, a non-edible oil source Cucumis melo var. agrestis(wild melon) was systematically identified and studied for biodiesel production and its characterization. The extracted oil was 29.1% of total dry seed weight. The free fatty acid value of the oil was found to be 0.64%, and the single-step alkaline transesterification method was used for conversion of fatty acids into their respective methyl esters. The maximum conversion efficiency of fatty acids was obtained at 0.4 wt% Na OH(used as catalyst), 30%(methanol to oil, v/v) methanol amount, 60 ℃ reaction temperature,600-rpm agitation rate and 60-min reaction time. Under these optimal conditions, the conversion efficiency of fatty acid was 92%. However, in the case of KOH as catalyst, the highest conversion(85%) of fatty acids was obtained at 40%methanol to oil ratio, 1.28 wt% KOH, 60 ℃ reaction temperature, 600-rpm agitation rate and 45 min of reaction time.Qualitatively, biodiesel was characterized through Fourier transform infrared spectroscopy(FTIR) and gas chromatography and mass spectroscopy(GC–MS). FTIR results demonstrated a strong peak at 1742 cm~(-1), showing carbonyl groups(C=O)of methyl esters. However, GC–MS results showed the presence of twelve methyl esters comprised of lauric acid, myristic acid, palmitic acid, non-decanoic acid, hexadecanoic acid, octadecadienoic acid and octadecynoic acid. The fuel properties were found to fall within the range recommended by the international biodiesel standard, i.e., American Society of Testing Materials(ASTM): flash point of 91 ℃, density of 0.873 kg/L, viscosity of 5.35 c St, pour point of-13 ℃, cloud point of-10 ℃, total acid number of 0.242 mg KOH/g and sulfur content of 0.0043 wt%. The present work concluded the potential of wild melon seed oil as excellent non-edible source of bioenergy.