Calculation and analysis of sub/supercritical methanol preheating tube for continuous production of biodiesel via supercritical methanol transesterification

Biodiesel is an important renewable energy. Supercritical methanol transesterification for biodiesel has recently been concerned because of its obvious advantages. The tubular reactor is an ideal reactor for continuous preparation of biodiesel via supercritical methanol transesterification. A methanol preheating tube is necessary for the tubular reaction system because the reaction temperature for supercritical methanol transesterification is usually 520–600 K. Therefore, in the range of 298–600 K, changes of the density, isobaric capacity, viscosity and thermal conductivity of sub/supercritical methanol with temperature are first discussed. Then on the basis of these thermophysical properties, an integration method is adopted for the design of sub/supercritical methanol preheating tube when methanol is preheated from 298 K to 600 K at 16 MPa and the influencing factors on the length of the preheating tube are also studied. The computational results show that the Reynolds number Re and the local convection heat-transfer coefficient α of sub/supercritical methanol flowing in Φ6× 1.5 mm preheating tube change drastically with temperature. For the local overall heat transfer coefficient K and the average overall heat transfer coefficient K _m, temperature also has an important influence on them when the inlet velocity of methanol is lower than 0.5 m/s. But when the inlet velocity of methanol is higher than 0.5 m/s, K and K _m almost keep invariable with temperature. Additionally, both the outlet temperature and the inlet velocity of methanol are the key affecting factors for the length of the preheating tube, especially when the outlet temperature is over the critical temperature of methanol. At the same time, the increase of tin bath’s temperature can shorten the required length of the preheating tube. At the inlet flow rate of 0.5 m/s, the required length of the preheating tube is 2.0m when methanol is preheated from 298 K to 590 K at 16 MPa with keeping the tin bath’s temperature 620 K, which is in good agreement with the experimental results.     

Heat transfer with water flowing upward in a tube for pressures up to supercritical region

A heat transfer experiment was conducted in a tube of 6.07mm in diameter with water flowing upward, covering the ranges of pressure of 10―23MPa, mass flux of 288―1298kg/(m²·s), local water temperature of 78°C―270°C, heat flux of 0.23―1.18MW/m² and Reynolds number of 5.5×10³―3.9×10⁴. The experimental results were compared with the predictions of the Dittus-Boelter correlation, Jackson correlation, Bishop correlation, Swenson correlation and Yamagata correlation. Significant deterioration in heat transfer was observed in both subcritical and supercritical region due to the effect of buoyancy force, but it was not predicted reasonably by the existing correlations.     

Simulation analysis of methanol flash distillation circulation process in biodiesel production with supercritical method

High methanol-to-oil ratio is required to obtain a high conversion of oil for the production of biodiesel with supercritical methanol. Recovering the methanol of a stream issuing from a transesterification supercritical reactor by flash distillation instead of evaporation was analyzed. The one-stage and two-stage flash distillation processes were presented and compared. The difference of the recovery percentage of methanol of the above two flash processes is less than 0.5% and the methanol concentration in the vapor for the one-stage process decreases rapidly when feed temperature increases. The process in which the product of transesterification of soybean oil with supercritical methanol is cooled to an appropriate temperature (about 240°C) first and then flashed was put forward. The effect of cooling temperature, feed pressure and flash pressure on methanol concentration and recovery percentage was investigated. According to this study, when the feed pressure range is 15–30 MPa, the flash pressure equals 0.4 MPa, and cooling temperature range is 240°C–250°C, the recovery percentage of methanol is not less than 85%, and the concentration of the vapor in mass fraction of methanol is approximately 99%. Thus, the vapor leaving the flash tank can be directly circulated to the transesterification reactor.     

Air-side heat transfer and friction characteristics of biofouled evaporator under wet conditions

The effects of biofouling on air-side heat transfer and friction characteristics under wet conditions of three biofouled finned tube heat exchangers and one clean finned tube heat exchanger were investigated experimentally. Experimental results indicate that the biofouled fin efficiency of the evaporator decreases by 15.5% compared with the clean evaporator under the condition of the biofouled area ratio of 60% at the inlet air velocity of 2.0m/s; The ranges of friction fouling factor and heat transfer fouling factor are 19.8%―43.1% and ―15.6%―13.1%, respectively; a small quantity of biofouled particles can enhance heat transfer at low Reynolds number, and the enhancement effect decreases with the increase of Reynolds number.     

Transesterification of rapeseed and palm oils in supercritical methanol and ethanol

The results of the rapeseed and palm oils transesterification with supercritical methanol and ethanol were presented. The studies were performed using the experimental setups which are working in batch and continuous regimes. The effect of reaction conditions (temperature, pressure, oil to alcohol ratio, reaction time) on the biodiesel production (conversion yield) was studied. Also the effect of preliminary ultrasonic treatment (ultrasonic irradiation, emulsification of immiscible oil and alcohol mixture) of the initial reagents (emulsion preparation) on the stage before transesterification reaction conduction on the conversion yield was studied. We found that the preliminary ultrasonic treatment of the initial reagents increases considerably the conversion yield. Optimal technological conditions were determined to be as follows: pressure within 20-30 MPa, temperature within 573-623 K. The optimal values of the oil to alcohol ratio strongly depend on preliminary treatment of the reaction mixture. The study showed that the conversion yield at the same temperature with 96 wt.% of ethanol is higher than with 100 wt.% of methanol.     

Design and analysis of dual fuel methanol-power poly-generation

A dual fuel head poly-generation flowsheet was designed based on coal gas and coke oven gas. To help clearly understand the system performance, a 1.2×10⁸−3.2×10⁸kg methanol and 274―496MW power poly-generation system was simulated by using the commercially available software ASPEN Plus and GT Pro. The technology scheme, the operating parameters, and the efficiency of the system were also analyzed and evaluated, which will be used for building industrial devices.     

Simulation analysis of methanol flash distillation circulation process in biodiesel production with supercritical method

High methanol-to-oil ratio is required to obtain a high conversion of oil for the production of biodiesel with supercritical methanol. Recovering the methanol of a stream issuing from a transesterification supercritical reactor by flash distillation instead of evaporation was analyzed. The one-stage and two-stage flash distillation processes were presented and compared. The difference of the recovery percentage of methanol of the above two flash processes is less than 0.5% and the methanol concentration in the vapor for the one-stage process decreases rapidly when feed temperature increases. The process in which the product of transesterification of soybean oil with supercritical methanol is cooled to an appropriate temperature (about 240°C) first and then flashed was put forward. The effect of cooling temperature, feed pressure and flash pressure on methanol concentration and recovery percentage was investigated. According to this study, when the feed pressure range is 15–30 MPa, the flash pressure equals 0.4 MPa, and cooling temperature range is 240°C–250°C, the recovery percentage of methanol is not less than 85%, and the concentration of the vapor in mass fraction of methanol is approximately 99%. Thus, the vapor leaving the flash tank can be directly circulated to the transesterification reactor.     

Production of FAME by palm oil transesterification via supercritical methanol technology

The present study employed non-catalytic supercritical methanol technology to produce biodiesel from palm oil. The research was carried out in a batch-type tube reactor and heated beyond supercritical temperature and pressure of methanol, which are at 239 °C and 8.1 MPa respectively. The effects of temperature, reaction time and molar ratio of methanol to palm oil on the yield of fatty acid methyl esters (FAME) or biodiesel were investigated. The results obtained showed that non-catalytic supercritical methanol technology only required a mere 20 min reaction time to produce more than 70% yield of FAME. Compared to conventional catalytic methods, which required at least 1 h reaction time to obtain similar yield, supercritical methanol technology has been shown to be superior in terms of time and energy consumption. Apart from the shorter reaction time, it was found that separation and purification of the products were simpler since no catalyst is involved in the process. Hence, formation of side products such as soap in catalytic reactions does not occur in the supercritical methanol method.     

Biodiesel from corn germ oil catalytic and non-catalytic supercritical methanol transesterification

Transesterifications of grain of corn oil samples in KOH catalytic and in supercritical methanol were studied without using any catalyst. Biodiesel, an alternative biodegradable diesel fuel, is derived from triglycerides by transesterification with methanol and ethanol. The transesterification reaction is affected by the molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable influence on methyl ester (biodiesel) conversion. The molar ratio of methanol to corn germ oil is also one of the most important variables affecting the yield of methyl esters. Higher molar ratios result in greater ester production in a shorter time. In the transesterification, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalysts, and reduces catalyst effectiveness, all of which result in a low conversion.     

Optimization of neem methyl ester from transesterification process and fuel characterization as a diesel substitute

The present work aimed at the standardization of transesterification process parameters for the production of methyl ester of filtered neem oil and fuel characterization for engine performance. The effect of process parameters such as molar ratio, preheating temperature, catalyst concentration and reaction time was studied to standardize the transesterification process for estimating the highest recovery of ester with lowest possible viscosity. Based on the observations of the ester recovery and kinematic viscosity, it was found that filtered neem oil at 6:1 M ratio (methanol to oil) preheated at 55 °C temperature and maintaining 60 °C reaction temperature for 60 min in the presence of 2 percent KOH and then allowed to settle for 24 h in order to get lowest kinematic viscosity (2.7 cSt) with ester recovery (83.36%). Different fuel properties of the neem methyl ester and neem oil were also measured. Results show that the methyl ester of neem obtained under the optimum condition is an excellent substitute for fossil fuels.     

Experimental investigations on the use of preheated animal fat as fuel in a compression ignition engine

The effect of fuel inlet temperature on performance, emission and combustion characteristics of a diesel engine is evaluated. A single cylinder direct injection diesel engine developing a power output of 2.8 kW at 1500 rev/min is tested using preheated animal fat as fuel. Experiments are conducted at the fuel inlet temperatures of 30, 40, 50, 60 and 70 °C. Animal fat at low temperature results in higher ignition delay and combustion duration than diesel. Preheated animal fat shows reduced ignition delay and combustion duration. Peak pressure and rate of pressure rise are found as high with animal fat at high fuel inlet temperatures. Heat release pattern shows reduced premixed combustion phase with animal fat as compared to neat diesel at normal temperature. Preheating improves the premixed combustion rate. At low temperature, animal fat results in lower smoke emissions than diesel. The maximum smoke density is K=6.5 m⁻¹ with diesel and K=3.6 m⁻¹ with animal fat at 30 °C. Preheated animal fat further reduces smoke levels at all temperatures. The smoke level is reduced up to K=1.7 m⁻¹ with preheated animal fat at the temperature of 70 °C. Hydrocarbon and carbon monoxide emissions are higher with animal fat at low temperature as compared to diesel. Fuel Preheating reduces these emissions. NO emission is found as low with animal fat at low temperature. Fuel preheating results in increased NO emission. However, the level is still lower than diesel even at high temperature (i.e. 70 °C). On the whole it is concluded that preheated animal fat can be used in diesel engines with reduced smoke, hydrocarbon and carbon monoxide emissions with no major detoriation in engine performance.     

Experimental study on heat transfer characteristics of supercritical carbon dioxide in horizontal tube

The heat transfer characteristics of supercritical carbon dioxide in a horizontal tube with water in the vertical cross flow form were experimentally investigated. The results indicate that the changes of inlet pressure, mass flow rate, and cooling water flow rate have major effects on heat transfer performance. The variations of Reynolds number and Prandtl number were obtained in counter flow and vertical cross flow. The four conventional correlations for convection heat transfer of supercritical carbon dioxide were verified by the experimental data in this study and the correlation agree with this experimental condition was determined. __________ Translated from Journal of Refrigeration, 2007, 28(1): 8–11 [译自:制 冷学报]     

A study of methanol steam reforming on distributed catalyst bed

Heterogeneous catalytic fixed bed usually suffers from severe limitations of mass and heat transfer. These disadvantages limit reformers to a low efficiency of catalyst utilization. Three catalyst activity distributions have been applied to force the reactor temperature profile to be near isothermal operation for maximization of methanol conversion. A plate-type reactor has been developed to investigate the influence of catalyst activity distribution on methanol steam reforming. Cold spot temperature gradients are observed in the temperature profile along the reactor axis. It has been experimentally verified that reducing cold spot temperature gradients contributes to the improvement of the catalytic hydrogen production. The lowest cold spot temperature gradient of 3 K is obtained on gradient catalyst distribution type A. This is attributed to good characteristics of local thermal effect. Low activity at the reactor inlet with gradual rise along with the reactor flow channel forms the optimal activity distribution. Hydrogen production rate of 161.3 L/h is obtained at the methanol conversion of 93.1% for the gradient distribution type A when the inlet temperature is 543 K.     

Hydrogen production by oxidative steam reforming of methanol over anodic aluminum oxide-supported Cu-Zn catalyst

Oxidative steam reforming of methanol (OSRM), which is a convenient reaction for producing hydrogen, suffers from the hot spot formation problem when conventional particle catalysts are used. Recently, an anodic aluminum oxide (AAO)-supported Cu-Zn catalyst was proposed as an OSRM catalyst for its high thermal conductivity through the aluminum metal body. In this study, OSRM was conducted in a prototype reactor packed with the AAO plate catalyst strips. It was verified that the high thermal conductivity of the catalyst effectively suppresses the hot spot formation and makes the temperature profile smooth along the reactor. The start-up time of the reactor depended on the preheating temperature and was very short (less than 2 min) for preheating over 503 K. The methanol conversion and reactor temperature increased with increasing O₂/CH₃OH mole ratio, indicating that the mole ratio can be used as a control variable to operate the reactor at desired conditions. Further, a reactor model was developed and verified, and the simulation showed that for a given total reactor volume, an optimal reactor configuration could be achieved by shortening the reactor length while widening the cross-sectional area.     

State of the art of biodiesel production under supercritical conditions

This paper reviews the current status of biodiesel production mainly under supercritical conditions. Various methods such as homogeneous acid- and alkali-catalyzed transesterification, heterogeneous acid and alkali-catalyzed transesterification, enzyme-catalyzed transesterification, and supercritical reactions have been employed so far to synthesize biodiesel. Herein, we review the reaction mechanisms and experimental results for these approaches. Recently, supercritical biodiesel production has undergone a vigorous development as the technology offers several advantages over other methods, including the fact that it does not require a catalyst, short residence time, high reaction rate, no pretreatment requirement, and applicability to a wide variety of feedstock. This technology was first designed for biodiesel production using methanol and ethanol. Biodiesel production without glycerol as a byproduct is attractive and has been achieved using supercritical methyl acetate and dimethyl carbonate (DMC). Most recently, biodiesel production in supercritical tert-butyl methyl ether (MTBE) has been developed also. In this review, supercritical biodiesel production will be discussed in detail. Empirical rate expressions are derived for biodiesel production in supercritical methanol, ethanol, methyl acetate, DMC, and MTBE in this study for the first time. These rate equations are critical to predicting biodiesel yields and to comparing the reaction behaviors in different solvents. Lastly challenges for improving energy recovery in supercritical biodiesel production and recommendations for future work are provided.     

Effect of property variations on the mixing of laminar supercritical water streams in a T-junction

The effect of variation of supercritical water properties with temperature and pressure on the mixing characteristics of streams having different temperatures in a T shaped channel is investigated numerically by considering steady, low Reynolds number flows with the assumption of negligible bouyancy effects. The Reynolds number of the cold stream in the range 0.1 to 100, inlet temperature of hot stream varying from 300 K to 800 K, the ratio of mass flow rate of cold stream to total mass flow rate in the range of 0.1 to 0.90 and the operating pressures from 25 MPa to 45 MPa at a cold fluid inlet temperature of 293.15 K are considered as parameters controlling the mixing of hot and cold streams. The effect of property variations on the outcome of the mixing is more important for low Reynolds numbers and hot fluid inlet temperatures above the pseudo-critical temperature and result in a non-uniform temperature distribution in the outlet section.     

Investigating the Effects of Natural Gas Preheating on Soot Formation,Flame Luminosity,and NOX Emissions: A Combined Experimental and Numerical Approach

One of the most problematic aspects of gas‐fired furnaces is their poor luminosity and radiative characteristics which are directly affected by the carbon percent of the fuel molecules. This study investigates the soot content, flame temperature, and efficiency of a 120 kW boiler resulting from inlet gas (natural gas) preheating. A probability density function (PDF) being parameterized by the mean and variance of mixture fraction was used to model chemical reactions. To describe the effects of turbulences on soot formation, a Moss–Brooks model and a β‐PDF in terms of normalized temperature is employed. Using Nickel–Chrome electrical heaters, the fuel was preheated to more than 573 K. Radiations emitting from the flame were measured by a laboratory pyranometer with a photovoltaic sensor; moreover, a Testo 350 XL gas analyzer was used for recording the temperature and combustion species. Results revealed that gas preheating up to about 510 K has no considerable effect on the flame luminosity. On the other hand, preheating the inlet gas up to 700 K increases the soot content of the flame up to 300% resulting in a serious augmentation of flame luminosity. This increase causes a significant reduction in flame temperature (150 K) and NO emission. The predicted results have good agreement with measurement results.     

Investigations on the performance and exhaust emissions of a diesel engine using preheated waste frying oil as fuel

In the present experimental investigation, waste frying oil a non-edible vegetable oil was used as an alternative fuel for diesel engine. The high viscosity of the waste frying oil was reduced by preheating. The properties of waste frying oil such as viscosity, density, calorific value and flash point were determined. The effect of temperature on the viscosity of waste frying oil was evaluated. It was determined that the waste frying oil requires a heating temperature of 135 °C to bring down its viscosity to that of diesel at 30 °C. The performance and exhaust emissions of a single cylinder diesel engine was evaluated using diesel, waste frying oil (without preheating) and waste frying oil preheated to two different inlet temperatures (75 and 135 °C). The engine performance was improved and the CO and smoke emissions were reduced using preheated waste frying oil. It was concluded from the results of the experimental investigation that the waste frying oil preheated to 135 °C could be used as a diesel fuel substitute for short-term engine operation.     

An investigation into the heat transfer characteristics of spiral wall with internal rib in a supercritical sliding-pressure operation once-through boiler

Within the pressure range of 9–28 MPa, mass velocity range of 600–1 200 kg/(m²·s), and heat flux range of 200–500 kW/m², experiments were performed to investigate the heat transfer to water in the inclned upward internally ribbed tube with an inclined angle of 19.5 degrees, a maximum outer diameter of 38.1 mm, and a thickness of 7.5 mm. Based on the experiments, it was found that heat transfer enhancement of the internally ribbed tube could postpone departure from nucleate boiling at the sub-critical pressure. However, the heat transfer enhancement decreased near the critical pressure. At supercritical pressure, the temperature difference between the wall and the fluid increased near the pseudo-critical temperature, but the increase of wall temperature was less than that of departure from nucleate boiling at sub-critical pressure. When pressure is closer to the critical pressure, the temperature difference between the wall and the fluid increased greatly near the pseudo-critical temperature. Heat transfer to supercritical water in the inclined upward internally ribbed tube was enhanced or deteriorated near the pseudo-critical temperature with the variety of ratio between the mass velocity and the heat flux. Because the rotational flow of the internal groove reduced the effect of natural convection, the internal wall temperature of internally ribbed tube uniformly distributed along the circumference. The maximum internal wall temperature difference of the tube along the circumference was only 10 degrees when the fluid enthalpy exceeded 2 000 J/g. Considering the effect of acute variety of the fluid property on heat transfer, the coreelation of heat transfer coefficient on the top of the internally ribbed tube was provided. Translated from Proceedings of CSEE, 2005, 25(16): 90–95 [译自: 中国电机工程学报]     

Comparison of biodiesel production from crude Jatropha oil and Krating oil by supercritical methanol transesterification

This work compared the production of biodiesel from two different non-edible oils with relatively high acid values (Jatropha oil and Krating oil). Using non-catalytic supercritical methanol transesterification, high methyl ester yield (85–90%) can be obtained in a very short time (5–10 min). However, the dependence of fatty acid methyl ester yield on reaction conditions (i.e., temperature and pressure) and the optimum conditions were different by the source of oils and were correlated to the amount of free fatty acids (FFAs) and unsaturated fatty acid content in oils. Krating oil, which has higher FFAs and unsaturated fatty acid content, gave higher fatty acid methyl ester yield of 90.4% at 260 °C, 16 MPa, and 10 min whereas biodiesel from Jatropha oil gave fatty acid methyl ester yield of 84.6% at 320 °C, 15 MPa and 5 min using the same molar ratio of methanol to oil 40:1. The product quality from crude Krating oil met the biodiesel standard. Pre-processing steps such as degumming or oil purification are not necessary.