Continuous Esterification Process Research Articles

Investigation of free fatty acid reduction from mixed crude palm oil using 3D-printed rotor–stator hydrodynamic cavitation: An experimental study of geometric characteristics of the inner hole

A continuous esterification process is employed to decrease the free fatty acid (FFA) concentration of FFA-rich mixed crude palm oil. Both optimal and recommended conditions are determined for the esterification reaction conditions and the geometry of the 3D-printed rotor design in the rotor–stator hydrodynamic cavitation reactor. This study is primarily concerned with the effect of the cavitation device configuration, especially the rotor design, on FFA reduction. Instead of conventional spherical or cylindrical drilled holes, a point angle cone-shaped hole is used to create cavities over the rotor surface. These point angles are adjusted to clarify their effect on FFA reduction. The response surface methodology is applied to determine the optimal concentrations of methanol and sulfuric acid, rotor speed, hole diameter and depth, and cone point angle. The recommended conditions are 20.8 wt% methanol, 2.6 wt% sulfuric acid, 3000 rpm, 5 mm hole diameter, 5 mm hole depth, and 110°, respectively. Under this configuration, the FFA content is reduced from 12.014 wt% to around 1 wt%. A maximum yield of 97.34 vol% esterified oil is obtained through a completed phase separation step, and 93.31 vol% pure oil is collected after the cleansing step. The recommended conditions result in reduced chemical usage, cheaper FFA reduction, and lower environmental impact. This creative rotor design effectively improves our understanding of the geometry of the cavitation device, thus enhancing the cavitation effect in industrial operations.

Continuous Double-Step Esterification Production of Palm Fatty Acid Distillate Methyl Ester Using Ultrasonic Tubular Reactor.

Double-step esterification to produce biodiesel from palm fatty acid distillate (PFAD) was performed by utilizing an ultrasound clamp reactor. Six pairs of ultrasonic clamps were attached to the left and right sides of the stainless-steel tube, and each pair was separated 100 mm apart from each other. Therefore, a total of 12 units of ultrasound clamps distributed 4800 W maximum power (12 × 400 W) throughout the continuous reactor by an ultrasonic generator. To optimize each step of the continuous esterification process for producing methyl ester from PFAD, a response surface methodology was used. The final 93.32 wt % methyl ester purity was attained under a double-step esterification process. For the first step, a 3.75:1 molar ratio of methanol to PFAD (46.4 vol % methanol), 6.6 vol % sulfuric acid, and 400 mm length of ultrasound clamp at 25 L/h PFAD flow rate for converting the PFAD to 60.24 wt % methyl ester were recommended. For the second step, the esterification was repeated under a molar ratio of methanol to the first esterified oil of 2.87:1 (61.6 vol % methanol), 5.6 vol % of sulfuric acid, and 400 mm length of ultrasound clamp at 25 L/h esterified oil flow rate. The ultrasonic clamp reactor achieved high yields of esterified oil and the crude biodiesel in a relatively short residence period of 32 s. To determine the product yields of a double-step esterification process, the maximum yields were 103.9 wt % first esterified oil, 107.6% crude biodiesel, and 98 wt % purified biodiesel when calculated on the basis of 100 vol % initial PFAD. The average energy consumed in the production of double-step esterification biodiesel was 0.05796 kWh/L. Therefore, this current approach has a high potential for producing biodiesel with less energy and requires less time to convert the PFAD to a high purity of methyl ester.

Continuous acid-catalyzed esterification using a 3D printed rotor–stator hydrodynamic cavitation reactor reduces free fatty acid content in mixed crude palm oil

Free fatty acid (FFA) content in FFA-rich mixed crude palm oil (MCPO) was reduced through a continuous esterification process. The reaction conditions were optimized, the yield purified esterified oil was determined, and the average total electricity consumption of the entire process was evaluated. The key component of this study was the cost-effective, 3D-printed rotor that was installed in a continuous rotor–stator hydrodynamic reactor. The surface of the rotor was designed with spherical holes where the center-to-center distance between them was fixed. Response surface methodology (RSM) using central composite design (CCD) was employed to analyze the design of experiments (DOE) and optimize FFA-content reduction. The optimized conditions were 17.7 vol% methanol, 2.9 vol% sulfuric acid, a 3000 rpm rotor speed, and surface holes measuring 4 mm in diameter and 6 mm in depth. The experimental results showed that the FFA content in MCPO was reduced from 11.456 to 1.028 wt% upon esterification under these optimal conditions. The maximum yield of esterified oil from the phase separation step was 96.07 vol%, and that of the purified esterified oil was 91.27 vol%. The average total energy consumed by this hydrodynamic cavitation reactor to produce this esterified oil was 0.0264 kW h/L. This 3D printed rotor–stator reactor is a promising, novel reactor technology for producing biodiesel from FFA-rich oils.

Biodiesel continuous esterification process experimental study and equipment design

Biodiesel is a particularly attractive renewable fuel because it can be used in existing engines, it is environmentally friendly and it is readily synthesized from animal fats and vegetable oils. Waste oil combined with heterogeneous catalysts offers exciting possibilities for improving the economics of biodiesel synthesis. The effects of methanol influx rate, reaction temperature, catalysis dosage and operation approaches on pre-esterification deacidification of trap grease were studied in a laboratory with solid acid catalysts. The results showed the maximum acid value reduction efficiency (96.73%) was obtained, and the acid value decreased sharply (from 120 to 3.92 mgKOH g−1) at a methanol influx rate of 0.825 mL/m in, a reaction temperature of 115 °C, a catalysis dosage of 2.5%, and a reaction time of 2 h using 50 g of oil. An acid value of 0.89 mgKOH g−1 and an esterification rate of 99.26% were obtained. When the operational approach was changed to a methanol influx of 1.32 mL/min (methanol to oil molar ratio 6: 1), a reaction time of 30 min under pressure, the methanol influx rate changed to 0.825 mL/min, and then, coupled methanol recovered and purified immediately at atmospheric pressure. A continuous esterification deacidification equipment that is suitable for factory pretreatment deacidification of biodiesel produced from trap grease with a high acid value was designed according to laboratory experiments.

Simulation of Continuous Esterification Process of Polyester Polyols

Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the continuous esterification process of polyester polyols was developed, which was carried out in an innovational bubbling reactive distillation tower (BRDT) at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esterification process of poly (ethylene adipate) (PEA). In the continuous operation, linear oligomers were discharged from the bottom of the column, while water passed a few column trays and a packing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for developing and optimizing this process.

Biodiesel production by esterification of palm fatty acid distillate

Production of fatty acid methyl ester (FAME) from palm fatty acid distillate (PFAD) having high free fatty acids (FFA) was investigated in this work. Batch esterifications of PFAD were carried out to study the influence of: including reaction temperatures of 70–100 °C, molar ratios of methanol to PFAD of 0.4:1–12:1, quantity of catalysts of 0–5.502% (wt of sulfuric acid/wt of PFAD) and reaction times of 15–240 min. The optimum condition for the continuous esterification process (CSTR) was molar ratio of methanol to PFAD at 8:1 with 1.834 wt% of H 2 SO 4 at 70 °C under its own pressure with a retention time of 60 min. The amount of FFA was reduced from 93 wt% to less than 2 wt% at the end of the esterification process. The FAME was purified by neutralization with 3 M sodium hydroxide in water solution at a reaction temperature of 80 °C for 15 min followed by transesterification process with 0.396 M sodium hydroxide in methanol solution at a reaction temperature of 65 °C for 15 min. The final FAME product met with the Thai biodiesel quality standard, and ASTM D6751-02.

A simulation study on continuous direct esterification process for poly(ethylene terephthalate) synthesis

A simulation study on continuous direct esterification process for poly(ethylene terephthalate) synthesis

A mathematical model for a continuous esterification process with recycle between terephthalic acid and ethylene glycol

AbstractA new mathematical model for a continuous recycle esterification process has been derived by basically the same procedure as the continuous process of a cascade type, reported earlier, which includes material and heat balances. Such a model can give extensive information about the optimum design of a new plant through the predictions of oligomer characteristics (concentrations of carboxyl and hydroxyl end groups, number average molecular weight, number average degree of polymerization, esterification and saponification degree, DEG content, melting point of oligomer, etc.), distillate properties (concentrations of EG and water in the vapor phase), heat transfer area, mass flow rate of heating medium, amount of heat supplied by heating medium, enthalpy moving with recycle, and amount of heat removed from each reactor. © 1992 John Wiley & Sons, Inc.

Measurement of the melting points of oligomers obtained in the manufacture of poly(ethylene terephthalate)

AbstractThe melting points (Tm) were measured for oligomers obtained by a direct continuous esterification process between terephthalic acid and ethylene glycol. Multiple regression analyses of data were carried out, and an equation was obtained for predicting melting points with correlation coefficient of ∼0.99.

A mathematical model for computer simulation of a direct continuous esterification process between terephthalic acid and ethylene glycol

AbstractTo study the effect of potassium titanium oxyoxalate on the esterification reaction of terephthalic acid (TPA) and ethylene glycol (EG) in the first tank reactor of TPA/EG continuous esterification, experiments at various addition rates of potassium titanium oxyoxalate were made in the pilot plant. Potassium titanium oxyoxalate accelerated the esterification reaction of TPA and EG. Also, reaction rate constants of the reaction scheme reported in a previous report were fitted with the experimental results, and the calculated values of physical properties of oligomers obtained from these reaction rate constants showed relatively good agreement with experimentally obtained physical properties of the oligomers. The effect of potassium titanium oxyoxalate on the reaction rate constants was expressed by a set of seven equations: equation image Using the resultant reaction rate constants, the esterification reaction at various addition rates of potassium titanium oxyoxalate were stimulated and the following conclusions drawn: Under low pressure close to atmospheric, when the amount of water in the reaction mixture is very low, the decomposition of potassium titanium oxyoxalate proceeds slowly and decomposition can be practically neglected. Potassium titanium oxyoxalate accelerates the esterification reaction. Potassium titanium oxyoxalate mainly accelerates the main reactions and its effects on side reactions are rather weak. As a result, the higher the addition rate of potassium titanium oxyoxalate, the lower the values of AV and DEG, as is preferable.

A mathematical model for computer simulation of the direct continuous esterification process between terephthalic acid and ethylene glycol. Part II: Reaction rate constants

AbstractIt has been confirmed that the reaction model proposed previously, which can express simultaneously the oligomer properties and the distillate properties under low esterification pressure, is applicable to a continuous direct esterification process in a practical plant. The experimental data of the first esterification reactor (RA‐1) was obtained under low reaction pressures (atomospheric or 1 kg/cm2G) with the pilot plant throughput based on poly(ethylene terephthalate) (PET) polymer production of about 50 kg/h. The Arrhenius' parameters, frequency factor, and apparent activation energy, were determined fitting the experimental data of the pilot plant by using the Simplex method as an optimization technique. The activation energy of diethylene glycol (DEG) formation, E7, is about twice as much as those of the esterifications, E1, E2, E3, and E4. The activation energies are E1, = 19640 cal/mol, E2 = 18140, E3 = 22310, E4 = 18380, E5 = 2810, E6 = 14960, and E7 = 42520 cal/mol. Good agreement was obtained between experimental data and calculated predictions for several oligomer and distillate properties. The vapor‐liquid equilibrium can be expressed by Raoult's law with little problem of practical use.

A mathematical model for computer simulation of a direct continuous esterification process between terephthalic acid and ethylene glycol: Part 1. Model development

AbstractA new mathematical model has been developed for the continuous esterification process of terephthalic acid (TPA) and ethlene glycol (EG) with consideration of oligomer characteristics. The liquid weight fraction in the reaction mixture, β, has been selected as a principal parameter in this model. The solubility of TPA in EG and bis β‐hydroxyethyl terephthalate (BHET) has been measured in order to estimate more precisely the concentration of each component. Good agreement has been obtained by plotting the log of solubility data of TPA in EG and BHET against the reciprocal of the absolute temperature with correlation coefficients of 0.998 and 0.989, respectively. The validity of these data has been verified in comparison with other data.

Modeling of poly(ethylene terephthalate) reactors: 4. A continuous esterification process

AbstractA mathematical model has been developed for the direct, continuous esterification process. Influence of process and operational variables, including temperature distribution, residence time distribution, bis(hydroxyethyl)terephthalate recycle, pressure, and ethylene glycol (EG) to terephthalic acid ratio on the reactor performance have been investigated in a range as close to industrial practice as possible. The variables influencing the amount of EG reflux (which governs the energy economy) and side products (which govern the product quality) have been discussed. This investigation provides an analysis of a continuous, direct esterification process, and the results indicate strategies for optimizing productivity and product quality.