Kinetic modelo to catalytic ketonization of carboxylic acids over zirconium oxide (ZrO2) in the mixalco process

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(1)KINETIC MODEL TO CATALYTIC KETONIZATION OF CARBOXYLIC ACIDS OVER ZIRCONIUM OXIDE (ZrO2) IN THE MIXALCO® PROCESS. Degree Project By. PEDRO FELIPE HUERTAS VARGAS. Submitted to the office of Graduate Studies of Universidad de los Andes In partial fulfillment to the requirements for the degree of. B.S. CHEMICAL ENGINEERING. Advisor ROCIO SIERRA, M.Sc, Ph.D. UNIVERSIDAD DE LOS ANDES ENGINEERING FACULTY CHEMICAL ENGINEERING DEPARTMENT BOGOTA D.C 2011.

(2) KINETIC MODEL TO CATALYTIC KETONIZATION OF CARBOXYLIC ACIDS OVER ZIRCONIUM OXIDE (ZrO2) IN THE MIXALCO® PROCESS. Degree Project By. PEDRO FELIPE HUERTAS VARGAS. ____________________________________________ ROCÍO SIERRA RAMÍREZ, M.Sc., Ph.D Advisor. _____________________________________________ CAMILA CASTRO, M.Sc. Committee member. UNIVERSIDAD DE LOS ANDES ENGINEERING FACULTY CHEMICAL ENGINEERING DEPARTMENT BOGOTA 2011.

(3) iii. ABSTRACT. Kinetic model to catalytic ketonization of carboxylic acids over zirconium oxide (ZrO2) in the MixAlco® process Pedro Felipe Huertas Vargas, Universidad de los Andes, Colombia. Advisor: Rocío Sierra Ramírez, PhD. The goal of this project was to develop a kinetic model for catalytic ketonization of carboxylic acids at a laboratory scale. The acids were obtained from acetic acid reactant. In order to perform the ketonization, a packed-bed catalytic reactor using metal oxide catalysts, specifically zirconium oxide, was used. The conditions used were: pressure (14.696 psi, 100 psi, 200 psi and 400 psi), temperatures (573 K, 623 K, 673 K y 723 K) and flow feed rate (0.0002 L/min, 0.0004 L/min, 0.0006 L/min, 0.0008 L/min, and 0.001 L/min) where the optimal conditions of operation found were: pressure 14,696 psi, temperature 723 K and an initial flow range between 0.2 y 0.6 mL/min. With this data, it was determined that the controlling stage of the reaction is the surface reaction. The influence of the studied variables was shown in the conversion achieving an optimal range of operation. Finally, the initial parameters of the kinetic model based on the thermodynamic functions of each component were estimated. This data was optimized through the program MATLAB where the final parameters were obtained and therefore the kinetic model..

(4) iv. RESUMEN. Modelo cinético para la cetonización catalítica de ácidos carboxílicos sobre oxido de zirconio (zro2) en el proceso MixAlco®. Pedro Felipe Huertas Vargas, Universidad de los Andes, Colombia. Asesora: Rocío Sierra Ramírez, PhD. El objetivo de este proyecto fue desarrollar un modelo cinético para la cetonización catalítica de ácidos carboxílicos a una escala de laboratorio. Los ácidos se obtuvieron alimentando acido acético como reactivo. Para realizar la cetonización se usó un reactor catalítico empacado con óxidos metálicos como el oxido de zirconio como catalizador, las condiciones usadas fueron: presión (14.696 psi, 100 psi, 200 psi y 400 psi), temperatura (573 K, 623 K, 673 K y 723 K), y flujo de alimentación (0.0002 L/min, 0.0004 L/min, 0.0006 L/min, 0.0008 L/min, y 0.001 L/min), donde las condiciones optimas de operación encontradas fueron: presión 14,696 psi, temperatura 723K y un rango de flujo inicial entre 0.2 y 0.6 mL/min. Con estos datos se determinó que la etapa controlante de la reacción es la reacción de superficie. Se comprobó la influencia de las variables estudiadas en la conversión. logrando un rango óptimo de operación.. Finalmente, se estimaron los parámetros iniciales del modelo cinético basados en las funciones termodinámicas de cada componente, estos datos fueron optimizados a través del programa MATLAB, obteniéndose así los parámetros finales y por lo tanto el modelo cinético..

(5) v. DEDICATION. I dedicate this work to God, my parents and my sister. To God because He is my hope and inspiration every day; to my parents because they have given up everything for me and never doubted me; and to my sister because without her none of what I have or am would be possible. I love them.

(6) vi. ACKNOWLEDGEMENTS. I would like to thank God for giving me guidance and support to help me finish this work. I have received great satisfaction in my personal and professional development from him. Thanks also to Dr. Mark T. Holtzapple, for the great opportunity to be part of your team, and have the best technology and constant collaboration to develop the project. I am especially grateful to Dr Rocío Sierra for her unconditional support both academic and staff. The excellent results of this work are due to her leadership and commitment to research. I would also like to thank to the MixAlco® research group, especially Sebastian Taco for their valuable advice. Thanks also to the entire Chemical Engineering Department at Texas A&M. Finally, I would like to thank my family, my great new friends in College Station: David Serna, Amanda Niermann, Sandra Palomino, Camila Peña and Pablo Garcia, and my friends here in Colombia, who with their unconditional support were a motivation for the development of this project..

(7) vii. TABLE OF CONTENTS. DEDICACIÓN .................................................................¡Error! Marcador no definido. ACKNOWLEDGEMENTS .............................................¡Error! Marcador no definido. LIST OF FIGURES ..........................................................¡Error! Marcador no definido. LIST OF TABLES ............................................................................................................ix 1. INTRODUCTION .......................................................................................................... 1 2. OBJECTIVES ................................................................................................................ 6 2.1. GENERAL OBJECTIVES ...................................................................................... 6 2.2. SPECIFIC OBJETIVES .......................................................................................... 6 3. LITERATURE REVIEW ............................................................................................... 7 3.1. Highlights ................................................................................................................ 7 3.2 Ketonization ............................................................................................................. 8 3.3. Kinetic model ........................................................................................................ 16 3.3.1 Adsoption ........................................................................................................ 18 3.3.2 Desorption ....................................................................................................... 19 3.3.3 Surface reaction ............................................................................................... 20 3.4 Catalyst ................................................................................................................... 25 3.4.1 Fourier Transform Infrared (FTIR): ............................................................... 25 3.4.2 Temperature Programmed Desorption (TPD): ................................................ 27 4. METHODOLY ............................................................................................................. 29 4.1 Research plan ......................................................................................................... 29.

(8) viii. 4.2 Experimental procedure ......................................................................................... 30 4.3 Catalyst preparation................................................................................................ 32 4.4 Experimental design ............................................................................................... 33 5. RESULTS AND ANALYSIS ...................................................................................... 34 5.1 Conversion ............................................................................................................. 34 5.2 Selectivit ................................................................................................................. 41 5.3 Kinetic model ......................................................................................................... 45 5.3.1 Initial parameter estimation ............................................................................. 47 6. CONCLUSIONS .......................................................................................................... 53 REFERENCES ................................................................................................................. 55 APPENDIX A .................................................................................................................. 61 APPENDIX B .................................................................................................................. 61 APPENDIX C .................................................................................................................. 64 APPENDIX D .................................................................................................................. 84.

(9) ix. LIST OF FIGURES FIGURE. PAGE. 1 Overview of routes to chemical and fuel products via the carboxylate platform. 2. 2 Molecular interaction of acetic acid. 3. 3 Diagram of MixAlco Process. 4. 4. Schematic diagram of a process for converting biomass to liquid secondary alcohol fuel [1].. 6. 5. Schematic diagram of a thermal conversion acid to ketone [1].. 10. 6. Gas phase catalyst ketonization of carboxylic acids. 12. 7. Influence of concentration of active phase upon catalytic activity of CeO2/SiO. 14. 8. Catalytic activity of 20 wt.-% CeO2/SiO2 system in ketonization of acetic acid at various LHSV. Reaction selectivity > 96%.. 15. 9. Graph conversion - space time.. 17. 10. Adsorption: controlling stage in the process. Initial velocity –total pressure.. 18. 11. Desorption: controlling stage in the process. Initial velocity–total pressure.. 18. 12. Surface reactions: controlling stage in the process. Initial velocity –total pressure.. 19. 13. Reactor step used for the reaction kinetics experimental studies.. 21. 14. Ketonization reaction rates for varying partial pressures of hexanoic acid using 2-butanone as solvent at 547 K, 572 K, 597 K and 623 K.. 22.

(10) x. 15. Experimental data and simulation results for ketonization, partial pressure of hexanoic varied.. 23. 16. Packed Bed Reactor. 28. 17. Schematic diagram of the oligomerization process. 29. 18. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 14.696 psi. 35. 19. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 100 psi. 37. 20. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 200 psi. 39. 21. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 300 psi. 40. 22. Concentration of ketones on the product for varying temperature at low WHSV. 42. 23. Concentration of ketones on the product for varying temperature at high – WHSV. 43. 24. Controlling stage. 44. 25. Arrhenius Graphic (Christian, 2009).. 48. 26. Comparison of experimental results with theoretical calculations obtained from kinetic model.. 49.

(11) xi. LIST OF TABLES TABLE. PAGE. 1. Initial dates. 33. 2. Conversion results at pressure 14.696 psi. 33. 3. Conversion results at pressure 100 psi. 36. 4. Conversion results at pressure 200 psi. 39. 5 Conversion results at pressure 300 psi. 40. 6. Constants for the calculation of enthalpy (C.L, 2003). 46. 7. Constants for the calculation of the Gibbs free energy (C.L, 2003). 46. 8. Entropy calculated. 47. 9. Initial parameters. 48. 10. Final parameters for the kinetic model.. 49.

(12) 1. 1. INTRODUCTION. Our planet is suffering serious environmental and energetic problems. This reality calls for the development of new technologies that give priority to contamination prevention, efficient power supply and usage, and optimal use of existing resources. In addition to satisfying all of these requirements, new biofuel generations are required to use feedstocks that are not food resources.. “Biofuels” are fuels derived from renewable resources such as crops, firewood, manure, industrial and agricultural residues, microbial biomass and others.. Due to the last advances in biofuel research, there are different and new processes of biofuel production involving the combination of biological and chemical processes. One of them is the MixAlco Process developed by Dr. Mark Holtzaple at the Chemical Engineering Department of Texas A&M University. A diagram including major stages of the MixAlco process is depicted in Figure 3. This technology converts feedstock residues into useful chemicals such as carboxylic acids and ketones.. 1.1. Ketonization. The ketones are one of the products of the carboxylate platform; the resulting ketones are converted to alcohols, which may be used as transportation fuels..

(13) 2. Figure 1. Overview of routes to chemical and fuel products via the carboxylate platform. Ketones may be obtained from carboxylic acids or salts by thermal decomposition or by catalysis. The reaction is:. (1). Thermal conversion (not considered in this study) is a process involving precipitating metal salts of volatile fatty acids (VFAs) by means of a heat transferred agent which can be present in the reacting media in hollow (steel, glass or ceramic) balls that are filled with a substance that melts at the temperature of thermal decomposition of VFAs..

(14) 3. As the temperature increases and the VFAs thermally decompose the reaction specified in Eq. 1 takes place, resulting in ketones (vapor) and metal carbonate salts mixed with the heat transfer agent.. Once the reaction is complete, the metal carbonate residue and heat transfer agent can be removed to a lock hopper which has previously evaporated to vacuum. The metal carbonate and heat transfer agent will have interstitial ketones vapors which are removed using a vacuum pump and sent to a condenser for recovery (Holtzapple, 1999). The method of interest for the purposes of this study is the catalytic conversion, which uses direct ketonization of carboxylic acids in the gas phase over solid under flowing conditions to the synthesis of ketones. The catalyst is maintained at the lowest reaction temperature for 60 min, and then it enters into the reactor at the temperature range 523723 K. To obtain liquid ketones, the obtained gases are taken to a condensing stage. Finally, the analysis of the reactor effluent is done using gas-liquid chromatography (Glinski, 2004). The general chemical reaction which converts carboxylic acids to ketones is:. Figure 2. Molecular interaction of acetic acid..

(15) 4. The aim of this project is to find the kinetic model for the catalytic ketonization process. Afterwards, experiments were performed to determine the most appropriate reaction conditions based on the kinetic model. Finally these reaction conditions were tested. Furthermore, the effect of control variables such as temperature, pressure and weight hourly space velocity (WHSV) was studied to obtain a global optimum condition..

(16) 5. Figure 3. Diagram of MixAlco Process.

(17) 6. 2. OBJECTIVES. 2.1. GENERAL OBJECTIVES. Evaluate ketonization stage of the MixAlco® process on a laboratory scale and develop the kinetic models and find the global optimal conditions for the process.. 2.2. SPECIFIC OBJETIVES. Become familiar with the equipment and protocols used to safely and effectively run the ketonization process. Use experimental design to select the best pressure, temperature, WHSV and catalyst composition. Determine conversion and selectivity of the reaction using protocols for gas chromatography with flame ionization detector (GC-FID) analysis. Calculate the model parameters using data collected on previous tests..

(18) 7. 3.. LITERATURE REVIEW. 3.1. Highlights. We must first understand the process for producing mixed secondary alcohols. The fed biomass enters into a pretreatment stage, and then is carried to fermentation. Here it is converted to salts of volatile fatty acids (VFAs). Afterwards, the fermented liquor (contains VFAs) is transferred to amine dewatering and then all the water is extracted. The concentrated solution of VFAs enters into the recovery stage, where the solution is evaporated and thermally converted to ketones and calcium carbonate. Finally, the ketones are transferred to the hydrogenation stage where hydrogen gas, using a suitable catalyst and alcohol mix, is produced and able to be used as fuel. This process is shown below. Hydrogen gas Mixed alcohols. Hydrogenation Undigested residue. Ketones Biomass. VFAs. Pretreatment. Lime Kiln. Fermentation. Amine Dewatering. Recovery. Calcium carbonate. Figure 4. Schematic diagram of a process for converting biomass to liquid secondary alcohol fuel (Holtzapple, 1999)..

(19) 8. On the other hand, if the desired product is a concentrated acid, the process remains the same as the above, but the resultant acid stream in the amine dewatering stage may be used directly. Calcium carbonate must be recycled to fermentation to neutralize acid produced or burnt in the lime kiln which could be used in pretreatment or added into a fermentor to maintain a higher pH (Holtzapple, 1999). In this project, we will work in the recovery stage, where the VFAs may be transformed. The first method mentioned produces ketones, while the other four methods produce acids. For the purpose of the project we are only interested in the first method. The methods used in this part are: Thermal conversion of VFAs to ketones Displacement of inorganic cation by low-molecular-weight tertiary, then making a thermal decomposition of the amine carboxylate to release the acids and regenerate the amines. Change of the inorganic cation by low-molecular-weight, then high-molecularweight tertiary amines, followed by thermal decomposition of the amine carboxylate. Displacement of the inorganic cation by ammonia, then high-molecular-weight tertiary amines, followed by thermal decomposition of the amine carboxylate to release the acids and regenerate the amines..

(20) 9. 3.2 Ketonization. Using a thermal conversion to salts from volatile fatty acids a good yield is obtained. In the metal salts of VFAs, the anion portion is provided by the VFAs, while the cations are usually alkalines. The most common ones are lithium, sodium, potassium, magnesium, calcium or barium salts, or a mixture of two or more of these salts. In figure 5, a schematic representation of this method is shown. The VFAs from an amine dewatering system should have approximately a 20% concentration of salt and the pH of the concentrated salt solution should be alkaline. In this process a thermal convertor is used to avoid undesirable reactions. If the pH value is too high, it should be decreased by adding carbon dioxide.. Now these VFAs enter a multiple effect evaporator which consists of vapor disentrainers, heat exchangers and circulating pumps. In the multiple effect evaporator each vapor disentrainer operates at successively lower pressures, the vapor disentrainer 1 has the highest pressure and the vapor disentrainer 3 has the lowest pressure. The process steam is fed to heat exchanger 1 which produces vapors to vapor disentrainer 1, which is fed to heat exchanger 2 and finally to heat exchanger 3. The vapor generated in the last exchanger could be carried to a previous stage, as the amine dewatering to provide the latent heat to separate water from amine. The final vapor stream of the multiple effect evaporator stage is partitioned into two parts, one agitated and the other quiescent. Liquid from the agitated part is transported through the heat exchanger and is returned to the agitated part. As vapors are removed, salt precipitates and settles into.

(21) 10. the quiescent part. It is then pumped through a solids separator and the solid free liquid is returned to the agitated part of the vapor disentrainer (Holtzapple, 1999).. The salts revealed from separation are carried to the drier. The saturated water vapor coming out of the drier is propelled by a blower heat exchanger A which superheats the vapors. It is then returned to the drier for sensible heat provides the latent heat necessary for water to vaporize from the wet salt. The dry salt stream is transferred to the thermal convertor. The ketone stream is recovered as product or carried to hydrogenation. The high stream contains calcium carbonate, but it may contain soluble minerals that must be purged. The other streams are fed back to any above stage (Holtzapple, 1999)..

(22) 11. Figure 5. Schematic diagram of a thermal conversion acid to ketone (Holtzapple, 1999). Dr. Holtzapple described one embodiment, where a method for thermally converting volatile fatty acid (VFA) salts to ketones is used. The first part includes the steps of mixing dry metal of VFAs with a heat transfer agent in a container (evacuated). The heat agent, containing vapor and metal salt of carbonates, is sufficient to raise the temperature of metal salts of VFAs to cause a thermal decomposition, which results in the formation of ketones. Then it is time for separation, where the ketones containing vapor is separated from the metal carbonate salt and heat transfer agent. The liquid ketones are recovered by condensing the ketone containing vapor. The container is.

(23) 12. maintained in a vacuum by condensing the ketones from ketone containing vapor and removing non condensable gas from the container. The heat transfer agents are hollow balls that are filled with a substance that melts at the temperature of thermal decomposition of VFAs; another option is that the heat transfer agent is selected from steel, glass, or ceramic balls. Preferably the metal carbonate and heat transfer agent are removed in a container separate from each other, followed by reheating and recycling of the heat transfer agent back to the container (Holtzapple, 1999).. Conant and Blatt studied a method for producing ketones as fatty acids by passing them over a catalyst, like MnO or ThO2 at 300° C like Figure 5. According to the following equation, the pure acetic acid yields only produce acetone, but a mixture of acids will yield mixed ketones.. For example, if acetic acid and propionic acid were fed, the products would be acetones, methyl ethyl ketones, and diethyl ketones..

(24) 13. Figure 6. Gas phase catalyst ketonization of carboxylic acids.. The above method shows how the ketone is produced from VFAs, and no catalyst is necessary. It decomposes at temperatures between 300 to 400° C,. According to the. following equation:. Acording to Dr. Hurt in The Pyrolysis of Carbon Compounds, this reaction may have a fairly high yield, as long as the ketone decomposition temperature is not exceeded. One of the best experimental results for the decomposition of calcium acetate (salt of acetic.

(25) 14. acid) was obtained by Ardagh et al. (1924). They found a satisfactory decomposition between 290 to 500 °C, and between 430 to 490 °C. However, he reported that the reaction actually begins as low as 160 ° C. They calculated the yield for the process (acetone from calcium acetate) to be 99.5 % of the theoretical yield, during a 7 hour reaction at 430 °C; after one hour, the yield was 96%. One important conclusion of this work was to determine two primary factors that contribute to the low yield: the presence of oxygen in the reaction vessel and the slow removal of the acetone from the hot vessel, both which directly affect the reaction (Ardagh et al., 1924).. Another advance in the synthesis of ketones from carboxylic acids is the catalytic ketonization. This process has been carried out through the pyrolytic decomposition of metal carboxylates, mostly salts of calcium and thorium. Advancement was the direct ketonization of carboxylic acids in the gas phase over solid catalysts under flowing condition. Some compounds used in the literature were metal oxides supported on inorganic carriers like pumice, alumina, silica and titania or active carbon, also, oxides of thorium, cerium, manganese and zirconium as well as rare earth metals and alkaline earth metals (Christian, 2009).. Dr. Glinski did important research of the ketonization process. He studied catalytic mixtures such as propanoic/pentanoic, ethanoic/10-undecanoic and hexanoic/ ocatadecenoic acids. The result was a high yield of ketones irrespective of molecular weights and molecular ratios of reacting acids. The analytical determinations were.

(26) 15. done using GC and HPLC techniques; the reaction was selectivity determined directly from GC measurements and reaction products were identified by GC-MS or by comparing the retention time with that of an authentic sample. The results shown are in the Figure 7 and Figure 8 (Glinski, 2004).. Figure 7. Influence of concentration of active phase upon catalytic activity of CeO2/SiO 2 in ketonization of acetic acid, LHSV = 2 cm 3 g t h ~. Reaction selectivity >/94%..

(27) 16. Figure 8. Catalytic activity of 20 wt.-% CeO2/SiO2 system in ketonization of acetic acid at various LHSV. Reaction selectivity > 96%.. 3.3. Kinetic model. This could be a differential reactor, which has the velocity of reaction constant in all the points of the reactor. Due to small conversions, small or not very deep reactors, big reactor-slow reaction and order reaction zero, another option is an integral reactor, which has the velocity of reaction variable along the reactor due to high conversions. According to the results reported by Osorio (2010), the obtained maximum conversion is between 95% and 96% (Osorio, 2010). Therefore our kinetic model will be for an integral reactor.. The experimental design consists in several trials with a constant initial concentration, varying the initial flow or the mass of catalyst. According to the following chart:.

(28) 17. FA0. W/FA0. CA,SAL/CA0. XA. Where: FA0 = initial flow (mL/min) W = mass of the catalyst (Kg) W/FA0 = space time (Kg cat h/ mL) CA,SAL = Final concentration CA0 = Initial concentration XA = this given by the equation:. εA = Variation fractions of the volume for the complete conversion of A. This given by the equation:. The reaction velocity for any value of X is the slope of this curve shown in Figure 9..

(29) 18. Figure 9. Graph conversion - space time. 3.3.1 Adsoption. In order to obtain a kinetic model we have to know which the controlling stage is. Levenspiel, in his book Chemical Reaction Engineering, describes the process to know the controlling stage; it is based on the graphic initial velocity - total pressure..

(30) 19. If the adsorption is the controlling stage, the graph will be:. Figure 10. Adsorption: controlling stage in the process. Initial velocity –total pressure.. When the adsorption is in the controlling stage the initial velocity is a lineal function of the pressure.. 3.3.2 Desorption If the desorption is the controlling stage, the graph will be:. Figure 11. Desorption: controlling stage in the process. Initial velocity–total pressure..

(31) 20. When the desorption is in the controlling stage, the velocity does not depend on the total pressure.. 3.3.3 Surface reaction. If the surface reaction is the controlling stage, the graph will be:. Figure 12. Surface reactions: controlling stage in the process. Initial velocity –total pressure.. When the surface reaction is in the controlling stage, the initial velocity increases when the total pressure increases, until the saturation point, later the speed falls..

(32) 21. Gaertner et to the (2009) studied the conversion of ketones from carboxylic acids for ketonization. Their study to use hexanoic acid, as a representative carboxylic acid, in presence of 2-butanona like solvent, they worked with controlled conditions of temperature, pressure mass of the catalyst. Their objective was to study the effects, partial pressures of the reactants and products, and reaction temperature on the rates of ketonization (Glinski, 2004).. The reaction is following:. The diagram used for the reaction kinetic studies is shown in the figure 13..

(33) 22. Figure 13. Reactor step used for the reaction kinetics experimental studies.. The hexanoic acid is introduced through a HPLC pump into the system, afterwards; the feed is preheated to achieve the gaseous state. Then, it is sent t to the reactor, where the catalyst is loaded. The final stream was collected at room temperature in a gas-liquid separator and drained for gas chromatography analysis (Glinski, 2004). They did that some graphs that summarize their results..

(34) 23. Figure 14. Ketonization reaction rates for varying partial pressures of hexanoic acid using 2-butanone as solvent at 547 K, 572 K, 597 K and 623 K.. The velocity is shown to several temperatures like function of the partial pressure of the hexanoic acid (Figure 14). Also the velocity is shown to several pressures as function of the temperature (Figure 15). The reactor is a total pressure of 1atm..

(35) 24. Figure 15. Experimental data and simulation results for ketonization, partial pressure of hexanoic varied.. The kinetic model was implemented in MATLAB to solve the differential equations. For the parameters of the model they noticed initial values to be optimized using the algorithm Levenberg Marquardt (Glinski, 2004).. Where:.

(36) 25. These reactions involve non linear parameter estimation problems, applying optimization methods like Levenberg-Marquardt that helps to find a numerical solution to the problem of minimizing a function. The user should add a vector of observations or wanted values of the non well-known parameters. It is an iterative procedure preferably developed with programs like Matlab. The following equation shows their search.. 3.4 Catalyst There are simple methods for evaluating the physical properties of different catalyst:. 3.4.1 Fourier Transform Infrared (FTIR): It works to determine the chemical composition and show the chemical changes, polymerization and impurities with known samples. FTIR is based on the interactions of electromagnetic radiation and molecules. These interactions will be of a different nature depending on the region of the spectrum in which they are occurring; these interactions comprise electron excitation, molecular vibrations and molecular rotations. This technique uses an interferometer, for example the Michelson interferometer, which consists of two mirrors facing each other at a 90 degree angle. Furthermore, the interferometer has a ray refractor which is positioned at a 45 degree angle from the.

(37) 26. mirrors. One of these mirrors is located at a stationary position, while the other one can move at a constant speed in a direction perpendicular to the frontal plane.. The device that is in charge of splitting the rays allows the mirrors to capture the light emanating from the source. Fifty percent of the light it absorbs is transmitted while the rest is reflected. The interferometer also has information about the intensity of all the frequencies in the light spectra. The information that comes out of the detector is digitalized and transformed to the Fourier series. Then the signals are converted to the conventional infrared spectra. FTIR has different applications: Characterization and identification of materials. Polymers and plastics. Inorganic solids (minerals, catalyst ) Analysis and synthesis of pharmaceutical products. Analysis of impurities Tracking of chemical processes Polymerization. Catalytic reactions. Analysis of oils and fuels..

(38) 27. 3.4.2 Temperature Programmed Desorption (TPD): It is a technique that allows the determination of the number, the type and the strength of the active sites present on the surface of the catalyst by measuring the quantity of the compound that adsorbs at different temperatures. The ammonia present would be the principal molecule to characterize the acidic centers of the catalyst.. To run the analysis the following equipment was used a temperature control system for gas stream, a detector of thermal conductivity and valve gases; a temperature control system for furnace, flowmeter, gas flow and pressure control panel and a calibrated loop to control the injection of different gases or vapors in the sample There are three types of molecular probes commonly used for characterizing acid sites using TPD: Ammonia Non-reactive vapors Reactive vapors TPD of ammonia is a widely used method for characterization of site densities in solid acids due to the simplicity of the technique. Ammonia often overestimates the quantity of acid sites. Its small molecular size allows ammonia to penetrate into all pores of the solid where larger molecules commonly found in cracking and hydrocracking reactions only have ess to large micropores and mesopores..

(39) 28. Also, ammonia is a very basic molecule which is capable of titrating weak acid sites which may not contribute to the activity of catalysts. The strongly polar adsorbed ammonia is also capable of adsorbing additional ammonia from the gas phase..

(40) 29. 4. METHODOLY. 4.1. Research plan Reactions will be carried in a fixed bed tubular quartz reactor (Figure 16). A constant metric pump will be used to drive acid into the system; stainless steel tubing will be used throughout. The acid will pass through coils of tubing inside an oven, which will be heated to 45 °C; the preheated acid will then pass through a segment of tube wrapped in heating tape, insulation, and aluminum. This tape will be set to 150 °C using a variable transformer.. Figure 16. Packed Bed Reactor The acid vapor will then pass into the reactor where it contacts the zirconia catalyst and reacts, which will also be wrapped with heating tape covered with insulation, and.

(41) 30. aluminum; this tape will be set to 400 °C. Both tapes will be monitored. Later, the reaction products go through a stabilizer where the temperature is around 200 °C. Product analysis will be done through gas chromatography (GC) connected in line. This process is similar to oligomerization process shown in Figure 17.. Figure 17. Schematic diagram of the oligomerization process. 4.2 Experimental procedure. 1. Catalyst is weighed and loaded into the reactor. The catalyst is supported by two layers of α-alumina. 2. The system is purged for 2 min with N2 at 500 cm3/min..

(42) 31. 3. The reactor temperature is set. The temperature is controlled by three controllers (top, medium, and bottom). The objective is to maintain the same temperature along the catalyst bed. To get the same temperature, the controllers must be set at the following temperatures:.  Top  TR – 40 °C  Middle  TR – 30 °C  Bottom  TR. The system has a Type-K thermocouple that measures the temperature along the catalyst bed, which allows verification of a constant temperature along the reactor. The reactor temperature stabilizes after 15 minutes. 4. The liquid reactants are fed to the system with a syringe pump. 5. If hydrogen is added to the acetone reaction, the hydrogen is measured with a mass flow controller. 6. After the reaction temperature is stabilized (after 10 minutes of feeding), the liquid products are collected. 7. Then, an on-line analysis of the product stream is performed using a GC connected to the reactor exit. This GC has two detectors: FID and TCD. The analysis intervals are 30 minutes, so the samples can be taken every 30 minutes. 8. The liquid sample is collected and analyzed with a GC-MS. This GC-MS analysis has more detailed compound analysis of the liquid phase..

(43) 32. 9.. Reactions are terminated by cutting off the feed. Then, the reactor is heated to 500°C.. 10. Finally, air is fed into the system to regenerate the catalyst (return to Step 1).. The above experimental procedure was taken for Taco & Nieves in their research Hydrogenation of Ketones and Alcohols Conversion to Hydrocarbons Using HZSM-5 Catalyst.. 4.3 Catalyst preparation. For 30 g of catalyst use 12 gr ZrO2, 6 gr TiO2, 6 silica fumed, 6 gr ZrO(NO3)2 · xH2O, the experimental procedure is shown below. 1. Prepare a solution A of 12 gr of ZrO2 on distilled water. A volumetric flask is used to make the mixture. 2. Prepare the solution B by mixing 6 gr TiO2, 6 silica fumed and 6 gr ZrO(NO3)2 · xH2O. 3. Mix the solution A with the solution B. 4. Add water until a uniform gel is formed. 5. Dry at 120 °C on an oven for approximately 24 hours. 6. Calcinate at 450 °C for approximately 8 hours. A furnace is used to calcinate. 7. Make pellets between 3-5 mm..

(44) 33. The above experimental procedure was taken for Osorio in their research catalytic ketonization of carboxylic acids over zirconium oxide (ZrO2) 4.4 Experimental design The experimentation will be a factorial design combined which has 3 factors:. Temperature Pressure Initial Flow Each variable have the following ranges: T1 and T4  (573.15 – 723.15) K P1 and P4  (14 – 300) psi F1 and F5  (0.0002 – 0.001) l/min.

(45) 34. 5. RESULTS AND ANALYSIS. 5.1 Conversion Table 1. Initial dates Mass of catalyst W (kg) Variation fractions of the volume Ea Initial concentration of Acid CA,0. 0,005 0,500 0,729. Table 2. Conversion results at pressure 14.696 psi Temperature (°C) 300. 350. 400. 450. Initial Flow (mL/min) 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1. CA,sal 0.106 0.075 0.125 0.125 0.123 0.075 0.153 0.147 0.161 0.160 0.125 0.161 0.120 0.152 0.149 0.125 0.125 0.087 0.048 0.154. W/FAO (Kg cat h/ mL) 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050. CAsal/Ca 0.146 0.103 0.171 0.171 0.168 0.103 0.210 0.201 0.221 0.219 0.171 0.220 0.164 0.209 0.204 0.171 0.171 0.119 0.066 0.211. Xa 0.829 0.840 0.847 0.853 0.894 0.839 0.848 0.851 0.875 0.900 0.846 0.855 0.875 0.913 0.934 0.865 0.877 0.900 0.925 0.952.

(46) 35. Table 1 shows the calculations performed based on the data obtained, for a pressure of 14.696 psi, in the first two columns it is shown the temperature and flow conditions that correspond to it. First, the space-time is estimated given by the ratio of the mass of catalyst loaded into the reactor in kg to the initial flow in mL / min. If space-time has a small value, this corresponds to a value greater than the initial flow. The space-time is symbolized by W/FAO. The value of x -axis on the Figure 1 represents the space-time measuring, which will be useful to calculate the initial rate of the reaction. The outlet concentration is measured in the chromatographic analysis for each sample, where the area under each peak is roughly proportional to the concentration of the species in the sample.. The initial concentration of acid is the same for all the runs, the solution is made of 450 g of acetic acid and 50 g of water, thus the fraction of acetic acid and water in the solution are 0.9 and 0.1 respectively. It is necessary to know the moles entering the system for this, the above data is important to know that you are working with 7.5 moles of acetic acid and 2.7 moles of water. Thus, we estimate the initial concentration of acetic acid, resulting in 0.729 mole fraction. After calculating the initial concentration and final, and knowing that the fractional volume change for complete conversion of acetic acid (εA) is given by the reaction as follows:.

(47) 36. The results above were used to create a plot, which shows conversion for varying space-time in order to determine the initial rate of the reaction for any conversion value. The method consists in determining the slope of the line, this slope is equivalent to initial rate of the reaction. 1,00 T=300 °C. Conversion (Xa). 0,98. T=350°C. 0,96. T=400 °C. 0,94. T=450 °C. 0,92 0,90 0,88 0,86 0,84 0,82 0,80 0,0050. 0,0150 Space time (W/FAO ). 0,0250. Figure 18. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 14.696 psi.

(48) 37. When the system is at atmospheric pressure, the conversion is higher at slow flows and high space-time. This could be because the reactants are in a longer contact time with the catalyst, therefore the reaction will be favored. Thus, it can be concluded that when the temperature increases the conversion also increases. The isotherms presents the same behavior, as long as the space-time is increasing the conversion is decreasing. However, the conversion results are good. Table 3. Conversion results at pressure 100 psi Temperature (°C) 300. 350. 400. 450. Initial flow CA,sal (mL/min) 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1. 0.832 0.838 0.845 0.860 0.916 0.827 0.830 0.841 0.843 0.862 0.847 0.853 0.853 0.854 0.868 0.880 0.883 0.892 0.905 0.905. W/FAO (Kg cat h/ mL) 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050. CAsal/Ca 0.146 0.103 0.171 0.171 0.168 0.103 0.210 0.201 0.221 0.219 0.171 0.220 0.164 0.209 0.204 0.171 0.171 0.119 0.066 0.211. Xa 0.832 0.838 0.845 0.860 0.916 0.827 0.830 0.841 0.843 0.862 0.847 0.853 0.853 0.854 0.868 0.879 0.883 0.892 0.905 0.905.

(49) 38. 1,00 T=300 °C. 0,98 T=350°C. 0,96. T=400 °C. Conversion (Xa). 0,94. T=450 °C. 0,92 0,90 0,88 0,86 0,84 0,82 0,80 0,005. 0,01. 0,015. 0,02. 0,025. Space time (W/FAO). Figure 19. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 100 psi. The figure 19 shows how the tendency curves remain constant. To enhance the reaction, the temperature and space-time should increases. The space-time depends of the catalyst mass and the initial flow; there are two ways to increase its value: it can be increasing the catalyst mass or decreasing the initial flow. In order to analyze the economic part of the process, the best option would be decreases the initial flow, thus the raw materials such as acetic acid would be less used and the measured conversion will not be affected. The problem in this part would be the time; if the initial flow is too.

(50) 39. slow, the reaction takes more time than usual and the quantity produced ketones would not be the same compared to the ones with higher flows. If the amount of the catalyst is increased the flows could be faster, in this way, the reaction will be optimized but the catalyst costs will be increased. A cost-benefit analysis shout be implemented and then infer the most appropriate and effective way to increase the space-time.. If we compare the values of conversion at the same temperature and initial flow rate, the conversion does not have a significant change when pressure is increased from 14.696 psi to 100 psi. Conversion reduces only when it is combined with lower temperatures. Temperature is lower due to the lack of energy to achieve the best results from the reaction as the pressure increases. We know that the equilibrium of high pressure is not as efficient as in lower pressures, because the reaction goes from two moles to three, meaning that the ideal conditions to produce fewer moles are high pressures. Taken this case in consideration, we want to produce more moles; therefore low pressures make the reaction more efficient..

(51) 40. Table 4. Conversion results at pressure 200 psi Temperature (°C) 300. 350. 400. 450. IInitial flow CA,sal (mL/min) 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1. 0.830 0.834 0.841 0.844 0.863 0.839 0.845 0.849 0.855 0.864 0.841 0.843 0.852 0.853 0.858 0.859 0.866 0.872 0.880 0.903. W/FAO (Kg cat h/ mL) 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050. CAsal/Ca 0.146 0.103 0.171 0.172 0.168 0.103 0.210 0.201 0.220 0.219 0.171 0.220 0.164 0.208 0.204 0.171 0.172 0.119 0.066 0.211. Xa 0.829 0.834 0.841 0.844 0.863 0.839 0.845 0.849 0.856 0.864 0.841 0.843 0.852 0.853 0.858 0.859 0.866 0.872 0.879 0.902.

(52) 41. 1,00 T=300 °C. 0,98. T=350°C. 0,96 T=400 °C. Conversion (Xa). 0,94. T=450 °C. 0,92 0,90 0,88 0,86 0,84 0,82 0,80 0,005. 0,01. 0,015. 0,02. 0,025. Space time (W/FAO). Figure 20. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 200 psi.

(53) 42. 1,00 T=300 °C. 0,98. T=350°C. 0,96 T=400 °C. Conversion (Xa). 0,94. T=450 °C. 0,92 0,90 0,88 0,86 0,84 0,82 0,80 0,005. 0,01. 0,015. 0,02. 0,025. Space time (W/FAO). Figure 21. Conversion of ketonization reaction for varying t space-time of feed at different temperature values and a total pressure of 300 psi.

(54) 43. Table 5 Conversion results at pressure 300 psi Temperature I Initial Flow (°C) (mL/min) 300. 350. 400. 450. 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8 1. CA,sal 0.844 0.847 0.858 0.861 0.861 0.826 0.838 0.842 0.845 0.850 0.845 0.851 0.855 0.860 0.880 0.862 0.867 0.879 0.880 0.881. 5.2 Selectivity The selectivity can be written as follows:. Where: ND = moles of desired product U=. moles of undesired product. W/FAO (Kg cat h/ mL) 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050 0.0250 0.0125 0.0083 0.0063 0.0050. CAsal/Ca. Xa. 0.148 0.103 0.171 0.171 0.168 0.103 0.210 0.201 0.220 0.219 0.171 0.220 0.164 0.208 0.204 0.171 0.172 0.119 0.066 0.211. 0.844 0.847 0.857 0.860 0.861 0.826 0.838 0.842 0.845 0.850 0.845 0.851 0.855 0.860 0.879 0.862 0.867 0.879 0.879 0.881.

(55) 44. 1. Selectivity (%). 0,9. 0,8. 0,7 14 atm. 0,6 100 atm 200 atm. 0,5 300 atm. 0,4 300. 350. 400. 450. Temperature (°C). Figure 22. Concentration of ketones on the product for varying temperature at low WHSV The Figure 22 shows how the selectivity decreases when the temperature increases. One of the most concentrated side components were aromatic hydrocarbons such as 1,3,5 trimethylbenzene. Mattox et to the (1960) studied the conversion of aromatics from ketones in the presence of a alumino-silicate catalyst [xx], the results show a highly effective process when the operating conditions are at temperature 204°C to about 537°C and a total pressure of 1000 psig. These temperature and pressure conditions are similar of ketonization conditions, the fact that the selectivity decreases.

(56) 45. in high pressure support the production of aromatic, finally, the metal catalyst, zirconium oxide, is supported over silica and alumina as in the Mattox’s studies.. 1,0. Selectivity (%). 0,9. 0,8. 0,7. 0,6. 14 atm 200 atm. 0,5 300 atm 100 atm. 0,4 300. 350 400 Temperature (°C). 450. Figure 23. Concentration of ketones on the product for varying temperature at high WHSV. 5.3 Kinetic model The initial rate of reaction is the slope in the initial point. Each point represents an initial rate for a total pressure in the reactor. In order to determine the controlling stage, it is necessary to check the tendency graph (initial rate - total pressure), and finally clarify if it is adsorption, desorption or surface reaction..

(57) 46. 195 T=300°C. 190 T=350°C. Initial rate. 185. T=400°C. 180. T=450°C. 175. 170. 165. 160 14. 114. 214 Pressure total (psi). Figure 24. Controlling stage. As shown in Figure 24, the initial velocity is not a linear function of the pressure but it does depend on the total pressure. Therefore the controlling stages are neither adsorption nor desorption. The result shows the initial velocity as a function of pressure. For this reason the surface reaction is the controlling stage where the initial velocity decreases when the total pressure increases and the initial velocity increases when the temperature increases..

(58) 47. The rate expression for the ketonization can be written as:. Where: krs = ketonization rate constant KA = rate constant for the adsorption KRS = rate constant for the surface reaction KD, CO2 = rate constant for the desorption of CO2 KD,H2O = rate constant for the desorption of H2O PCH3COOH= acetic acid vapor pressure PCH3COCH3= acetone vapor pressure PCO2 = carbon dioxide vapor pressure PH2O = wáter vapor pressure. 5.3.1 Initial parameter estimation Ki, j is the equilibrium constants for species j..

(59) 48. In the initial parameter estimation, the equilibrium constants for species and the forward rate constant for ketonization reaction will be used. These are given as thermodynamic functions. (Christian, 2009).. (17) Where: Ki,eq= equilibrium constant -∆H°i =enthalpy of formation ∆S°i = entropy of formation R= gas constant T= temperature. For each one of the species it was necessary to know the values of the constants that allowed for the calculation of the values of enthalpy and entropy used inside of the model. The data is shown in Table 6. Table 6. Constants for the calculation of enthalpy (C.L, 2003) Component. A. B. C. ∆Hi. Acetic Acid. C2H4O2. -422.548. -0.048354. 0.000023337. -445.3112. Acetone. C3H6O. -199.175. -0.071484. 0.000032534. -233.8551. Carbon Dioxide. CO2. -393.422. 0.00015913. -1.3945E-06. -394.0362. Water. H2O. 33.933. -0.0084186. 0.000029906. 43.4843. Where:. (18). For the calculation of the formation entropy, Equation 18 was used, where the previous calculated entropy is related to the value of the Gibbs free energy, calculated in the same way as the enthalpy but with different constants (Table 7)..

(60) 49. Table 7. Constants for the calculation of the Gibbs free energy (C.L, 2003) Component. A. B. C. ∆Gi. Acetic Acid. C2H4O2. -425.963. 1.93E-01. 0.000016362. -277.506. Acetone. C3H6O. -218.777. 2.12E-01. 0.000026619. -51.715. Carbon Dioxide. CO2. -393.422. -0.0038212. 1.3322E-06. -395.489. Water. H2O. -255.422. -0.02486. 0.00008456. -228.600. (19) With these two terms and the optimal operating conditions, the value for each one of equilibrium constants for species was obtained. The final values of entropy are shown in Table 8.. Table 8. Entropy calculated ∆Si. Component Acetic Acid. C2H4O2. -0.232048. Acetone. C3H6O. -0.251870. Carbon Dioxide. CO2. 0.002009. Water. H2O. 0.376249. Furthermore, it was necessary to calculate the forward rate constant for ketonization reaction, described by the following equation.. (20) Where: ki,= Arrhenius rate constant Ai = pre-exponential factor Eai = activation energy.

(61) 50. R= gas constant T= temperature For this equation, the Ai and Eai terms were found graphically, that is to say, Figure 25 represents the Arrhenius graphic where the slope is equivalent to the activation energy and the intercept to the pre-exponential value. 5,5. ln rate ( mol min-1 kg Cat-1). 5 4,5 4 3,5 3. y = -3822,x + 10,42 R² = 0,982. 2,5 2 0,0013. 0,0015 0,0017 Temperature (K-1). 0,0019. Figure 25. Arrhenius Graphic (Christian, 2009).. The optimization process began with the calculated values based on the thermodynamic functions, shown in Table 4. This result will be optimized in an iterative process developed in Matlab. The equation involves non-linear, parameter estimation problems. It is necessary to apply optimization methods like Levenberg-Marquardt that help to find a numerical solution..

(62) 51. Table 9. Initial parameters KC2H4O2. 0.97. KC3H6O. 0.97. KCO2. 1.00. KH2O. 1.04. Finally, the program in Matlab accomplished an iterative process where the values of the constants were optimized and the final kinitic model was obtained. Table 10. Final parameters for the kinetic model. Ea. 7,44. ± 4,99. A. 2,33. ± 1,56. KC3H4O2. 0,02. ± 0,07. KC3H6O. 5,18. ± 3,46. KCO2. 37,6. ± 8,24. KH2O. 110. ± 11,6.

(63) 52. 1,02 1. Therorical convertion. 0,98. Experimental convertion. Conversion (Xa). 0,96 0,94 0,92 0,9. 0,88 0,86 0,84 0,82 0,0063. 0,0113. 0,0163. 0,0213. Space time (W/FAO ). Figure 26. Comparison of experimental results with theoretical calculations obtained from kinetic model..

(64) 53. 6. CONCLUSIONS. The ketonization reaction was carried out over a catalyst of zirconium oxide supported on silica, alumina and titanium oxides. According to the analysis of the conversion results, the most appropriated conditions for the ketones production are slow initial flows, low pressures and high temperatures. The recommended conditions were 450 °C, 14.6 psi and a flow rate between 0.2 y 0.6 mL/min. Residence time is higher when the experimental flow is slow; this can be explained because the interaction between catalyst and reactants is favored producing more ketones. For any reaction, when the number of moles increases, such as in the case of ketonization low pressures are recommended, the experimental results confirm this hypothesis because when the pressures are high the conversion is significantly low.. In regards to the selectivity, the results vary depending on the experimental conditions, for example, when the temperatures and pressures are high; the GC-MS shows presence of aromatic hydrocarbons.. The initial velocity for each experiment is a function of the pressure; hence the surface reaction between the adsorbed species is the controlling stage of the process. Based on this result the rate expression for the ketonization was found. It is suggested to expand the experimental range in order to have greater certainty of the controlling step..

(65) 54. Although in Figure 24 the initial rate is a function of total pressure, the behavior of the graph could present significant changes in other conditions.. For the estimation of the initial parameters, thermodynamic functions based on the characteristics of each compound give a good initial approximation of the parameters that are being looked for. The optimized parameters give a fairly accurate solution to the kinetic model which is reflected in the closeness between the experimental and theoretical values..

(66) 55. REFERENCES. Ardagh, E. G. R., Bbarbour, A. D., McClellan, G. E & McBride, E. W., 1924, Distillation of Acetate of Lime., Industrial and Engineering Chemistry, 16 (11) 1133-1139. Conant, J.B. & Blatt A.H., 1947, The Chemistry of Organic Compounds, Macmillan Co., New York. D.B.Ingram, Ketonization of acetic acid, 2002, Department of Chemical Engineering, Texas A&M University.. Gaertner,C, 2008, Catalytic coupling of carboxylic acids by ketonization as a processing step in biomass conversion, Journal of Catalysis, Vol. 266, pp.7178.. Glinski, M., 2004, Catalytic ketonization of carboxylic acids synthesis of saturated and. reaction kinetics and catalysis letters, vol 69, pp. 123-128. Holtzapple, M. T, 1999, Thermal conversion of volatile fatty acid salts to ketones. United States Patent Office. Patent No. WO/1999/000348. Texas A & M university, College Station, Texas, US. Johnson V, Champan J, Chen L, Kimmich B, & Zink J, 2009, Ethanol production from acetic acid utilizing a cobalt catalyst. United States Patent Office. Patent No. 7.608.744..

(67) 56. Kang S, Sung S & Sang K, 2008. Reaction kinetics of reduction and oxidation of metal oxides for hydrogen production. Daejeon, South Korea.. Kawano, T, 2005. Water vapor decomposition reaction on ZrNi alloy. Japan.. Kunihiko M, Ichihara-shi, & Tatsuo S, 2011, Alcohol production process and acidtreated. raney. cataly.. United. States. Patent. Office,. patent. No. 2011/0015450A1.. Martinez, M.C. Huff and M.A. Barteau, 2003, Ketonization of acetic acid on titania functionalized silica monoliths. Journal of Catalysis Vol. 222, pp. 404-409.. Nieves, E & Holtzapple M, 2010, Hydrogenation of Ketones and Alcohols Conversion to Hydrocarbons Using HZSM-5 Catalyst. ARTIE McFERRIN Department of Chemical Engineering, Texas A&M University, College Station, Texas, US.. Osorio, C. 2010, Catalytic Ketonization of carboxylic acids over zirconium oxide (ZrO2). Texas A&M University, College Station, Texas, US.. Taco, S 2009, Alcohols and Ketones Conversion to Hydrocarbons Using HZSM-5, Department of Chemical Engineering, Texas A&M University..

(68) 57. Jackson D, 2006. Processes occurring during deactivation and regeneration of metal and metal oxide catalysts. Scotland,UK.. Yang YC, Weng H, 2010, Regeneration of Coked Al-Promoted Sulfated Zirconia Catalysts by High Pressure Hydrogen. Taiwan..

(69) 58. APPENDIX A Experimental Procedure Catalyst is weighed and loaded into the reactor. The catalyst is supported by two layers of α-alumina. The system is purged for 2 min with N2 at 500 cm3/min. The reactor temperature is set. The temperature is controlled by three controllers (top, medium, and bottom). The objective is to maintain the same temperature along the catalyst bed. To get the same temperature, the controllers must be set at the following temperatures: o Top  TR – 40 °C o Middle  TR – 30 °C o Bottom  TR The system has a Type-K thermocouple that measures the temperature along the catalyst bed, which allows verification of a constant temperature along the reactor. The reactor temperature stabilizes after 15 minutes. The liquid reactants are fed to the system with a syringe pump. If hydrogen is added to the acetone reaction, the hydrogen is measured with a mass flow controller. After the reaction temperature is stabilized (after 10 minutes of feeding), the liquid products are collected..

(70) 59. Then, an on-line analysis of the product stream is performed using a GC connected to the reactor exit. This GC has two detectors: FID and TCD. The analysis intervals are 30 minutes, so the samples can be taken every 30 minutes. The liquid sample is collected and analyzed with a GC-MS. This GC-MS analysis has more detailed compound analysis of the liquid phase. Reactions are terminated by cutting off the feed. Then, the reactor is heated to 500°C. Finally, air is fed into the system to regenerate the catalyst (return to Step 1). The above experimental procedure was taken for Taco & Nieves in their research Hydrogenation of Ketones and Alcohols Conversion to Hydrocarbons Using HZSM-5 Catalyst.. Catalyst preparation. For 30 g of catalyst use 12 gr ZrO2, 6 gr TiO2, 6 silica fumed, 6 gr ZrO(NO3)2 · xH2O, the experimental procedure is shown below. Prepare a solution A of 12 gr of ZrO2 on distilled water. A volumetric flask is used to make the mixture. Prepare the solution B by mixing 6 gr TiO2, 6 silica fumed and 6 gr ZrO(NO3)2 · xH2O. Mix the solution A with the solution B. Add water until a uniform gel is formed..

(71) 60. Dry at 120 °C on an oven for approximately 24 hours. Calcinate at 450 °C for approximately 8 hours. A furnace is used to calcinate. Make pellets between 3-5 mm. The above experimental procedure was taken for Osorio in their research catalytic ketonization of carboxylic acids over zirconium oxide (ZrO2).

(72) 61. APPENDIX B Calculations. Adsorption. Surface reaction. Desorption. Where.

(73) 62. When the adsorption is the controlling stage:.

(74) 63. When the surface reaction is the controlling stage:.

(75) 64. APPENDIX C GC-MS results T=573 K, P=14 atm, F=0.2 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.86. 6.36. 2-Propanone. 8.91164. 2. 0.94. 21.67. No matches found. 19.36962. 3. 1.89. 7. 2-Pentanol. 6.25692. 4. 2.42. 0.43. 2-Hexanone. 0.38435. 5. 2.69. 53.93. Acetic acid. 10.62442. 6. 2.8. 2.12. 3-Hexanol. 3.11952. 7. 4.79. 7.11. 2-Heptanone. 6.35524. 8. 5.63. 4.96. Hydrazine, ethyl-, ethanedioate (1:. 4.43347. 9. 6.01. 0.12. cis-3a-Methyl-2,3,4a,6,7,7a-hexahyd. 0.10726. 10. 6.79. 0.35. Benzene, 1,3,5-trimethyl-. 0.31285. 11. 7.07. 0.18. 2-Octanone. 10.93173. 12. 7.91. 1.09. 3-Octanol. 2.61003. 13. 9.35. 0.63. 4-Nonanone. 4.19213. 14. 10.23. 10.17. Hexanoic acid. 9.09041. 15. 11.13. 0.24. 5-Undecanone, 2-methyl-. 0.21452. 16. 11.6. 12.55. Heptanoic acid. 12.22780. 17. 12.68. 0.29. 5-Decanone. 0.25922. 18. 13.04. 0.29. Cyclohexane, (1-methylethyl)-. 0.25922. 19. 14.04. 0.22. 6-Dodecanone. 0.19665. 20. 15.32. 0.16. 7-Tridecanone. 0.14302 100. T=623 K, P=14 atm, F=0.2 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.8. 3.61. Carbon dioxide. 3.33864. 2. 0.94. 11.93. 2-Propanone. 11.0332. 3. 2.11. 0.34. 2-Pentanol. 0.31444. 4. 2.34. 0.14. 3-Hexanone. 1.13754. 5. 2.45. 36.88. Acetic acid. 7.51702. 7. 3.83. 8.28. Propanoic acid. 7.65759. 8. 5.23. 9.21. 2-Heptanone. 8.51768. 9. 7.08. 14.81. Butanoic acid. 13.6967. 10. 7.69. 2.12. 2-Octanone. 8.18474. 12. 8.15. 0.11. 3-Octanol. 0.10173. 13. 8.81. 4.28. Butanoic acid. 3.95827.

(76) 65. 14. 9.37. 0.1. 4-Nonanone. 1.31326. 17. 10.89. 15.87. Hexanoic acid. 14.677. 18. 11.25. 1.03. 4-Decanone. 0.95257. 19. 12.27. 16.05. Heptanoic acid. 14.8435. 20. 12.8. 1.57. 6-Dodecanone. 1.45198. 21. 14.16. 0.72. 5-Undecanone, 2-methyl-. 0.66588. 22. 15.4. 0.52. 7-Tridecanone. 0.63813 100. T=673 K, P=14 atm, F=0.2 ml/min Pk#. RT. Area% Library/ID. Molar fraction. 1 2 3 4 5 6 7 8 9 11 12 13 14 16 17 18 19 20 21 22 23. 0.32 0.82 0.87 1.06 2.37 2.46 3.39 4.13 4.79 5.71 6.02 6.82 7.25 9.88 10.36 11.17 11.85 12.6 12.72 14.07 15.33. 1.78 7.82 64.63 0.98 0.36 0.43 0.11 0.17 9.33 2.06 0.93 1.46 0.32 7.79 11.82 0.18 14.97 1.83 0.25 0.2 0.13. 11.37233 6.846162 12.47068 0.857959 0.315169 0.376451 0.096302 0.14883 10.40932 1.803465 0.814185 1.278184 20.66981 6.819898 10.34803 0.157584 13.10576 1.602107 0.218867 0.175094 0.113811. 2-Propanone 1-Propene, 2-methylAcetic acid 2-Butanone No matches found 2-Hexanone 2-Hexanol 1-Octene, 2-methyl2-Heptanone 1,2,3,3-TETRAMETHYL-4-METHYLENE-CYC Isoterpinolene Benzene, 1,3,5-trimethyl2-Octanone 2-Nonanone Butanoic acid 4-Decanone Heptanoic acid Octanoic acid 5-Undecanone, 2-methyl6-Dodecanone 7-Tridecanone. 100 T=723 K, P=14 atm, F=0.2 ml/min Pk#. RT. Area% Library/ID. Molar fraction. 1. 0.32. 1.78. 2-Propanone. 11.37233. 2. 0.82. 7.82. 1-Propene, 2-methyl-. 6.846162. 3. 0.87. 64.63. Acetic acid. 12.47068.

(77) 66. 4. 1.06. 0.98. 2-Butanone. 0.857959. 5. 2.37. 0.36. No matches found. 0.315169. 6. 2.46. 0.43. 2-Hexanone. 0.376451. 7. 3.39. 0.11. 2-Hexanol. 0.096302. 8. 4.13. 0.17. 1-Octene, 2-methyl-. 0.14883. 9. 4.79. 9.33. 2-Heptanone. 10.40932. 11. 5.71. 2.06. 1,2,3,3-tetramethyl-4-methylene-cyc. 1.803465. 12. 6.02. 0.93. Isoterpinolene. 0.814185. 13. 6.82. 1.46. Benzene, 1,3,5-trimethyl-. 1.278184. 14. 7.25. 0.32. 2-Octanone. 20.66981. 16. 9.88. 7.79. 2-Nonanone. 6.819898. 17. 10.36 11.82. Butanoic acid. 10.34803. 18. 11.17 0.18. 4-Decanone. 0.157584. 19. 11.85 14.97. Heptanoic acid. 13.10576. 20. 12.6. Octanoic acid. 1.602107. 21. 12.72 0.25. 5-Undecanone, 2-methyl-. 0.218867. 22. 14.07 0.2. 6-Dodecanone. 0.175094. 23. 15.33 0.13. 7-Tridecanone. 0.113811. 1.83. 100 T=523 K, P=14 atm, F=0.4 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.94. 47.6. 2-Propanone. 41.1815. 2. 1.94. 11.23. 2-Pentanol. 9.71573. 3. 2.77. 3.33. 3-Hexanol. 5.84847. 4. 2.87. 70.67. Acetic acid. 13.4755. 5. 4.85. 2.17. 4-Heptanol. 15.4085. 6. 7.66. 1.84. 4-Octanol. 5.82251. 7. 9.31. 1.58. Hexanoic acid. 1.36695. 8. 9.76. 4.66. 4-Octanol, 7-methyl-. 4.03164. 9. 9.95. 0.9. 2-Nonanol. 0.77864. 10. 10.82. 1.06. Heptanoic acid. 0.91707. 11. 11.43. 0.92. 5-Decanol. 0.79595. 12. 12.91. 0.76. 6-Undecanol. 0.65752 100. T=623 K, P=14 atm, F=0.4 ml/min Pk#. RT. Area%. Library/ID. 1. 0.85. 70.79. 2-Propanone. Molar fraction 59.94825.

(78) 67. 2 3 4 5 6 7 8. 1.8 3.73 4.25 5.82 9.37 9.8 10.55. 4.14 8.73 82.01 6.38 2.1 1.82 6.05. 2-Hexanol 2-Heptanol Acetic acid Benzene, 1,3,5-trimethyl4-Nonanol Benzene, 1,2,3,4-tetramethylHexanoic acid. 3.505944 7.392969 15.3069 5.40288 1.778377 1.54126 5.12342 100. T=673 K, P=14 atm, F=0.4 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.88. 97.49. 2-Propanone. 81.8207. 2. 2.95. 86.89. Acetic acid. 16.0727. 3. 4.43. 2.51. 2-Heptanol. 2.10658 100. T=723 K, P=14 atm, F=0.2 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.7. 16.1. 2-Propanone. 21.7015. 2. 2.52. 22.78. 3-Hexen-2-one. 19.9339. 3. 3.66. 0.73. Benzene, 1,3-dimethyl-. 0.63879. 4. 4.9. 3.57. 1,3-Cyclohexadiene, 1,5,5,6-tetrame. 3.12397. 5. 5.65. 0.9. 1,4-Cyclohexadiene, 3,3,6,6-tetrame. 0.78755. 6. 5.96. 2.76. ,alpha,-Terpinene. 2.4151. 7. 6.55. 0.92. Benzene, 1,3,5-trimethyl-. 30.8109. 8. 6.92. 64.78. Acetic acid. 12.4938. 9. 7.47. 0.41. 1,3-Cyclohexadiene, 1,2,6,6-tetrame. 0.35877. 10. 8.06. 0.36. Benzene, 1,2,3-trimethyl-. 0.31502. 11. 10.01. 0.66. Benzene, 1,2,3,5-tetramethyl-. 0.5775. 12. 10.11. 1.94. Benzene, 1,2,3,4-tetramethyl-. 1.6976. 13. 10.25. 5.32. 2-Cyclohexen-1-one, 3,5,5-trimethyl. 4.6553. 14. 12.61. 0.56. Benzene, 4-(2-butenyl)-1,2-dimethyl. 0.4900 100. T=573 K, P=14 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 2. 0.95. 28.76. 2-Propanone. 36.16619. 3. 1.47. 26.86. Acetic acid. 5.590179.

(79) 68. 4. 1.92. 8.21. 2-Pentanol. 10.32106. 13. 9.79. 4.93. 1,2-Heptanediol. 6.203966. 12. 7.99. 2.98. 2-Octanol. 3.74882. 8. 2.86. 2.69. 2-Hexanol. 3.380548. 18. 12.94. 2.66. 1,2-Heptanediol. 3.342776. 11. 7.83. 2.27. 3-Octanol. 2.86119. 16. 11.45. 2.17. 5-Decanol. 2.72899. 7. 2.75. 2.12. 2-Butanol. 2.66289. 15. 9.99. 2.05. 2-Nonanol. 2.587347. 10. 7.64. 1.47. 4-Octanol. 1.84136. 9. 4.81. 1.36. 4-Heptanol. 1.699717. 14. 9.88. 0.62. 3-Nonanol. 0.774315. 19. 14.27. 0.5. 6-Dodecanol. 0.623229. 5. 2.09. 0.49. Benzene, methyl-. 0.613787. 17. 11.54. 0.42. 3-Heptanol. 0.528801. 6. 2.67. 0.35. 2-Butanol, 2-methyl-. 0.434372 100. T=623 K, P=14 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. 1 2 3 4. 0.84 1.15 1.35 2.52. 87.23 77.96 4.49 8.28. 2-Propanone Acetic Acid 2-Hexanol 2-Heptanol. Molar fraction 74.43941 14.66306 3.831629 7.065899 100. T=673 K, P=14 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1 2 3 4 5 6 7 8 9 10 11. 0.78 0.81 0.9 1.07 2.15 2.36 2.49 3.54 3.74 4.54 4.85. 2.31 0.33 61.6 17.25 12.27 0.19 0.27 0.23 0.24 0.2 0.49. Carbon dioxide 2-Propanone Acetic acid 2-Butanol 2-Pentanol Octane 2-Hexanol Benzene, ethylUndecane, 5,6-dimethylNonane 4-Heptanol. 2.0335 27.2015 11.9517 15.1853 10.8014 0.1673 6.6903 0.2025 0.2113 0.1761 2.8962.

(80) 69. 12 13 14 15 16 17 18. 5.23 5.74 7.74 9.35 9.81 11.43 12.91. 0.42 14.61 1.49 0.33 3.29 0.56 0.41. 2-Propanol, 1-ethoxy2-Heptanol 4-Octanol 4-Nonanone 4-Nonanol 5-Decanol 2,3-Octanediol. 0.3697 12.8613 4.6744 0.2905 3.4332 0.4930 0.3609 100. T=723 K, P=14 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.77. 13.21. Carbon dioxide. 12.06486. 2. 0.84. 29.35. 2-Propanone. 26.80573. 3. 1.03. 19.76. 2-Pentanol. 18.04706. 4. 1.13. 7.99. 5-Hexen-2-one. 7.297368. 5. 1.34. 13.46. 2-Pentene, 4,4-dimethyl-, (E)-. 12.29319. 6. 2.31. 2.2. 3-Hexanol, 2-methyl-. 2.009288. 7. 2.64. 10.36. 2-Heptanol. 9.461919. 8. 4.36. 43.11. Acetic acid. 8.677871. 9. 6.17. 1.09. 3-Octanol. 1.844891. 10. 8.94. 1.64. 1,2-Heptanediol. 1.497833 100. T=623 K, P=14 atm, F=0.8 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.83. 10.7. Carbon dioxide. 8.980643. 2. 0.9. 85.92. 2-Propanone. 72.11372. 3. 3.09. 0.57. 3-Hexen-2-one. 0.478408. 4. 3.92. 0.24. 2-Pentanone, 4-hydroxy-4-methyl-. 0.201435. 5. 4.27. 86.91. Acetic acid. 16.07715. 6. 5.51. 0.47. 2-Heptanol. 0.394477. 7. 6.73. 1.48. Benzene, 1,2,3-trimethyl-. 1.242182. 8. 10.23. 0.61. 2-Cyclohexen-1-one, 3,5,5-trimethyl. 0.511981 100. T=673 K, P=14 atm, F=0.8 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.81. 16.77. 2-Propanone. 66.4391.

(81) 70. 2. 0.86. 81.34. Acetic acid. 15.2021. 3. 2.23. 9.35. 3-Hexen-2-one. 7.9286. 4. 2.62. 1.02. 3-Penten-2-one, 4-methyl-. 0.8649. 5. 3.38. 1.42. 2-Pentanone, 4-hydroxy-4-methyl-. 1.2041. 6. 4.3. 0.89. 1,3-Cyclohexadiene, 1,2,6,6-tetrame. 0.7547. 7. 5.09. 0.45. 1,4-Cyclohexadiene, 3,3,6,6-tetrame. 0.3816. 8. 5.46. 1.72. cis-3a-Methyl-2,3,4a,6,7,7a-hexahyd. 1.4585. 9. 6.4. 5.04. Benzene, 1,2,3-trimethyl-. 4.2738. 10. 10.16. 1.76. 2-Cyclohexen-1-one, 3,5,5-trimethyl. 1.4924 100. T=723 K, P=14 atm, F=0.8 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.86. 5.06. 2-Propanone. 9.0159. 2. 0.97. 8.57. 2-Propanol. 8.1590. 3. 1.14. 19.53. 2-Butanol. 18.5934. 4. 1.62. 4.4. 2-Butanol, 3-methyl-. 4.1890. 5. 2.47. 0.75. 3-Penten-2-one, 4-methyl-. 0.7140. 6. 2.55. 1.34. 3-Hexanol. 4.5317. 7. 2.7. 22.9. Acetic acid. 4.8052. 8. 3.52. 0.17. Benzene, ethyl-. 0.1618. 9. 3.7. 0.42. 2-Pentanone, 4-hydroxy-4-methyl-. 0.3999. 10. 5.52. 26.05. 2-Heptanol. 24.8007. 11. 7.72. 1.74. 4-Octanol. 8.9302. 12. 7.94. 1.52. 3-Heptanol, 5-methyl-. 1.4471. 13. 9.29. 0.3. Cyclopentanol, 1-methyl-. 0.2856. 14. 9.89. 9.58. 4-Nonanol. 12.5670. 15. 11.45. 1.29. 6-Dodecanol. 1.2281. 16. 11.54. 0.18. 3-Decanol. 0.1714 100. T=573 K, P=14 atm, F=1.0 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.88. 98.54. 2-Propanone. 86.4600. 2. 1.36. 87.04. Acetic acid. 12.2589. 3. 2.09. 0.75. 3-Hexen-2-one. 0.6580. 4. 9.88. 0.71. n-Octyl acetate. 0.6229 100.

(82) 71. T=623 K, P=14 atm, F=1.0 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.89. 98.66. 2-Propanone. 82.92078. 2. 1.99. 86.12. Acetic acid. 15.9530. 3. 2.31. 1.34. 3-Hexen-2-one. 1.12623 100. T=673 K, P=14 atm, F=1.0 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.8. 19.21. Carbon dioxide. 16.3557. 2. 0.85. 80.79. 2-Propanone. 68.78588. 3. 1.23. 79.18. Acetic acid. 14.85843 100. T=723 K, P=14 atm, F=1.0 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0.9. 88.72. 2-Propanone. 75.06711. 2. 1.68. 82.52. Acetic acid. 15.38874. 3. 2.13. 10.06. 3-Hexen-2-one. 8.511893. 4. 3.2. 1.22. 2-Pentanone, 4-hydroxy-4-methyl-. 1.032257 100. T=573 K, P=100 atm, F=0.2 ml/min Pk#. RT. Area%. Library/ID. Molar Fraction. 1. 0,82. 81,11. 2,Propanone. 67,4842. 2. 1,21. 18,89. 2-Hexanol. 16,7991. 3. 1,64. 91,61. Acetic acid. 15,7166 100. T=673 K, P=100 atm, F=0.2 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0,89. 67,2. 2-Propanone. 57,31624. 2. 1,85. 13,74. 3-Hexen-2-one. 11,71912.

(83) 72. 3. 2,6. 1,33. 2-Pentanone, 4-hydroxy-4-methyl-. 1,134384. 4. 6,14. 17,73. Benzene, 1,2,4-trimethyl-. 15,12228. 78,24. Acetic acid. 14,70798 100. T=723 K, P=100 atm, F=0.2 ml/min Molar Fraction. Pk#. RT. Area%. Library/ID. 1. 0,81. 12,12. Carbon dioxide. 2. 0,86. 32,88. 2-Propanone. 26,343. 3. 1,5. 2,19. 2-Pentanone, 4-methyl-. 1,755. 4. 1,57. 2,15. 5-Hexen-2-one. 11,081. 5. 1,83. 0,29. 2-Hexanone, 5-methyl-. 9,358. 6. 2,07. 11,68. Acetic acid. 10,763. 7. 2,97. 0,73. 2-Pentanone, 4-hydroxy-4-methyl-. 0,585. 8. 3,16. 0,64. Benzene, 1,3-dimethyl-. 0,513. 9. 4,28. 0,66. 1,3-Cyclohexadiene, 1,5,5,6-tetrame. 0,529. 10. 5,43. 0,69. Isoterpinolene. 0,553. 11. 6,48. 22,22. Benzene, 1,2,4-trimethyl-. 18,259. 12. 8,25. 0,42. Cyclohexanone, 3,3,5-trimethyl-. 0,337. 13. 9,88. 0,65. Phenol, 3-methyl-. 0,521. 14. 9,97. 0,89. Benzene, 1,2,3,5-tetramethyl-. 0,713. 15. 10,05. 2,13. 2-Cyclohexen-1-one, 3,5,5-trimethyl. 1,707. 16. 10,12. 3,1. Furan, 3-pentyl-. 2,484. 17. 11,24. 5,63. Phenol, 2,5-dimethyl-. 4,511. 18. 12,56. 0,35. Benzene, 1-(2-butenyl)-2,3-dimethyl. 0,280. 9,710. 100 T=573 K, P=100 atm, F=0.4 ml/min Pk#. RT. Area%. Library/ID. Molar Fraction. 1. 0,83. 3,19. Carbon dioxide. 2,673. 2. 0,94. 96,81. 2-Propanone. 81,112. 3. 1,2. 87,81. Acetic acid. 16,215 100. T=623 K, P=100 atm, F=0.4 ml/min.

(84) 73. Pk#. RT. Area%. Library/ID. Molar Fraction. 1. 0,85. 98,67. 2-Propanone. 85,074. 2. 5,25. 1,33. Benzene, 1,3,5-trimethyl-. 1,147. 3. 7,31. 72,51. Acetic acid. 13,779 100. T=673 K, P=100 atm, F=0.4 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0,8. 18,33. Carbon dioxide. 15,911. 2. 0,86. 71,85. 2-Propanone. 62,369. 3. 1,44. 7,44. 3-Hexen-2-one. 6,458. 4. 5,16. 2,39. Benzene, 1,2,3-trimethyl-. 2,075. 5. 6,45. 68,93. Acetic acid. 13,188 100,000. T=723 K, P=100 atm, F=0.4 ml/min Pk#. RT. Area% Library/ID. Molar Fraction. 1. 0,86. 16,78. 1-Propene, 2-methyl-. 15,185. 2. 0,92. 27,82. 2-Propanone. 25,176. 3. 1,12. 1,16. 2-Butanol. 1,050. 4. 1,93. 1,92. 5-Hexen-2-one. 1,738. 5. 2,53. 9,47. tert-Butylketene. 8,570. 6. 2,6. 0,88. 2-Hexanol. 0,796. 7. 3,62. 0,29. 2-Pentanone, 4-hydroxy-4-methyl-. 0,262. 8. 4,53. 0,91. 3-Hexanol, 2-methyl-. 0,824. 9. 4,93. 2,25. 2,6,6-Trimethyl-3-methylenecyclohex. 2,036. 10. 5,12. 4,34. 2-Heptanol. 3,928. 11. 5,68. 0,31. 1,4-Cyclohexadiene, 3,3,6,6-tetrame. 0,281. 12. 5,97. 1,01. cis-3a-Methyl-2,3,4a,6,7,7a-hexahyd. 0,914. 13. 6,9. 15,88. Benzene, 1,3,5-trimethyl-. 14,371. 14. 7,53. 1,38. 4-Octanol. 6,127. 15. 8,5. 0,21. Cyclohexanone, 3,3,5-trimethyl-. 0,190. 16. 9,25. 0,22. 4-Octanone, 7-methyl-. 0,199. 17. 9,69. 2,85. 4-Nonanol. 2,833. 18. 10,09 0,3. Benzene, 1,2,3,5-tetramethyl-. 0,271. 19. 10,25 3,85. 2-Cyclohexen-1-one, 3,5,5-trimethyl. 3,484.

(85) 74. 20. 11,33 1,83. Phenol, 3,5-dimethyl-. 1,656. 21. 12,6. Benzene, 1,2,4-trimethyl-5-(1-methy. 0,317. 22. 16,53 0,35. 1,2-DIHYDRO-4-ETHYL-5-METHYLPYRROLO. 0,317. 23. 18,34 47,51. Acetic acid. 9,476. 0,35. 100 T=623 K, P=100 atm, F=0.6 ml/min Pk# RT. Area%. Library/ID. Molar fraction. 1. 0,84. 35,87. Propanone. 30,167. 2. 0,89. 64,13. 2-Propanone. 53,933. 3. 1,12. 85,78. Acetic acid. 15,900 100. T=673 K, P=100 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0,84. 93,73. 2-Propanone. 79,986. 2. 1,74. 0,52. 3-Penten-2-one, 4-methyl-. 0,444. 3. 1,82. 1,62. 3-Hexen-2-one. 1,382. 4. 3,42. 0,54. 4-Heptanol. 0,461. 5. 3,75. 2,31. 2-Heptanol. 1,971. 6. 5,86. 0,48. Benzene, 1,2,4-trimethyl-. 0,410. 7. 7,04. 0,36. 3-Octanol. 0,307. 8. 9,35. 0,44. 4-Octanol, 7-methyl-. 0,375. 9. 10,91. 77,96. Acetic acid. 14,663 100,000. T=723 K, P=100 atm, F=0.6 ml/min Pk#. RT. Area%. Library/ID. Molar fraction. 1. 0,81. 20,88. Carbon dioxide. 18,898. 2. 0,89. 39,25. 2-Propanone. 35,525. 3. 1,88. 9,92. 3-Hexen-2-one. 8,979. 4. 2,03. 1,02. 3-Hexen-2-one. 0,923. 5. 2,69. 0,55. 2-Pentanone, 4-hydroxy-4-methyl-. 0,498. 6. 3,97. 2,98. 2-Hexanol. 2,697. 7. 4,11. 2,09. 2-Heptanol. 1,892. 8. 5,12. 0,63. ,alpha,-Terpinene. 0,570.