KINETIC MODEL TO CATALYTIC KETONIZATION OF CARBOXYLIC

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

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

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.

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.

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

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.

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

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

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

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


different temperature values and a total pressure of 100 psi

37



39



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

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

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.

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.

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 523-

723 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.

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.

5

Figure 3. Diagram of MixAlco Process

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.

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.

Figure 4. Schematic diagram of a process for converting biomass to liquid secondary

alcohol fuel (Holtzapple, 1999).

Ketones

Calcium carbonate

Mixed alcohols

Biomass

Hydrogen

gas

VFAs Pretreatment Fermentation

Amine

Dewatering Recovery

Hydrogenation

Lime

Kiln

Undigested

residue

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-molecular-

weight 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.

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

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).

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

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.

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

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

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%.

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:

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.

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.

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.

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.

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.

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.

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.

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:

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

http://en.wikipedia.org/wiki/Numerical_analysis

http://en.wikipedia.org/wiki/Iteration

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.

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.

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.

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

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.

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.

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.

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:

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

Temperature

Pressure

Initial Flow

34

5. RESULTS AND ANALYSIS

5.1 Conversion

Table 1. Initial dates

Mass of catalyst W (kg) 0,005

Variation fractions of the volume Ea 0,500

Initial concentration of Acid CA,0 0,729

Table 2. Conversion results at pressure 14.696 psi

Temperature

(°C)

Initial Flow

(mL/min) CA,sal

W/FAO

(Kg cat h/

mL)

CAsal/Ca Xa

300 0.2 0.106 0.0250 0.146 0.829

0.4 0.075 0.0125 0.103 0.840

0.6 0.125 0.0083 0.171 0.847

0.8 0.125 0.0063 0.171 0.853

1 0.123 0.0050 0.168 0.894

350 0.2 0.075 0.0250 0.103 0.839

0.4 0.153 0.0125 0.210 0.848

0.6 0.147 0.0083 0.201 0.851

0.8 0.161 0.0063 0.221 0.875

1 0.160 0.0050 0.219 0.900

400 0.2 0.125 0.0250 0.171 0.846

0.4 0.161 0.0125 0.220 0.855

0.6 0.120 0.0083 0.164 0.875

0.8 0.152 0.0063 0.209 0.913

1 0.149 0.0050 0.204 0.934

450 0.2 0.125 0.0250 0.171 0.865

0.4 0.125 0.0125 0.171 0.877

0.6 0.087 0.0083 0.119 0.900

0.8 0.048 0.0063 0.066 0.925

1 0.154 0.0050 0.211 0.952

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:

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.

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

0,80

0,82

0,84

0,86

0,88

0,90

0,92

0,94

0,96

0,98

1,00

0,0050 0,0150 0,0250

Co

nve

rsio

n (

Xa)

Space time (W/FAO )

T=300 °C

T=350°C

T=400 °C

T=450 °C

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)

Initial flow

(mL/min) CA,sal

W/FAO

(Kg cat h/

mL)

CAsal/Ca Xa

300 0.2 0.832 0.0250 0.146 0.832

0.4 0.838 0.0125 0.103 0.838

0.6 0.845 0.0083 0.171 0.845

0.8 0.860 0.0063 0.171 0.860

1 0.916 0.0050 0.168 0.916

350 0.2 0.827 0.0250 0.103 0.827

0.4 0.830 0.0125 0.210 0.830

0.6 0.841 0.0083 0.201 0.841

0.8 0.843 0.0063 0.221 0.843

1 0.862 0.0050 0.219 0.862

400 0.2 0.847 0.0250 0.171 0.847

0.4 0.853 0.0125 0.220 0.853

0.6 0.853 0.0083 0.164 0.853

0.8 0.854 0.0063 0.209 0.854

1 0.868 0.0050 0.204 0.868

450 0.2 0.880 0.0250 0.171 0.879

0.4 0.883 0.0125 0.171 0.883

0.6 0.892 0.0083 0.119 0.892

0.8 0.905 0.0063 0.066 0.905

1 0.905 0.0050 0.211 0.905

38



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

0,80

0,82

0,84

0,86

0,88

0,90

0,92

0,94

0,96

0,98

1,00

0,005 0,01 0,015 0,02 0,025

Co

nve

rsio

n (

Xa)

Space time (W/FAO)

T=300 °C

T=350°C

T=400 °C

T=450 °C

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.

40

Table 4. Conversion results at pressure 200 psi

Temperature

(°C)

IInitial flow

(mL/min) CA,sal

W/FAO

(Kg cat h/

mL)

CAsal/Ca Xa

300 0.2 0.830 0.0250 0.146 0.829

0.4 0.834 0.0125 0.103 0.834

0.6 0.841 0.0083 0.171 0.841

0.8 0.844 0.0063 0.172 0.844

1 0.863 0.0050 0.168 0.863

350 0.2 0.839 0.0250 0.103 0.839

0.4 0.845 0.0125 0.210 0.845

0.6 0.849 0.0083 0.201 0.849

0.8 0.855 0.0063 0.220 0.856

1 0.864 0.0050 0.219 0.864

400 0.2 0.841 0.0250 0.171 0.841

0.4 0.843 0.0125 0.220 0.843

0.6 0.852 0.0083 0.164 0.852

0.8 0.853 0.0063 0.208 0.853

1 0.858 0.0050 0.204 0.858

450 0.2 0.859 0.0250 0.171 0.859

0.4 0.866 0.0125 0.172 0.866

0.6 0.872 0.0083 0.119 0.872

0.8 0.880 0.0063 0.066 0.879

1 0.903 0.0050 0.211 0.902

41



0,80

0,82

0,84

0,86

0,88

0,90

0,92

0,94

0,96

0,98

1,00

0,005 0,01 0,015 0,02 0,025

Co

nve

rsio

n (

Xa)

Space time (W/FAO)

T=300 °C

T=350°C

T=400 °C

T=450 °C

42



0,80

0,82

0,84

0,86

0,88

0,90

0,92

0,94

0,96

0,98

1,00

0,005 0,01 0,015 0,02 0,025

Co

nve

rsio

n (

Xa)

Space time (W/FAO)

T=300 °C

T=350°C

T=400 °C

T=450 °C

43

Table 5 Conversion results at pressure 300 psi

Temperature

(°C)

I Initial Flow

(mL/min) CA,sal

W/FAO

(Kg cat h/

mL)

CAsal/Ca Xa

300 0.2 0.844 0.0250 0.148 0.844

0.4 0.847 0.0125 0.103 0.847

0.6 0.858 0.0083 0.171 0.857

0.8 0.861 0.0063 0.171 0.860

1 0.861 0.0050 0.168 0.861

350 0.2 0.826 0.0250 0.103 0.826

0.4 0.838 0.0125 0.210 0.838

0.6 0.842 0.0083 0.201 0.842

0.8 0.845 0.0063 0.220 0.845

1 0.850 0.0050 0.219 0.850

400 0.2 0.845 0.0250 0.171 0.845

0.4 0.851 0.0125 0.220 0.851

0.6 0.855 0.0083 0.164 0.855

0.8 0.860 0.0063 0.208 0.860

1 0.880 0.0050 0.204 0.879

450 0.2 0.862 0.0250 0.171 0.862

0.4 0.867 0.0125 0.172 0.867

0.6 0.879 0.0083 0.119 0.879

0.8 0.880 0.0063 0.066 0.879

1 0.881 0.0050 0.211 0.881

5.2 Selectivity

The selectivity can be written as follows:

Where:

ND = moles of desired product

U = moles of undesired product

44

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

0,4

0,5

0,6

0,7

0,8

0,9

1

300 350 400 450

Sele

ctiv

ity

(%)

Temperature (°C)

14 atm

100 atm

200 atm

300 atm

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.

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.

0,4

0,5

0,6

0,7

0,8

0,9

1,0

300 350 400 450

Sele

ctiv

ity

(%)

Temperature (°C)

14 atm

200 atm

300 atm

100 atm

46

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.

160

165

170

175

180

185

190

195

14 114 214

Init

ial

rate

Pressure total (psi)

T=300°C

T=350°C

T=400°C

T=450°C

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.

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)

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).

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

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

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

Component ∆Si

Acetic Acid C2H4O2 -0.232048

Acetone C3H6O -0.251870

Carbon Dioxide CO2 0.002009

Water H2O 0.376249

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.

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.

y = -3822,x + 10,42

R² = 0,982

2

2,5

3

3,5

4

4,5

5

5,5

0,0013 0,0015 0,0017 0,0019

ln r

ate

( m

ol

min

-1k

g C

at-1

)

Temperature (K-1)

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

52

Figure 26. Comparison of experimental results with theoretical calculations obtained

from kinetic model.

0,82

0,84

0,86

0,88

0,9

0,92

0,94

0,96

0,98

1

1,02

0,0063 0,0113 0,0163 0,0213

Co

nve

rsio

n (

Xa)

Space time (W/FAO )

Therorical convertion

Experimental convertion

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.

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.

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.71-

78.

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.

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 acid-

treated 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.

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.

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.

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.

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)

61

APPENDIX B

Calculations

Adsorption

Surface reaction

Desorption

Where

62

When the adsorption is the controlling stage:

63

When the surface reaction is the controlling stage:

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

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


22 15.4 0.52 7-Tridecanone 0.63813

100

T=673 K, P=14 atm, F=0.2 ml/min


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

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


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 1.83 Octanoic acid 1.602107


22 14.07 0.2 6-Dodecanone 0.175094

23 15.33 0.13 7-Tridecanone 0.113811

100

T=723 K, P=14 atm, F=0.2 ml/min


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

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


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 1.83 Octanoic acid 1.602107


22 14.07 0.2 6-Dodecanone 0.175094

23 15.33 0.13 7-Tridecanone 0.113811

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


fraction

1 0.85 70.79 2-Propanone 59.94825

67

2 1.8 4.14 2-Hexanol 3.505944

3 3.73 8.73 2-Heptanol 7.392969

4 4.25 82.01 Acetic acid 15.3069


6 9.37 2.1 4-Nonanol 1.778377

7 9.8 1.82 Benzene, 1,2,3,4-tetramethyl- 1.54126

8 10.55 6.05 Hexanoic acid 5.12342

100

T=673 K, P=14 atm, F=0.4 ml/min


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


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


6 5.96 2.76 ,alpha,-Terpinene 2.4151


8 6.92 64.78 Acetic acid 12.4938





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


fraction

2 0.95 28.76 2-Propanone 36.16619

3 1.47 26.86 Acetic acid 5.590179

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


fraction

1 0.84 87.23 2-Propanone 74.43941

2 1.15 77.96 Acetic Acid 14.66306

3 1.35 4.49 2-Hexanol 3.831629

4 2.52 8.28 2-Heptanol 7.065899

100

T=673 K, P=14 atm, F=0.6 ml/min


fraction

1 0.78 2.31 Carbon dioxide 2.0335

2 0.81 0.33 2-Propanone 27.2015

3 0.9 61.6 Acetic acid 11.9517

4 1.07 17.25 2-Butanol 15.1853

5 2.15 12.27 2-Pentanol 10.8014

6 2.36 0.19 Octane 0.1673

7 2.49 0.27 2-Hexanol 6.6903

8 3.54 0.23 Benzene, ethyl- 0.2025

9 3.74 0.24 Undecane, 5,6-dimethyl- 0.2113

10 4.54 0.2 Nonane 0.1761

11 4.85 0.49 4-Heptanol 2.8962

69

12 5.23 0.42 2-Propanol, 1-ethoxy- 0.3697

13 5.74 14.61 2-Heptanol 12.8613

14 7.74 1.49 4-Octanol 4.6744

15 9.35 0.33 4-Nonanone 0.2905

16 9.81 3.29 4-Nonanol 3.4332

17 11.43 0.56 5-Decanol 0.4930

18 12.91 0.41 2,3-Octanediol 0.3609

100

T=723 K, P=14 atm, F=0.6 ml/min


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


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



100

T=673 K, P=14 atm, F=0.8 ml/min


fraction

1 0.81 16.77 2-Propanone 66.4391

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




8 5.46 1.72 cis-3a-Methyl-2,3,4a,6,7,7a-hexahyd 1.4585



100

T=723 K, P=14 atm, F=0.8 ml/min


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


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


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

71

T=623 K, P=14 atm, F=1.0 ml/min


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


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


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


100

T=573 K, P=100 atm, F=0.2 ml/min


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


fraction

1 0,89 67,2 2-Propanone 57,31624

2 1,85 13,74 3-Hexen-2-one 11,71912

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


Fraction

1 0,81 12,12 Carbon dioxide 9,710

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


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


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

100

T=573 K, P=100 atm, F=0.4 ml/min


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

73


Fraction

1 0,85 98,67 2-Propanone 85,074


3 7,31 72,51 Acetic acid 13,779

100

T=673 K, P=100 atm, F=0.4 ml/min


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


5 6,45 68,93 Acetic acid 13,188

100,000

T=723 K, P=100 atm, F=0.4 ml/min


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


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


12 5,97 1,01 cis-3a-Methyl-2,3,4a,6,7,7a-hexahyd 0,914


14 7,53 1,38 4-Octanol 6,127


16 9,25 0,22 4-Octanone, 7-methyl- 0,199

17 9,69 2,85 4-Nonanol 2,833



74

20 11,33 1,83 Phenol, 3,5-dimethyl- 1,656

21 12,6 0,35 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

100

T=623 K, P=100 atm, F=0.6 ml/min


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


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


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


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


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

75


10 7,02 0,46 4-Octanol 0,416

11 7,08 0,45 4-Octanol 0,407

12 7,19 0,7 3-Octanol 0,634

13 7,26 0,82 3-Octanol 0,742

14 7,34 0,58 2-Octanol 0,525

15 7,41 1,25 2-Octanol 1,131

16 9,45 1,72 4-Nonanol 1,557



19 11,24 1,66 Phenol, 3,5-dimethyl- 1,502

20 13,34 47,53 Acetic acid 9,482

100

T=573 K, P=100 atm, F=0.8 ml/min


fraction

1 0,84 37,58 2-Propanone 31,773

2 0,87 60,76 2-Propanone 51,371


4 8,29 82,92 Acetic acid 15,452

100

T=673 K, P=100 atm, F=0.8 ml/min


fraction


2 0,86 1,59 1-Propene, 2-methyl- 1,357

3 0,94 66,05 2-Propanone 56,386

4 2,05 5,1 2-Pentanol 4,354

5 2,85 1,26 3-Hexanol 1,076

6 2,93 1,59 2-Pentanol, 4-methyl- 1,357

7 4,91 1,7 4-Heptanol 1,451

8 5,14 0,97 2-Heptanol 0,828

9 5,38 8,31 2-Heptanol 7,094

10 7,63 1,05 4-Octanol 0,896

11 7,79 1,68 3-Octanol 1,434

12 7,92 1,45 2-Octanol 1,238

13 9,72 3,17 2,3-Octanediol 2,706

14 9,9 0,64 2-Nonanol 0,546

76

15 12,76 77,72 Acetic acid 14,623

100

T=723 K, P=100 atm, F=0.8 ml/min


fraction

1 0,82 27,4 2-Propanone 24,101

2 0,85 51,85 2-Propanone 45,608

3 1,29 7,23 3-Hexen-2-one 6,360

4 2,34 1,28 2-Heptanol 1,126



7 10,9 0,79 Phenol, 2,4-dimethyl- 0,695

8 13,45 62,1 Acetic acid 12,039

100

T=573 K, P=100 atm, F=1.0 ml/min


fraction

1 0,79 24,06 2-Propanone 56,977

2 1,86 4,59 3-Hexen-2-one 4,205



5 5,09 0,31 ,alpha,-Terpinene 0,284


7 6,46 0,27 1-Heptanol 0,247


9 9,68 0,38 Phenol, 3-methyl- 0,348

10 9,78 0,53 Phenol, 4-methyl- 0,485



13 11,18 7,03 Phenol, 2,5-dimethyl- 6,440

14 14,23 41,55 Acetic acids 8,389

100

T=623 K, P=100 atm, F=1.0 ml/min


fraction

1 0,81 15,12 Carbon dioxide 12,512

2 0,83 3,21 2-Propanone 2,656

77

T=673 K, P=100 atm, F=1.0 ml/min


fraction

1 0,77 1,22 Ammonia 1,033

2 0,82 35 Carbon dioxide 29,647

3 0,87 54,85 2-Propanone 46,461


5 3,35 81,92 Acetic acid 15,294




100

T=723 K, P=100 atm, F=1.0 ml/min


fraction

1 0,79 16,48 Carbon dioxide 14,547

2 0,85 67,46 2-Propanone 59,547

3 1,29 14,27 3-Hexen-2-one 12,596


5 6,86 60,34 Acetic acid 11,739

100

T=573 K, P=200 atm, F=0.2 ml/min


fraction

1 0,79 1,65 2-Propanone 1,377

2 0,93 98,35 2-Propanone 82,070

3 1,24 90 Acetic acid 16,553

100

T=623 K, P=200 atm, F=0.2 ml/min


fraction

1 0.97 100 2-Propanone 83,892

3 0,91 79,6 2-Propanone 65,868


5 8,34 94,59 Acetic acid 17,251

100

78

2 1,35 87,12 Acetic acid 16,108

100

T=673 K, P=200 atm, F=0.2 ml/min

Pk# RT Area% Library/ID Molar fraction

1 0,92 86,15 2-Propanone 72,591

2 2,55 4,29 3-Hexen-2-one 4,963

3 2,96 84,75 Acetic acid 15,739



100

T=723 K, P=200 atm, F=0.2 ml/min


fraction

1 0,88 23,65 2-Propanone 21,351

2 0,91 22,4 No matches found 20,223

3 1,1 0,38 2-Butanone 0,343

4 2,54 9,16 3-Hexen-2-one 8,270





9 5,97 1,73 Isoterpinolene 1,562

10 7 32,6 Benzene, 1,3,5-trimethyl- 29,432





15 11,27 0,87 Phenol, 2,5-dimethyl- 0,785

16 12,59 0,34 (Z)-2-(1'-PROPENYL)MESITYLENE 0,307

17 14,78 48,8 Acetic acid 9,710

100

T=573 K, P=200 atm, F=0.4 ml/min


fraction

1 0.94 100 2-Propanone 82,990865

2 1,45 92,99 Acetic acid 17,009135

79

T=623 K, P=200 atm, F=0.4 ml/min


fraction

1 0,79 21,43 Carbon dioxide 18,524

2 0,82 78,57 2-Propanone 67,915

3 1,67 71,18 Acetic acid 13,561

100

T=673 K, P=200 atm, F=0.4 ml/min


fraction

1 0.81 100 2-Propanone 85,1847

2 0,96 78,91 Acetic acid 14,8153

100

T=723 K, P=200 atm, F=0.4 ml/min


fraction


2 0,84 61,17 2-Propanone 53,012

3 1,59 13,89 3-Hexen-2-one 12,038



6 6,12 69,82 Acetic acid 13,336

100

T=573 K, P=200 atm, F=0.6 ml/min


fraction

1 0,88 57,55 Ammonia 48,590

2 0,94 42,45 2-Propanone 35,841

3 1,59 83,66 Acetic acid 15,568

100

T=623 K, P=200 atm, F=0.6 ml/min


fraction

1 0,8 24,88 Carbon dioxide 21,291

2 0,84 75,12 2-Propanone 64,283

3 1,45 76,49 Acetic acid 14,426

100

80

T=723 K, P=200 atm, F=0.6 ml/min


fraction

1 0,82 29,52 2-Propanone 75,190

2 0,96 66,39 Acetic acid 12,764

3 1,42 6,29 3-Hexen-2-one 5,487




100

T=573 K, P=200 atm, F=0.8 ml/min


fraction

1 0,86 27,15 Propanone 55,065

2 1,75 84,99 Acetic acid 15,864

3 2,03 5,98 2-Pentanol 5,030

4 2,84 1,9 3-Hexanol 1,598

5 2,91 1,93 2-Hexanol 1,624

6 4,87 1,9 4-Heptanol 1,598

7 5,07 0,89 Ethanol, 2-(2-methoxyethoxy)- 0,749

8 5,3 8,35 2-Heptanol 7,024

9 7,62 1,28 4-Octanol 1,077

10 7,77 2,03 3-Octanol 1,708

11 7,89 1,63 2-Octanol 1,371

12 9,73 5,35 4-Octanol, 7-methyl- 4,500

13 9,82 0,19 3-Nonanol 0,160

14 9,91 1,01 2-Nonanol 0,850

15 11,39 1,38 5-Decanol 1,161

16 12,9 0,74 1,2-Heptanediol 0,622

100

T=623 K, P=200 atm, F=0.8 ml/min


fraction

1 0.81 40 Carbon dioxide 33,9577

2 0.86 60 2-Propanone 50,9366

3 0,94 80,19 Acetic acid 15,1056

100

81

T=673 K, P=200 atm, F=0.8 ml/min


fraction

1 0,81 42,71 Carbon dioxide 35,907

2 0,86 57,29 2-Propanone 48,165

3 1,14 85,38 Acetic acid 15,928

100

T=723 K, P=200 atm, F=0.8 ml/min


fraction

1 0,8 34,5 2-Propanone 74,877

2 0,88 73,87 Acetic acid 14,083





100

T=573 K, P=200 atm, F=1.0 ml/min


fraction


2 0,85 5,53 Ammonia 29,107

3 2,24 8,73 2-Pentanol 7,536

4 2,41 0,15 Octane 0,129

5 2,94 1,19 2-Hexanol 5,870

6 4,57 0,11 Nonane 0,095

7 5,11 2,48 4-Heptanol 15,865

8 5,24 1,38 2-Propanol 1,191

9 6,65 0,12 4-Octanol 7,656


11 9,85 9,36 4-Octanol, 7-methyl- 8,079

12 9,93 0,61 3-Nonanol 2,184

13 10,03 71,43 Acetic acid 13,681

14 11,46 2,68 6-Dodecanol 2,313

15 11,56 0,48 3-Heptanol 0,414

16 12,94 3,07 1,2-Heptanediol 2,650

17 14,27 0,23 6-Dodecanol 0,199

100

82

T=623 K, P=200 atm, F=1.0 ml/min


fraction

1 0,84 34,87 Ammonia 29,479

2 0,89 65,13 2-Propanone 55,060

3 1,25 82,42 Acetic acid 15,461

100

T=673 K, P=200 atm, F=1.0 ml/min


Molar

fraction

1 0,8 30,08 Carbon dioxide 25,807

2 0,85 49,74 2-Propanone 42,674

3 1,95 1,7 3-Hexen-2-one 1,459


5 5,22 0,72 Alloocimene 0,618




9 11,15 3,67 Phenol, 2,5-dimethyl- 3,149

74,62 Acetic acid 14,205

100

T=723 K, P=200 atm, F=1.0 ml/min


fraction

1 0,8 29,73 Carbon dioxide 26,156

2 0,87 12,85 2-Propanone 11,305

3 1,46 1,7 5-Hexen-2-one 9,106



6 3,74 0,2 2,2-Dimethyl-1-isopropenyl-cyclopen 0,176


8 4,76 0,45 Tricyclo[3,1,0,0(2,4)]hexane, 3,3,6 0,396

9 5,16 1,52

2,2,3-TRIMETHYL-1-VINYL-3-

CYCLOPENT 1,337


11 8,59 0,22 Benzene, 1-methyl-4-(1-methylethyl) 0,194

83

12 9,73 0,18 Phenol, 4-methyl- 0,158

13 9,81 1 Benzene, 1,2,3,5-tetramethyl- 0,880



16 11,15 2,89 Phenol, 3,5-dimethyl- 2,543

17 11,51 0,18 Benzene, 1-(2-butenyl)-2,3-dimethyl 0,484

18 13,28 0,31 1-Butyl-2,3,6-trimethylbenzene 0,554

19 13,55 61,49 Acetic acid 12,004

20 16,5 0,21 3-o-Methoxyphenyl-pyridine 0,185

100

84

APPENDIX D

MATLAB®

code

clc;

clear all;

'MaxIter',100000000,...

'TolX',1e-4,... %default: 1e-4

'LevenbergMarquardt','on',... %default: on

'LargeScale','on',... %default: on

'MaxFunEvals',1E1000050,...;

global data

data=[

%Rexp %Pa %Pw %Pc %Temperature

0.829 12.182 0 0 573

%0.840 131.971 0 0

%0.847 880.94 0 0

%0.853 1093.887 0 0

0.840 12.343 0 0 573

0.847 12.446 0 0 573

0.853 12.534 0 0 573

0.894 13.137 0 0 573

%0.839 1202.36 0 0

%0.848 976.32 0 0

0.839 12.329 0 0 623

0.848 12.461 0 0 623

0.851 12.505 0 0 623

%0.875 167.12 0 0

0.875 12.858 0 0 623

0.900 13.225 0 0 623

%0.846 1103.11 0 0

0.846 12.431 0 0 673

0.855 12.564 0 0 673

%0.875 167.116 0 0

%0.913 177.293 0 0

0.875 12.858 0 0 673

0.913 13.416 0 0 673

0.934 13.725 240.347 14 673

%0.865 605.162 0 0

85

%0.877 1270.53 0 0

0.865 12.711 0 0 723

0.877 12.887 0 0 723

0.900 13.225 177.293 17 723

%0.925 162.133 49.061 0

%0.952 132.488 0 0

0.925 13.592 49.061 0 723

0.952 12.989 0 0 723

];

% experimental data

data1=[

%Rexp

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

];

Rexp=data(:,1);

Pa=data(:,2);

Pw=data(:,3);

Pc=data(:,4);

T=data(:,5);

86

b0=[

3822

10.4249

%0.972548763763648

1.047236081

%0.970198731337977

1.008638298

%1.00030715356418

1.067988632

%1.04628462455179

1.038752445

];

LB=[0,0,0,0,0,0];

UB=[Inf,Inf,Inf,Inf,Inf,Inf];

[b,resnorm]=lsqnonlin('recfun2',b0,LB,UB)

[b,r,J,SIGMA]=nlinfit(data,data1,'recfun',b0)

bci=nlparci(b,r,J)

newX = data(:,:);

[YPRED, DELTA] = NLPREDCI('recfun',newX,b,r,'jacobian',J)

%Rcal= (b(1).*(Pa.^2))./ (1+b(2).*Pa + b(3).*Pw + b(4).* Pc).^2;

%Rcal=(b(1).*((b(2).^2*Pa.^2)-

((Pa.*Pc.*Pw)./(b(3).*b(4).*b(5))))./(1+sqrt((Pa.*Pc.*Pw)./(b(3).*b(4).*b(5))+(Pc./b(4)

)+(Pw./b(5))).^2));

Rcal=(b(1).*exp(b(2)/(T.*0.082))*((b(3).^2*Pa.^2)-

((Pa.*Pc.*Pw)./(b(4).*b(5).*b(6))))./(1+sqrt((Pa.*Pc.*Pw)./(b(4).*b(5).*b(6))+(Pc./b(5)

)+(Pw./b(6))).^2))

Documents

KINETIC MODEL TO CATALYTIC KETONIZATION OF CARBOXYLIC