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CATALYTIC CONVERSION OF GLUCOSE, FRUCI‘OSE, AND SUCROSE TO
HIGH-VALUED CHEMICALS

By

Jennifer Elizabeth Jacobs

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Chemical Engineering

2000

ABSTRACT

CATALYTIC CONVERSION OF GLUCOSE, FRUCTOSE, AND SUCROSE TO
HIGH-VALUED CHEMICALS

By

Jennifer Elizabeth Jacobs

Many industrially important chemicals are currently produced using petroleum
and natural gas as feedstocks. These fossil fuel resources are finite and nonrenewable.
Development of new technology for the conversion of sugars to major industrial
chemicals namely glycerol, propylene glycol, and ethylene glycol may replace the current
petroleum or fermentation based processes. Selectivity-controlled hydrogenolysis is a
promising pathway for conversion of sugars to polyhydric alcohols with no carbon atom
loss. In this research with substrates glucose, fructose, and sucrose, I examine the
efficacy of nine different catalysts and two solvents in the sugar hydrogenolysis process.
Catalysts or catalyst combinations that favored the desired reaction pathway included 5%
ruthenium on carbon; nickel on kieselguhr; palladium 1% on carbon and boron oxide;
and nickel on alumina/silica and iron (III) oxide. Yields as high as 39%, 33%, and 12%
were attained for propylene glycol, glycerol, and ethylene glycol, respectively. Also, a
total selectivity of 63% for the products propylene glycol, glycerol, and ethylene glycol
was achieved under the studied reaction conditions. Barium promoted copper chromite
yielded 100% conversions for substrates glucose, fructose, and sucrose. The catalytic
conversion of glucose, fructose, and sucrose in this work has demonstrated that further
development of an efficient selectivity-controlled sugar hydrogenolysis process would

inevitably lead to an industrially, economically, and environmentally significant process.

ACKNOWLEDGEMENTS

I would like to thank Dr. Martin C. Hawley for his support and guidance
throughout this project. I would also like to thank the members of the faculty of the
Department of Chemical Engineering at Michigan State University for their help in
transforming a chemist into a chemical engineer. I would especially like to thank Julie
Caywood, Mary Lehnert, Jean Rooney, and Lynn Atzenhoffer, who answered all of my
questions. I am extremely grateful to Paul Loconto for his assistance with the high
pressure liquid chromatograph and gas chromatograph work. Also, I would like to thank
my two undergraduate students, Eric Schlegel and Ann Marie O’Donnell, who helped to
run many experiments.

This work was supported by the Crop and Food Bioprocessing Center, the
Consortium for Plant Biotechnology Research, the Amoco Foundation, Proctor and

Gamble, and the Department of Chemical Engineering at Michigan State University.

iii

TABLE OF CONTENTS

LIST OF TABLES .............................................................................................................. v
LIST OF FIGURES ............................................................................................................ vi
Chapter 1: General Introduction .................................................................................... l
1.1 Literature Survey on Sugar Hydrogenolysis ................................... 2
1.2 Mechanism and Selectivity Development ....................................... 6
1.3 Project Background ......................................................................... 9
1.4 Objectives and Scope of Current Research ................................... 10
Chapter 2: Experimental System and Methods ....... 11
2.1 Description of Apparatus ............................................................... 11
2.2 Experimental Procedure ................................................................ 14
2.3 Chemical Components .................................................................. 14
2.4 Sample Analysis ............................................................................ 15
Chapter 3: Results and Discussion .............................................................................. 19
3.1 Solvent Comparison: ..................................................................... 26
Final Conversion ............................................................... 26
Total Selectivity ................................................................. 26
Yield of Desired Product ................................................... 30
3.2 Analysis of Nine Catalysts and their Efficacy in Sugar

Hydrogenolysis .............................................................................. 33
Final Conversion ............................................................... 35
Total Selectivity ................................................................. 39
Yield of Desired Product ................................................... 39

3.3 Analysis of the Reaction Products formed During Catalytic
Hydrogenolysis of D-glucose, Fructose and Sucrose .................... 45
Chapter 4: Conclusions and Implications .................................................................... 49
Chapter 5: Future Work ............................................................................................... 51
APPENDIX ITEMS .......................................................................................................... 54
Appendix A: HPLC Calibration Curves ................................................................ 56
Appendix B: GC - glycols Calibration Curves ...................................................... 61
Appendix C: Error Estimation ............................................................................... 64
Appendix D: Detailed Experimental Data ............................................................. 69
Appendix E: Intermediate Calculations .............................................................. 106
BIBLIOGRAPHY ........................................................................................................... 109

iv

LIST OF TABLES

Table 1. Summary of Experiments with Substrate D-Glucose, Solvent Water, 210 °C, and
3.5 MPa ................................................................................................................ 21

Table 2. Summary of Experiments with Substrate D-Glucose, Solvent 1M Ethanol,
210 °C, and 3.5 MPa ............................................................................................ 22

Table 3. Summary of Experiments with Substrate D-Glucose, Solvent 1M Ethanol,
210 °C, and 3.5 MPa ............................................................................................ 23

Table 4. Summary of Experiments with Substrate D-Glucose, Solvent 1M Ethanol,
210 °C, and 3.5 MPa ............................................................................................ 24

Table 5. Summary of Results for Substrates Glucose, Fructose, and Sucrose, and Solvents
Water and 1M EtOH over the Nine Catalysts or Catalyst Combinations ............ 25

LIST OF FIGURES

Figure 1. Mechanism of Sugar and Sugar Alcohol Hydrogenolysis ................................... 4
Figure 2. Illustration of Hydrogenolysis Reactor .............................................................. 12
Figure 3. Schematic Illustration of Experimental System ................................................. 13

Figure 4. Conversion (%) versus reaction time (min) for substrate D-glucose, solvent
water, 210 °C, and 3.5 MPa hydrogen partial pressure .................................... 27

Figure 5. Conversion (%) versus reaction time (min) for substrate D-glucose, solvent 1M
EtOH, 210 °C, and 3.5 MPa hydrogen partial pressure .................................... 28

Figure 6. Total Selectivity for the desired products, propylene glycol, ethylene glycol,
and glycerol, for the nine different catalysts or catalyst combinations at 210 °C
reactor temperature, and 3.5 MPa hydrogen partial pressure ........................... 29

Figure 7. Yields (%) of propylene glycol, ethylene glycol, and glycerol for substrate D-
glucose, solvent water, 210 °C reactor temperature, and 3.5 MPa hydrogen
partial pressure for the nine different catalysts or catalyst combinations ......... 31

Figure 8. Yields (%) of propylene glycol, ethylene glycol, and glycerol for substrate D-
glucose, solvent 1M EtOH, 210 °C reactor temperature, and 3.5 MPa hydrogen
partial pressure for the nine different catalysts or catalyst combinations ......... 32

Figure 9. Conversion (%) versus reaction time (min) for substrate fructose, solvent 1M
EtOH, 210 °C, and 3.5 MPa hydrogen partial pressure .................................... 37

Figure 10. Conversion (%) versus reaction time (min) for substrate sucrose, solvent 1M
EtOH, 210 °C, and 3.5 MPa hydrogen partial pressure .................................. 38

Figure 11. Yields (%) of propylene glycol, ethylene glycol, and glycerol for substrate
fructose, solvent 1M EtOH, 210 °C reactor temperature, and 3.5 MPa
hydrogen partial pressure for the nine different catalysts or catalyst
combinations ................................................................................................... 41

Figure 12. Yields (%) of propylene glycol, ethylene glycol, and glycerol for substrate
sucrose, solvent lM EtOH, 210 °C reactor temperature, and 3.5 MPa
hydrogen partial pressure for the nine different catalysts or catalyst
combinations ................................................................................................... 42

Figure A-l. Calibration Curve for D-Glucose ................................................................... 56

vi

Figure A-2. Calibration Curve for Fructose ...................................................................... 57

Figure A-3. Calibration Curve for Sucrose ....................................................................... 58
Figure A-4. Calibration Curve for Glycerol ...................................................................... 59
. Figure 8-1. Calibration Curve for Propylene Glycol ........................................................ 61
Figure B-2. Calibration Curve for Ethylene Glycol .......................................................... 62

vii

CHAPTER 1

GENERAL INTRODUCTION

Many industrially important chemicals are currently produced using petroleum
and natural gas as feedstocks. These fossil fuel resources are finite and nonrenewable;
thus their depletion is an enduring concern. Due to the diminishing reserves of petroleum
and natural gas, the chemical process industry may eventually face feedstock problems.
Alternative sources and pathways will need to be developed in order to continue
production of our many synthetic chemicals, which are largely responsible for our current
standard of living. In this research, I explored the development of a biomass catalytic
conversion process, namely sugar hydrogenolysis, that will produce high-valued
chemicals such as glycerol, propylene glycol, and ethylene glycol, from renewable
biomass resources. The term “biomass” refers to organic matter, which can be converted
to energy. It is a complex material made up of three major organic fractions with
representative compositions on a dry-weight basis being as follows: 35-50% cellulose,
20-35% hemicellulose, and 12-20% lignin (Wyman, 1999). Some of the most common
organic materials include wood, agricultural residues, solid waste, animal waste, sewage,
corn, sugarcane, and crops grown specifically for energy (Wyman, 1999). Biomass is
made up mainly of the elements carbon and hydrogen, and technologies exist that can
free the energy from the chemical compounds which consist of these elements.

Currently, glycerol, ethylene glycol and propylene glycol are all produced from
petroleum-based processes. Sugar hydrogenolysis is potentially an economically viable

process to produce these chemicals from renewable biomass resources. The development

and application of this process is significant because there are both considerable
economic and environmental incentive. A selective sugar hydrogenolysis process will
address the petroleum depletion concern as well as potentially eliminate the
environmentally unfriendly chlorohydrin intermediates that result from the current
production methods. Another process to produce these hi gh-valued chemicals is
fermentation. However, fermentation causes loss of carbons from the starting material by
producing carbon dioxide. The hydrogenolysis of sugars to useful chemicals while
preserving all the carbon atoms in the starting material supercedes fermentation
processes.

Biomass is a copious material and it is estimated that the US. generates about 1
billion dry tons of it each year (Barrier and Bulls, 1992). The annual production of
biomass in the world is estimated to be as high as 10“ to 1012 dry tons (Grohman et al.,
1993). Development of a selective conversion process can enhance utilization of the
abundant biomass by converting the biomass into a variety of value-added chemicals.
Current glucose hydrogenation technology involves either a batch or continuous-slurry
process (Arena, 1992). One important result of biomass use is likely to be development
of a compatible set of products, such as organic acids, alcohols, and natural polymers,
where these products could integrate with one another in a similar way that the complex

infrastructure of fuels, solvents, plastics, etc have evolved (W yman, 1999).

1.1 Literature Survey on Sugar Hydrogenolysis
Sugar hydrogenolysis is a chemical process that selectively converts simple

sugars to glycerol, ethylene glycol, and propylene glycol, which have extensive uses and

large markets at the present time. Carbohydrates exhibit unusually rich chemical
functionality but limited stability (Andrews and Klaeren, 1989). Hydrogenolysis refers to
the cleavage of a molecule under conditions of catalytic hydrogenation. Under high
hydrogen pressure and high temperature, sugars and sugar alcohols can be catalytically
hydrocracked into lower polyhydric alcohols in the presence of transition metal catalysts
and enhanced by the addition of bases (Andrews and Klaeren, 1989). In the literature,
sugar hydrogenolysis is discussed indistinguishably from sugar alcohol hydrogenolysis,
because of the close relationship between these two reactions. In this process, both C-C
and C-0 bonds are susceptible to cleavage:
R3C-CR’3 + H; ——> R3CH + HCR’;
R3C-OH + H2 —> R3CH 4- H20

The reaction mechanism described in Figure 1 can explain all of the reaction products
found so far in the hydrogenolysis of sugars and sugar alcohols (Fumey, 1995). The
products which have been reported for the hydrogenolysis of glucose, fructose, and
sucrose, and sugar alcohols include glycerol, ethylene glycol, propylene glycol, 1,4-
butanediol, 2,3-butanediol, erythritol, threitol, xylitol, 3,4-dideoxygenated hexitol,
ethanol, methanol, and sometimes hydrocarbons and carboxylic acids, depending on the
process. Selectivity is the main shortcoming with sugar hydrogenolysis and of the
compounds listed above, glycerol, ethylene glycol, and propylene glycol are the most
industrially important. However, homogenous transition-metal catalysts offer the unique
combination of high selectivity and reactivity needed to effectively manipulate these

important substrates (Andrews and Klaeren, 1989).

O O OH
II II +H2 l
RCCHzOH + HCR’ —> RCHCH20H + HOCHzR’

retro-aldol I

OH OH O OH

I l -H2 II I
RCHCHCHR’ —> RCCHCHR’

OH OH
dehydration 1 -H20

0 OH
II +H2 |
RCC=CHR’ —-> RCHCHCHZR’

I |
OH OH

Figure l. Mechanism of Sugar and Sugar Alcohol Hydrogenolysis

Currently, glych is produced from the chlorination and subsequent hydrolysis
of propylene (Fumey, 1995). Several commercial processes exist to produce glycerol
from propylene and the predominant pathway includes the environmentally harmful
intermediates ally chloride, dichlorhydrin and epichlorohydrin. A small portion of
glycerol is also produced from fatty material as a by-product of soap production.
Glycerol is often used in food and personal hygiene industries and can be found in
liqueurs, inks, lubricants, alkyd resin, ester gums, polyethers, pharmaceuticals and
humectants. Additionally, glycerol is a valued intermediate in many industrial chemical
processes.

Ethylene glycol is a highly valuable chemical in industry and is currently
produced by the hydration of ethylene oxide (Fumey, 1995), a petroleum based process.
Ethylene glycol is used as an antifreeze, and used in hydraulic fluids, paints, deicers and
alkyd and polyester resins.

Propylene glycol is produced from propylene with propylene chlorohydrin and
propylene oxide as intermediates. Propylene glycol and ethylene glycol have similar uses
and applications, and propylene glycol is often used as a substitute for the more toxic
ethylene glycol. Propylene glycol is used as a biodegradable antifreeze. Additionally
propylene glycol is used in food additives, tobacco humectants. cosmetic softening
agents, lotions, and sunscreens.

Due to poor selectivity, sugar hydrogenolysis is currently not an industrially
important process. The process is uneconornical due to a wide distribution of products
from sugar molecules under hydrogenolysis conditions. A sugar molecule contains many

C-C and C-0 bonds that are susceptible to cleavage. Knowledge of the bond cleavage

mechanism governing sugar and sugar alcohol hydrogenolysis is important in order to
control the selectivity and greatly increase production of the most highly valued

compounds.

1.2 Mechanism and Selectivity Development

Sugar hydrogenolysis reactions have been studied since the 1930’s (Conner and
Adkins, 1932). However, research for the purpose of biomass conversion has only been
carried out since the 1950’s. Clark (1958) was the pioneer for this research at the US.
Forestry Products Laboratory. In this early report, Clark claimed to obtain glycerol from
sorbitol with yields as high as 40%. In his experiments sorbitol was reacted under the
hydrogenolysis conditions in the presence of a nickel on kieselguhr catalyst. Reactions
were carried out in the aqueous phase at temperatures between 215 and 240 C, and
hydrogen pressures between 2000 and 5600 psi. The identified products included
glycerol, propylene glycol, ethylene glycol, erythritol and xylitol.

Greater yields (75%) of distillable polyalcohols were attained by using beryllium
oxide activated c0pper chromite catalyst to hydrogenate sucrose (Boelhouwer et al.
1960). The reaction was performed in a rotating autoclave with methanol being used as
the solvent. Experiments were run between a temperature range of 195 and 250 C, and
the hydrogen pressure range was between 2204.4 and 2939.3 psi (150 and 200 atrn). The
reaction products were separated by distillation. In one experiment, the glycerol fraction
was reported to account for 61% of the product. However, since this fraction covers a
wide range of boiling points, exact products were not determined. Glycerol, propylene

glycol, and ethylene glycol were believed to be included in the products.

Since these early reports, the body of literature on sugar hydrogenolysis has been
steadily increasing. In the mid-to late-1970’s many biomass conversion projects
experienced an “explosion” in the amount of research being conducted. In the United
States the government initiated major programs to fund the development of new energy
sources in response to tightening petroleum supplies and high energy costs. The oil crisis
in the 1970’s may have stimulated this general interest in biomass conversion. As energy
prices dropped, interest and development of new energy sources declined, thus petroleum
remains the largest single source of energy in the United States, providing about 40% of
the total energy use (W yman, 1999). Various sugar alcohols including sorbitol, xylitol,
erythritol and even glycerol, were subjected to hydrogenolysis conditions (Montassier et
al. 1988). Montassier et al. (1988) proposed that the cleavage of C-0 bonds occurs
through dehydration of a B-hydroxyl carbonyl:

OH OH O OH O OH

| | -H2 II | -H20 ll +H2 |_
RCHCHCHR’ —>RCCHCHR’ —-> RCC=CI-IR’ —> RCHCHCHzR’

0's o'H o'a o'a

The structure of the B—hydroxyl carbonyl is already contained in an open-chain sugar
molecule, and may be generated from a sugar alcohol by dehydrogenation. In this
reaction scheme, the dehydration step is catalyzed by bases while the dehydrogenation
and hydrogenation steps are catalyzed by transition metal complexes.

The original mechanism proposed by Montassier et al. (1988) to explain the C-C

cleavage in sugar and sugar alcohol hydrogenolysis is the retro-aldol reaction:

OH OH O OH O . O O OH
I I -H2 II I II II II I
RCHCHCHR’ -) RCCHCHR’ —-) RCCHzOH -) RCCHZOH + HCR’ -) RCHCH20H + HOCHzR’
I | Retro-aldol
OH OH

The C-C cleavage precursor is again a B-hydroxyl carbonyl. Cleavage of this B-hydroxyl
carbonyl leads to an aldehyde and a ketone, which are subsequently hydrogenated to
alcohols. Andrews and Klaren (1989) suggested the same mechanism, based on their
observation that the primary C-C cleavage site is B to the carbonyl group in sugar
hydrogenolysis.

Montassier et al. (1988) proposed another mechanism, namely, the retro-Claisen
reaction for the C-C cleavage in glycerol hydrogenolysis. This mechanism was proposed
in order to explain the absence of methanol and the presence of carbon dioxide in the
hydrogenolysis products of glycerol and sugar alcohols. The formation of formaldehyde
and its subsequent hydrogenation to methanol can be predicted from the retro-aldol
reaction. The retro-Claisen mechanism allows for formation of formic acid rather than
formaldehyde, which decomposes under hydrogenolysis conditions to form C02. The
retro-Claisen was proposed to better explain the experimental hydrogenolysis products
obtained from sugar and sugar alcohols. Montassier et al. (1988) also proposed the retro-
Michael reaction, which requires a 8-dicarbonyl as the bond cleavage precursor, to
explain the C-C cleavage in the hydrogenolysis of xylitol and sorbitol.

The reaction mechanisms just reviewed are all consistent with the products
obtained in sugar hydrogenolysis. The major product of fructose cleavage is glycerol and
for glucose cleavage the major product is ethylene glycol and erythritol. Propylene
glycol is formed by the hydrogenation of glycerol (Clark, 1958). This cleavage site
selectivity along with the strong base catalysis further supports that a retro-aldol reaction
may be involved. Furthermore, recent research on sugar hydrogenolysis conducted by

our group (Wang et al., 1996) identified the retro-aldol reaction of a B—hydroxyl carbonyl

precursor as the C-C cleavage mechanism, and excluded the other mechanisms due to

two theoretical considerations and experimental results (Figure 1).

1.3 Project Backgron

The previous researchers on this project at Michigan State University (Wang et
al., 1996) performed a mechanism study of sugar and sugar alcohol hydrogenolysis using
1,3-Diols. Based on the possible bond cleavage mechanisms governing sugar and sugar
alcohol hydrogenolysis they were able to conclude that cleavage of the C-C bonds and C-
0 bonds in hydrogenolysis is through retro-aldolization and dehydration of a B-hydroxyl
carbonyl, respectively. Their results prevented them from believing that either retro-
Claisen or retro-Michael is a dominating C-C cleavage mechanism over the retro-aldol in
hydrogenolysis.

Twigg (1998) continued research on this project and investigated use of a l, 3-
diol, specifically, 2,4-pentanediol (2,4-PD). The focus was on developing a catalyst to
increase the selectivity of the hydrogenolysis process. Numerous metals, in the presence
of hydrogen, can hydrogenate aldehyde groups of carbohydrate molecules in aqueous
solution (Montassier et al., 1991). Two types of catalysts, namely metal oxides and
nickel on alumina/silica, were found to have desirable effects on the hydrogenolysis
reaction and it were these catalysts that were chosen for study in the current research.
Barium promoted copper chromite; copper (II) oxide; palladium 1% on carbon and boron
oxide; and nickel on alumina/silica and copper (II) oxide were found to promote highest

selectivity toward C-C cleavage. Twigg (1998) also examined the effects of temperature

and pressure and found limited effects from temperature change (above 190 °C) and

pressure inversely affects the reaction rate and 3.5MPa is adequate.

1.4 Objectives and Scope of Current Research

Our focus is to understand the mechanisms controlling the hydrogenolysis of

 

sugars. Our hypothesis is that sugars and sugar alcohols will hydrolyze similarly to the
simpler 1,3-diol model compounds. Based on the mechanisms of selective sugar
hydrogenolysis, a large scale process can be optimized to compete economically and
environmentally with our existing petroleum based processes.

Specific Aims

1) develop analytical methods for detecting the various products produced in the
hydrogenolysis of D—glucose, fructose, and sucrose; 2) determine the efficacy of nine
different catalysts or catalyst combinations and two different solvents in the conversion
of D-glucose, fructose, and sucrose into propylene glycol, ethylene glycol and glycerol;
and 3) explore the mechanism of sugar hydrogenolysis by identifying some of the many

intermediates and products of sugar hydrogenolysis.

10

CHAPTER2

EXPERIMENTAL SYSTEM AND METHODS

2.1 Description of Apparatus

A specially designed, stainless steel continuously stirred steady-state batch reactor
with a 50 ml capacity and capable of withstanding high pressures and temperatures was
used for all hydrogenolysis reactions. The detailed design of this reactor is shown in
Figure 2. .

Compressed hydrogen from a cylinder equipped with a pressure regulator was
used to maintain a constant pressure of 3.5 MPa during the course of the reaction. An
additional pressure gauge was added to the hydrogen supply line to monitor the pressure
near the reactor. A vacuum line connected to the reactor was used to purge the system
before the experiment. The desired reaction temperature was maintained by a lOOOW
electric coil immersed in a silicone oil bath and controlled with a proportional
temperature controller and platinum RTD probe. A uniform temperature distribution of
210 :I: 3 °C was sustained by stirring the oil bath with nitrogen bubbles.

The continuously stirred batch reactor was equipped with one sampling port that
was composed of a sampling valve, 1/16-in. stainless steel tubing and a 0.45 pm pore size
stainless filter at the inlet immersed in the reaction medium. The filter prevented the
contamination of the samples with solid catalyst particles, which could interfere with the
high pressure liquid chromatograph (HPLC) and gas chromatograph (GC) analyses. The
total hold volume was several microliters which allowed for an accurate representation of

the mixture components at the time of sampling. A magnetic stirring bar was used to

11

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Sampling Valve — 5311199118 Tubing

 

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Stirring Bar

Figure 2. Illustration of Hydra {analysis Reactor

 

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—>

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Figure 3. Schematic Illustration of Exporiruental System

13

blend the mixture in the reactor. The entire reactor assembly was placed on a magnetic

stir plate. A schematic illustration of the whole experimental system is provided in

Figure 3.

2.2 Experimental Procedure

To carry out the reaction, about 0.5 g of starting sugar, 0.05 g of selected catalyst,
1 ml of 1N sodium hydroxide, and proper amounts of solvent were placed in the reactor,
giving a total volume of about 40 ml. The reactor was purged by alternately connecting it
to nitrogen and a vacuum, and then was heated until the reactor reached 210 °C.
Hydrogen pressure was applied to the reactor and maintained at 3.5 MPa. During the
reaction course, the reaction medium was constantly stirred and its composition was
monitored using gas chromatography (GC) and high pressure liquid chromatography
(HPLC).

2.3 Chemical Components

The following chemicals are from Aldrich Chemical Co. (Milwaukee, WI):
copper (II) oxide (99.9999%); copper chromite, barium promoted; palladium, 1 wt. % on
carbon; boron oxide (99.999%); iron (III) oxide (99.998%); Ruthenium, 5 wt. % on
carbon; nickel on kieselguhr (60-62% Ni); sodium hydroxide (97 + %); 1.4-butandiol;
ethyl alcohol-d (99%); and or-D-glucose (96%). D-fructose, sucrose (99.9%), and methyl
alcohol were purchased from Fisher Scientific (Fair Lawn, NJ), Boehringer Mannheim
(Indianapolis, IN) and Mallinckrodt, respectively. The water used came from a reverse

osmosis system (DA-15, Filterchem, Alhambra, CA). The hydrogen (99.9%) and

14

nitrogen was obtained from Purity Cylinder Gases (Lansing, MI) and AGA Gas Products

(Lansing, MI).

2.4 Sample Analysis

Prior to each collection about 0.5 ml of sample was discarded due to dead space
volume. Following this, a 1 ml sample was collected every 30 minutes for a total of 240
minutes from the reaction vessel and placed into a small vial.
Internal Standards For analysis an internal standard (IS) calibration method was
performed. The internal standard used must be well resolved from the other peaks, elute
close to the peaks of interest, and have a structural similarity to the unknown. For HPLC
analysis with starting substrate glucose and fructose the internal standard used was
sucrose, and with starting substrate sucrose the internal standard used was fructose. The
final concentration of either of the internal standards for HPLC analysis in solution was
4.72 mM sucrose or 8.97 mM fructose. For GC analysis the internal standard used for all
experiments was 1,4-butanediol. The final concentration of 1,4—butanediol in solution
was 10.47 mM.
Liquid Chromatography The starting sugar and glycerol were separated in a Shodex
Asahipak NH2P-50 packed column, 4.6 mm id. x 150 mmL, particle size 5 pm
(Keystone Scientific Inc., Bellefonte, PA) and maintained at 30 °C. The HPLC system
consisted of a Dionex gradient pump, a Waters injector, and a Sedex Model 55
evaporative light scattering detector (Richard Scientific, Novato, CA). The detector was
operated at 46 °C and pressure was held at 2.2 MPa with nitrogen. A 75/25

acetonitrilelwater mixture was used as the mobile phase at a flow rate of 1.0 mllmin, and

15

10 ul portions of the solution were injected into the HPLC chromatographic system in
order to calculate the concentrations. The approximate HPLC retention times for
glycerol, fructose, glucose, and sucrose were 3.0, 5.7, 6.8 and 9.1 min, respectively. The
liquid chromatography results were entered into a spreadsheet which automatically
calculated the selectivity and overall conversion of the starting sugar and the yield of
glycerol.

Gas Chromatography A 3.0 u] aliquot of solution was injected into a Hewlett Packard
Model 5890 Series II gas chromatograph (Hewlett Packard, Avondale, PA), equipped
with a 30 m x 0.53 mm i.d., 0.50 micron megabore Supelco capillary column (Supelco,
Bellefonte, PA) and flame ionization detector for separation of ethylene glycol and
propylene glycol. The column temperature was programmed for a l-rnin hold at 100 °C
followed by a 12.5-min ramp at 4 °C/min up to 150 °C. The injector and detector
temperatures were 250 and 350 °C, respectively. The approximate retention times for
propylene glycol, ethylene glycol, and 1,4-butanediol were 5.7, 6.3 and 12.4 min,
respectively. The gas chromatography results were entered into a spreadsheet which
automatically calculated the yields of propylene glycol and ethylene glycol.

Standard Preparation The HPLC and GC were calibrated for each individual
compound using an internal standard (IS) calibration method. The internal standard
calibration method helps to standardize the amount of sample manually injected. This is
very important due to the small amounts of sample injected, namely 3 pl for GC and 10
pl for HPLC analysis. The HPLC and GC calibration curves are listed in Appendix A
and B, respectively. An internal calibration verification (ICV) was prepared for both

instruments. The ICV was performed by preparing a standard and injecting it three

16

consecutive times into either the HPLC or GC. Using the reported area and the prepared
calibration curves, the concentration of each compound in the standard was calculated.
The standard deviation for each compound was calculated for the three consecutive runs,
and it is desired to receive a RSD value of less than 5%. Relative standard deviation
(RSD) values of 0.51, 1.58, 3.65 and 18.4% were obtained for propylene glycol, ethylene
glycol, glucose and glycerol, respectively. It was found that glycerol has a much higher
RSD value. The RSD value is higher because glycerol is a very viscous material and it is
difficult to prepare samples and inject accurate amounts into the HPLC due to its
tendency to retain to glass, therefore causing the accuracy of measurement to be less.
Error Estimation Error is present due to both the small volumes used in sample
analysis and associated instrumental error. In order to better measure the amount of
instrumental error, the ICV standard was run prior to using the instruments for each
individual experiment. This enabled an instrumental error to be calculated over the entire
course of using these instruments. For the experiments in which D-glucose was the
substrate a relative standard deviation (RSD) of 11%, 18%, 14% and 20% was calculated
for D-glucose, glycerol, propylene glycol, and ethylene glycol, respectively. The
instruments were recalibrated after these experiments with fructose as the substrate and
RSD values of 21%, 32%, 20% and 22%, were calculated for fructose, glycerol,
propylene glycol and ethylene glycol, respectively. Again the instruments were
recalibrated for the final set experiments with sucrose as the substrate and RSD values of
5% and 16% were calculated for sucrose and glycerol, respectively. Although

instrumental error is present it is estimated that the average error was not more than 15%

17

between experiments. Although this may seem high, the results are qualitatively correct

and can be used to identify general efficacy of the nine catalysts or catalyst combinations.

18

CHAPTER3

RESULTS AND DISCUSSION

The focus of this research was to understand the mechanisms controlling the
hydrogenolysis of sugars, namely glucose, fructose, and sucrose. Hydrogenolysis can be
described as the cleavage of carbon to carbon or carbon to oxygen bonds, accompanied
by the addition of hydrogen (Connor and Adkins, 1932). In order to examine the
hydrogenolysis reaction of glucose, fructose, and sucrose, I developed analytical methods
to detect for the various intermediates and products. Additionally, the efficacy of nine
different catalysts and two different solvents in the conversion and selectivity of glucose,
fructose, and sucrose into propylene glycol, ethylene glycol, and glycerol was
determined.

In sugar hydrogenolysis it has been determined that catalyst is essential in order to
convert the starting sugar (Tronconi et al., 1992). Extensive studies have been done on
developing effective catalysts for the hydrogenolysis of carbohydrates. Two types of
catalysts promoted the desired results, favoring retro-aldolization over the dehydration
reaction pathway: the first type was a series of metal oxides, most notably copper oxide,
which promoted high selectivities, and the second type was nickel on alumina/silica,
which promoted high conversions (Twigg, 1998).

A total of 36 experiments (Tables 1-4, details in Appendix D) were run during the
current phase of the project, resulting in valuable catalytic hydrogenolysis data for
various combinations of substrates, solvents, and catalysts. Several catalysts were

studied in addition to those previously investigated by Wang and Fumey (1995). The

19

catalysts used in the current study included palladium 1% on carbon, nickel on
alumina/silica, copper (II) oxide, iron (III) oxide, boron oxide, aluminum oxide, nickel on
kieselguhr, 5% ruthenium on carbon, and barium promoted copper chromite. Catalysts
were studied individually, and in some cases up to three were combined to determine
their effectiveness in obtaining both a high conversion of the starting sugar chain and a
high selectivity toward C-C cleavage versus C-O cleavage (Figure 1).

A number of physical parameters are important to this type of process, including
temperature, hydrogen partial pressure, and base. Twigg (1998) used a model compound,
2,4-pentanediol (2,4-PD) to establish a set of optimal reactor conditions that were ~
selected for this study. The conditions chosen included a reactor temperature of 210 °C,
3.5 MPa hydrogen partial pressure, and NaOH as base. Two variables, solvents and
catalysts, were studied during the current phase of the project. For these reaction
conditions and the two variables, data were collected and catalysts or catalyst
combinations most effective in sugar hydrogenolysis were identified. Table 5 presents a
summary of the best catalytic results. However, it should be noted that each catalyst may
have different optimum reaction conditions, thus further optimization will need to be

explored.

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3.1 Solvent Comparison

Two solvents, 1M EtOH and water, were studied with substrate D-glucose. The
preferred solvent was determined to be 1M EtOH. In determining the better solvent for
sugar hydrogenolysis at these conditions, final conversion, total selectivity, and yields of
the desired products were considered.
FINAL CONVERSION

When comparing the efficiency of both solvents in converting D-glucose in sugar
hydrogenolysis, the best result indicated almost 100% final conversion for both with the
same catalyst, barium promoted Cu-chromite. For water and 1M EtOH, final conversion
of D-glucose was 99.26% and 97.34%, respectively (Figures 4 and 5). Conversions were
comparable with both solvents for each catalyst or catalyst combination.
TOTAL SELECIYVITY

For 1M EtOH five of the nine catalysts or catalyst combinations yielded a greater
total selectivity than water. The greatest total selectivity calculated for water was 0.4962
with nickel on kieselguhr, and for 1M EtOH, 0.4893 for the catalyst combination nickel

on alumina/silica and iron (III) oxide. Figure 6 illustrates the compiled selectivity results.

26

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YIELD OF DESIRED PROD U CT

1M EtOH proved to give higher yields of the desired products for the same five
catalysts or catalyst combinations. The greatest yield of propylene glycol obtained with
solvent 1M EtOH was 25.73%, where, as with solvent water the greatest propylene glycol
yield was 23.70%. Both these yields are for the catalyst 5% ruthenium on carbon. For
ethylene glycol, the greatest yield with solvent 1M EtOH was 6.23%, and for water, the
greatest yield was 5.08%. These yields were obtained using nickel on kieselguhr as the
catalyst. For glycerol, using solvent 1M EtOH, the greatest yield was 20.61% with
catalyst combination palladium 1% on carbon and boron oxide, and for solvent water, the
greatest yield was 16.25% with catalyst combination nickel on alumina/silica, aluminum
oxide, and copper (II) oxide (Figures 7 and 8).

Tables 1 and 2 present the above results for D-glucose with either water or IM
EtOH as the solvent. Although some of the best results are similar for the two solvents,
1M EtOH may be preferred over water because it is easier to separate from the end
products and could thereby reduce separation costs. Some studies have used methanol as
opposed to water as a solvent, but the results are contradictory. Tronconi et al. (1992) in
batch studies concluded that methanol as a solvent led to low conversion of the sugar
sorbitol and a very low selectivity. However, Boelhouwer et al. (1960) attained yields of
nearly 75% of distillable polyalcohols, in a rotating autoclave with methanol as solvent,
using beryllium oxide activated copper chromite catalyst to hydrogenate sucrose. 1M
EtOH has not received much attention. However, from the current results it warrants

further study as a possible solvent choice.

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3.2 Analysis of Nine Catalysts and their Efficacy in Sugar Hydrogenolysis

The ultimate goal of the current phase of the project was to identify catalysts that
would promote C-C cleavage, and thus the production of propylene glycol, ethylene
glycol, and glycerol, in sugar hydrogenolysis. The two main parameters used to
determine the effectiveness of a given catalyst were the selectivity towards C-C cleavage
and the overall conversion of the starting sugar chain.

As mentioned, Twigg (1998) established a set of optimum reactor conditions for a
model compound, 2,4-pentanediol, and these conditions were adopted for this project.
Reactor temperature was maintained at 210°C because Twigg (1998) determined that an
increase in temperature resulted in greater C-C selectivity and overall 2,4-pentanediol
conversion. Twigg (1998) indicated that the hydrogenolysis reaction is not occurring to
any great extent at 150°C, and that the optimum operating temperature was between
190°C and 220°C. From a computer simulation study using model compound 2,4-
pentanediol, conducted by Wang et al. (1999), increased temperature was found to
greatly enhance the reaction rate; however it had little effect on selectivity.

In the current work, hydrogen partial pressure was held constant in the reactor at
3.5 MPa because it was in the optimum range determined by Twigg (1998). The effect of
hydrogen partial pressure varies with the catalyst used. For a given catalyst, selectivity
increases with the hydrogen pressure at low pressures (hydrogen concentration less than
110 mM, at medium pressures (hydrogen concentration greater than 110 mM and less
than 150 mM) selectivity appears to be unaffected, and for high hydrogen pressure
(hydrogen concentration greater than 150 mM) selectivity decreases (Wang et al., 1999).

Twigg (1998) concluded hydrogen partial pressure was inversely related to C-C

selectivity. Tronconi et al. (1992) observed with ruthenium on carbon catalyst in batch
experiments, that a high hydrogen partial pressure was not required for sorbitol (feed
30% w/w) conversion; however, the use of low partial pressure gives rise to the
formation of condensation products. Montassier et al. (1991) found when studying
hydrogen partial pressures between 0-7 MPa, with substrate glucitol over Cu-Ru at 493K,
that in the absence of hydrogen partial pressure, cyclodehydration was accompanied by
the production of large quantities of degradation products (namely, carbon dioxide).
Final optimization might benefit from a redesign of the current specifications of the
reaction vessel, thereby allowing lower pressure systems to be studied (< 3.0MPa).

The base selected to promote the hydrogenolysis reaction was 1N NaOH.
Tronconi et al. (1992) found in the absence of base, NaOH, low conversion of sugar
sorbitol and a low selectivity of desired products resulted. Sorbitol is formed via
hydrogenolysis of fructose (Andrews and Klaeren, 1989). Muller et al. (1991) noted that
base promotes selectivity to propylene glycol with substrate saccharose, catalyst 5%
ruthenium on carbon, 220°C, and 5.5 MPa. The role of NaOH seems associated with the
cleavage of CC bonds, the desired pathway in sugar hydrogenolysis (Tronconi et al.,
1992, Wang et al., 1999).

All results were calculated on a per mole carbon basis. Multiplying the calculated
concentrations of each compound by the number of carbons in the compound serves to
normalize the results. Thus, for each of the reported yields, selectivities, and for

conversion of starting substrate, a per mole carbon basis was used.

FINAL CONVERSION

Conversion is defined as the number of carbon moles of substrate reacted per
carbon moles of starting substrate. The same number of carbon moles for glucose,
fructose, and sucrose was provided for each experiment. However, the number of
starting moles for D-glucose and fructose was twice the amount of sucrose. The catalyst
that resulted in the greatest overall conversion of each of the three starting sugar chains
was determined (Figures 5, 9, 10). In the experiments with D-glucose and 1M EtOH as
the solvent, conversion of 97.34% was obtained with catalyst barium promoted copper
chromite. Fructose and sucrose reached conversions of 100% for several different
catalysts or catalyst combinations. Fructose reached 100% conversion over six of the
nine catalysts or catalyst combinations and a conversion greater than 99.5% for all nine
studied. The six were copper (II) oxide; barium promoted copper chromite; nickel on
alumina/silica; nickel on alumina/silica and iron (III) oxide; nickel on alumina/silica,
aluminum oxide, and copper (II) oxide; and nickel on kieselguhr. For sucrose 100%
conversion was reached with two of the nine catalysts or combinations. The two catalyst
combinations were nickel on alumina/silica, aluminum oxide, and copper (II) oxide; and
5% ruthenium on carbon. Tables 2-4 present the results of conversion for each starting
substrate, D-glucose, fructose, and sucrose with solvent 1M EtOH. Figures 5, 9, and 10
illustrate the conversion data for each starting substrate over the nine catalysts or catalyst
combinations. For detailed results of the amount of converted starting substrate at each
30 minute sample time interval refer to Appendix D. At this point, because conversion is

so high, it is not the main issue or focus in determining the most effective catalyst or

35

catalyst combination for this reaction optimization. If conversion less than 100% is

achieved, separation and recycle technologies can be employed.

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TOTAL SELECITVH'Y

Selectivity is defined as the ratio of carbon moles of desired products formed per
carbon moles of starting substrate reacted. Again, the desired products are formed via C-
C cleavage opposed to C-0 cleavage and are propylene glycol, ethylene glycol, and
glycerol. Sucrose yielded the highest total selectivity, 0.6339, with nickel on
alumina/silica and iron (III) oxide as the catalyst. A total selectivity of 0.6339 achieved
for substrate sucrose indicates that the desired products comprised more than 63% of the
total products. This is promising because when comparing these results to fermentation
we find the yield of desired products to be about 43%, with nearly 40% of the other
remaining products going to C02. This is an important result because the selective
conversion of sugars to useful chemicals while preserving all the carbon atoms in the
starting material supercedes fermentation processes. Fermentation, which can also
produce these high valued chemicals, causes loss of carbons from the starting material by
producing carbon dioxide. For glucose with l M EtOH as the solvent a total selectivity
of 0.4893 resulted with nickel on alumina/silica and iron (III) oxide as the catalyst
combination. Using fructose as the starting sugar chain, a total selectivity of 0.4559 with
palladium 1% on carbon and boron oxide was achieved. Again, refer to Tables 2-4 and
Figure 6 for a summary of total selectivity results. For detailed results of the total
selectivity at each 30 minute sample time interval refer to Appendix D.
YIELD OF DESIRED PROD U C?

Yield of desired product is defined as the carbon moles of the desired product
divided by the carbon moles of starting substrate and is equivalent to conversion

multiplied by the selectivity. The yields of the desired products propylene glycol,

39

ethylene glycol, and glycerol were calculated at each 30 minute sample time interval and
detailed results can be found in Appendix D.

a) Propylene Glycol

For D—glucose with 1M EtOH as the solvent, the greatest yield of propylene
glycol was 25.73% with 5% ruthenium on carbon as the catalyst. For experiments with
fructose as the starting substrate a yield of 24.49% was obtained with 5% ruthenium on
carbon. Using sucrose as the starting substrate a yield of 39.41% also resulted with 5%
ruthenium on carbon. It can be concluded that 5% ruthenium on carbon promotes the
production of propylene glycol for starting substrates D-glucose, fructose, and sucrose.
This supports previous research in sugar hydrogenolysis preformed with catalyst 5%
ruthenium on carbon. The role of 5% ruthenium on carbon catalyst consists in promoting
the hydrogenation and dehydrogenation reactions. Both the conversion of D-glucose,
fructose, and glycerol involve a first dehydration step to give a reactive aldehydic
species. Thus, the reactions can not proceed in the absence of the catalyst, which also
diminishes the selectivities to the most reduced products (glycols) (Tronconi et al., 1992).

Propylene glycol is primarily formed by the hydrogenation of glycerol (Clark,
1958). If the reaction proceeds for too long, the glycols could degrade to alcohols or
hydrocarbons. If glycerol was hydrated alone a 2:1 ratio of propylene glycol to ethylene
glycol resulted (Clark, 1958). The current work illustrated a ratio greater than 3:1 for
propylene glycol to ethylene glycol in the hydrogenolysis of D-glucose, fructose, or

sucrose. Refer to Figures 8, 11, and 12 for a summary of the compiled results.

40

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b) Ethylene Glycol

For D-glucose with 1M EtOH as the solvent, the greatest yield of ethylene glycol
achieved was 6.23% with nickel on kieselguhr as the catalyst. For fructose as the
substrate the greatest yield was 6.70% and was obtained with 5% ruthenium on carbon.
Using sucrose as the substrate a yield of 12.44% resulted with nickel on kieselguhr as the
catalyst. Again, refer to Figures 8, 11, and 12 for a summary of the results.

c) Glycerol

For D-glucose with 1M EtOH as the solvent, the greatest yield of glycerol was
20.61% with palladium 1% carbon and boron oxide catalyst combination. For
experiments with fructose as the substrate a yield of 30.14% was obtained with palladium
1% on carbon and boron oxide. Using sucrose as the substrate a yield of 32.54% resulted
with palladium 1% on carbon and boron oxide as the catalyst combination. Refer to
Figures 8, 11, 12 for a summary of the complete results.

Montassier et al. (1991) found at temperatures near 373K, hydrogenolysis of
glucose yields sorbitol and hydrogenolysis of xylose yields xylitol. For higher
temperatures, 423K or greater, these compounds react further resulting in dehydration
products. These reactions are generally considered to be the result of C-C and C-0
bonds, therefore sorbitol can be converted into glycerol, 1,2-propanediol and ethylene
glycol in a mixture with numerous other alcohols and polyols but the yield of glycerol
remains below 40% of the initial sorbitol (Montassier er al., 1991).

Again, results for the specific yields for each of the three desired compounds,
propylene glycol, ethylene glycol, and glycerol, at each 30 minute time interval for each

experiment can be found in Appendix D.

These results are competitive and supereede many of the other reported yields for
these commercially viable compounds. Tronconi er al. (1992) reported yields between
7.3-36.2 wt % for propylene glycol and 5-18.1 wt % for ethylene glycol with starting
substrate sorbitol and 5% ruthenium on carbon as the catalyst in a continuous reactor.
VanLing et al. (1967) reported a yield of 10 wt % for ethylene glycol and 35.1 wt % for
glycerol with sucrose as the starting substrate and catalyst CuO-CeOz-Sioz in a batch
reactor. At very mild conditions, temperature 100 °C and pressure 2.0 MPa with catalyst
HzRu(PPh3)4 catalyst in N-methyl-Z—pyrrolidinone and starting sugar fructose, Andrews
and Klaeren (1989) obtained yields of 8 wt % ethylene glycol and 26 wt % glycerol. Our
preliminary results with substrates glucose, fructose, and sucrose compare well with the

optimized systems and scale-up of others, as illustrated.

3.3 Analysis of the Reaction Products formed During Catalytic Hydrogenolysis
of D-glucose, Fructose and Sucrose

Hydrogenolysis sugars yield a complex mix of products because of the multiple
GO and C-0 bonds of sugar available for cleavage. It is very difficult to tie the various
reaction products of sugar hydrogenolysis to a specific bond cleavage reaction due to the
existence of more than one pathway to the same product. In this work, to examine and
explore the mechanism of sugar hydrogenolysis, gas chromatography/mass spectrometry
and liquid chromatography/mass spectrometry . were employed. Products that were
identified included ethylene glycol, propylene glycol, lactic acid, glycolic acid, glycerol,
glyceraldehyde, glyceric acid, 3-deoxy-tetronic acid, erythritol, threitol, erythronic,
threonic, deoxy hexons lactonic, 3-deoxyhexonic, methanol, ethanol, acetone, 3-methyl-
2-butanone, 2-methyl pentane, 3-buten-2-one, and l-hydroxy—Z-propanone. This is in
agreement with the findings of VanLing et al. (1967) who reported glycerol, ethylene
glycol, and propane—1,2-diol composed 58.2 wt % of the products and the remaining
products included tetritols, pentitols, hexitols, dehydrated hexitols, butane-2,3-diol,
methyl D-glucopyranosides, and dehydrated hexitols.

It is desirable to make the hydrogenolysis of sugars more selective. The C-O
cleavage is to a great extent responsible for the complication of sugar hydrogenolysis
products; therefore minimizing the C-0 cleavage is expected to make the reaction more
selective. Reduction of C-0 cleavage is expected to increase the yield of glycerol, the
highest valued major product of sugar hydrogenolysis. Glycerol preserves all the oxygen
atoms in the starting sugar molecule. Muller et al. (1991) observed that the
hydrogenolysis of fructose yields an enediol as a reaction intermediate and the formation

of polyols in the presence of less catalyst. More specifically, hydrogenolysis of fructose

45

yields a combination of mannitol and glucitol (sorbitol) and glycerol, where glycerol is
15% of the product (Andrews and Klaeren, 1989). It also has an intermediate selectivity
between glucose and mannose. The glycerol is produced from the hydrocracking of the
single C(3)-C(4) bond. The glucitol can continue to react under the conditions of base,
NaOH, and ruthenium catalyst and produce an aldehydic intermediate which further
yields either glycerol or lactic acid. The production of lactic acid facilitated by base
produces 1,2-propanediol. 1,2-ethanediol is a by-product of glycerol production
(Tronconi et al., 1992). '

Most of the work reported in the literature has focused on hydrogenolysis of D-
glucitol; however some studies have included xylitol as a feedstock. With xylitol as a
feedstock, 25% of the products were unidentified and the remaining 75% consisted of
1,2-propanediol and glycerol, with an equal amount of ethylene glycol and ethanol
(Montassier er al., 1991). It was concluded that the retro-Claisen reaction dominated
over the retro-Michael with this substrate. Erythritol is converted mainly into
dehydroxylation products. The majority, 80%, is 1,2-butanediol and small amounts of
2,3-butanediol are formed. The other 20% are retro-Claisen products, namely glycerol,
1,2-propanediol, C02, and ethylene glycol. Initially the presence of 1,2,3 and 1,2,4—
butanetriols were observed (Montassier et al., 1991). Some experiments on the
hydrogenation of glycerol show that it is not converted into 1,2-propanediol; however,
glyceraldehyde is converted to a mixture of 1,2-propanediol and glycerol.
Glyceraldehyde was detected and can be considered a reaction intermediate.

Referring to Figure 1, the proposed mechanism of sugar and sugar alcohol

hydrogenolysis, we can identify numerous reactions. The dehydration and retro-

aldolization of the B-hydroxy carbonyl are reversible reactions catalyzed by the base
catalyst (hydroxide ion). This base catalyst is also directly involved in the rate limiting
step of dehydrogenation of the substrate and activation of hydrogen. The
dehydrogenation of the open chain sugar chain is promoted by a transition metal catalyst,
which also is responsible for activating the hydrogen. This activation is required in order
to reduce any unsaturated compounds and hydrogenate ketones and aldehydes. The
reaction of hydrogen with the metal catalyst forms a metal hydride species which has the
ability to hydrogenate both C-C and C-0 double bonds (Collman er al., 1987; Masters,
1981; Pignolet, 1983). The hydrogenation reaction between the metal hydride and the
unsaturated species must regenerate the metal catalyst, so that it can be re-used in the
next cycle of catalysis. The metal hydride works as a hydrogen carrier to transport
hydrogen from the substrate and the molecular hydrogen to those unsaturated
intermediate products. Hydrogenation of ketones and aldehydes and dehydrogenation of
alcohols are both reversible reactions (Wang er al., 1991). The hydrogenation of alkene
species is irreversible because the reaction equilibrium lies far to the product end
(Collman er al., 1987, Masters, 1981).

Head space sampling was used in addition to mass spectrometry for the further
identification and quantification of the intermediates and products of sugar
hydrogenolysis. The products that were quantified included acetone, ethanol,
butyraldehyde, 2-pentanone, isobutanol, monomethyl ether, 2-pentanol, 3-pentanol, 3-
penten-2-one, and 2-hexanol. The reaction pathway was studied and possible
intermediates identified, then using headspace sampling the samples could be spiked in

order to conclusively determine if a compound was present. In brief, the method of

47

analysis included bringing our sample volume up to a volume of 10 ml, followed by
heating in a hot water bath to 80 °C. An internal standard was used and 0.6 ml of gas
were injected into a gas chromatograph with a capillary column and flame ionizing
detector. This preliminary work may serve as a foundation for further quantification of
the many intermediates and products of sugar hydrogenolysis.

The knowledge surrounding this complex sugar hydrogenolysis process continues
to increase through concentrated research studies. The findings presented in this paper
lend insight on effective catalysts in the hydrogenolysis of D-glucose, fructose, and
sucrose and support the proposed mechanism described in Figure 1 (Wang et al., 1991).
Preliminary work in identifying some of the various products and intermediates is a first
step in furthering our understanding of the mechanisms involved and controlling the C-0

selectivity.

CHAPTER4

CONCLUSIONS AND INIPLICATIONS

Development of new technology is required for the economic conversion of
sugars to industrial chemicals including glycerol, propylene glycol, and ethylene glycol.
Selectivity controlled hydrogenolysis is a promising approach for conversion of sugars to
polyhydric alcohols with no carbon atom loss. In this research with substrates D-glucose,
fructose, and sucrose I examined the efficacy of nine different catalysts and two solvents
in the sugar hydrogenolysis process. The reaction conditions chosen for this study were
an isothermal batch reactor held at temperature 210°C, 3.5 MPa hydrogen partial
pressure, and NaOH as base catalyst.

Catalysts or catalyst combinations which favored the desired reaction pathway
included 5% ruthenium on carbon; nickel on kieselguhr; palladium 1% on carbon and
boron oxide; and nickel on alumina/silica and iron (III) oxide. Yields as high as 39%,
33%, and 12% were attained for propylene glycol, glycerol, and ethylene glycol,
respectively. Also, a total selectivity of 63% for the desired products was achieved under
the studied reaction conditions. Barium promoted copper chromite yielded 100%
conversions for substrates D-glucose, fructose, and sucrose.

This work supports previous findings (Wang et al., 1999; Fumey, 1995; Twigg,
1998) suggesting that carbon-carbon cleavage occurs through retro-aldolization and that
carbon-oxygen cleavage occurs through dehydration. Using model compound, 2,4-
pentanediol, Twigg (1998) concluded that barium promoted copper chromite]; copper (II)

oxide; palladium 1% on carbon and boron oxide; and nickel on alumina/silica and copper

49

(II) oxide promoted high selectivities. Through this work we have identified possible
catalysts or catalyst combinations that favor the retro-aldolization reaction of sugars.
However, it should be noted that each catalyst may have different optimum reaction
conditions, and when a sole catalyst or catalyst combination is selected for optimization
further reaction conditions will have to be explored. Our research thus far has been
centered about developing a detailed understanding of the mechanism governing sugar
hydrogenolysis, understanding the role of reaction conditions in selectivity control, and
experimentation with a variety of catalysts to determine their selectivity. We have
defined a set of reaction conditions which favor the retro-aldolization reaction pathway in
sugar hydrogenolysis, determined effective catalysts or catalyst combinations, and
identified many of the products in the sugar hydrogenolysis process.

As optimization of this process continues, a developed biomass conversion
process to produce the afromentioned high valued chemicals will potentially replace
current petroleum and fermentation based processes. Our process will have several
advantages over the current industrial processes. These include potentially lower
production costs, renewable feedstocks versus depleting fossil fuel feedstocks, and better
environmental conditions - less toxic substances are used in the process. If this process
can become highly selective, this process may have an immediate impact on the industrial

production of propylene glycol, ethylene glycol, and glycerol.

CHAPTERS

FUTURE WORK

As the process continues to be developed it is important to further study the
industrial technologies of this process. Three recycle and separation technologies,
namely distillation (evaporation), solvent extraction, and crystallization have been
considered and reviewed to separate the sugar hydrogenolysis products. Distillation or
evaporation may be employed to address the problems arising from separating any
unconverted sugar from the products. However, we have seen that nearly 100%
conversion for substrates D-glucose, fructose, and sucrose can be achieved. Examining
the many byproducts of sugar hydrogenolysis reveals that their different boiling points
may allow a distillation or evaporation technology to be used for effective separation. If
some of the products were not separated completely, unconverted sugar and sugar
alcohols could be recycled back to the reactor. An evaporation column may be more
effective than a distillation column because it is less likely to accumulate sugar residue.

Solvent extraction is a possibility, but not likely to be a promising technology to
pursue. It poses numerous problems including finding a suitable leachate that would
selectively remove the byproducts and leave behind the sugar water. Crystallization is
another technology that could be further studied; however, a non-aqueous environment is
desired and a chemical to aid the crystallization process would need to be sought.

On the subjects of recycle and separation technologies, further study on possible
solvents should be considered. In the current work ethanol was selected and compared

with water. Ethanol proved to be effective. It may aid the separation technology and also

51

favor the desired selectivity. Other solvents such as propylene glycol and ethylene glycol
should also be considered.

Reaction conditions used in this study were based on previous results using model
compound, 2,4-pentanedio, on this project (T wigg, 1998). Temperature, hydrogen partial
pressure, base concentration, and catalyst amount were constant for each experiment.
However, now that catalyst testing has begun on actual sugar chains more studies need to
be done. Optimum conditions may be different for each catalyst or catalyst combination.
From literature and previous research on this project a reaction vessel which allows for a
wider range of temperatures and pressures may result in greater yields of desired products
and a higher selectivity. A reaction vessel should be constructed which would allow
lower pressures (< 3.0 MPa) and higher temperatures (> 240°C) to be studied. A
redesign of the reactor, including greatly increasing the diameter and reducing the height,
would increase the surface area thereby allowing more of the reactants to be in contact
with the hydrogen partial pressure. This increased contact may greatly enhance the
reactions. A larger reaction vessel or scale-up should be developed that would better
model an industrial batch study.

Another point which requires further study is the pH during the reaction.
Hydrogenolysis produces an enediol as a reaction intermediate which is unfavored in
acidic media, and hydrogenation occurs at acidic pH (pH 5 to 6) (Muller er al., 1991).
Therefore, separation between hydrogenation and hydrogenolysis could be obtained by
modification of the pH during the reaction. If the reaction starts at an acidic pH, namely
pH 6, then after the hydrogenation step base can be added up to pH 10 and this may result

in an increased yield of the desired products. It can be assumed that when the reaction

52

begins the pH of the solution drops during the first hour, as acidic compounds are
produced. A reaction vessel which would allow for the testing of the pH during the
reaction and the later addition of the base catalyst, NaOH, could prove to enhance the
desired selectivity.

Future research on the mechanisms controlling the selectivity of sugar
hydrogenolysis will focus on understanding the chemistry involved in the complex
reaction. If some of the other byproducts can be quantified and tied to one of the reaction
pathways, then the effects of different reaction parameters on the process can be more
readily understood. From this work using a one step sugar hydrogenolysis reaction
process, we have been able to produce the high valued chemicals propylene glycol,
ethylene glycol, and glycerol. Using this current catalyst research with sugar chain
substrates, further development of an efficient selectivity-controlled sugar hydrogenolysis
process should be sought which would inevitably lead to an industrially, economically,

and environmentally significant process.

APPENDIX ITEMS

Appendix A: HPLC Calibration Curves
Appendix B: GC - glycols Calibration Curves
Appendix C: Error Estimation
Appendix D: Detailed Experimental Data

Appendix E: Intermediate Calculations

54

APPENDIX A

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Exp #1 Date 7/21/99
Reaction Components:
113 Amoun
Substrate D-Gluoose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 ml
Catalyst Copper (II) oxide 0.05 3
Reaction Conditions
HPLC Run GC Run
W I ection Amount Elm—mm
210 °C 10 ml 3 ml
Pressure Internal tandard Internal §tandard
3.5 Mpa 0.231 ml sucroselml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 429231.59 0.00 170313.98
30 190045.56 0.00 165519.18
60 56108.68 0.00 158672.77
90 84619.39 5351.53 152565.66
120 30784.29 462.43 1499649
150 684.92 637.82 1547257
180 2055.26 583.22 153358.33
210 3489.35 423.88 144183.76
240 14934.29 2073.24 149174.44
' GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 23967.80 18486.76 650033.16
30 15562.96 27779.24 665469.25
60 46299.71 55313.65 623255.12
90 67464.63 72497.73 6524339
120 96584.66 70635.03 684861.56
150 116939.09 60980.95 6455652
180 163810.25 68543.16 548257.34
210 21 1726.04 67600.80 676663.92
240 254743.41 78628.53 638829.14
YIELDS (%) Total
C‘m‘m" (%) Glycerol Propylene Glycol Ethylene Glycol seleeumy
53.83 8.97 0.42 0.55 0.1846
78.56 8.97 0.14 0.78 0.1258
92.89 8.97 1.21 1.59 0.1267
89.26 10.41 1.82 1.98 0.1591
95.56 9.10 2.61 1.84 0.1417
99.18 9.14 3.45 1.69 0.1440
99.02 9.13 5.92 2.22 0.1743
98.83 9.09 6.22 1.78 0.1730
97.46 9.54 8.02 2.18 0.2026

 

 

 

 

 

 

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Exp #2 Date 7/22/99
Reaction Components:
113 Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base IN N aOI-I 1 ml
Catalyst Ba prom. Cu-Chromite 0.05 &
Reaction Conditions
HPLC Run GC Run
Mara—M's Medium 1 ection Amount
210 °C 10 ml 3 ml
m Internal Standard Internal Standard
3.5 Mpa 0.231 ml sucroselml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 316954.85 610.43 167239.61
30 84609.99 681.76 157639.29
60 529.13 2019.87 153133.03
90 144.47 1 123.78 150452.46
120 173.10 3422.39 146985.36
150 308.92 2913.21 152865.02
180 351.79 699.88 147439.42
210 191.21 3063.21 1554465
240 0.00 4754.90 149452.89
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 27079.84 14361.09 639740.76
30 12501.92 33492.85 648791.42
60 32461.76 50957.85 602155.14
90 38563.42 46210.86 593410.20
120 63376.94 54891.11 620894.49
150 83176.09 65876.22 727633.16
180 98981.61 48203.82 675961.42
210 136800.54 61349.96 704980.91
240 155395.30 69693.84 687256.75
YIELDS (96) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
65.10 9.12 0.53 0.45 0.1552
89.59 9.15 0.05 0.95 0.1 133
99.20 9.51 0.78 1.52 0.1190
99.24 9.28 1.01 1.40 0.1178
99.24 9.93 1.79 1.58 0.1340
99.23 9.75 2.05 1.62 0.1353
99.22 9.17 2.72 1.29 0.1328
99.24 9.78 3.72 1.56 0.1518
99.26 10.28 4.39 1.81 0.1660

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Exp #3 Date 7/27/99
Reaction Components:
11E Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05i
Reaction Conditions
HPLC Run GC Run
Islam 1 action Amount 191m
210 °C 10 ml 3 ml
13mg Internal Standard Internal Standard
3.5 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-buL/ml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Resglnse Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 310052.71 588.55 1550943
30 272258.82 385.82 156319.58
60 86626.61 1984.54 164228.68
90 4805.99 2089.21 156896.14
120 30803.07 7285.83 155018.77
150 56299.93 10564.35 163865.65
180 65814.50 11010.85 157399.27
210 30352.18 8226.36 160031.96
240 70618.87 15749.07 144320.35
GC Response Area:
TIME (mm) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 31929.75 35707.50 677540.99
30 40659.34 70532.37 546476.97
60 102061.51 126924.23 641620.73
90 288061.02 134424.06 618194.00
120 606239.75 163765.40 697706.61
150 614056.21 156289.05 642979.67
180 659130.33 167312.81 662146.16
210 736905.87 166341.87 759853.02
240 743468.53 169146.24 696494.35
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
63.23 9.13 0.63 0.97 0.1697
67.87 9.07 1.21 2.28 0.1851
89.75 9.47 2.99 3.47 0.1774
98.71 9.52 9.43 3.81 0.2306
95.68 10.90 17.90 4.1 1 0.3439
93.07 1 1.62 19.71 4.25 0.3823
91.72 1 1.84 20.56 4.42 0.4014
95.84 1 1.08 20.02 3.83 0.3645
90.44 13.45 22.07 4.25 0.4397

 

 

 

 

 

 

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Exp #4 Date 7/28/99
Reaction Components:
1m Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 llll
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 3
Copper (11) Oxide .053
Reaction Conditions
HPLC Run GC Run
em mm mm W
210 °C 10 ml 3 ml
Pressure Internal Standard Internal Standard
3.5 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 658996.51 1339.55 132988.91
30 385654.50 1907.31 131133.16
60 2751.29 172.77 153029.96
90 98457.69 0.00 139878.83
120 50070.33 7751.24 145880.83
150 10426.28 5434.09 145880.83
180 34632.68 5545.94 142804.19
210 9732.35 5494.01 152094.54
240 11979.18 11014.23 136056.53
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 22715.54 25313.10 565434.22
30 11477.28 30260.93 647410.74
60 57251.73 61934.73 617303.94
90 151014.61 63352.32 600200.22
120 328249.51 75981.04 712313.27
150 697148.27 169992.51 712313.27
180 518884.67 107222.64 642247.11
210 492299.68 89939.1 1 583796.47
240 561294.24 110597.23 615596.82
YIELDS (%) .
“mm (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
9.94 9.38 0.49 0.83 1.0770
46.25 9.57 0.02 0.86 0.2260
98.94 9.02 1.59 1.79 0.1253
86.57 8.97 4.93 1.88 0.1823
93.07 1 1.15 9.33 1.90 0.2404
97.97 10.50 20.20 4.18 0.3560
94.89 10.57 16.62 2.94 0.3174
98.11 10.45 17.36 2.72 0.3112
97.67 12.30 18.80 3.16 0.3507

 

 

 

 

 

 

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Ex #5 Date 7/29/99
Reaction Components:
HE Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 m1
Emlyn Palladium 1% on Carbon 0.05 g
Boron Oxide 0.053
Reaction Conditions
HPLC Run GC Run
132mm Islam-mu new
210 °C 10 ml . 3 ml
ml: Ingmal Sum Internal tandard
3.5 Mpa 0.231 ml sucrosdml 0.1875 ml 1.4-butJml
1615.385 ppm sucrose 943.5 ppm 1,4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrme (IS)
0 925941.88 1266.76 144581.89
30 539098.13 7950.05 174944.56
60 45258.32 5139.81 252954.51
90 16866.84 5342.56 286530.55
120 16098.54 7014.65 285346.28
150 3358.48 8389.21 187987.09
180 9185.08 10834.26 173238.45
210 20677.34 16205 .58 148842.47
240 11412.72 19549.45 117972.04
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4»butanediol (IS)
0 16391.67 11848.67 496186.41
30 13073.64 7297.08 437646.03
60 13511.22 13444.98 412861.45
90 33988.30 24071.62 451727.59
120 50716.09 21 135.45 393922.58
150 98999.70 24062.81 456730.32
180 139854.52 29186.69 498561.19
210 157299.52 24062.85 513980.94
240 16348557 23511.65 473143.34
YIELDS (%) Total
cums” (%) Glycerol Propylene Gchol Ethylene Glycol Selectivity
-16.18 9.33 0.34 0.47 06267
43.71 10.84 0.27 0.35 0.2621
96.04 9.81 0.33 0.62 0.1120
98.20 9.74 1.23 0.98 0.1216
98.24 9.98 2.35 0.98 0.1355
98.94 10.80 4.20 0.97 0.1614
98.31 11.54 5.54 1.07 0.1846
96.76 13.44 6.07 0.87 0.2106
97.52 15.78 6.90 0.92 0.2420

 

 

 

 

 

 

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Exp #6 Date 8/2/99
Reaction Components:
. 1‘ng Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 m1
Catalyst Nickel on Alumina/Silica 0.05 g
Iron (III) oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
mm MM 1 cotton Amount
210 °C 10 ml 3 m1
[m Internal tandard Internal tandard
3.5 Mpa 0.231 ml sucroselml 0.1875 ml 1,4-but./ml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Respome Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 335389.88 0.00 114463.38
30 226087.09 261.65 144564.58
60 6446.93 806.92 142675.86
90 11348.80 4619.38 141705.73
120 5283.63 6794.18 118256.33
150 5791.37 2874.83 119893.48
180 5699.07 6456.25 125184.35
210 12514.90 5100.53 147912.36
240 769.54 1822.33 1351 11.6
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4.butanediol (IS)
0 41656.87 23834.33 450034.55
30 26018.46 25534.50 572965.89
60 104656.74 52773.45 506894.91
90 382459.74 85580.01 624228.75
120 475289.67 81506.00 522126.11
150 552048.06 67778.43 617849.27
180 505584.03 60028.99 501719.84
210 627705.87 85259.02 686536.86
240 593888.80 89747.79 734303.65
YIELDS (9E3) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glmol Selectivity
46.44 8.97 1.59 0.97 0.2483
71.07 9.05 0.60 0.83 0.1473
98.45 9.20 3.98 1.85 0.1528
97.82 10.31 12.52 2.42 0.2581
98.46 11.33 18.77 2.75 0.3336 ‘
98.39 9.96 18.41 1.95 0.3082
98.44 11.09 20.81 2.12 0.3456
97.74 10.39 18.85 2.20 0.3217
99.16 9.53 16.64 2.17 0.2857

 

 

 

 

 

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Exp #7 Date 8/3/99
Reaction Components:
has AM!!!
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Aluminum Oxide 0.05 g
Copper (11) Oxide 0.05 L
Reaction Conditions
HPLC Run GC Run
M 21W mm
210 °C 10 m1 3 ml
Pressure MM Internal tandard
3.5 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJm1
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Respome Area:
TIME (min) Glume Glycerol Sucrose (IS)
0 652442.96 0.00 129923.16
30 78599.42 78.56 137026.63
60 47370.18 189.08 126149.14
90 24705.34 3964.54 124686.17
120 27318.47 18990.01 143149.14
150 28825.11 21425.47 123255.19
180 29624.59 21627.16 141372.84
210 18442.07 20291.04 142055.51
240 29800.24 25733.44 145162.63
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-hutanediol (IS)
0 50439.86 32431.61 562013.80
30 47820.30 80089.24 634828.53
60 46662.97 88099.10 496281.02
90 200440.10 103915.71 498419.80
120 562076.99 158456.42 615171.31
150 481921.35 149431.06 513825.32
180 650965.49 164180.33 638023.31
210 683877.81 170414.94 612968.17
240 671083.89 174645.83 635060.58
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
8.74 8.97 1.53 1.05 1.3221
88.92 8.99 1.23 2.23 0.1401
92.49 9.03 1.62 3.12 0.1489
95.69 10.28 8.09 3.65 0.2302
95.82 14.42 18.84 4.50 0.3941
95.05 16.1 1 19.35 5.07 0.4264
95.48 15.25 21.08 4.50 0.4276
96.92 14.84 23.08 4.85 0.4413
95.56 16.25 21.84 4.80 0.4489

 

 

 

 

 

 

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Exp #8 Date 8I9/99
Reaction Components:
Tm Amount
Substrate D—Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOI-I 1 ml
Catalyst 5% Ruthenium on Carbon 0 05 L
Reaction Conditions
HPLC Run GC Run
W Wm WM
210 °C 10 ml 3 m1
PM In rnal tandard nternal tandard
3.5 Mpa 0.231 ml sucrose/m1 0.1875 m1 1,4-but.lml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 284923 .28 0.00 1 14459.39
' 30 74822.07 102.30 137873.35
60 22233.69 3748.34 132327.57
90 8806.92 1820.24 134662.63
120 16056.78 3138.57 118466.32
150 16048.36 8321.60 107172.44
180 12638.76 5410.12 1191055
210 13281.01 7722.31 119332.88
240 1380.83 5838.63 121078.98
GC Regionse Area:
TIME (min) Propylene Glycol Ethylene Gchol 1,4-hutanediol (IS)
0 140351.16 76509.88 495788.03
30 44990.23 43863.39 497180.73
60 109358.77 87079.13 531743.54
90 450323.01 58316.38 515655.79
120 645793.75 1 16222.64 674200.26
150 711697.11 114958.98 672165.35
180 706936.05 129920.02 698134.92
210 671055.27 101973.19 625607.11
240 745824.40 138835.06 651216.47
YIELDS (96) Total
cm'm‘” (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
54.39 8.97 5.59 2.72 0.3178
89.48 9.00 1.55 1.58 0.1355
96.23 10.13 3.97 2.88 0.1765
98.08 9.53 17.99 2.01 0.3010
96.82 10.06 19.77 3.03 0.3394
96.56 12.16 21.89 3.01 0.3837
97.35 10.84 20.92 3.27 0.3598
97.26 1 1.63 22.18 2.87 0.3771
99.06 10.95 23.70 3.74 0.3876

 

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Exp #9 Date 8/10/99
Reaction Components:
11% Amount
Substrate D-Glucose 0.5 g
Solvent Water 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Kieselguhr 0.05 g
Reaction Conditions
HPLC Run GC Run
W mom I oction Amount
210 °C 10 ml 3 ml
Pressure Internal §tandard Internal Standard
3.5 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-but./ml
1615.385 ppm sucrose 943.5 ppm 1,4»but.
HPLC Response Area:
m (“n“) Glucose Glycerol Sucrose (IS)
0 49433.83 374.83 122020.42
30 151716.09 0.00 118231.69
60 92542.33 0.00 1 16772.1 1
90 82075.90 5607 .19 1 18627.47
120 80368.89 16175.11 94734.67
150 137343.31 18476.03 135908.19
180 143726.65 20712.38 143245.15
210 112976.60 15525.64 127773.01
240 126663.97 18812.25 116715.74
GC Response Area:
TIME (min) Propylene Gchol Ethylene Glycol 1,4-hutanediol (IS)
0 40349.82 78278.44 507044.18
30 22526.02 50597.27 558217.74
60 68988.26 105861.13 477852.97
90 280513.94 103625.24 543873.10
120 437715.39 134363.09 599258.80
150 395100.62 169965.01 454539.54
180 564389.95 154676.51 482304.86
210 585959.36 141296.19 572098.09
240 601488.85 191398.66 657048.16
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
91.96 9.10 1.32 2.72 0.1428
76.13 8.97 0.49 1.62 0.1456
84.98 8.97 2.68 3.88 0.1827
86.79 10.91 10.48 3.35 0.2850
83.97 15.98 14.99 3.93 0.4156
81.05 14.55 17.91 6.51 0.4808
81.18 14.91 24.23 5.59 0.5510
83.32 13.96 21.16 4.32 0.4733
79.70 15.59 18.88 5.08 0.4962

 

 

 

 

 

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Exp #10 Date 8I10/99
Reaction Components:
m; Amount
Substrate D-Glucose 05 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Copper (11) Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
W I ection Amount 1 ection Amount
210 °C 10 ml 3 ml
My; Internal tan Internal Standard
35 Mpa 0.231 ml sucrose/m1 0.1875 ml 1,4-buL/ml
1615.385 ppm sucrose 9435 ppm 1.4—but.
' HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 496999.83 346.65 126072
30 257554.82 266.12 122382.83
60 10763855 0.00 124171.1
90 105248.06 854.15 128044.05
120 119736.85 314.25 139295.61
150 105354.26 1727.03 120900.14
180 75528.63 1525.92 124012.4
210 106607.61 2001.33 11910253
240 88244.87 246753 12445656
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol .(IS)
0 20639.92 36390.63 426892.29
30 ' 15847.60 29366.27 55604559
60 20883.24 57532.30 615701.01
90 61985.13 89022.92 629574.33
120 96047.84 82441.12 556929.94
150 190169.90 114413.10 703623.99
180 231805.86 1031 17.67 600726.97
210 262573.68 107136.61 585838.05
240 323766.67 130555.20 651728.18
YIELDS (%) Total
C‘mm‘i” (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
28.20 9.08 0.66 153 0.3998
61.33 9.06 0.24 0.97 0.1675
83.64 8.97 0.36 1.67 0.1315
84.44 9.25 1.71 250 0.1593
83.77 9.06 3.27 2.61 0.1784
8355 956 5.32 2.86 0.2124
88.28 9.48 7.75 3.02 0.2293
83.13 9.66 9.06 3.21 0.2639 _
86.48 9.79 10.08 351 0.2704

 

 

 

 

 

 

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Exp #11 Date 8/11I99
Reaction Commnents:
DE Amgunt
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 at]
Catalyst Ba prom. Cu-Chromite 0%
Reaction Conditiom
HPLC Run GC Run
15.122923. 1 ection Amount new
210 °c 10 ml 3 ml '
Pressure Internal Standard Internal
3.5 Mpa 0.231 ml sucroselml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 684511.05 78.30 131258.32
30 216791.14 37.28 129401.02
60 ’ 18607.19 9454 131872.62
90 31017.31 60.81 120055.26
120 3221.37 104.13 127049.77
150 7681.09 872.17 131511.94
180 3171.11 0.00 131115.18
210 9734.37 1817.29 126528.65
240 13921.17 0.00 130282.92
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-hutanediol (IS)
0 0.00 0.00 465355.44
30 2680.40 21010.37 64836858
60 . 5297.84 4714556 620688.68
90 9456.12 53847.79 652382.91
120 82771.04 62938.86 647945.34
150 128133.24 62187.30 617222.87
180 142926.13 72383.43 656558.12
210 86928.61 55946.35 588946.91
240 216402.76 76502.19 605593.69
YIELDS (%) Total
C°°"“‘°" (%) Glycerol Propylene Glycol Ethylene Glycol Selectivi
5.26 9.00 -0.36 0.06 1.6547
69.06 8.98 -0.27 0.62 0.1351
96.72 9.00 -0.18 1.37 0.1054
94.60 8.99 -0.05 1.48 0.1 102
98.80 9.00 2.33 1.73 0.1323
98.21 9.24 4.01 1.80 0.1532
98.83 8.97 4.22 1.96 0.1533
97.87 956 2.75 1.70 0.1431
97.34 8.97 7.15 2.24 0.1886

 

 

 

 

 

 

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Exp #12 Date 8/15/99
Reaction Components:
In; Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Reaction Conditions
HPLC Run GC Run
Temgrature I ection Amount Igiection Amount
210 °C 10 ml 3 ml
m Internal Standard Internal §tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 496989.47 0.00 139381.07
30 126542.33 0.00 137295.42
60 41125.17 537.28 139941.17 '
90 39391.71 4025.97 139597.28
120 4802.93 8081.41 14626051
150 4995.41 7790.95 142608.18
180 23365.04 12286.67 157331.79
210 45319.70 8186.42 145108.43
240 51870.84 1 1229.03 150059.92
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-hutanediol (IS)
0 35165.85 36181.43 387068.11
30 35435.64 35723.33 45894353
60 7905459 75809.13 53011 1.43
90 154534.32 72573.01 506538.42
120 433536.76 159416.82 555033.97
150 414952.01 153923.36 508345.45
180 407246.80 131310.35 500338.99
210 563079.16 16031257 659706.24
240 585579.05 175893.81 667619.76
YIELDS (96) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
34.99 8.97 155 1.67 0.3486
82.65 8.97 1.27 1.40 0.1408
93.96 9.13 2.78 253 0.1536
94.18 10.16 6.05 2.53 0.1990
98.67 1 1.24 16.05 5.01 0.3274
98.63 1 1.21 16.79 5.28 0.3375
9658 12.18 16.74 459 0.3469
93.63 1 1.29 1758 4.25 0.3537
93.03 12.04 18.07 4.60 0.3732

 

 

 

 

 

80

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #13 Date 8/ 16199
Reaction Components:
In; Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Ctmgr (II) Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
W I ection Amount 1 ection Amount
210 °C 10 ml 3 ml
Pressure Internal Standard Internal tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-buL/ml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 576021.32 983.78 157597.27
30 127162.96 1222.10 140345.36
60 36774.96 1097.20 1351 19.66
90 52730.11 359254 156222.84
120 41633.46 3314.25 141704.02
150 54698.40 6665.32 169582.23
180 59586.01 5702.40 175461.49
210 62448.07 5885.49 161882.16
240 56506.61 5644.47 169461.4
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 29101.28 33562.01 446857.80
30 18230.17 4395757 527553.93
60 135011.06 87701.11 543418.03
90 271573.99 101360.01 648300.02
120 321421.04 112242.49 588749.12
150 361411.10 120709.60 604643.15
180 517330.90 1507 83.63 76880154
210 422592.05 130041.16 553729.92
240 433485.20 103252.04 587580.16
YIELDS (%) Total
“mm" (9") Glycerol Propylene Glycol Ethylene Glycol Selectivity
33.38 9.23 1.01 1.35 0.3474
82.93 9.33 0.37 150 0.1350
94.36 9.30 4.86 2.84 0.1803
93.18 9.92 8.44 2.76 0.2266
93.97 9.93 1 1.1 1 3.35 0.2596
93.45 1059 12.20 350 0.2813
93.14 10.31 13.78 3.44 0.2956
92.31 10.46 15.68 4.1 1 0.3277
93.25 10.34 15.14 3.09 0.3064

 

 

 

 

 

 

81

 

 

Exp #14 Date 8/17/99

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Reaction Components:

113 Amount

Substrate D-Glucose 0.5 g

Solvent 1 M EtOH 40 m1

Base 1N NaOH 1 m1

Catalyst Palladium 1% on Carbon 0.05 g

Boron Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
lot—um mm 1 ection Amount
210 °C 10 ml ' 3 ml
My; Internal Standard Internal tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucwe Glycerol Sucrose (IS)
0 52233423 716.38 129190.41
30 141686.64 539.28 126300.27
60 23340.88 101854 134850.1
90 42368.18 7677.76 127898.72
120 49113.18 18047.94 1163755
150 49191.74 23948.07 124490.02
180 82301.49 48463.61 150494.27
210 46103.81 27334.22 127019.98
240 55802.93 36720.71 129575.9
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 14443.75 8993.82 285124.71
30 7577.94 10995.92 276965 .29
60 34277.84 26923.26 38633355
90 43143.46 20764.08. 316984.08
120 92576.38 41366.92 335955.85
150 1 17668.40 68004.83 348878.20
180 127639.66 55732.97 323567.98
210 164870.32 57636.95 400128.74
240 158814.89 43473.03 378006.30
YIELDS (%)

m'm‘” (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
26.38 9.20 0.71 0.60 0.3984
79.04 9.15 0.22 0.74 0.1279
96.14 9.28 151 1.26 0.1253
93.29 11.44 2.50 1.19 0.1622
91.65 15.34 5.43 2.18 0.2505
92.14 16.87 6.73 3.42 0.2933
89.40 22.19 7.93 3.03 0.3708
92.72 17.81 8.30 254 0.3090
91.50 20.61 8.47 2.04 0.3401

 

 

 

 

 

82

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #15 Date 8I23/99
Reaction Components:
m Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Iron (11]) Oxide 0.055
Reaction Conditions
HPLC Run GC Run
M I ection Amount I ection Amount
210 °C 10 ml 3 ml
Pressure Internal Standard Internal tandard
35 Mpa 0.231 ml sucrose/m1 0.1875 ml 1,4-but./ml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Ghlcose Glycerol Sucrose (IS)
0 584322.76 0.00 149054.6
30 92974.70 182.42 155824.93
60 51752.92 8424.10 148253.24
90 48160.65 21029.29 159995.63
120 67883.94 25222.37 181979.27
150 63472.23 29242.34 183487.01
180 8451.76 31709.06 193828.23
210 56591.16 25858.86 15459654
240 57587.83 28372.84 168879.13
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 67124.62 42220.91 360862.62
30 56365.36 104030.75 516592.19
60 302266.20 189154.97 628539.01
90 575993.37 235847.32 583063.92
120 645677.08 176665.70 590911.78
150 65861240 221788.78 589153.76
180 638042.32 237172.26 607910.06
210 717618.36 224299.00 60609653
240 725672.35 225803.44 638160.45
YIELDS (%) Total
“mm” (9") Glycerol Propylene Glycol Ethylene Glycol Selectivity
28.60 8.97 355 2.08 05106
8851 9.02 1.94 3.53 0.1637
92.97 11.30 9.75 5.25 0.2829
93.84 14.37 20.40 7.04 0.4455
92.54 14.66 22.60 5.22 0.4590
93.03 1551 23.13 655 0.4858
98.48 15.69 21.69 6.79 0.4485
92.66 15.84 2452 6.44 05050
93.11 15.87 23.53 6.16 0.4893

 

 

 

 

 

 

83

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #16 Date 8l24/99
Reaction Components:
1‘13 Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOI-I 40 ml
Base 1N NaOH 1 m1
Catalyst Nickel on Alumina/Silica 0.05 g
Aluminum Oxide 0.05 g
Copper (11) Oxide 0.05 g
Reaction Conditiom
HPLC Run GC Run
Te- ture I ection Amount W
210 °C 10 ml 3 ml
Pressure Internal Standard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 m1 1,4-but.lm1
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Respome Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 659292.16 69.94 131060.72
30 227286.13 129.62 133501.33
60 34118.41 1420.77 178655.47
90 3616.30 282756 172544.85
120 4662654 3744.34 154517.98
150 5332.27 360652 1581988
180 65751.83 6247.67 18530255
210 5564.29 5189.75 171552.49
240 39887.22 3384.82 150017.88
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 69179.81 56568.68 444807.23
30 44702.97 3092456 469267.22
60 91367.80 38267.83 534960.41
90 233973.31 128428.22 573449.32
120 297671.32 107274.95 619800.69
150 433485.20 103252.04 587580.16
180 346465.77 10915654 608791.43
210 490076.70 115736.61 660586.06
240 475719.29 70904.90 557434.89
YIELDS (%L Total
Mm“ (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
8.58 8.99 2.91 2.25 1.6493
68.57 9.01 1.65 1.20 0.1728
95.82 9.30 3.23 1.29 0.1443
98.88 9.64 8.22 3.92 0.2203
93.82 9.97 9.73 3.04 0.2424
98.65 9.91 15.14 3.09 0.2852
92.87 10.36 1 1.60 3.15 0.2704
98.68 10.21 15.23 3.08 0.2891
94.47 9.90 1757 2.25 0.3146

 

 

 

 

 

 

84

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #17 Date 8’25/99
Reaction Components:
m Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst 5% Ruthenium on Carbon O-OSL
Reaction Conditions
HPLC Run GC Run
My. 1 ection Amount MW
210 °C 10 ml 3 ml
m Internal tanda Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrwe (IS)
0 0.00 0.00 0
30 i 0.00 0.00 0
60 0.00 0.00 0
90 0.00 0.00 0
120 0.00 0.00 0
150 0.00 0.00 0
180 0.00 0.00 0
210 36140.79 10121.17 138960.18
240 33944.08 1 1783.81 156592.46
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 0.00 0.00 0.00
30 0.00 0.00 0.00
60 0.00 0.00 0.00
90 0.00 0.00 0.00
120 0.00 0.00 0.00
150 0.00 0.00 0.00
180 0.00 . 0.00 0.00
210 78219559 208159.23 686085.23
240 850787.71 178987.21 685112.83
. YIELDS (%) Total
“mm (9" Glycerol Propylene Glycol Ethylene Glycol SelectivitL
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
#DIVIO! #DIVIO! #DIVIO! #DIVIO! #DIVIO!
9457 1 1.96 2359 5.29 0.4319
95.35 12.06 25.73 456 0.4442

 

 

 

 

 

 

85

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #18 Date 8l26l99
Reaction Components:
1125 Amount
Substrate D-Glucose 0.5 g
Solvent 1 M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Kieselgullr 0.05 g
Reaction Conditions
HPLC Run GC Run
m l ection Amount mm
210 °C 10 ml 3 m1
Presalg Internal Sggam Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Glucose Glycerol Sucrose (IS)
0 539424.78 341.46 1361012
30 167788.72 261.65 120507.69
60 192907.75 4069.81 1 19680.43
90 199323.70 8164.67 1 12092.87
120 281090.65 15484.25 13610852
150 141869.15 6468.27 11868755
180 26721 1.91 10457.76 146087.79
210 154405.91 9170.05 1239219
240 22588.52 913053 122705.85
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 41246.40 18163.90 424306.63
30 60277.33 130360.58 53129254
60 138746.13 39664.75 482468.97
90 296078.63 202652.84 580533.98
120 174985.77 1 1325.24 402412.44
150 372264.06 16107058 502897.89
180 437092.99 203784.74 59159850
210 454624.65 208351.28 659537.22
240 44742355 210370.33 588167.58
YIELDS (%) Total
C°"""i°" (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
27.82 9.07 1.69 0.80 0.4155
74.16 9.06 2.03 4.29 0.2074
70.21 10.37 5.69 1.48 0.2497
67.21 1 1.96 10.36 6.08 0.4226
62.03 13.64 8.78 054 0.3702
77.72 11.21 15.20 558 0.4116
66.29 1 1.91 15.17 6.00 0.4990
76.80 12.01 14.13 551 0.4120
95.94 12.03 15.63 6.23 0.3531

 

 

 

 

 

86

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #19 Date 9/21/99
Reaction Components:
m Amount
Substrate Fructose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Copper (11) Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
Emma—tum 191mm 121W
210 °C 10 ml 3 ml
m; Internal tandard Internal tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 m1 1,4-but.lml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 405135.08 0.00 127699.97
30 19031852 0.00 13320359
60 2472.70 0.00 129434.28
90 177.10 1941.64 134014.65
120 0.00 3437.00 127706.91
150 0.00 5907.36 120107.05
180 0.00 7259.65 128577.23
210 0.00 7417.44 129860.19
240 0.00 9928.10 124108.14
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 0.00 40505.43 331951.70
30 16254.16 38272.84 57031 1.89
60 32290.83 94158.1 1 60969256
90 1 19451.25 83068.02 582590.24
120 279747.78 97206.46 710034.76
150 384657.41 1 12350.02 515366.24
180 553874.16 120439.03 646987.20
210 535391.80 118064.99 681645.31
240 660921.43 177496.99 645955.72
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glml Selectivity
45.65 8.97 -0.36 2.16 0.2361
7552 8.97 0.24 1.22 0.1381
99.67 8.97 0.76 2.72 0.1249
99.98 957 3.95 252 0.1604
100.00 10.08 7.92 2.42 0.2042
100.00 10.99 15.32 3.82 0.3013
100.00 1 1.29 17.63 3.27 0.3219
100.00 1 1.32 16.14 3.05 0.3051
100.00 12.26 21.14 4.80 0.3819

 

 

 

 

 

 

87

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #20 Date 12’10/1999
Reaction Components:
Type Amount
Substrate Fructose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Ba prom. Cu-Cliromite 0.05 g
Reaction Conditions
HPLC Run GC Run
lemming mm W
210 °C 10 ml 3 ml
m Internal a Internal tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-buL/ml
1615.385 ppm sucrose 9435 ppm 1,4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 45601358 900.92 170093.83
30 99181.93 961.33 16249056
60 83555 0.00 168127.73
90 349.13 192.12 136988.02
120 36254 661.79 154986.69
150 460.26 2383.49 184142.37
180 0.00 2785.14 155394.14
210 0.00 1002.45 189601.48
240 0.00 4861.53 180041.28
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 47061.63 20950.12 264140.24
30 48285.85 31018.97 347104.31
60 35967.84 8057.13 503885.04
90 26860.83 33217.01 559886.29
120 26806.32 6947.12 439198.92
150 78487.92 63748.12 472460.61
180 113884.23 64283.80 467118.02
210 172249.35 73441.20 609532.05
240 208318.66 72932.46 601449.35
‘ YIELDS (%) Total
“mm (9" Glycerol Propylene Glycol Ethylene Glycol Selectivity
54.07 9.19 3.39 1.43 0.2590
8954 9.21 257 1.60 0.1494
99.91 8.97 1.14 0.33 0.1046
99.96 9.03 0.65 1.08 0.1077
99.96 9.15 0.93 0.33 0.1041
99.96 950 3.13 2.39 0.1503
100.00 9.71 4.77 2.43 0.1691
100.00 9.19 558 2.14 0.1691
100.00 10.08 6.92 2.15 0.1915

 

 

 

 

 

 

88

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #21 Date 9/28/99
Reaction Components:
I‘m Amount
Substrate Fructose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Reaction Conditions
HPLC Run GC Run
Te rature WW I ection Amount
210 °C 10 ml 3 ml
M Integal Standard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 9435 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 439827.79 0.00 130364.85
30 293269.16 189.08 168490.02
60 1518.04 37.28 139478.04
90 544.64 3368.18 14833557
120 195.18 6418.78 1363249
150 342.22 5890.81 1428565
180 0.00 5589.88 124256.33
210 0.00 8410279 126093.48
240 0.00 10125.36 138049.27
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 17856.47 13715.68 338315.37
30 18013.11 2441057 641545.72
60 101607.94 113186.19 54857052
90 270327.93 84694.81 513458.70
120 329748.66 112218.67 510442.12
150 444839.99 1 16527.96 57931853
180 49133457 106301.44 575962.63
210 475697.44 69949.05 608690.10
240 428486.49 67198.34 649741.65
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
42.20 8.97 0.75 0.76 0.2484
70.18 9.02 0.23 0.71 0.1420
99.81 8.98 354 3.62 0.1617
99.94 9.90 10.70 2.90 0.2353
99.98 10.90 13.22 3.85 0.2798
99.96 10.66 15.78 3.53 0.2998
100.00 10.82 1757 3.24 0.3163
100.00 1 1.71 16.06 2.04 0.2981
100.00 1 1.98 1350 1.84 0.2732

 

89

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #22 Date 10/5/99
Reaction Components:
113 Amount
Substrate Fructose 0.5 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Copper (11) Oxide 0.054
Reaction Conditions
HPLC Run GC Run
199% I ection Amount I ection Amount
210 °C 10 ml 3 ml
Pressure Internal tandard Internal Standard
35 Mpa 0.231 ml sucrose/m1 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 475169.92 0.00 150509.99
30 129057.06 188.42 153076.13
60 7192.25 11219.35 160291.64
90 3787.94 8346.21 14609854
120 5618.87 25604.38 142314.25
150 ' 6082.02 22466.05 142334.14
180 3472.70 13919.21 153000.89
210 2226.12 12882.82 138875.37
240 3878.71 27218.00 1483709
GC Respome Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 5970.28 8610.44 564759.60
30 48580.35 64828.95 37088750
60 223875.93 179365.62 488344.34
90 436056.32 214758.10 616063.43
120 53578551 256677.11 615283.18
150 615438.34 267847.91 680728.26
180 453195.64 134716.46 60026357
210 513260.88 199628.36 545259.60
240 641 195.46 215266.42 678766.55
YIELDS (%) Total
“mm” (%) Glycerol Propylene Glycol Ethylene Glycol SelectivitL
45.92 8.97 -0.13 0.32 0.1995
8556 9.02 2.40 3.07 0.1694
99.23 1 1.85 9.28 6.39 0.2773
9956 1 1.32 1451 6.07 0.3204
99.32 16.36 17.94 7.25 0.4183
99.27 15.45 18.64 6.85 0.4124
99.61 12.71 1551 3.93 0.3227
99.73 12.78 19.42 6.37 0.3868
99.55 1650 19.49 553 0.4171

 

 

 

 

 

 

90

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #23 Date 9l21/99
Reaction Components:
1‘12; Amount
Substrate Fructose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Boron Oxide 0.05 g
Palladium 1% on Carbon 0.05 g
Reaction Conditions
I-IPLC Run GC Run
1mm 1 ection Amount Islam—mow
210 °C 10 ml 3 ml
M W W
35 Mpa 0231 ml sucroselml 0.1875 m1 1,4-butJml
1615.385ppm sucrose 943.5 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 478617.05 0.00 155374.17
30 286356.12 0.00 2025508
60 14601.60 0.00 203908.41
90 542.57 35871.19 203568.36 1
120 177.76 68727.48 16856259
150 206.39 67439.04 218771.37
180 159.76 65791.38 214314.06
210 213.72 87623.15 19934752
240 239.68 75360.18 146190.42
GC Response Area:
TIME (min) Propylene Glycol Egylene Glycol 1,4-butanediol (IS)
0 33055.82 29562.61 294773.63
30 5337.14 5796.30 244856.36
60 33129.99 20068.87 383585.03
90 100707.42 33956.10 415532.90
120 217865.96 5581353 501729.20
150 289800.01 78271.17 456995.10
180 29167853 89131.46 410776.76
210 304118.18 39182.43 46745151
240 343930.71 5715753 521802.32
YIELDS (%) Total
“mm“ ‘95) Glycerol Prppylene Glycol Ethylene Glycol Selectivity
47.23 8.97 2.00 1.79 0.2702
75.78 8.97 0.10 0.47 0.1259
98.77 8.97 1.46 0.96 0.1 153
99.95 16.21 4.74 1.47 0.2242
99.98 25.71 8.77 1.98 0.3646
99.98 21.63 12.97 3.01 0.3761
99.99 21.58 1456 3.80 0.3994
99.98 27.02 13.31 150 0.4184
99.97 30.14 13.49 1.95 0.4559

 

 

 

 

 

 

91

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #24 Date 1211 1/ 1999
Reaction Components:
112 Amount
Substrate Fructose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 m1
Catalyst Nickel on Alumina/Silica 0.05 g
Iron (III) Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
W I ection Amount 1 ection Amount
210 °C 10 ml 3 ml
Pressure Internal tandard Internal tandard
' 35 Mpa 0231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 516331.84 190.14 125117.85
30 129853.34 0.00 . 145276.97
60 695650 759654 198341.49
90 86.01 14418.11 153161.12
120 0.00 30047.27 19313855
150 0.00 23352.86 189641.43
180 103.86 32634.23 177302.46
210 14437.94 30466.71 185737.69
240 0.00 36989.35 178425.47
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 60220.92 30883.31 53934754
30 60252.39 71402.36 329089.46
60 85349.68 146046.94 36786058
90 441541.07 216665.74 646100.18
120 503172.27 190080.07 518223.69
150 525364.36 171241.84 56459357
180 636194.18 179522.65 651307.67
210 51738554 146379.82 467659.30
240 587968.15 220728.61 606946.28
YIELDS (%) Total
C‘m‘m (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
29.31 9.03 1.98 1.04 0.41 14
84.69 8.97 3.48 3.78 0.1916
99.40 1054 450 6.88 0.2205
99.99 12.84 13.94 5.82 0.3259
100.00 15.36 19.95 6.36 0.4167
100.00 14.03 19.10 5.27 0.3840
99.99 1653 20.07 4.79 0.4140
98.67 15.71 22.78 5.43 0.4451
100.00 17.48 19.90 6.30 0.4369

 

 

 

 

 

 

92

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #25 Date 12113/ 1999
Reaction Components:
113 Amount
Substrate Fructose 0.5 g
Solvent 1M EtOH 40 ml
Base 1N NaOI-I 1 m1
Catalyst Nickel on Alumina/Silica 0.05 g
Aluminum Oxide 0.05 g
Copper (II) Oxide 0.05J
Reaction Conditions
HPLC Run GC Run
m 151mm W
210 °C 10 m1 3 ml
Pressure Internal tandard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butlml
1615.385 ppm sucrose 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 51336253 1740.08 157057.93
30 1 12279.63 1072.83 17519052
60 5490.32 1 1594.96 159386.82
90 0.00 19875.80 149648.47
120 0.00 22595.87 191668.26
150 0.00 2458455 166136.49
180 0.00 21341.36 167412.41
210 0.00 23683.81 201580.11
240 0.00 24998.67 173128.17
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 59310.16 46643.14 468008.29
30 4392557 60814.23 682169.23
60 24023058 219516.13 66558757
90 522609.12 186482.15 646447.27
120 600469.10 192977.48 70100757
150 506621.42 130032.46 381226.35
180 489961.08 201692.39 469614.73
210 54779152 242915.01 452228.46
240 686042.46 208408.08 633074.83
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol SelectivitL
44.01 9.43 2.30 1.77 0.3066
89.02 9.22 0.99 1.59 0.1326
99.41 11.96 7.19 5.72 0.2502
100.00 14.42 1655 5.01 0.3599
100.00 13.81 1756 4.79 0.3616
100.00 15.05 27.44 5.91 0.4840
100.00 14.21 21.46 7.43 0.4310
100.00 13.80 24.98 9.28 0.4805
100.00 14.90 22.31 5.71 0.4292

 

 

 

 

 

 

93

 

 

 

Exp #26 Date 12./1411999

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Reaction Components:
m Amount
Substrate Fructose 0.5 g
Solvent 1M EtOH 40 m1
Base 1N NaOH 1 m1
Catalyst 5 % Ruthenium on Carbon 0.05 L
Reaction Conditions
HPLC Run GC Run
My. . 1mm Lilla—um l
210 °C 10 ml 3 ml '
m Internal Staflard Internal Standard 1 “
35 Mpa 0.231 ml sucrose/n11 0.1875 ml 1,4-butJml
1615.385 ppm sucrose 939.1875 ppm 1.4-but. ‘
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 135762.99 2503.33 155428.76
30 1 17440.41 0.00 156191.08
60 488.68 2171.77 157952.39
90 126.78 9459.39 156010.66
120 29157 14599.20 156061.92
150 38.62 18824.23 197389.86
180 15.98 20274.30 197855.65
210 720.17 27782.92 210708.98
240 249.22 17025.30 146500.91
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanedio1 (IS)
0 75088.06 53585.82 36881 1.98
30 40852.42 52005.27 391622.28
60 61658.33 149056.77 519575.94
90 359927.35 17053656 561307.95
120 448280.96 205300.49 443231.19
150 695704.08 238539.18 652977.86
180 694540.44 17276059 627906.98
210 697493.32 197570.60 568820.64
240 763642.35 248694.93 642887.90
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
85.04 9.63 3.90 255 0.1892
87.12 8.97 1.83 2.34 0.1508
99.95 954 2.13 4.98 0.1666
99.99 11.46 13.06 5.27 0.2980
99.97 12.81 20.80 8.01 0.4163
100.00 12.89 21.93 6.33 0.41 14
100.00 13.18 22.78 4.78 0.4074
99.94 14.38 25.29 6.02 0.4572
99.97 13.74 24.49 6.70 0.4494

 

 

 

 

 

 

 

94

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

!11: ‘

 

 

 

 

Exp #27 Date 1/7/2000
Reaction Components:
Iypg Amount
Substrate Fructose 0.5 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Kieselguhr 0.05 g
Reaction Conditions
HPLC Run GC Run
mm 15mm W
210 °C 10 ml 3 ml
Pressure Internal Standard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-but.lml
1615.385 ppm sucrose 939.18753pm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 271837.47 959.39 199803.13
30 91516.75 0.00 166999.34
60 168753 1740.35 150904.13
90 180.95 12596.84 2250156
120 1 1651 29204.98 198371.62
150 22.64 35659.19 1511265
180 0.00 30882.22 1656245
210 68.35 30266.31 157445.41
240 0.00 32225.70 154721.04
GC Response Area:
TIME (min) Prppylene GLycol Ethylene Glycol 1,4-butanediol (IS)
0 75088.06 53585.82 36881 1.98
30 36763.03 34480.30 599377.09
60 71400.52 140792.74 475473.01
90 141871.80 43758.67 471112.30
120 557077.60 151012.40 572458.70
150 599506.14 202296.71 533803.98
180 533288.78 194337.27 498984.00
210 657128.44 191185.32 599029.90
240 595529.80 18886055 559244.44
YIELDS (%) Total
“mm (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
76.69 9.17 3.90 255 0.2037
90.61 8.97 0.93 1.05 0.1208
99.81 9.44 2.79 5.14 0.1741
99.99 1 1.27 5.94 1.65 0.1887
99.99 15.02 20.00 459 0.3960
100.00 18.66 23.13 6.57 0.4836
100.00 16.63 22.00 6.75 0.4537
99.99 16.86 22.59 554 0.4499
100.00 1752 21.91 5.86 0.4529

 

 

 

 

 

 

 

95

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #28 Date 1/10I2000
Reaction Components:
Iypg Amount
Substrate Type 05 g
Solvent Sucrose 40 ml
Base 1N NaOH 1 ml
Catalyst Copper (11) Oxide 0.05j
Reaction Conditions
HPLC Run GC Run
Te rature 131W 1 ection A t
210 °C 10 ml 3 ml
Pressure Inte tandard Internal
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 976880.01 0.00 130442.47
30 660368.13 434.09 197544.61
60 357961.30 81758 3386916
90 30998.55 449.67 171 125.84
120 4093.21 1949.52 151113.62
150 0.00 6780.13 194683.92
180 87207.11 16214.38 173004.61
210 11073453 14400.80 185610.72
240 134178.80 16793.48 2122712
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanedlol (IS)
0 79743.37 47704.01 424943.88
30 71 185.65 70830.14 555045.82
60 59129.61 67895.15 553955.39
90 57589.1 1 52241.93 503404.12
120 124631.71 136617.21 568498.24
150 515009.52 226586.66 628054.47
180 653091.87 158418.30 63157855
210 593347.64 136659.98 435553.61
240 841719.27 234833.18 668490.62
YIELDS (%)
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Total Selectivity
-47.14 851 3.39 1.89 -02926
34.32 8.60 2.21 2.14 0.3772
79.23 8.61 1.78 2.05 0.1571
96.44 8.62 1.94 1.75 0.1275
99.47 9.02 4.02 3.98 0.1710
100.00 9.87 15.95 5.94 0.3176
90.10 12.16 20.21 4.15 0.4053
88.28 1 154 26.73 5.17 0.4920
8758 1 1.60 24.68 5.79 0.4802

 

 

 

 

 

 

96

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #29 Date 2f7/2000
Reaction Components:
112°. Amount
Substrate Sucrose 0.5 g
Solvent 1M EtOH 40 m1
Base 1N NaOH 1 ml
Catalyst Ba prom. Cu—Chromite 0.05 g
Reaction Conditions
HPLC Run GC Run
W W I ection Amount
210 °C 10 m1 3 ml
Pmre Internal Standard Internal Standard
35 Mpa 0.231 ml sucrose/m1 0.1875 ml 1,4-but./ml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructwe Glycerol Sucrose (IS)
0 93736158 0.00 9500952
30 98388158 131.16 86424.14
60 31307.59 29974.18 147770.97
90 4976.20 3169351 13693324
120 295.61 2665654 144935.42
150 1780559 41230.03 181705.73
180 513.98 30987.93 153998.67
210 1883.87 28935.39 157094.71
240 1135.82 30373.49 133691.19
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanedio1 (IS)
0 88219.35 49005.84 473221.57
30 64056.67 46765.42 346159.96
60 79898.94 69213.92 360622.08
90 103779.12 103326.00 547787.46
120 65137.33 13369255 495848.74
150 94720.85 160990.35 538375.30
180 154970.76 150013.86 655517.39
210 254598.71 140825.93 451838.68
240 37391658 155384.06 52351 1.35
YIELDS (%) Total
“mm (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-93.84 851 3.37 1.74 -0.1452
-123.67 857 3.34 226 -0.1146
95.84 16.42 4.07 3.19 02470
99.29 1753 3.43 3.13 0.2426
99.96 15.68 2.27 4.45 02241
98.07 17.35 3.16 4.93 0.2595
99.93 16.35 4.36 3.79 02452
99.76 15.69 10.86 5.14 0.3176
99.83 17.36 13.85 4.90 0.3617

97

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #30 Date 1/20/2000
Reaction Components:
1m Amount
Substrate Sucrose 0.5 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Reaction Conditions
HPLC Run GC Run
Mrs Emu-29m I ection Amount
210 °C 10 ml 3 ml
Pressure Internal tandard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 875093.22 1432.42 165966.71
30 955758.76 1056.81 19904156
60 288958.42 1667.11 195210.39
90 56601.98 482.69 177717.05
120 2426.10 20079.19 154968.94
150 93244.03 1912653 171788.86
180 51521.49 34235.01 154006.22
210 6631853 33497.36 151162.45
240 19596.79 23274.89 145758.06
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 1 12055.82 44774.62 567067.27
30 71691.41 67190.94 514490.65
60 93493.09 131680.42 555502.44
90 241323.20 216560.40 580931.16
120 424890.04 277332.28 615450.68
150 689377.14 319329.22 585484.98
180 927299.84 368688.76 659054.73
210 915242.10 281306.99 566735.23
240 1048081 .36 325563.43 659817.04
YIELDS (%) Total
C‘m'mi‘m (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-3.59 8.85 359 1.34 -3.8340
5.66 8.72 2.43 2.19 2.3577
70.92 8.85 3.01 3.92 0.2224
93.74 8.62 7.92 6.14 0.2418
99.69 13.56 13.38 7.41 0.3445
89.34 12.85 23.05 8.95 05021
93.43 17.17 27.62 9.18 05777
91.38 17.15 31.75 8.15 0.6242
97.36 14.73 31.22 8.10 05552

 

 

 

 

 

 

98

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #31 Date 1’20/2000
Reaction Components:
113 Amount
Substrate Sucrose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOI-l 1 ml
Catalyst Nickel on Alumina/Silica 0.05 g
Clipper (II) Oxide 0.05 1
Reaction Conditions
HPLC Run GC Run
Ignatius. I ection Amount 131W
210 °C 10 ml 3 ml
Preswre Internal tandard Internal Standard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJm1
1615.385 ppm suc. 939.1875 ppm 1,4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 872047 .95 2293.53 147921.44
30 917497.18 2031.63 138288.67
60 179688.78 2170.19 173915.79
90 10802.35 5454.06 12113.18
120 nla nla nla
150 3676.25 6892.14 155605.86
180 1402.34 22254.71 140334.89
210 52994.73 23918.78 168655.02
240 12348.88 22747.00 142324.64
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1.4-butanedlol (IS)
0 nla lVa nla
30 85428.15 67755.80 704951.60
60 100999.09 139429.19 64373729
90 241626.76 217465.95 53991557
120 485312.97 307727.03 695151.93
150 627016.31 31091850 63206959
180 752373.02 302908.89 526448.64
210 919238.75 296586.49 660941.20
240 892227.42 346205.00 625438.42
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-15.83 9.12 #VALUE! #VALUE! #VALUE!
-30.35 9.09 2.07 1.62 -0.4210
79.70 9.00 2.78 359 0.1928
82.48 26.06 855 6.63 0.4999
#VALUE! #VALUE! 13.53 728 #VALUE!
9954 10.24 19.37 8.08 0.3786
99.80 14.69 28.05 9.44 05229
93.83 14.04 2729 7.37 05191
98.30 14.74 28.00 9.08 05273

 

 

 

 

 

99

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #32 Date 2/4/2000
Reaction Components:
1m Amount
Substrate Sucrose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Palladium 1% on Carbon 0.05 g
Boron Oxide 0.05 L
Reaction Conditions
HPLC Run GC Run
Imam I ection Amount MW
210 °C 10 ml 3 ml
Pressure Internal Standard Internal Standard
35 Mpa 0.231 ml sucroselml 0.1875 m1 1,4-butJm1
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 1 100663.16 669.77 119780.96
30 654099.88 195.95 126392.81
60 157154.96 3432.34 167754.82
90 24605.86 16846.79 144899.33
120 3702.27 43298.30 120871.64
150 4187.44 55326.94. 124971.37
180 224.25 101489.28 146369.69
210 370.17 ‘ 10894053 131920.28
240 452.73 89438.03 145022.08
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanedio1 (IS)
0 66674.47 51072.53 274322.98
30 50441.09 40460.20 315531.95
60 3489559 20803.99 399776.44
90 108113.60 129608.47 351887.41
120 297514.24 218889.85 482978.32
150 381527.68 225817.15 474812.92
180 55096554 283855.34 491167.35
210 582274.41 276463.55 523779.00
240 577241.71 266301.03 598576.97
‘ YIELDS (%) Total
Conversion (70' Glycerol Pmpylene Glycol Ethylene Glycol Selectivity
-8054 8.73 4.49 3.09 -0.2026
-1.68 857 2.84 2.15 -8.0822
8159 9.31 1.40 0.90 0.1423
96.66 13.04 5.77 6.06 0.2573
99.40 22.47 1 1.90 7.45 0.4207
99.34 25.76 15.63 7.81 0.4953
99.97 3553 21.95 9.48 0.6698
.9994 40.69 21.75 8.67 0.71 14
99.94 3254 18.82 7.31 0.5871

 

 

 

 

 

 

100

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #33 Date 2/10/2000
Reaction Components:
112 Amount
Substrate Sucrose 05 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 ml
Catalyst Nickel on Alumina/Silica 0.05 3
Iron (III) Oxide 0.05 g
Reaction Conditions
HPLC Run GC Run
mm W Law
210 °C 10 ml 3 ml
Pressure Internal Standard Internal tandard
35 Mpa 0.231 ml sucrose/ml 0.1875 ml 1,4-butJm1
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 ’ 952810.34 687.08 164024.64
30 1066394.16 96.15 146372.15
60 178159.12 1000.67 160406.91
90 2180559 1669.77 194212.16
120 28073.90 . 14402.80 1832024
150 2878.19 22134.82 160172.78
180 2163.37 26262.18 161312.92
210 2115.18 29518.64 159361.07
240 752.64 24655.08 135575.24
GC Regronse Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 6422351 46168.22 351342.82
30 34328.12 29338.26 406251.71
60 1 1 1387.34 132149.08 597059.89
90 96921.38 159587.95 411846.98
120 480712.57 257405.38 567796.09
150 795338.61 277171.44 641031.09
180 96741056 285212.43 555871.09
210 932648.21 309552.77 611939.88
240 104178008 391245.40 564110.11
YIELDS (%) Total
0mm” (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-14.13 8.68 3.30 220 -1.0028
-43.14 854 1.34 123 -02576
78.18 8.76 3.37 3.67 0.2020
97.79 8.85 4.34 6.38 02000
96.99 1158 16.48 7.45 0.3661
99.65 13.90 24.31 7.1 1 0.4548
99.74 14.86 34.24 8.42 05767
99.74 15.73 29.94 8.31 05412
99.89 15.60 36.35 1 1.37 0.6339

 

 

 

 

 

 

101

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #34 Date 2/10I2000
Reaction Components:
1m Amoun
Substrate Sucrose 0.5 g
Solvent 1M EtOH 40 ml
Base 1N NaOH 1 m1
Catalyst Nickel on Alumina/Silica 0.05 g
Aluminum Oxide 0.05 g
Copper (11) Oxide 0.053
Reaction Conditions
HPLC Run GC Run
Imam—nut. gimme-921 MW
210 °C 10 ml 3 ml
Pressure Intgrnal Standard Internal tandard
35 Mpa 0.231 ml sucrose/m1 0.1875 ml 1.4-butJml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 955929.48 1097.20 159818.91
30 887229.30 0.00 1374747
60 396587.02 1522028 147103.86
90 77340.88 319257 153398.8
120 14289.37 6734.94 129338.88
150 2430.76 11803.60 149387.13
180 553.93 21491.24 142717.71
210 952.06 32749.33 133055 26
240 0.00 28349.92 148315.46
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 85205.17 110134.98 342144.31
30 58189.07 60387.41 461936.79
60 142192.23 190659.88 68736950
90 21779559 270322.83 668528.61
120 371960.07 36160853 61103559
150 59713055 385490.04 519332.08
180 859053.32 407725.12 569208.16
210 928717.75 45888355 532283.48
240 104669170 244157.81 619539.37
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-17.52 8.78 4.61 5.31 -1.0674
-26.80 851 2.17 2.19 -0.4801
47.03 1254 3.77 458 0.4443
90.09 9.32 6.14 6.65 0.2454
97.83 1054 11.76 9.71 0.3272
99.68 1159 2251 12.16 0.4641
99.92 14.38 29.65 11.74 05581
99.86 18.10 34.32 14.12 0.6664
100.00 15.96 33.23 6.48 05567

 

102

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #35 Date 2/17/2000
Reaction Components:
DB Amount
Substrate Sucrose 05 g
Solvent 1M EtOH 40 m1
Base 1N NaOH 1 m1
Catalyst 5% Ruthenium on Carbon 0.05 L
Reaction Conditions
HPLC Run GC Run
Lemme 101W MW
210 °C 10 m1 3 m1
mgr. 1_mu_l___nte Standard was
35 Mpa 0.231 ml sucrose/ml 0.1875 m1 1,4-butJml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 968775.65 827.73 131300.81
30 109595608 2342.72 152887.69
60 543856.20 14472.31 166382.16
90 4991658 2854.97 157194.39
120 959920 9162.12 132031.96
150 1723.04 15723.88 127507.33
180 187.92 18752.23 117597.87
210 335.71 17008.76 134999.19
240 0.00 18817.64 119543.28
GC Response Area:
TIME (min) Propylene jSol Ethylene Glycol 1,4-butanediol (IS)
0 67349.55 112501.27 345816.98
30 50000.00 76449.28 34358127
60 96105.19 180875.35 486699.27
90 232681.03 311224.83 665184.37
120 443023.26 290887.01 470994.87
150 784259.34 424104.32 601951.05
180 954310.97 379745.47 541960.48
210 985961.43 405109.42 55971952
240 153178978 431148.88 765588.33
YIELDS (%) Total
“n"“m (%) Gcherol Propylene Glycol Ethylene Glycol Selectivity
-44.96 8.76 353 5.36 -0.3926
-40.84 9.1 1 2.56 3.68 -0.3759
35.78 1 1.90 3.59 6.12 0.6039
93.76 9.22 6.61 7.69 0.2509
9857 11.22 18.35 10.13 0.4027
99.73 13.32 2555 1 1.55 05055
99.97 14.73 34.64 1 1.48 0.6087
99.95 13.42 34.66 1 1.86 05997
100.00 14.65 39.41 9.24 0.6330

 

 

 

 

 

 

103

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp #36 Date 2/17/2000
Reaction Components:
11m Amount
Substrate Sucrose 0.5 g
Solvent 1M EtOH 40 m1
Base 1N NaOH 1 ml
Catalyst Nickel on Kieselguir 0.05 5
Reaction Conditions
HPLC Run GC Run
1m 1 ection Amount 131mm
210 °C 10 ml 3 ml
Pressure Internal Standard Internal Standard
35 Mpa 0231 m1 sucrose/m1 0.1875 ml 1,4-butJml
1615.385 ppm suc. 939.1875 ppm 1.4-but.
HPLC Response Area:
TIME (min) Fructose Glycerol Sucrose (IS)
0 891025.31 840.21 10159454
30 767229.71 737.62 124251.67
60 325611.19 5000.18 161824.65
90 35187.10 1245.01 129874.84
120 176528 898.80 119255.66
150 287.62 4489.41 121936.75
180 108.95 724856 1 17972.04
210 514.65 13883.68 133733.69
240 301.69 16327.13 134754.33
GC Response Area:
TIME (min) Propylene Glycol Ethylene Glycol 1,4-butanediol (IS)
0 0.00 0.00 168517.49
30 46602.95 77507.89 421207.70
60 751 16.31 136199.75 600470.42
90 104920.68 186213.49 440069.69
120 175694.89 20540.22 572539.08
150 299803.92 231701.00 678628.37
180 463005.07 29113057 523442.40
210 38231 1.35 288721.57 340493.75
240 62848356 366633.17 483055.20
YIELDS (%) Total
Conversion (%) Glycerol Propylene Glycol Ethylene Glycol Selectivity
-72.32 8.84 -0.34 0.06 -0.1 183
-21.32 8.74 1.86 3.06 -0.6409
60.47 9.72 2.15 3.76 02583
94.68 8.89 4.40 6.96 0.2138
99.71 8.81 5.76 0.64 0.1525
99.95 9.95 8.44 5.62 0.2402
99.98 10.91 17.24 9.13 0.3728
99.92 1256 21.97 13.89 0.4845
99.96 13.23 2551 12.44 0.5120

 

 

 

 

 

 

104

 

APPENDIX E

105

Intermediate Calculations

Substrate: Sucrose

Solvent: 1 M EtOH

Base: 1 N NaOH

Catalyst: Nickel on Alumina/Silica and Iron (III) Oxide

 

 

 

 

1) Obtain response areas
HPLC Response Area GC Response Area
sucrose 752.64 propylene glycol 104178008
glycerol 24655.08 ethylene glycol 391245.4
fructose (IS) 135575.24 1,4rbutanediol (IS) 564110.11

 

 

 

 

 

 

 

 

2) Using calibration curves, determine concentration (ppm)
ie. Sucrose: y = 0.8541x - 0.1956 y area/area‘s
x = conchonc.,s

([(752.64/135575.24)l-0.1956]/8541)* 1613.54 = cone. of sucrose
= 380.01

3) Adjust the calculated concentration (due to the addition of IS)
Clvl = C2V2

 

[ HPLC 0c
sucrose: c,t(0.5rnl) = (380.01ppm)"(0.65ml) C ,*(o.5m1) = o;*(0.80rnl)

' Concentration was obtained from step 2 calculate Cl for propylene glycol. ethylene
also calculate C, for glycerol and fructose (18) glycol, and 1,4-butanediol (IS)

 

 

 

 

 

4) Calculate Conversion
Conversion = substrate reacted/substrate fed (per mole carbon basis)

ie. sucrose fed:
(12500 ug/ml)*(g110"6 ug)*(mol sucrose/342.3 g)*(12 mol Cll mol sucrose) =

0.000438 mol C sucrose/ml
w
(494.01 uyml)*(g/10"6 ug)*(mo1 sucrose/342.3 g)*(12 mol 01 mol sucrose) =

0.0000173 mol C sucrose/ml
W

sucrose reacted = sucrose fed - sucrose left
= (0.000438-0.0000173) mol C sucrose/ml
= 0.0004207 mol C sucrose/ml

conversion = 0.0004207/0.000438 = .9605‘100 = 96.05%

5) Calculate Yield of desired product

106

 

Yield = mole desired product formed/mol substrate fed (per mole carbon basis)

ie. Propylene glycol (pg)

(4040.77 ug/ml)“(g/10"6 ug)*(mol pgf76.1 g)*(3 mol C/l mol pg)l(0.000438 mol C sucrose fed)
= 0.3637 mol C pg produced! mol C sucrose fed

': concentration was calculated from steps 1, 2 and 3
same procedure for ethylene glycol and glycerol yields

6) Calculate Total Selectivity
Total Selectivity = Sum of Yields of all desired products/Final Conversion (per mole carbon basis)

ie. ((36.37 + 11.37 + 15.60)/96.05) = 0.6594

Yield = (Y ield)PG + (Y ield)EG + (Y ield)Glycerol

107

BIBLIOGRAPHY

108

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