U.S. patent application number 14/781756 was filed with the patent office on 2016-03-24 for process for the preparation of glycols.
The applicant listed for this patent is SHELL OIL COMPANY. Invention is credited to Evert VAN DER HEIDE, Govinda Subbanna WAGLE.
Application Number | 20160083318 14/781756 |
Document ID | / |
Family ID | 48092714 |
Filed Date | 2016-03-24 |
United States Patent
Application |
20160083318 |
Kind Code |
A1 |
VAN DER HEIDE; Evert ; et
al. |
March 24, 2016 |
PROCESS FOR THE PREPARATION OF GLYCOLS
Abstract
The invention provides a process for the preparation of ethylene
glycol and 1,2-propylene glycol from starting material comprising
one or more saccharides, by contacting said starting material with
hydrogen in a reactor in the presence of a solvent and a catalyst
system with catalytic hydrogenation abilities, wherein the process
comprises the steps of: i) introducing a first portion of the
starting material into the reactor such that the initial
concentration of the saccharide in the solvent in the reactor is no
more than 2 wt %; ii) allowing at least 90 wt % of the saccharide
in the first portion of the starting material to react; iii)
subsequently adding further portions of starting material to the
reactor over time; and removing reaction product from the
reactor.
Inventors: |
VAN DER HEIDE; Evert;
(Amsterdam, NL) ; WAGLE; Govinda Subbanna;
(Bangalore, IN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHELL OIL COMPANY |
Houston |
TX |
US |
|
|
Family ID: |
48092714 |
Appl. No.: |
14/781756 |
Filed: |
April 1, 2014 |
PCT Filed: |
April 1, 2014 |
PCT NO: |
PCT/EP2014/056524 |
371 Date: |
October 1, 2015 |
Current U.S.
Class: |
568/861 |
Current CPC
Class: |
C07C 31/202 20130101;
C07C 29/132 20130101; C07C 29/60 20130101; C07C 29/00 20130101;
C07C 29/60 20130101; C07C 31/205 20130101; C07C 29/132
20130101 |
International
Class: |
C07C 29/132 20060101
C07C029/132 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 5, 2013 |
EP |
13162503.0 |
Claims
1. A process for the preparation of ethylene glycol and
1,2-propylene glycol from starting material comprising one or more
saccharides, by contacting said starting material with hydrogen in
a reactor in the presence of a solvent and a catalyst system with
catalytic hydrogenation abilities, wherein the process comprises
the steps of: i) introducing a first portion of the starting
material into the reactor such that the initial concentration of
the saccharide in the solvent in the reactor is no more than 2 wt
%; ii) allowing at least 90 wt % of the saccharide in the first
portion of the starting material to react; iii) subsequently adding
further portions of starting material to the reactor over time; and
iv) removing reaction product from the reactor.
2. A process according to claim 1, wherein the catalyst system
comprises at least two active catalytic components comprising, as a
first active catalyst component, one or more materials selected
from transition metals from groups 8, 9 or 10 or compounds thereof,
with catalytic hydrogenation capabilities; and, as a second active
catalyst component, one or more materials selected from tungsten,
molybdenum and compounds and complexes thereof.
3. A process according to claim 1, wherein the process is a batch
process, wherein in step iii), further portions are added until the
total concentration of saccharide in the solvent in the reactor is
at least 5 wt %; and wherein in step iv) the reaction product is
removed from the reactor after the reaction is complete.
4. A process according to claim 1, wherein the process is a
continuous flow process and the reaction product is removed from
the reactor in step iv) in a continuous manner.
5. A process according to claim 1, wherein a first portion of the
starting material is introduced into the reactor such that the
initial concentration of the saccharide in the solvent in the
reactor is no more than 1 wt %.
6. A process according to claim 1, wherein the starting material
comprises one or more saccharide selected from the group consisting
of glucose, sucrose and starch.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a process for the
preparation of ethylene and propylene glycols from
saccharide-containing feedstock.
BACKGROUND OF THE INVENTION
[0002] Ethylene glycol and propylene glycol are valuable materials
with a multitude of commercial applications, e.g. as heat transfer
media, antifreeze, and precursors to polymers, such as PET.
Ethylene and propylene glycols are currently made on an industrial
scale by hydrolysis of the corresponding alkylene oxides, which are
the oxidation products of ethylene and propylene, produced from
fossil fuels.
[0003] In recent years, increased efforts have focused on producing
glycols from renewable feedstocks, such as sugar-based materials.
The conversion of sugars to glycols can be seen as an efficient use
of the starting materials with the oxygen atoms remaining intact in
the desired product.
[0004] Current methods for the conversion of saccharides to sugars
revolve around a hydrogenation/hydrogenolysis process as described
in Angew. Chem. Int. Ed. 2008, 47, 8510-8513. Continuous processes
for generating at least one polyol from a saccharide-containing
feedstock are described in WO 2013/015955 and CN 103731258A. A
process for the co-production of bio-fuels and glycols is described
in WO 2012/174087.
[0005] An important aim in this area is the provision of a process
that is high yielding in desirable products, such as ethylene
glycol and propylene glycol, and that can be carried out on a scale
that makes it industrially viable. A key consideration, therefore,
is the level of dilution of the catalytic process. Carrying out the
process at high levels of dilution can lead to inefficiencies and
will add to the difficulties in separating the desired
products.
[0006] Although acceptable conversion levels to the desired
products are now possible for the catalytic conversion of
saccharides to glycols, these are generally achieved at low
concentrations of saccharides in the catalytic reactors. In
general, the use of higher concentrations of saccharides leads to
reduced overall yields.
[0007] It would be desirable, therefore, to provide a process for
the catalytic conversion of saccharides to glycols in which higher
concentrations of saccharides can be used while maintaining
acceptable yields of the desirable glycols.
SUMMARY OF THE INVENTION
[0008] Accordingly, the present invention provides a process for
the preparation of ethylene glycol and 1,2-propylene glycol from
starting material comprising one or more saccharides, by contacting
said starting material with hydrogen in a reactor in the presence
of a solvent and a catalyst system with catalytic hydrogenation
abilities, wherein the process comprises the steps of: [0009] i)
introducing a first portion of the starting material into the
reactor such that the initial concentration of the saccharide in
the solvent in the reactor is no more than 2 wt %; [0010] ii)
allowing at least 90 wt % of the saccharide in the first portion of
the starting material to react; [0011] iii) subsequently adding
further portions of starting material to the reactor over time; and
[0012] iv) removing reaction product from the reactor.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The present inventors have surprisingly found that the
reduction in overall yield obtained when carrying out the catalytic
conversion of saccharides to glycols with saccharide solutions,
suspensions or slurries at higher concentrations can be reduced by
using a procedure in which an initial portion of starting material
is added to the reactor and allowed to react to near completion
before any further material is added.
[0014] The starting material for the subject process comprises at
least one saccharide selected from the group consisting of
monosaccharides, disaccharides, oligosaccharides and
polysaccharides. Examples of polysaccharides include cellulose,
hemicelluloses, starch, glycogen, chitin and mixtures thereof. If
the starting material comprises oligosaccharides or
polysaccharides, it is preferable that it is subjected to
pre-treatment before being fed to the reactor in a form that can be
converted in the process of the present invention. Suitable
pre-treatment methods are known in the art and one or more may be
selected from the group including, but not limited to, sizing,
drying, grinding, hot water treatment, steam treatment, hydrolysis,
pyrolysis, thermal treatment, chemical treatment, biological
treatment.
[0015] Preferably, the starting material comprises one or more
saccharide selected from the group consisting of glucose, sucrose
and starch. Said saccharide is suitably present as a solution, a
suspension or a slurry in the solvent.
[0016] The solvent present in the reactor may be water or a C.sub.1
to C.sub.6 alcohol or mixtures thereof. Preferably, the solvent is
water. If the starting material is provided to the reactor as a
solution, suspension or slurry in a solvent, said solvent is also
suitably water or a C.sub.1 to C.sub.6 alcohol or mixtures thereof.
Preferably, both solvents are the same. More preferably, both
solvents comprise water. Most preferably, both solvents are
water.
[0017] The catalyst system used preferably comprises at least two
active catalytic components comprising, as a first active catalyst
component, one or more materials selected from transition metals
from groups 8, 9 or 10 or compounds thereof, with catalytic
hydrogenation capabilities; and, as a second active catalyst
component, one or more materials selected from tungsten, molybdenum
and compounds and complexes thereof.
[0018] Preferably, the first active catalyst component consists of
one or more of the group selected from iron, cobalt, nickel,
ruthenium, rhodium, palladium, iridium and platinum. This component
may be present in the elemental form or as a compound. It is also
suitable that this component is present in chemical combination
with one or more other ingredients in the catalyst system. It is
required that the first active catalyst component has catalytic
hydrogenation capabilities and it is capable of catalysing the
hydrogenation of material present in the reactor.
[0019] Preferably, the second active catalyst component comprises
of one or more compound, complex or elemental material comprising
tungsten, molybdenum, vanadium, niobium, chromium, titanium or
zirconium. More preferably the second active catalyst component
comprises one or more material selected from the list consisting of
tungstic acid, molybedic acid, ammonium tungstate, ammonium
metatungstate, ammonium paratungstate, tungstate compounds
comprising at least one Group I or II element, metatungstate
compounds comprising at least one Group I or II element,
paratungstate compounds comprising at least one Group I or II
element, heteropoly compounds of tungsten, heteropoly compounds of
molybdenum, tungsten oxides, molybdenum oxides, vanadium oxides,
metavanadates, chromium oxides, chromium sulfate, titanium
ethoxide, zirconium acetate, zirconium carbonate, zirconium
hydroxide, niobium oxides, niobium ethoxide, and combinations
thereof. The metal component is in a form other than a carbide,
nitride, or phosphide. Preferably, the second active catalyst
component comprises one or more compound, complex or elemental
material selected from those containing tungsten or molybdenum.
[0020] The catalyst components may be heterogeneous or homogeneous
with respect to the solvent or solvents present in the reactor
during the process of the present invention. The catalyst
components may be preloaded into the reactor or, if they are in
liquid form or present as a solution or slurry in a solvent, they
may be fed into the reactor as required in a continuous or
discontinuous manner during the process of the present
invention.
[0021] Preferably, at least one of the active catalyst components
is supported on a solid support. In this embodiment, any other
active catalyst component may be present in either heterogeneous or
homogeneous form. Said any other active catalyst component may also
be supported on a solid support. In one embodiment, the first
active catalyst component is supported on one solid support and the
second active catalyst component is supported on a second solid
support which may comprise the same or different material. In
another embodiment, both active catalyst components are supported
on one solid support.
[0022] The solid supports may be in the form of a powder or in the
form of regular or irregular shapes such as spheres, extrudates,
pills, pellets, tablets, monolithic structures. Alternatively, the
solid supports may be present as surface coatings, for examples on
the surfaces of tubes or heat exchangers. Suitable solid support
materials are those known to the skilled person and include, but
are not limited to aluminas, silicas, zirconium oxide, magnesium
oxide, zinc oxide, titanium oxide, carbon, activated carbon,
zeolites, clays, silica alumina and mixtures thereof.
[0023] Suitably, the weight ratio of the first active catalyst
component to the second active catalyst component is in the range
of from 0.02:1 to 3000:1, preferably in the range of from 0.1:1 to
100:1, on the basis of the weight of metal present in each
component.
[0024] The weight ratio of the first active catalyst component
(based on the amount of metal in said component) to sugar is
suitably in the range of from 1:100 to 1:10000. The weight ratio of
the second active catalyst component (based on the amount of metal
in said component) to sugar is suitably in the range of from 1:10
to 1:1000.
[0025] The temperature in the reactor is suitably at least
130.degree. C., preferably at least 150.degree. C., more preferably
at least 170.degree. C., most preferably at least 190.degree. C.
The temperature in the reactor is suitably at most 300.degree. C.,
preferably at most 280.degree. C., more preferably at most
270.degree. C., even more preferably at most 250.degree. C.
Preferably, the reactor is heated to a temperature within these
limits before addition of any starting material and is maintained
at such a temperature until all reaction is complete.
[0026] The pressure in the reactor is suitably at least 1 MPa,
preferably at least 2 MPa, more preferably at least 3 MPa. The
pressure in the reactor is suitably at most 16 MPa, more preferably
at most 12 MPa, more preferably at most 10 MPa, even more
preferably at most 8 MPa, most preferably at most 6 MPa.
Preferably, the reactor is pressurised to a pressure within these
limits by addition of hydrogen before addition of any starting
material and is maintained at such a pressure until all reaction is
complete. This can be achieved by subsequent addition of
hydrogen.
[0027] The process of the present invention takes place in the
presence of hydrogen. Preferably, the process of the present
reaction takes place in the absence of air or oxygen. In order to
achieve this, it is preferable that the atmosphere in the reactor
be evacuated and replaced with hydrogen repeatedly, after loading
of any initial reactor contents. It may also be suitable to add
further hydrogen to the reactor as the reaction proceeds.
[0028] The reactor in the present invention may be any suitable
reactor known in the art.
[0029] In step i) of the process of the present invention, a first
portion of starting material is introduced into the reactor such
that the initial concentration of sugar in the solvent in the
reactor is no more than 2 wt %. The solvent includes any solvent
already present in the reactor as well as any solvent present in
the slurry, solution or suspension of the starting material. The
initial concentration is preferably no more than 1.8 wt %, more
preferably no more than 1.5 wt %, more preferably no more than 1.3
wt %, more preferably no more than 1.0 wt %, even more preferably
no more than 0.8 wt %, most preferably no more than 0.5 wt %.
[0030] The initial concentration of the sugar in the solvent in the
reactor is suitable at least 0.1 wt %, preferably at least 0.2 wt
%, more preferably at least 0.3 wt %.
[0031] In step ii), at least 90 wt % of the saccharide in the first
portion of the starting material is allowed to react. Preferably,
at least 95 wt %, more preferably at least 98 wt %, even more
preferably at least 99 wt %, most preferably substantially 100 wt %
is allowed to react before further portions of starting material
can be added in step iii).
[0032] The process may be carried out as a batch process or as a
continuous flow process.
[0033] In one embodiment of the invention, the process is a batch
process. In said process, after initial loading of catalyst and,
optionally, solvent, the reactor is heated and pressurised with
hydrogen and then the first portion of starting material is
introduced into the reactor and allowed to react until at least 90
wt % of the saccharide has reacted.
[0034] In this embodiment of the invention, further portions of
starting material are then added to the reactor over time until the
total concentration of saccharide in the solvent in the reactor is
at least 5 wt %. Total concentration as used herein refers to the
concentration calculated as a weight percentage of the total amount
of saccharide added in the total amount of solvent present in the
reactor. The total amount of saccharide added corresponds to the
sum total of the amount of saccharide added in the first portion
and all further portions. The total amount of solvent in the
reactor includes any solvent already present in the reactor as well
as any solvent present in the slurry, solution or suspension of the
starting material. Preferably, further portions of starting
material are added to the reactor over time until the total
concentration of sugar in the solvent in the reactor is at least 7
wt %, more preferably at least 8 wt %, even more preferably at
least 10 wt %. Suitably the total concentration of sugar in the
solvent is no higher than 30 wt %, preferably no higher than 25 wt
%.
[0035] In this embodiment of the invention, adding further portions
of starting material may occur in a continuous manner or the
portions may be added in a discontinuous manner with time elapsing
between the end of the addition of one portion and the start of the
addition of the next portion. In the embodiment of the invention
wherein the portions are added in a discontinuous manner, the
number and size of each portion will be dependent on the scale of
the reactor. Preferably, the total number of portions including the
first portion is no less than 5, more preferably no less than 8,
even more preferably no less than 10. The amount of time over which
each portion is added and the time to be elapsed between the end of
the addition of one portion and the start of the addition of the
next portion will also depend on the scale of the reactor.
Preferably, the time to be elapsed between the end of the addition
of one portion and the start of the addition of the next portion
will be greater than the amount of time over which each portion is
added.
[0036] In this embodiment of the invention, wherein the process is
a batch process, after addition of all of the portions of the
starting material, the reaction may then be allowed to proceed to
completion for a further period of time. The reaction product will
then be removed from the reactor in step iv).
[0037] In the embodiment of the invention wherein the process is
carried out as a continuous flow process, after initial loading of
catalyst and, optionally, solvent, the reactor is heated and
pressurised with hydrogen and then the first portion of starting
material is introduced into the reactor and allowed to react until
at least 90 wt % of the saccharide has reacted. Further portions of
starting material are then provided to the reactor. Reaction
product is removed from the reactor in a continuous manner.
[0038] In this embodiment, the starting material is suitably a
saccharide feedstock comprising at least 1 wt % saccharide as a
solution, suspension or slurry in a solvent. Preferably, said
saccharide feedstock comprises at least 2 wt %, more preferably at
least 5 wt %, even more preferably at least 10 wt %, most
preferably at least 20 wt % saccharide in a solvent. Suitably, the
saccharide feedstock contains no more than 50 wt %, preferably no
more than 40 wt % saccharide in a solvent.
[0039] The present invention is further illustrated in the
following Examples.
EXAMPLES
[0040] In each of the following examples, yields of monoethylene
glycol (MEG), monopropylene glycol (MPG) and 1,2-butanediol
(1,2-BDO) were quantified by GC-FID, applying a CPSil-5 column and
are shown in Tables 1 to 3.
Example 1
[0041] 0.3 g of glucose (portion 1) was dissolved in 30 ml of
deionised water and charged into a 60 ml autoclave equipped with a
gas stirrer and hydrogen supply along with 0.5 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.5 g of a
Ru(1.0)/SiO.sub.2 catalyst. The autoclave was closed, the gas phase
was replaced by nitrogen, then by hydrogen and the autoclave was
pressurised to 3000 kPa (absolute). The autoclave was stirred at
1450 rpm, heated to 195.degree. C. in 12-15 minutes and kept at
195.degree. C. and 8500 kPa (absolute) for 5 minutes. The reactor
was then cooled to room temperature over 15 minutes, depressurised
and opened. A liquid sample of 0.3 ml was taken for analysis. 1.0 g
glucose was added (portion 2), and the procedure was repeated, with
a 10 minute reaction time at 195.degree. C. Three more lots of
glucose (portions 3, 4 and 5) were added following the same
procedure. Finally, portion 6, comprising 1.7 g of glucose was
added and the reaction was continued for 30 minutes. The total
amount of glucose added to 30 ml water was 6 gram, corresponding to
a total concentration of 20 wt % glucose. The total reaction time
was 75 minutes at 195.degree. C.
Example 2
[0042] The procedure of Example 1 was repeated, with the difference
that 0.25 g of a W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and
0.25 g of a Ru(1.0)/SiO.sub.2 catalyst were used and portions 2 to
5 each contained 0.5 g of glucose. The total amount of glucose
(portions 1 to 6) added to 30 ml water was 3 g, corresponding to a
total concentration of 10 wt % glucose.
Example 3
[0043] 15 ml of deionised water, 0.5 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.5 g of a
Ru(1.0)/SiO.sub.2 catalyst were charged into a 60 ml autoclave,
equipped with a gas stirrer and hydrogen supply. The autoclave was
closed, the gas phase replaced by nitrogen, then by hydrogen and
the autoclave was pressurised to 3000 kPa (absolute). The autoclave
was stirred at 1450 rpm, heated to 195.degree. C. in 12-15 minutes
and the pressure increased to 8500 kPa (absolute). 1.5 ml of a 40
wt % glucose solution in water was pumped into the autoclave every
nine minutes at a rate of 5 ml per minute until 10 portions had
been added. After the addition of the tenth portion, the autoclave
was maintained for an additional 10 minutes at 195.degree. C. The
total amount of glucose added was 6 g, corresponding to a total
concentration of 20 wt % glucose. The total reaction time was 100
minutes at 195.degree. C.
Example 4
[0044] 20 ml of deionised water, 0.250 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.250 g of a
Ru(1.0)/SiO.sub.2 catalyst were charged into a 60 ml autoclave,
equipped with a gas stirrer and hydrogen supply. The autoclave was
closed, the gas phase replaced by nitrogen, then by hydrogen and
the autoclave was pressurised to 3000 kPa (absolute). The autoclave
was stirred at 1450 rpm, heated to 195.degree. C. in 12-15 minutes
and the pressure increased to 8500 kPa (absolute). 1.0 ml of a 30
wt % glucose solution in water was pumped into the autoclave every
nine minutes at a rate of 5 ml per minute until 10 portions had
been added. After the addition of the tenth portion, the autoclave
was maintained for an additional 10 minutes at 195.degree. C. The
total amount of glucose added was 3 g, corresponding to a total
concentration of 10 wt % glucose. The total reaction time was 100
minutes at 195.degree. C.
Example 5 (Comparative)
[0045] 6.0 g of glucose were dissolved in 30 ml of deionised water
and charged into a 60 ml autoclave, equipped with a gas stirrer and
hydrogen supply along with 0.200 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.100 g of a
Ru(1.0)/SiO.sub.2 catalyst. The autoclave was closed, the gas phase
replaced by nitrogen, then by hydrogen and the autoclave was
pressurised to 3000 kPa (absolute). The autoclave was stirred at
1450 rpm, heated to 195.degree. C. in 12-15 minutes and the
pressure increased to 8500 kPa (absolute). The autoclave was
maintained at this temperature and pressure for 75 minutes. The
reactor was then cooled to room temperature over 15 minutes,
depressurized, opened, and a liquid sample of 0.3 ml was taken for
analysis.
Example 6 (Comparative)
[0046] Example 5 was repeated with 0.200 g of a W
(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.200 g of a
Ru(1.0)/SiO.sub.2 catalyst.
Example 7
[0047] 15 ml of deionised water, 0.500 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.500 g of a
Ru(1.0)/SiO.sub.2 catalyst were charged into a 60 ml autoclave,
equipped with a gas stirrer and hydrogen supply. The autoclave was
closed, the gas phase replaced by nitrogen, then by hydrogen and
the autoclave was pressurised to 3000 kPa (absolute). The autoclave
was stirred at 1450 rpm, heated to 195.degree. C. in 12-15 minutes
and the pressure increased to 8500 kPa (absolute). A 40 wt %
solution of glucose (total 15.5 ml) in water was added in 28
portions, with each portion being added over one minute, and the
reaction being allowed to proceed for 3 minutes between each
addition. The details of each portion are shown in Table 4. The
reaction was continued for a further 60 minutes after the additions
were completed. The total amount of glucose added was 6 gram,
corresponding to a total concentration of 20 wt % glucose. The
total reaction time was 170 minutes at 195.degree. C.
Example 8
[0048] Example 7 was repeated using 0.0750 g of a W
(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.0750 g of a
Ru(1.0)/SiO.sub.2 catalyst and with 5 minutes reaction time after
the addition of each portion. The details of quantity of different
lots are shown in Table 5.
Example 9
[0049] Example 7 was repeated using 0.100 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.050 g of a
Ru(1.0)/SiO.sub.2 catalyst with 5 minutes reaction time after
addition of each portion. The details of quantity of different lots
are shown in Table 5.
Example 10
[0050] Example 7 was repeated using 0.050 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.100 g of a
Ru(1.0)/SiO.sub.2 catalyst with 5 minutes reaction time after
addition of each lot. The details of quantity of different lots are
shown in Table 5.
Example 11 (Comparative)
[0051] 0.3 g of glucose was dissolved in 30 ml of deionised water
charged into a 60 ml autoclave, equipped with a gas stirrer and
hydrogen supply, along with 0.025 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.025 g of a
Ru(1.0)/SiO.sub.2 catalyst. The autoclave was closed, the gas phase
replaced by nitrogen, then by hydrogen and the autoclave was
pressurised to 3000 kPa (absolute). The autoclave was stirred at
1450 rpm, heated to 195.degree. C. in 12-15 minutes and the
pressure increased to 8500 kPa (absolute). The temperature and
pressure were maintained for 75 minutes. The reactor was then
cooled to room temperature over 15 minutes, depressurized, opened
and a liquid sample of 0.3 ml was taken for analysis.
Example 12 (Comparative)
[0052] 3.0 g of glucose was dissolved in 30 ml of deionised water
and charged into a 60 ml autoclave, equipped with a gas stirrer and
hydrogen supply, along with 0.250 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.250 g of a
Ru(1.0)/SiO.sub.2 catalyst. The autoclave was closed, the gas phase
replaced by nitrogen, then by hydrogen and the autoclave was
pressurised to 3000 kPa (absolute). The autoclave was stirred at
1450 rpm, heated to 195.degree. C. in 12-15 minutes and the
pressure increased to 8500 kPa (absolute). The temperature and
pressure were maintained for 75 minutes. The reactor was then
cooled to room temperature over 15 minutes, depressurized, opened
and a sample was taken for analysis.
Example 13 (Comparative)
[0053] Example 12 was repeated using 6.0 g of glucose dissolved in
30 ml of deionised water, 0.500 g of a
W(10.88)-Ni(3.63)-Pt(0.05)/ZrO.sub.2 catalyst and 0.500 g of a
Ru(1.0)/SiO.sub.2 catalyst.
TABLE-US-00001 TABLE 1 glycol yields in Example 1 cumulative
glucose concentration MEG yield MPG yield 1,2-BDO yield (wt %) (%)
(%) (%) 1.0 7.7 6.6 0.8 4.3 26.8 7.7 2.0 7.7 29.3 6.7 2.3 11.0 29.2
6.3 2.7 14.3 27.8 6.0 2.8 20.0 26.5 6.8 3.7
TABLE-US-00002 TABLE 2 glycol yields in Example 2 cumulative
glucose concentration MEG yield MPG yield 1,2-BDO yield (wt %) (%)
(%) (%) 1.0 19.4 6.4 0.6 2.7 30.9 7.2 1.4 4.3 33.8 6.8 1.8 6.0 34.9
6.6 2.1 7.7 33.8 6.7 2.4 10.0 32.9 7.2 2.8
TABLE-US-00003 TABLE 3 glycol yields in Examples 3 to 13 Yield of
Yield of Yield of Example MEG (%) MPG (%) 1,2-BDO (%) 3 30.0 5.5
3.0 4 33.0 5.0 2.0 5* 3.8 0.3 0.3 6* 11.0 2.0 2.0 7 30.0 8.0 2.6 8
25.0 4.0 3.2 9 23.0 2.7 2.0 10 22.0 4.7 3.7 11* 42.9 11.7 4.8 12*
22.0 7.0 4.5 13* 14.5 5.0 4.0 *comparative
TABLE-US-00004 TABLE 4 addition of portions in Example 7 Time of
addition in Portion minutes number start finish Vol (ml) 1 0 1
0.3846 2 4 5 0.3945 3 8 9 0.4046 4 12 13 0.4150 5 16 17 0.4256 6 20
21 0.4365 7 24 25 0.4477 8 28 29 0.4592 9 32 33 0.4710 10 36 37
0.4830 11 40 41 0.4954 12 44 45 0.5081 13 48 49 0.5212 14 52 53
0.5345 15 56 57 0.5482 16 60 61 0.5623 17 64 65 0.5767 18 68 69
0.5915 19 72 73 0.6067 20 76 77 0.6222 21 80 81 0.6382 22 84 85
0.6545 23 88 89 0.6713 24 92 93 0.6885 25 96 97 0.7062 26 100 101
0.7243 27 104 105 0.7429 28 108 109 0.7619 Total(Vol) 15.4763
TABLE-US-00005 TABLE 5 addition of portions in Examples 8 to 10
Time of addition in Portion minutes number start finish Vol (ml) 1
0 1 0.3846 2 6 7 0.3945 3 12 13 0.4046 4 18 19 0.4150 5 24 25
0.4256 6 30 31 0.4365 7 36 37 0.4477 8 42 43 0.4592 9 48 49 0.4710
10 54 55 0.4830 11 60 61 0.4954 12 66 67 0.5081 13 72 73 0.5212 14
78 79 0.5345 15 84 85 0.5482 16 90 91 0.5623 17 96 97 0.5767 18 102
103 0.5915 19 108 109 0.6067 20 114 115 0.6222 21 120 121 0.6382 22
126 127 0.6545 23 132 133 0.6713 24 138 139 0.6885 25 144 145
0.7062 26 150 151 0.7243 27 156 157 0.7429 28 162 163 0.7614
Total(Vol) 15.4758
* * * * *