NZ732809B2 - Solar collector - Google Patents
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- NZ732809B2 NZ732809B2 NZ732365A NZ73236514A NZ732809B2 NZ 732809 B2 NZ732809 B2 NZ 732809B2 NZ 732365 A NZ732365 A NZ 732365A NZ 73236514 A NZ73236514 A NZ 73236514A NZ 732809 B2 NZ732809 B2 NZ 732809B2
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Abstract
ultra-high frequency identification tag for attachment to an animal, said identification tag comprising: a body; an integrated circuit; an ultra-high frequency antenna device electrically connected to said integrated circuit; wherein the antenna device comprises: a meander line antenna; and a substrate; wherein said antenna device is operable to use the body of the animal to which it is attached as part of the tuning circuit of said antenna device such that said antenna device is operable to use the body of the animal as a ground plane; and wherein said antenna device is purposely detuned such that it is only tuned to a desired frequency when the tag is attached to the animal; and wherein said meander line antenna is a three-dimensional meander line antenna comprising two layers; and wherein one or more of: the dimensions of the meander line antenna, spacing between elements and layers of the meander line antenna, the number of turns of the meander line antenna; and the substrate thickness, is tuned to impedance match the antenna device to the integrated circuit to which it is to be attached, and such that no further external impedance matching components are required. strate; wherein said antenna device is operable to use the body of the animal to which it is attached as part of the tuning circuit of said antenna device such that said antenna device is operable to use the body of the animal as a ground plane; and wherein said antenna device is purposely detuned such that it is only tuned to a desired frequency when the tag is attached to the animal; and wherein said meander line antenna is a three-dimensional meander line antenna comprising two layers; and wherein one or more of: the dimensions of the meander line antenna, spacing between elements and layers of the meander line antenna, the number of turns of the meander line antenna; and the substrate thickness, is tuned to impedance match the antenna device to the integrated circuit to which it is to be attached, and such that no further external impedance matching components are required.
Description
Title: PROCESS FOR PREPARING ESTERS OF LACTIC ACID, AND 2-
HYDROXYBUTENOIC ACID OR ALFA-HYDROXY METHIONINE ANALOGUES
FROM SUGARS
Description:
The present invention relates to a novel process for the
production of esters of lactic acid and 2-hydroxybutenoic
acid or α-hydroxy methionine analogues suitable for
continuous flow processes.
Background
It is to be understood that if any prior art publication is
referred to herein, such reference does not constitute an
admission that the publication forms a part of the common
general knowledge in the art in New Zealand or any other
country.
Carbohydrates represent the largest fraction of biomass and
various strategies for their efficient use as a feedstock for
the preparation of commercial chemicals are being established.
Biomass is of particular interest due to its potential for
supplementing, and ultimately replacing, petroleum. One such
commercial chemical obtainable from biomass is lactic acid. A
lactic acid derivative, methyl lactate, is a convenient
building block towards renewable and biodegradable solvents and
polymers.
Lactic acid derivatives, in particular esters of lactic acid,
may be obtainable from sugars via a variety of reaction process
routes including biochemical (enzymatic fermentation;
enantiopure product), and synthetic (catalytic conversion;
focused on
racemic product). Particular attention has been
synthetic (catalytic) routes as they provide a
18075065_1 (GHMatters) P42926NZ00
commercially and environmentally advantageous alternative
to biochemical routes, in addition to providing a racemic
product. A racemic product is advantageous if, for example,
polymers that require stoichiometric amounts of both enan-
tiomers of lactic acid enantiomers are desired as the
starting materials, for example, polylactic acid (PLA).
The prior art establishes that racemic mixtures of esters
of lactic acid and 2-hydroxybutenoic acid may be pre-
pared from sugars in the presence of a Lewis acid catalyst.
Esters of lactic acid and 2-hydroxybutenoic acid or α-
hydroxy methionine analogues may be prepared by a batch or
continuous flow process from sugars in the presence of a
Lewis acid catalyst. Both Science (2010) 328, pp 602 - 605
and EP 2 184 270 B1 disclose batch reactions for the pro-
cess wherein the solvent is methanol only or methanol and
2.5 wt% water. Both references also disclose a batch reac-
tion where the solvent is water, consequently producing
lactic acid (30%) from sucrose.
In order to obtain an industrially feasible process for
preparing the esters described above, it is essential that
the Lewis acid catalyst remains stable, i.e. active, for a
prolonged process duration. It is a well-known problem that
Lewis acid catalysts deactivate over time during a reaction
and must be regenerated by calcination. Deactivation of the
Lewis acid catalyst requires the process to be stopped and
the catalyst to be isolated and regenerated by calcination
for at least 12 - 18 hours. Science (2010) 328, pp 602 -
605 and EP 2 184 270 B1 disclose that for all batch reac-
17831788_1 (GHMatters) P42926NZ00
tions the catalyst is regenerated by calcination after 20
hours.
Science (2010) 328, pp 602 - 605 also discloses a continu-
ous flow process for the conversion of a sugar (fructose)
to methyl lactate in the presence of a Lewis acid catalyst
(Sn-BEA) and an organic solvent (methanol). Figure 7 of the
supporting data indicates that the percentage yield of me-
thyl lactate from fructose with time on stream (TOS) is re-
duced by at least 50%, from about 23% at 3 hours to about
11% at 80 hours. This figure shows that Sn-BEA deactivates
gradually as a function of time on stream. Similarly to the
batch reactions, the catalyst is regenerated by calcina-
tion. It is noted that Sn-BEA and Sn-Beta (as used here)
are identical.
Additionally, Science (2010) 328, pp 602 - 605 illustrates
that the presence of water to the reaction process is a
disadvantage with regard to catalyst stability. When the
solvent of the process is only water, the carbon deposition
on the catalyst is greatly increased, contributing signifi-
cantly to the deactivation of the catalyst. For example,
when the solvent of the process is water, 7 wt% of carbon
per gram of catalyst is deposited on the catalyst, in com-
parison to 1.3 wt% when the process employs methanol only
as the solvent.
A further example of the disadvantage of the addition of
water to a process that employs a Lewis acid catalyst has
been reported in Journal of Catalysis (2003) 220, pp 326 –
332. This reference discloses the Mukiyama-type aldol con-
densation of aldehydes with a silyl enol ether over a tita-
17831788_1 (GHMatters) P42926NZ00
nium silicate Lewis acid catalyst (Ti-BETA or TS-1). The
reference reports that the addition of a small amount of
water to the batch reaction medium during the initial reac-
tion period decreases the activity of the catalyst. It is
believed that the Lewis acid catalysts are poisoned by wa-
ter and therefore become inactive. For alternative reac-
tions, ChemSusChem (2014) 7, pp 2255–2265, reports the same
effect for Sn-BEA catalysed batch reactions.
A still further example of the disadvantage of the addition
of water to a process that employs a Lewis acid catalyst
has been reported in Journal of Catalysis (2014) 311, pp
244 – 256. This reference is directed towards the study of
reaction pathways of the catalytic deoxygenation of pro-
panal (propionaldehyde). The reference discloses that Lewis
acid sites of the catalyst are prevented from participating
in the catalytic reaction when water is present because the
water rehydrates or is physisorbed onto these sites.
It would be desirable to provide a means for stabilising a
Lewis acid catalyst for use in a continuous reaction pro-
cess for preparing esters of lactic acid and 2-hydroxy
butenoic acid from a sugar. It would also be desirable to
provide esters of lactic acid and α-hydroxy methionine ana-
logues from a sugar.
In addition to reducing carbon deposition on the catalyst,
it would also be desirable to provide a means for stabilis-
ing a Lewis acid catalyst comprising Sn, wherein leaching
of Sn from the catalyst is reduced and a significantly
higher yield of esters of 2-hydroxybutenoic acid is ob-
tained. The reduction in Sn leaching results in a more pure
17831788_1 (GHMatters) P42926NZ00
product and a cheaper process (as less Sn is required). In
addition, the esters of 2-hydroxybutenoic acid by-
product are valuable chemicals and may provide an addition-
al commodity from the process. More explicitly, the addi-
tion of a significantly increased yield of esters of 2-
hydroxybutenoic acid provide a higher combined yield of
esters of lactic acid and 2-hydroxybutenoic acid, to-
gether with providing a higher conversion of the sugar.
These advantages also apply to the preparation of the α-
hydroxy methionine analogues.
Disclosure of the invention
It has now been discovered that the presence of water in
the organic solvent of a continuous flow reaction facili-
tates Lewis acid catalyst stability for continuous flow re-
actions. Deposition of carbonaceous species on the catalyst
leading to deactivation or poisoning of the catalyst Lewis
acid active sites is not observed to any industrially sig-
nificant extent. Retention in activity, i.e. stability of
the catalyst, results in the continued high yields of the
desired product for sustained reaction durations of contin-
uous flow reactions.
The present invention relates to a continuous flow process
for the preparation of one or more esters of lactic acid
and 2-hydroxybutenoic acid from a sugar in the presence
of a solid Lewis acid catalyst and a solvent comprising an
organic solvent and water, wherein the water is present in
an amount of up to or equal to 10 vol. % of the organic
solvent.
17831788_1 (GHMatters) P42926NZ00
The present invention also relates to a continuous flow
process for the preparation of α-hydroxy methionine ana-
logues from a sugar in the presence of a compound compris-
ing sulfur, a solid Lewis acid catalyst and a solvent com-
prising an organic solvent and water, wherein the water is
present in an amount of up to or equal to 10 vol. % of the
organic solvent.
In the claims which follow and in the proceeding descrip-
tion of the invention, except where the context requires
otherwise due to express language or necessary implication,
the word “comprise” or variations such as “comprises” or
“comprising” is used in an inclusive sense, i.e. to specify
the presence of the stated features, integers, steps or
components but not to preclude the presence or addition of
further features integers, steps, components or groups
thereof in various embodiments of the invention.
Continuous flow process means a reaction or process that
occurs over a (prolonged) period of time and the reactant
is fed through a reaction chamber in a solvent. A general
reference demonstrating continuous flow processes is Per-
ry's Chemical Engineers' Handbook, eighth edition, McGraw-
Hill, 2008.
The terms continuous flow process, process, reaction and
reaction process are intended to be interchangeable.
More specifically, the present invention relates to a con-
tinuous flow process wherein the amount of water present in
the solvent is up to 10 volume percent (vol. %) of the or-
ganic solvent. Volume percent means a volume to volume ra-
17831788_1 (GHMatters) P42926NZ00
tio of two solvents; for example, 10 volume % means a ratio
of 10:90 of a first solvent and a second solvent. For exam-
ple, in the present invention 10 volume % of water in an
organic solvent means a volume ratio of 10:90 of water to
an organic solvent. The invention may be performed where
the vol. % of water present in the organic solvent is from
greater than 0 to 30 vol. % or from greater than 0 to 20
vol. %. In a preferred embodiment, the vol. % of water pre-
sent in the organic solvent is from greater than 0 to equal
to or less than 10 vol. %. For example, the vol. % of water
present in the organic solvent may be about 5 vol. %, about
1 vol. % or about 0.25 vol. %.
In an embodiment of the invention, the vol. % of water pre-
sent in the organic solvent may be chosen to influence the
yield of either the esters of lactic acid or the esters of
2-hydroxybutenoic acid or α-hydroxy methionine analogues
produced. For example, where the vol. % of water present in
the organic solvent is from greater than 0 to 2 vol. %, the
optimal yield of esters of lactic acid may be obtained. Ad-
ditionally, where the vol. % of water present in the organ-
ic solvent is from 3 to 10 vol. %, the optimal yield of es-
ters of 2-hydroxybutenoic acid (MVG) may be obtained.
The present invention also relates to the use of a sugar
syrup as feed. Sugar syrups are low cost mixtures of sugar
and water which constitute a particularly useful feedstock
for the present invention. In one embodiment, sugar syrup
is mixed with an organic solvent to provide the final reac-
tion mixture containing sugar, water and the organic sol-
vent. The water content may optionally be adjusted by
choice of syrup concentration or by addition of more water
17831788_1 (GHMatters) P42926NZ00
independently of the syrup. The sugar syrups have a sugar
dry matter content of higher than 30%, more preferably
higher than 50% or yet more preferably higher than 64%. The
term “sugar” refers to mono- and disaccharides and it can
be selected from the group consisting of glycolaldehyde,
glyceraldehyde, dihydroxyacetone, erythrose, erythrulose,
threose, xylose, arabinose, glucose, fructose, mannose, ga-
lactose, sucrose, lactose, maltose and mixtures thereof.
Examples of sugar syrups are dextrose syrup, high fructose
corn syrup, sugar cane juice syrups, inverted sucrose syr-
up, sugar beet juice syrup (thick juice), hemicellulose
syrups (containing mixtures of xylose, glucose, mannose and
other sugars) and glycolaldehyde syrups (primarily contain-
ing glycolaldehyde, obtained e.g. as described in WO
2014/131743).
Organic solvent means one or more solvents selected from
the group consisting of methanol, ethanol, 1-propanol, 1-
butanol and isopropanol.
Esters of lactic acid and 2-hydroxybutenoic acid means
one or more esters of lactic acid and one or more esters of
2-hydroxybutenoic acid. For example, if the organic sol-
vent of the process is methanol only, then only the methyl
ester of lactic acid and 2-hydroxybutenoic acid would be
formed.
The present invention additionally relates to a process
wherein the yield of the one or more lactic acid esters de-
creases over the course of the continuous flow process. For
example, the yield of the one or more lactic acid esters
17831788_1 (GHMatters) P42926NZ00
may decrease by up to 0.01, 0.02, 0.03, 0.05, 0.10, 0.15,
0.20 or 0.25 % per hour on stream on average.
Decrease in yield per hour on stream on average means the
decrease in the percentage yield of the one or more lactic
acid esters over a period of time, once the continuous flow
process has reached a steady state, divided by the number
of hours in that period. For example: for a process that
has reached a steady state, a 5% decrease in yield of one
or more lactic acid esters from, for example from 50% to
45%, is observed over a period of 100 hours, corresponding
to a decrease of 0.05 % yield per hour on stream on aver-
age.
The decrease in the yield of the one or more lactic acid
esters may also be expressed by the decrease in yield after
a time period on stream, in particular once the process has
reached a steady state. For example, the yield of one or
more lactic acid esters may decrease by up to and including
5% in total after 50, 100, 150, 200, 250, 300, 400, 500 or
6000 hours on stream. This example is directly related to
the process described in Example 1; the variation of the
time may vary and is likely to depend on the process and
industrial scale.
Steady state means that continuous flow process conditions
have reached a constant state; e.g. the flow of solvent and
reactants through the reaction chamber is consistent. This
can be determined, for example, in the observation that the
yield of the one or more lactic acid esters does not in-
crease by about 5% over a period of about 5 h. This example
is directly related to the process in Example 1 and is for
17831788_1 (GHMatters) P42926NZ00
illustrative purposes; the variation of the yield is likely
to depend on the process and industrial scale and is not
intended to limit the invention.
Time (hours) on stream (TOS) means time that the feed has
passed through the catalyst bed.
The present invention also relates to a process wherein the
yield of the one or more lactic acid esters or the combined
yield of both the esters of lactic acid and 2-hydroxy
butenoic acid is greater than 40% after 50 hours on stream.
For example: the yield of the one or more lactic acid es-
ters is greater than 40% after 50, 100, 150, 200, 250, 300,
400 or 500 hours on stream.
The present invention also relates to a process wherein the
yield of the one or more lactic acid esters or the combined
yield of both the esters of lactic acid and 2-hydroxy
butenoic acid is greater than 40% after 50 hours on stream.
For example: the yield of the one or more lactic acid es-
ters is greater than 40%, 45 %, 50%, 55%, 60%, 65%, 70% or
75% after 50 hours on stream.
In a further embodiment of the present invention, a com-
pound comprising sulfur is added to the process if it is
desired to obtain an α-hydroxy methionine analogue.
The compound comprising sulfur is selected from the group
consisting of C -C alkyl thiol, C -C alkyl thiol salts,
1 5 1 5
dimethylmercaptan and dimethyl disulfide. C -C alkyl thiol
means mono- and di-substituted thiols with a substituent
comprising straight or branched chain saturated aliphatic
alkyl group comprising one, two, three, four or five car-
17831788_1 (GHMatters) P42926NZ00
bons. Specifically, C -C alkyl thiol means an alkyl thiol
selected from the group consisting of methane thiol, ethane
thiol, straight or branched chain propane thiol, straight
or branched chain butane thiol and straight or branched
chain pentane thiol.
C -C alkyl thiol salt means the alkali or alkaline earth
metal salt of a C -C alkyl thiol. Specifically, C -C alkyl
1 5 1 5
thiol salt means a C1-C5 alkyl thiol in the salt form
wherein the cation is selected from the group consisting of
sodium, potassium, lithium, magnesium and calcium. Specifi-
cally, C -C alkyl thiol salt means a C -C alkyl thiol se-
1 5 1 5
lected from one or more of the group consisting of NaSCH ,
KSCH , Ca(SCH ) and Mg(SCH ) .
3 3 2 3 2
The α-hydroxy methionine analogues are selected from the
group consisting of 2-hydroxy(C alkylthio)butanoic ac-
id, salts and esters thereof. C alkylthio corresponds to
the C alkyl thio compound comprising sulfur present in
the process. Preferably, the α-hydroxy methionine analogues
are selected from the group consisting of 2-hydroxy
(methylthio)butanoic acid, salts and esters thereof. Pref-
erably, the α-hydroxy methionine analogues are selected
from the group consisting of 2-hydroxy(methylthio)-
butanoic acid, alkali and alkaline earth metal salts and
C alkyl esters thereof.
C alkyl esters means esters comprising the alkyl group
selected from the group consisting of methyl, ethyl, pro-
pyl, butyl, isopropyl, isobutyl, pentyl, hexyl, heptyl, oc-
tyl and 2-ethylhexyl. Alkali and alkaline earth metal salts
17831788_1 (GHMatters) P42926NZ00
are salts of the acid wherein the salt cation is selected
from the group I and group II metals.
In one embodiment of the invention the methionine α-hydroxy
analogue is 2-hydroxy(methylthio)butanoic acid.
In a second embodiment of the invention the methionine α-
hydroxy analogues are selected from the group consisting of
2-hydroxy(methylthio)butanoic acid methyl ester, 2-
hydroxy(methylthio)butanoic acid ethyl ester, 2-hydroxy-
4-(methylthio)butanoic acid propyl ester, 2-hydroxy
(methylthio)butanoic acid butyl ester, 2-hydroxy
(methylthio)butanoic acid isopropyl ester, 2-hydroxy
(methylthio)butanoic acid pentyl ester, 2-hydroxy
(methylthio)butanoic acid hexyl ester, 2-hydroxy
(methylthio)butanoic acid heptyl ester, 2-hydroxy
(methylthio)butanoic acid octyl ester and 2-hydroxy
(methylthio)butanoic acid 2-ethylhexyl ester.
Addition of a sulfur compound to the reaction process re-
sults in the preparation of an α-hydroxy methionine ana-
logue, as can be seen in Table 1, which summarizes batch
reactions of the conversion of sugars to methionine α-
hydroxy analogues.
The batch reactions are expected to be transferable to a
continuous process corresponding to the process wherein 2-
hydroxybutenoic acid and esters thereof are prepared.
Table 1: Batch Reactions of the conversion of sugars to me-
thionine α-hydroxy analogues. Amount of methanethiol: 25 mL
(gas), erythrulose initial concentration 13 g/l, glucose
17831788_1 (GHMatters) P42926NZ00
initial concentration 16 g/l, glycolaldehyde (GA) initial
concentration 16 g/l, MVG initial concentration 32 g/l. S-
MVG means methyl 2-hydroxy(methylthio)-butanoate
Sugar Catalyst Sol- S- Conver- Selectivity T. t.
vent MVG sion (%) (%) (°C) (h)
Yield
Erythru- Sn-BEA A 19.6 68.1 28.8 60 16
lose
Erythru- Sn-MFI A 23.7 81.3 29.1 100 4
lose
Erythru- Sn-BEA EtOH 13.5 68.7 19.7 100 4
lose
Glucose Sn-BEA A 5.2 96.8 5.3 170 16
GA Sn-BEA A 14.6 41.9 34.9 120 16
MVG Sn-BEA A 0 0 0 100 4
T. = temperature; t. = time Solvent A: MeOH + 0.13 mmol K CO
GA = glycolaldehyde
The present invention relates to a process in which the
solid Lewis acid catalyst is calcined after 80 hours, after
450 hours, after 500 hours or after 6000 hours of the con-
tinuous flow process.
The invention may also be illustrated by the mass of sugar
converted per mass of catalyst present. For example: The
decrease in yield per hour of the one or more lactic acid
esters is up to 0.25 % when at least 0.45 g of sugar per g
of catalyst has been converted; the decrease in yield of
the one or more lactic acid esters decreases by up to 5 %
when at least 25 g of sugar per g of catalyst has been con-
verted; the yield of the one or more lactic acid esters is
17831788_1 (GHMatters) P42926NZ00
greater than 40% when at least 25 g of sugar per g of cata-
lyst has been converted, when at least 30 g sugar per g of
catalyst has been converted, when at least 200 g sugar per
g of catalyst have been converted or when at least 2500 g
sugar per g of catalyst has been converted.
In the process according to the present invention the solid
Lewis acid catalyst is a zeotype material or a siliceous
porous material. A zeotype material is one in which the
aluminum atoms of a zeolite material are partly or fully
substituted by a metal (metal atoms) such as zirconium
(Zr), titanium (Ti) and tin (Sn). Zeolite materials are
crystalline alumino-silicates with a microporous crystal-
line structure, according to Corma et al., Chem. Rev. 1995,
95 pp 559-614. Alternatively, porous materials such as MCM-
41 and SBA-15 can be used.
In the process of the invention, the solid Lewis acid cata-
lyst framework structure is selected from the group con-
sisting of BEA, MFI, FAU, MOR, FER and MWW and porous mate-
rials such as MCM-41 and SBA-15.
The present invention relates to a process wherein the sol-
id Lewis acid comprises an active metal selected from one
or more of the group consisting of Sn, Ti, Pb, Zr, Ge and
The solid Lewis acid catalyst is preferably selected from
the group consisting of Sn-BEA, Sn-MFI, Sn-FAU, Sn-MOR, Sn-
MWW, Sn-MCM-41 and Sn-SBA-15.
17831788_1 (GHMatters) P42926NZ00
The amount of Sn lost is calculated as the loss of Sn from
the solid Lewis acid catalyst at a point in time after the
process has started, divided by the initial amount of Sn in
the solid Lewis acid catalyst at the start of the process.
It is preferred that the solid Lewis acid catalyst compris-
es Sn and that the loss of Sn from the solid Lewis acid
catalyst is less than or equal to 0.11% of the initial
amount of Sn per hour on stream on average, preferably less
than or equal to 0.05% of the initial amount of Sn per hour
on stream, more preferably less than or equal to 0.02 % of
the initial amount of Sn per hour on stream.
The present invention relates to a process wherein the sol-
id Lewis acid catalyst comprises Sn and the loss of Sn from
the solid Lewis acid catalyst is less than or equal to 8%
of the initial amount of Sn after 50 hours on stream, less
than or equal to 50% of the initial amount of Sn after 400
hours on stream, preferably less than or equal to 40% of
the initial amount of Sn after 400 hours on stream, prefer-
ably less than or equal to 15% of the initial amount of Sn
after 400 hours on stream.
Preferably the yield of the one or more esters of 2-
hydroxybutenoic acid is greater than 10%, more prefera-
bly greater or equal to 12 %.
In the process of the present invention, the sugar is pref-
erably selected from one or more of the group consisting of
glucose, fructose, mannose, sucrose, xylose, erythrose,
erythrulose, threose and glycolaldehyde.
17831788_1 (GHMatters) P42926NZ00
In some cases it is preferred that an alkaline earth metal
or an alkali metal ion is present in the reaction process.
When GA is used as feed, alkali is not required.
According to the present invention, the alkali can be ob-
tained by the addition to the process of one or more com-
pounds selected from the group consisting of K CO , KNO ,
2 3 3
KCl, KOH, potassium acetate (CH CO K), potassium lactate
(CH3CH(OH)CO2K), NaCl, NaOH, Na2CO3, Li2CO3 and Rb2CO3.
In the present invention, the one or more esters of lactic
acid are preferably selected from the group consisting of
methyl lactate and ethyl lactate.
Experimental data for figures are collected in Examples 1
and 2. For the sake of clarity, data obtained in continuous
flow mode are represented using figures, while results from
batch experiments are collected in tables.
Figures 1-5 cover the conversion of C6-sugars (fructose) in
continuous flow mode. Figures 1-3 refer to diminishing of
Sn leaching and diminishing of catalyst deactivation. Fig-
ures 4 and 5 demonstrate the improvement in MVG yield when
water is present. More specifically, the figures have the
following meanings:
Fig 1: Improved stability of the Sn-BEA Lewis acid cata-
lysts with 1%, 5% and 10% water added to the process sol-
vent compared to no water added to the process solvent. The
catalyst stability is illustrated by a significantly con-
sistent yield of methyl lactate product.
17831788_1 (GHMatters) P42926NZ00
Fig 2: Improved stability of the Sn-BEA Lewis acid cata-
lysts with 1% water added to the process solvent (squares)
compared to no water added to the process solvent (trian-
gles). The catalyst stability is illustrated by a signifi-
cantly consistent yield of methyl lactate product observed
over a prolonged period of process time on stream (ca. 500
hours).
Fig 3: Improved stability of the Sn-BEA Lewis acid cata-
lysts with 1% water added to the process solvent (squares)
compared to no water added to the process solvent (trian-
gles). The improved stability is illustrated by a signifi-
cant decrease of Sn leaching (loss of Sn) from the cata-
lyst.
Fig 4: Improved yield of esters of 2-hydroxybutenoic ac-
id with the addition of water to the continuous flow pro-
cess: (a) Yield of 2-hydroxybutenoic acid methyl ester
(MVG); (b) Combined yield of esters of lactic acid (methyl
lactate) and 2-hydroxybutenoic acid methyl ester (MVG).
Fig 5: Yield of bio-monomers obtained from fructose when
using Sn-Beta zeolite in flow. Total yield [methyl lactate
(ML), glycolaldehyde dimethyl acetal (GLAD) and methyl vi-
nyl glycolate (MVG)] is 70% from fructose and it is stable
over 400 h. Methyl vinyl glycolate (MVG) is equivalent to
2-hydroxybutenoic acid methyl ester.
Figures 6-8 cover the conversion of C2-sugar (glycolalde-
hyde) in continuous flow mode. Figures 6 and 7 refer to the
improvement in MVG yield when water is present. Figure 8
17831788_1 (GHMatters) P42926NZ00
refers to the improvement in S-MVG yield when water and me-
thanethiol are present. More specifically, the figures have
the following meanings:
Fig. 6: Improved yield of methyl vinyl glycolate (MVG) from
glycolaldehyde with the addition of water in continuous
flow mode. Feed composition: 20 g/l glycolaldehyde in meth-
anol as solvent. Methyl vinyl glycolate (MVG) is equivalent
to 2-hydroxybutenoic acid methyl ester.
Fig. 7: Yield of bio-monomers obtained from glycolaldehyde
when using Sn-Beta zeolite in flow. Feed composition: 20
g/l glycolaldehyde in methanol as solvent, 8.5 wt% water.
Total yield [glycolaldehyde dimethyl acetal (GLAD), methyl
vinyl glycolate (MVG) and methylmethoxyhydroxy-
butenoate (MMHB)] is 65% from glycolaldehyde at the begin-
ning of the reaction. Methyl vinyl glycolate (MVG) is
equivalent to 2-hydroxybutenoic acid methyl ester.
Fig. 8: Yield of methyl ester of α-hydroxy methionine ana-
logue with Sn-BEA as catalyst in the presence of water and
methanol in continuous flow reaction from glycolaldehyde.
Feed composition: 9 g/l glycolaldehyde in methanol as sol-
vent, 8.5 wt% water, 1.2 g/l methanethiol.
Figure 9 exemplifies the use of syrup as feed in the reac-
tion. It demonstrates the improvement in MVG yield when wa-
ter is present and the use of sugar in the form of a sugar
syrup. More specifically, the figure has the following
meaning:
17831788_1 (GHMatters) P42926NZ00
Fig. 9: Yield of bio-monomers obtained from sucrose syrup
when using Sn-Beta zeolite in flow. Feed composition: 55
g/l sucrose. The total yield [methyl lactate (ML), methyl
vinyl glycolate (MVG)] is 80% from sucrose syrup and it is
stable. Methyl vinyl glycolate (MVG) is equivalent to 2-
hydroxybutenoic acid methyl ester.
The process of the invention is illustrated further by the
following examples.
Example 1
Preparation of catalyst
Sn-BEA (Si/Sn = 125) is prepared according to a modifica-
tion of the procedure described in US 4,933,161. Commercial
zeolite Beta (Zeolyst, Si/Al 12.5, ammonium form) is cal-
cined (550ºC for 6 h) to obtain the H form (de-aluminated
form) and treated with 10 grams of concentrated nitric acid
(Sigma-Aldrich, 65%) per gram of zeolite beta powder for 12
h at 80ºC. The resulting solid is filtered, washed with am-
ple water and calcined (550ºC for 6 h) to obtain the de-
aluminated Beta. This solid is impregnated by incipient
wetness methodology with a Sn/Si ratio of 125. For this
purpose, tin (II) chloride (0.128 g, Sigma-Aldrich, 98%) is
dissolved in water (5.75 ml) and added to the de-aluminated
Beta (5 g). After the impregnation process, the samples are
dried 12 h at 110 ºC and calcined again (550ºC for 6 h).
Catalytic reaction in continuous flow mode:
17831788_1 (GHMatters) P42926NZ00
Fructose (Sigma-Aldrich, 99%) was dissolved in methanol
(Sigma-Aldrich, 99.9%) at room temperature to reach a con-
centration of 12.5 g/l. Additionally, deionized water (0,
, 50 or 100 ml/l) and potassium carbonate (Sigma-Aldrich,
99%, 2.5 mg/l) were added to the feed solution. Catalyst
Sn-Beta (Si:Sn 125) prepared according to the above prepa-
ration was fractionized (0.25 g, 300-600 µm.) and loaded
into a stainless steel 0.25 inch reactor. Glass wool was
used to hold the catalyst in place. The reactor was intro-
duced into an oven and the temperature of the reactor in-
creased to 160 ºC. When the temperature was over 140ºC, the
pump was started with a flow of 0.15 ml/min of a 1.25 wt.%
fructose solution in methanol.
Glycolaldehyde (glycolaldehyde dimer, Sigma) was dissolved
in methanol (Sigma-Aldrich, 99.9%) at room temperature to
reach a concentration of 9 g/l. Additionally, deionized wa-
ter (0, 10, 30 ml/l) and if necessary methanethiol (Sigma,
1.7 bar) were added to the feed solution. Catalyst Sn-BEA
(Si:Sn 125) prepared according to the above preparation was
fractionized (0.25 g, 300-600 µm) and loaded into a stain-
less steel 0.25 inch reactor. Glass wool was used to hold
the catalyst in place. The reactor was introduced into an
oven and the temperature of the reactor increased to 160ºC.
When the temperature was over 140ºC, the pump was started
with a flow of 0.05 ml/min (see Fig. 8).
Sucrose syrup (65 wt%, KNO 1 g/l) and methanol (Sigma-
Aldrich, 99.9%) were pumped separately and mixed at 160ºC
to reach a sucrose concentration of 55 g/l. Catalyst Sn-BEA
(Si:Sn 125) prepared according to the above preparation was
extruded (40 g, 1/32” cylinders) and loaded into a stain-
17831788_1 (GHMatters) P42926NZ00
less steel reactor. Glass wool was used to hold the cata-
lyst in place. The reactor was introduced into an oven, and
the temperature of the reactor increased to 160ºC (see Fig.
Samples were collected after different times on stream and
analysed by HPLC (Agilent 1200, Biorad Aminex HPX-87H col-
umn at 65ºC, 0.05 M H SO , 0.6 ml/min) to quantify uncon-
verted hexoses and dihydroxyacetone (DHA), glyceraldehyde
(GLA); and GC (Agilent 7890 with a Phenomenex Solgelwax
column) was used to quantity: methyl lactate (ML), methyl
vinyl glycolate (MVG, methyl 2-hydroxybutenoate), gly-
colaldehyde dimethylacetal (GLAD) and sulfur-methylvinyl-
glycolate (S-MVG, methyl 2-hydroxy(methylthio)-
butanoate).
Example 2
Determination of the total amount of soluble tin in the
liquid medium:
The determination of the total amount of soluble tin (Sn)
was carried out using inductively coupled plasma mass spec-
trometry (ICP-MS). The methanol sample was diluted by
weight with an 80/20 xylene/2-propanol mixture. The total
Sn content is quantified by ICP-MS (Agilent 7500ce ICP-MS
instrument) at the Sn isotope masses 118 and 120 by compar-
ison with a calibration curve made from a 900 ppm Conostan
organo-metallic Sn standard diluted with xylene. Indium is
used as an internal standard to correct for drift and ma-
trix effects. Removal of molecular interferences in the
ICP-MS analysis is done with Helium kinetic energy discrim-
17831788_1 (GHMatters) P42926NZ00
ination. EnviroMAT “Used oil” certified reference standard
which gives an informational value for Sn (305 mg/kg) is
analyzed with each sample batch to verify the precision of
the method.
Example 3
This example illustrates the conversion of C2-sugars (gly-
colaldehyde) to MVG with increased yield due to the effect
of water in batch experiments.
Catalytic reactions in batch:
A stainless steel pressure vessel (40 cm , Swagelok) was
charged with 15.0 g of methanol (Sigma-Aldrich, >99.8%),
the required amount of water, 0.200 g glycolaldehyde (gly-
colaldehyde dimer, Sigma) and 0.150 g of catalyst. The re-
actor was closed and heated to 160°C under stirring (900
rpm). The reaction was continued for 16 hours, and after
this period, the reaction was quenched by submerging the
vessel in cold water. Samples from the reaction vessel were
filtered and analyzed by HPLC (Agilent 1200, Biorad Aminex
HPX-87H column at 65°C, 0.05 M H SO , 0.5 ml/min) to quan-
tify unconverted glycolaldehyde (GA); and GC (Agilent 7890
with a Phenomenex Solgelwax column was used to quantify the
following: Methyl lactate (ML), methyl vinylglycolate (MVG,
methylhydroxybutenoate), glycolaldehyde dimethyla-
cetal (GLAD) and methylmethoxyhydroxybutanoate
(MMHB).
Table 2 shows the effect of the amount of water in batch
experiments from glycolaldehyde using Sn-Beta in methanol.
17831788_1 (GHMatters) P42926NZ00
An improved yield of methyl vinylglycolate (MVG) and me-
thylmethoxyhydroxybutanoate (MMHB) is obtained with
the addition of water to the batch reaction. Methyl vinyl-
glycolate (MVG) is equivalent to 2-hydroxybutenoic acid
methyl ester.
17831788_1 (GHMatters) P42926NZ00
Table 2: Effect of the amount of water in batch experiments
from glycolaldehyde using Sn-BEA in methanol
Batch Wt% GLAD MVG MMHB Total C4
exp. No water yield yield yield yield
1 0 35% 32% ~11% 43%
2 3 wt% 0 52% ~14% 67%
3 8.5 wt% 0 55% ~15% 70%
4 21 wt% 0 46% ~12% 58%
In Table 3, the effect of the presence (amount) of alkali
in batch experiments from glycolaldehyde using Sn-Beta in
methanol is shown. An improved yield of methyl vinylglyco-
late (MVG) and methylmethoxyhydroxybutanoate (MMHB)
is obtained with the addition of water to the batch reac-
tion in the absence of alkali. This experiment shows that
water is the component responsible for the increase in
yields, while the presence of alkali is less important. It
is, however, preferred to operate in the absence of alkali.
The results in batch experiment No. 7 are comparable to
conditions mentioned in Green Chemistry 2012, 14, p. 702.
Results from said paper: ML 16%, MVG 27%, MMHB 6%.
Table 3: Effect of the presence (amount) of alkali in batch
experiments from glycolaldehyde using Sn-BEA in methanol
Batch Water mM GLAD ML MVG MMHB Total
exp.No wt% K CO yield yield yield yield C4
in yield
MeOH
3 8.5 0 0 0 55% ~15% 70%
17831788_1 (GHMatters) P42926NZ00
6 8.5 0.13 0 0 48% ~16% 66%
1 0 0 35% 0 32% ~11% 43%
7 0 0.13 0 13% 37% ~15% 52%
Table 4 shows the effect of the type of catalyst in batch
experiments from glycolaldehyde using different stannosili-
cates in methanol. Optimum yield of methyl vinylglycolate
(MVG) and methylmethoxyhydroxybutanoate (MMHB) is ob-
tained with Sn-BEA as catalyst.
Table 4: Effect of the type of catalyst in batch experi-
ments from glycolaldehyde using Sn-silicates in methanol
Batch Cata- GLAD ML MVG MMHB Total
exp.No lyst yield yield yield yield C4
yield
3 Sn-Beta 0 0 55% ~15% 70%
8 Sn-SBA- 8% 3% 2% 2% 4%
9 Sn-MCM- 1% 6% 6% 8% 14%
Example 4
This example relates to catalytic reactions in batch to
produce sulfur-methyl vinylglycolate (S-MVG, methyl 2-
hydroxy(methylthio)-butanoate) and sulfur-ethyl vinyl-
glycolate (S-EVG, ethyl 2-hydroxy(methylthio)-butanoate)
from C2-sugars (glycolaldehyde).
17831788_1 (GHMatters) P42926NZ00
1.6 g of an aqueous solution containing glycolaldehyde
(34.2 g/l) produced from commercial glycolaldehyde (Gly-
colaldehyde dimer, Sigma) or obtained from fragmentation of
a 40 wt% glucose syrup () was mixed either
with pure methanol (13.8 g; Sigma-Aldrich 99.9%) or with
pure ethanol (13.8 g; CCS Healthcare 99.9%). Then 0.16 g of
catalyst and the desired amount of methanethiol (Sigma, 1.7
bar) were added, and the mixture was reacted in a pressure
reactor at 160°C (temperature of the oil bath) with 900 rpm
stirring under autogenous pressure. An initial sample of
the reaction mixture was used for calculation of the con-
version and the yields. Samples were collected after 16 h
of reaction and analysed by HPLC (Agilent 1200, Biorad
Aminex HPX-87H column at 65°C, 0.05 M H SO , 0.6 ml/min) to
quantify unconverted C2 sugars and formed C4 sugars; and GC
(Agilent 7890 with Phenomenex Solgelwax column) was used to
quantify the following: Methyl vinylglycolate (MVG, methyl
2-hydroxybutenoate), ethyl vinylglycolate (EVG, ethyl 2-
hydroxybutenoate), sulfur-methyl vinylglycolate (S-MVG,
methyl 2-hydroxy(methylthio)-butanoate) and sulfur-ethyl
vinylglycolate (S-EVG, ethyl 2-hydroxy(methylthio)-
butanoate).
Table 5 shows batch reactions of the conversion of glycol-
aldehyde to esters of methionine α-hydroxy analogue with
Sn-BEA as catalyst in the presence of water and solvent.
Amount of methanethiol: 3.6 mmol. Optimum yield was ob-
tained in methanol to S-EVG.
17831788_1 (GHMatters) P42926NZ00
Table 5: Batch reactions of the conversion of glycolalde-
hyde to esters of methionine α-hydroxy analogue [Methyl vi-
nylglycolate (MVG, methyl 2-hydroxybutenoate), ethyl vi-
nylglycolate (EVG, ethyl 2-hydroxybutenoate), sulfur-
methyl vinylglycolate (S-MVG, methyl 2-hydroxy
(methylthio)-butanoate) and sulfur-ethyl vinylglycolate (S-
EVG, ethyl 2-hydroxy(methylthio)-butanoate)]
Batch Solvent Yield of MVG or Conversion Selectivity
exp. α-hydroxy EVG
No methionine yield
analogue
MeOH 39.4% S- 13.9% 98.6 39.9% S-MVG
MVG (MVG)
11 EtOH 47.3% S- 19.5% 100 47.3% S-EVG
EVG (EVG)
Table 6 shows batch reactions of the conversion of glycol-
aldehyde to esters of methionine α-hydroxy analogue with
Sn-Beta as catalyst in the presence of water and methanol.
The results illustrate the effect of the GA/thiol molar ra-
tio. Optimum yield to S-MVG is obtained with a molar ratio
of 0.8.
Table 6: Batch reactions of the conversion of glycolalde-
hyde to esters of α-hydroxy methionine analogue (S-MVG, me-
thyl 2-hydroxy(methylthio)-butanoate)
Batch experi- GA/thiol S-MVG yield MVG yield
ment No (molar ratio)
0.8 37.5 7.3
12 0.6 33.6 0
13 1 30.6 7.3
14 5 18.1 33.1
16 0.2 8.3 0
17 No thiol 0 55.0
17831788_1 (GHMatters) P42926NZ00
Claims (24)
1. A continuous flow process for the preparation of one or more esters of lactic acid and 2-hydroxybutenoic acid 5 from a sugar in the presence of a solid Lewis acid catalyst and a solvent comprising an organic solvent and water, wherein the water is present in an amount of up to or equal to 10 vol. % of the organic solvent. 10
2. A process according to claim 1, wherein the vol. % of water present in the organic solvent is from greater than 0 to equal to or less than 10 vol. %.
3. A process according to claim 1 or 2, wherein the vol. 15 % of water present in the organic solvent is from greater than 0 to 2 vol. %.
4. A process according to any one of claims 1 to 3, wherein the yield of the one or more lactic acid esters de- 20 creases by up to 0.25 % per hour on stream on average.
5. A process according to any one of claims 1 to 4, wherein the yield of the one or more lactic acid esters de- creases by up to 0.10 % per hour on average.
6. A process according to any one of claims 1 to 5, wherein the yield of the one or more lactic acid esters de- creases by up to 5 % after 50 hours on stream. 30
7. A process according to any one of claims 1 to 6, wherein the yield of the one or more lactic acid esters is greater than 40% after 50 hours on stream. 17831788_1 (GHMatters) P42926NZ00
8. A process according to any one of claims 1 to 7, wherein the yield of 2-hydroxybutenoic acid ester is greater than 12 % after 50 hours on stream.
9. A continuous flow process for the preparation of an α- hydroxy methionine analogue from a sugar in the presence of a compound comprising sulphur, a solid Lewis acid catalyst and a solvent comprising an organic solvent and water, 10 wherein the water is present in an amount of up to or equal to 10 vol. % of the organic solvent.
10. A process according to claim 9, wherein the compound comprising sulfur is selected from the group consisting of 15 C -C alkyl thiol, C -C alkyl thiol salts, dimethylmercap- 1 5 1 5 tan and dimethyl disulfide.
11. A process according to claims 9 or 10, wherein the yield of α-hydroxy methionine analogue is greater than 20 % 20 after 10 hours on stream.
12. A process according to any one of claims 9 to 11, wherein the vol. % of water present in the organic solvent is from 0.25 to 10 vol. %.
13. A process according to any one of claims 1 to 12, wherein the solid Lewis acid catalyst is calcined after 450 hours. 30
14. A process according to any one of claims 1 to 13, wherein the solid Lewis acid catalyst framework structure 17831788_1 (GHMatters) P42926NZ00 is selected from the group consisting of BEA, MFI, FAU, MOR, FER, MWW, MCM-41 and SBA-15.
15. A process according to any one of claims 1 to 14, 5 wherein the solid Lewis acid comprises an active metal se- lected from one or more of the group consisting of Sn, Ti, Pb, Zr, Ge and Hf.
16. A process according to any one of claims 1 to 15, 10 wherein the solid Lewis acid catalyst is selected from the group consisting of Sn-BEA, Sn-MFI, Sn-FAU, Sn-MOR, Sn-MWW, Sn-MCM-41 and Sn-SBA-15.
17. A process according to any one of claims 1 to 16, 15 wherein the solid Lewis acid catalyst comprises Sn and the loss of Sn from the solid Lewis acid catalyst is less than or equal to 0.11% of the initial amount of Sn per hour on stream. 20
18. A process according to any one of claims 1 to 17, wherein the solid Lewis acid catalyst comprises Sn and the loss of Sn from the solid Lewis acid catalyst is less than 8% of the initial amount of Sn after 50 hours on stream. 25
19. A process according to any one of claims 1 to 18, wherein the sugar is selected from one or more of the group consisting of glucose, fructose, mannose, sucrose, xylose, erythrose, erythrulose, threose and glycolaldehyde. 30
20. A process according to any one of claims 1 to 19, wherein an alkaline earth metal or alkali metal ion is pre- sent in the process. 17831788_1 (GHMatters) P42926NZ00
21. A process according to any one of claims 1 to 20, wherein the solvent is selected from one or more of the group consisting of methanol, ethanol, 1-propanol, 1- 5 butanol and isopropanol.
22. A process according to any one of claims 1 to 21, wherein the temperature of the process is from 140 C to 200 C.
23. A process according to any one of claims 1 to 22, wherein at least a fraction of the water is introduced to the solvent by mixing the organic solvent with an aqueous sugar solution.
24. A process according to any one of claims 1 to 23, wherein the aqueous sugar solution is a sugar syrup with a sugar dry matter content of 30% or higher. 17831788_1 (GHMatters) P42926NZ00
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