(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2016/114659 Al
July 2016 (21.07.2016) W PO PCT

(51) International Patent Classification: AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
C07C 29/132 (2006.01) C07C 31/20 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
(21) International Application Number: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
PCT/NL20 16/050027 KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG,
(22) International Filing Date: MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM,
13 January 2016 (13.01 .2016) PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC,
SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN,
(25) Filing Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
(26) Publication Language: English
(84) Designated States (unless otherwise indicated, for every
(30) Priority Data: kind of regional protection available): ARIPO (BW, GH,
2014 118 13 January 2015 (13.01.2015) NL GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ,
TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU,
(71) Applicant: AVANTIUM KNOWLEDGE CENTRE B.V. TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE,
[NL/NL]; 29, Zekeringstraat, 1014 BV Amsterdam (NL). DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU,
LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK,
(72) Inventors: VAN DER WAAL, Jan Cornells; c/o 29,
SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ,
Zekeringstraat, 1014 BV Amsterdam (NL). GRUTER,
GW, KM, ML, MR, NE, SN, TD, TG).
Gerardus Johannes Maria; c/o 29, Zekeringstraat, 1014
BV Amsterdam (NL). RAS, Erik-Jan; c/o 29, Zekering Published:
straat, 1014 BV Amsterdam (NL).
— with international search report (Art. 21(3))
(74) Agent: DE LANG, R.J.; P.O. Box 3241, 2280 GE — before the expiration of the time limit for amending the
Rijswijk (NL). claims and to be republished in the event of receipt of
(81) Designated States (unless otherwise indicated, for every amendments (Rule 48.2(h))
kind of national protection available): AE, AG, AL, AM,

(54) Title: PROCESS FOR PREPARING ETHYLENE GLYCOL FROM A CARBOHYDRATE SOURCE
(57) Abstract: Ethylene glycol is prepared from a carbohydrate source in a process, wherein hydrogen, the carbohydrate source, a li-
quid diluent and a catalyst system are introduced as reactants into a reaction zone; wherein the catalyst system comprises a tungsten
compound and ruthenium as hydrogenolysis metal and further at least one promoter metal, selected from transition and post-trans -
ition metals; wherein the carbohydrate source is reacted with hydrogen in the presence of the catalyst system to yield a product mix-
ture comprising ethylene glycol and butylene glycol. Butylene glycol may selectively be removed from the product mixture by azeo-
tropic distillation using an entraining agent.
Title: PROCESS FOR PREPARING ETHYLEN E GLYCOL FROM A CARBOHYDRATE
SOURCE

The present invention relates to a process for the preparation of ethylene glycol from a
carbohydrate source. In particular it relates to a process for preparing ethylene glycol from a
sustainable carbohydrate resource using a specific catalyst system.
The catalytic conversion of carbohydrates from a sustainable resource to valuable
chemicals such as alkylene glycols has gained interest. Alkylene glycols are interesting
chemicals that find application in the preparation of polyesters, such as poly(alkylene
terephthalate), poly(alkylene naphthenate) or poly(alkylene furandicarboxylate). Further
applications of alkylene glycols, in particular ethylene glycol, include its use as anti-freeze. By
enabling the preparation of such chemicals from sustainable resources, the dependence of
fossil fuel resources is reduced. Since there is a desire to reduce the dependence of fossil
fuels there is a growing need for different sustainable resources for the production of alkylene
glycols such as ethylene glycol.
In US 7,960,594 a process is described wherein ethylene glycol is produced from

cellulose. This process involves catalytic degradation and hydrogenation reactions under
hydrothermal conditions. More in particular, the process is carried out by contacting cellulose
at elevated temperature and pressure with a catalyst system comprising two sorts of active
components in the presence of hydrogen. The first active component comprises tungsten or
molybdenum in its metallic state or its carbide, nitride or phosphide. The second component
is selected from the hydrogenation metals from Groups 8 , 9 and 10 of the Periodic Table of
Elements, and includes cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum. In
experiments the compounds were used on a carrier, such as activated carbon. Moreover, it
appears that the reaction conditions that results in satisfactory yields include a temperature of
220 - 250 °C and a hydrogen pressure of 3 to 7 M Pa (measured at room temperature). When
a 1%wt slurry of cellulose is subjected to these compounds for 30 minutes, ethylene glycol is
obtained in yields of up to 69%. However, it also appears that when the reaction is continued
for a prolonged period the ethylene glycol yield reduces.
In US 8 ,4 0,31 9 a continuous process is described wherein a cellulose-containing

feedstock is contacted with water, hydrogen and a catalyst to generate at least one alkylene
glycol. The catalyst comprises a first metal component selected from the group consisting of
Mo, W , V, Ni, Co, Fe, Ta, Nb, Ti, Cr, Zr and combinations thereof. The first metal component
is in the elemental state or the metal is the carbide, nitride or phosphide compound. The
catalyst further comprises Pt, Pd, Ru and combinations thereof, wherein the metal is in the
elemental state. The catalyst components are comprised on a carrier.
 This reaction has been further studied on catalyst systems that contain nickel and
tungsten on a carrier. There it has been found that nickel and tungsten are leached into the
solution during the reaction, which accounts for the gradual deterioration of the catalyst
performance (cf. Na Ji et al., ChemSusChem, 201 2 , 5 , 939-944). The leaching of tungsten
and other metals has been confirmed in the study reported in . Zheng et al. , Chin. J . Catal .,
35 (201 4) 602-61 3 . The latter document also discloses that in addition to ethylene glycol
different by-products are obtained, including ,2-propylene glycol, erythritoi, glycerol, mannitol
and sorbitol.
US 201 1/031 2488 describes a catalyst system for the generation of alkylene glycols
from a carbohydrate as a potential alternative for a catalyst containing the metal components
in the elemental state; this catalyst system comprises at least one metal with an oxidation
state of at least +2. More in particular this US application discloses a catalyst system
comprising a first metal component with an oxidation state of at least +2 and a hydrogenation
component. The hydrogenation component can be selected from a wide range of metals in
any oxidation state, including in the elemental state. The hydrogenation component may in
particular comprise an active metal component selected from the group consisting of Pt, Pd,
Ru, Rh, Ni, Ir and combinations thereof. The first metal component may also be selected from
a range of metals, but in particular the compounds comprising the first metal component may
be selected from the group comprising tungstic acid, molybdic acid, ammonium tungstate,
ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at
least one Group 1 or 2 element, metatungstate compounds comprising at least one Group 1
or 2 element, paratungstate compounds comprising at least one Group 1 or 2 element,
tungsten oxides, heteropoly compounds of tungsten and various salts and oxides of
molybdenum, niobium , vanadium, zirconium, titanium and chromium. The catalyst system
according to US 20 1/031 2488 is stated to improve the selectivity to ethylene glycol and
propylene glycol, with a reduced production of butane diols. The ethylene glycol generation is
shown in some experiments, indicating that ammonium metatungstate is the preferred first
metal component and that as preferred hydrogenation component platinum and nickel may be
used. The use of nickel-containing catalyst systems results in the highest yields of ethylene
glycol and optionally propylene glycol.
In the above-mentioned article of . Zheng et al. , Chin. J . Catal. , 35 (201 4) 602-61 3 ,
the conclusion is drawn that tungsten acid-based catalysts are the most promising candidates
for future commercialization of the cellulose-to-ethylene-glycol process. A hydrogenation
component is added to such tungsten acid-based catalysts. Examples include ruthenium on
activated carbon, but Raney nickel is considered the most promising candidate for
commercialization.
The conversion of a carbohydrate to alkylene glycol involves complex reactions. It has
been shown in M . Zheng et al. , Chin. J . Catal. , 35 (201 4) 602-613, that lower concentrations
of carbohydrate and high reaction temperatures, i.e. above 200 °C, are beneficial to ethylene
glycol production. This appears to be confirmed in WO 201 4/1 6 1 852, containing experiments
wherein glucose solutions with increasing glucose concentrations, ranging from 1 %wt to 6
%wt, were contacted with hydrogen in the presence of a catalyst system comprising tungsten
and ruthenium. The higher the glucose concentration was, the lower the yield of ethylene
glycol became. In order to remedy this disadvantageous effect, it is proposed in
W O 201 4/161 852 to contact a first small portion of the carbohydrate with hydrogen and the
catalyst in a solution with a carbohydrate concentration of less than 2%wt, and only when the
first portion has reacted, to add further portions of the carbohydrate. In this respect the
process is similar to the semi-continuous reactions described in G . Zhao et al. , Ind. Eng.
Chem. Res. , 201 3 , 52, 9566-9572. Both WO 201 4/1 6 1852 and G . Zhao et al. in Ind. Eng.
Chem. Res. , 201 3 , 52, 9566-9572, mention that, in addition to ethylene glycol, 1,2-butane diol
(butylene glycol) is produced. The relative amount of butylene glycol can be in the order of
10%, based on the yield of ethylene glycol. Since butylene glycol and ethylene glycol form an
azeotrope, it is difficult to separate the compounds easily via distillation.
Therefore there is a desire to increase the yield of ethylene glycol and reduce the
relative amount of butylene glycol. There is further a need for an easy separation method for
removing this relatively small amount of butylene glycol. It has been found that the use of a
ruthenium-containing catalyst system that further comprises at least one other promoter metal
increases the yield of ethylene glycol.
Accordingly, the present invention provides a process for preparing ethylene glycol
from a carbohydrate source,
wherein hydrogen, the carbohydrate source, a liquid diluent and a catalyst system are
introduced as reactants into a reaction zone;
wherein the catalyst system comprises a tungsten compound and ruthenium as
hydrogenolysis metal and further at least one promoter metal, selected from transition and
post-transition metals;
wherein the carbohydrate source is reacted with hydrogen in the presence of the
catalyst system to yield a product mixture comprising ethylene glycol and butylene glycol.
The process according to the present invention employs a catalyst system that, in
addition to a tungsten compound, comprises ruthenium and at least one other transition or a
post-transition metal. By post transition metals are understood those elements classified as
post-transition metals by W . Masterton, C . Hurley & E . Neth, 20 1, Chemistry: Principles and
Reactions, 7th ed. , Brooks/Cole, Belmont, California, ISBN 1- 1 11-4271 0-0, viz., Ga, In, Tl,
Sn, Pb, B i and Po. It has been found that out of the post-transition metals, tin is very suitable.
The transition metals comprise the elements in groups 3 to 12 . Out of the transition metals,
not only the other hydrogenolysis metals from the groups 8 , 9 and 10 of the Periodic Table of
Elements can be selected, but also the metals from groups 11 and 12 have been found to be
very suitable. The at least one other transition metal is preferably selected from Cu and the
other hydrogenolysis metals from groups 8 , 9 and 10 of the Periodic Table of Elements.
Hydrogenolysis metals may suitably be selected from the group consisting of Fe, Ni, Co, Pt,
Pd, Rh, Ir, and combinations thereof. Preferably, the hydrogenolysis metal is selected from
the noble metals Pd, Pt, Ru, Rh, Ir and combinations thereof. It has been found that these
metals give good yields. The metal may suitably be present in its metallic form or as its
hydride or oxide. It is assumed that the metal oxide will be reduced during the reaction in the
presence of hydrogen.
The preferred metal combinations are those comprising ruthenium with one or more of
the metals selected from Cu, Ni, Sn, Pt, Pd, Ir and Rh,
Ruthenium and the at least one promoter metal are preferably present in the form of a
catalyst supported on a carrier. The carrier may be selected from a wide range of known
supports. Suitable supports include activated carbon, silica, zirconia, alumina, silica-alumina,
titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolitic aluminosilicates,
titanosilicates, magnesia, silicon carbide, clays and combinations thereof. The skilled person
will know that activated carbon is an amorphous form of carbon with a surface area of at least
800 m2/g. Such activated carbon thus has a porous structure. Most preferred supports are
activated carbon, silica, silica-alumina and alumina, since excellent results have been
obtained therewith. More preferably, the catalyst comprises activated carbon as the support.
The metals, i.e. ruthenium and the promoter metal or metals, are suitably included on
the carrier by impregnation. The impregnation can be achieved by impregnation of an
aqueous solution of a metal salt with subsequent removal of water. Calcination may result in
the metal oxide, which can subsequently be reduced to yield the metal in its metallic form. It
has been surprisingly found that the best results are obtainable when ruthenium and the at
least one promoter metal are co-impregnated. When catalysts are used that have similar or
the same compositions, but that differ in their preparation methods, it appears that the
catalyst that has been prepared by co-impregnation performs better than similar catalysts that
have been prepared by subsequent impregnations. Without wishing to be bound by any
theory it is believed that the metals during co-impregnation are intimately mixed and by the
calcinations and subsequent reduction form an alloy that provides the better performance.
The amount of the promoter metal or promoter metals is suitably selected such that
the amount of promoter metal or metals is at most equal 50 %wt, based on the weight of
ruthenium. The weight ratio of ruthenium to promoter metal or metals is suitably in the range
of 2 : 1 to 100: 1. More preferably, the weight ratio between Ru and the promoter metal or
promoter metals is in the range of 10 : 1 to 70: 1.
In the process of the present invention any butylene glycol formed may suitably be
selectively removed from the product mixture by azeotropic distillation using an entraining
agent.
 The entraining agent selectively removes butylene glycol from a mixture of alkylene
glycols by means of azeotropic distillation. The entraining agent can suitably be selected from
the group of hydrocarbon compounds, preferably consisting of ethy benzene, p-xy en n-
propyl benzene, o-diethyl benzene, m-diethy! benzene, m-di-isopropyi benzene,
cyclopeniane, methyl cyclohexane, 3-methyl peniane, 2,3-dimethyl butane, heptane, 1-
heptene, octane, 1-octene, 2,3,4-trimethyl pentane, decane, decalin, dicyc!o pentadiene,
alpha-phel!andrene, beta-pinene, myrcene, terpinoiene, p-mentha-1 .5-diene, 3-carene,
!imonene and a!pha-terpinene. A suitable heteroatom-containing compound is methyl ethyl
ke ox me,
In addition, higher poiyois, such as glycerol, erythritol, or sorbitol may function as an
entraining agent. These compounds tend to be produced as by-products in the process for
preparing ethylene glycol from carbohydrates, as shown in M . Zheng et al. , Chin. J . Catal. , 35
(201 4) 602-61 3 . These compounds may therefore be recycled to the process after separation
from the butylene glycol . If necessary, one or more of these compounds can also be added to
the product of the present process in order to enhance their concentrations and facilitate
thereby the obtaining of pure ethylene glycol, when they are used as entraining agents.
The procedure for performing an azetropic or extractive distillation using entraining
agents is known for the skilled person. Typically the product mixture is mixed with the
entraining agent and the resulting admixture is subjected to azeotropic distillation. Generally,
the entraining agent is selected such that the azeotrope of the butylene glycol and entraining
agent has a boiling point below the boiling point of ethylene glycol. More preferably, the
entraining agent is not soluble or miscible with butylene glycol, so that after distillation the
condensate will form two liquid phases, thereby facilitating the recovery of the entraining
agent. The recovered entraining agent may suitably be recycled to the azeotropic distillation.
Butylene glycol may optionally be further purified, and used for several applications.
Such further purification may e.g. entail that crude butylene glycol is converted to
dioxolane using a carbonyl group-containing compound. The resulting dioxolane-containing
mixture is then subjected distillation. The various dioxolane compounds derived from different
alkylene glycols can be easily separated by distillation. Other mono- or polyalcohols that may
be present are also easily separated in this way. Hence a pure dioxolane, derived from
butylene glycol is obtained. The dioxolane can subsequently be converted into butylene glycol
and carbonyl group-containing compound.
The distillation conditions for mixtures of alkylene glycols are known in the art. These
conditions tend to include temperatures up to 200 °C and pressures that may vary from
vacuum, e.g. 50 mbar, to atmospheric.
The carbohydrate source can be selected from a variety of sources. Suitably, the
carbohydrate source contains or consists of a carbohydrate selected from the group
consisting of polysaccharides, oligosaccharides, disaccharides, and monosaccharides.
Suitable examples include sustainable sources such as cellulose, hemicellulose,
hemicelluloses sugars, starch, sugars, such as sucrose, mannose, arabinose, glucose and
mixtures thereof. Sources that may include the above carbohydrates include paper pulp
streams, municipal waste water streams and other glucose units-containing streams can be
used as well , for example from wood waste, paper waste, agricultural waste, municipal waste,
paper, cardboard, sugar cane, sugar beet, wheat, rye, barley, other agricultural crops and
combinations thereof. These streams may require pre-treatment to remove components that
interfere with the present process such as basic fillers, e.g. calcium carbonate in waste paper.
In this way the process according to the invention may not only be used from natural sources,
but can even be used to upgrade and usefully re-use waste streams. Preferably, the
carbohydrate in the carbohydrate source is selected from the group consisting of cellulose,
starch, glucose, sucrose, glucose-oligomers, paper waste, and combinations thereof,
preferably glucose or starch. Since cellulose presents difficulties that are absent in other
carbohydrate sources, the carbohydrate source is preferably selected from the group
consisting of starch, hemicellulose and hemicellulose sugars, glucose and combinations
thereof.
The tungsten compound can be selected from a wide range of compounds. The
tungsten may be in the elemental state. Usually, the tungsten compound is then present on a
support. Similar to the supports for the at least one hydrogenolysis metal, the support may be
selected from a wide range of known supports. Suitable supports include active carbon, silica,
zirconia, alumina, silica-alumina, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-
zirconia, zeolitic aluminosilicates, titanosilicates and combinations thereof. Most preferred
are activated carbon, silica, silica-alumina and alumina as support, since excellent results
have been obtained therewith. It is also possible to use tungsten compounds in an oxidation
state of up to +2, such as in the form of its carbide, nitride or phosphide. Also in this case the
tungsten compound may be present in the form of a supported catalyst component. The
carrier may be selected from the supports described hereinabove.
Preferably, the tungsten compound has an oxidation state of at least +2, preferably
having an oxidation state of +5 or +6. The tungsten compound is then suitably selected from
the group consisting of tungstic acid (Η2ννθ ) , ammonium tungstate, ammonium
metatungstate, ammonium paratungstate, tungstate compounds comprising at least one
Group 1 or 2 element, metatungstate compounds comprising at least one Group 1 or 2
element, paratungstate compounds comprising at least one Group 1 or 2 element, tungsten
oxide (WO 3) , heteropoly compounds of tungsten, and combinations thereof. Whereas in the
prior art it has been found that certain tungsten compounds leached from their supports and
that such was considered a disadvantage, the present inventors have found that it is
advantageous to use tungsten compounds that dissolve in the reaction mixture. It has been
found that the catalytic activity of the tungsten compound increases if the tungsten compound
is dissolved. Without wishing to be bound to any theory it is believed that in the reducing
atmosphere that is created in the reaction zone by means of the presence of hydrogen,
hexavalent tungsten compounds may be reduced to pentavalent tungsten and the
pentavalent tungsten compound may dissolve into the diluent. In this partly reduced state the
tungsten ions are effective in attacking the carbon bonds in the carbohydrate source and form
alkylene glycol precursors. Therefore, a preferred tungsten compound is tungstic acid. In this
context it is noted that it has been found that polyols, including alkylene glycols, facilitate the
dissolution of the tungsten compound into the diluent, thereby promoting the catalytic activity
of the tungsten compound. The use of alkylene glycol as diluent is particularly suitable as
such use does not involve the introduction of an extraneous reagent into the reaction mixture,
which represents a further advantage.
According to the prior art the ratio between the hydrogenolysis metal and the tungsten
compound may vary between wide ranges. According to the prior art the weight ratio between
these components may vary from 0.02 to 3000. In the present invention the molar ratio of
tungsten to ruthenium is preferably in the rather narrow range of 1 to 25. More preferably the
molar ratio of tungsten to ruthenium is in the range of 2 to 20, most preferably from 10 to 20.
If the ratio is beyond the limits of these ranges, the relative yield of alkylene glycols other than
ethylene glycol is decreased and/or the conversion of the carbohydrate is slowed down.
The concentrations of the catalyst components may vary in the process according to
the present invention. The concentration of the tungsten compound may vary between very
wide ranges. The concentration of the tungsten compound may for instance be selected from
the range of 1 to 35%wt, calculated as tungsten and based on the weight of the carbohydrate
source introduced into the reaction zone. More preferably, the amount of tungsten is in the
range of 2 to 25%wt, based on the carbohydrate source introduced into the reaction zone.
Since the use of relatively high amounts of tungsten does not add significant advantages to
the process whereas the costs aspect may become significant, it is preferred to use amounts
of tungsten of 5 to 20 %wt, based on the amount of carbohydrate source.
The amount of ruthenium as hydrogenolysis metal and the promoter metal or metals
preferably ranges from 0.2 to 1.0 %wt, calculated as metals and based on the amount of
carbohydrate source introduced into the reaction zone. The weight ratio between ruthenium
and the promoter metal or metals is suitably in the range as indicated above, i.e. in the range
of 2 : 1 to 100: 1.
The carbohydrate source and the diluent are both introduced into the reaction zone.
Suitably, the carbohydrate source is introduced together with at least part of the diluent. More
preferably, the carbohydrate source is at least partially dissolved in the diluent. Suitably, the
diluent is an aqueous medium. In the process of the present invention the diluent comprises
suitably at least water and an alkylene glycol. Many carbohydrates such as sugars, glucose
and fructose are soluble in water. Moreover, cellulose, i.e. a carbohydrate that is regarded as
a very suitable starting material, and that is insoluble in water, can be converted into
cellodextrins which are water-soluble. Alternatively, the carbohydrate may be introduced into
the reaction zone in the form of a slurry. The more common examples of such slurries are
aqueous mixtures of water and cellulose and/or starch. In such embodiments aqueous
cellulose slurries, containing e.g. microcrystalline cellulose, can suitably be used.
The concentration of the carbohydrate source in the diluent can vary. For a
commercially interesting operation higher concentrations are desirable. However, the skilled
person is taught that at increasing concentration the yield of alkylene glycols will decrease.
Typically three modes of operation are feasible. The first mode is a batch operation in
which the carbohydrate source, the diluent and the catalyst system are introduced into a
reaction zone, exposed to hydrogen and reacted. In such a situation, the concentration of the
carbohydrate source in the diluent is suitably from 1 to 25 %wt.
A second mode is a method similar to the method according to WO 201 4/161 852,
wherein a reaction zone is charged with the catalyst system, a diluent and a small amount of
carbohydrate source, and wherein the amount of carbohydrate source is reacted with
hydrogen whilst additional carbohydrate source is added with or without additional diluent.
The reaction is then led to completion. The eventual amount of carbohydrate source added to
the reaction zone is then suitably in the range of 10 to 35 %wt, calculated as carbohydrate
source based on the amount of diluent.
The third mode of operation is a continuous operation. In one continuous operation
mode a feedstock comprising at least the diluent and the carbohydrate source is passed
through a plug flow reactor in the presence of hydrogen and also in the presence of a catalyst
system. The concentration of the carbohydrate in the diluent may suitably be in the range of 1
to 15 %wt of carbohydrate source, calculated as amount of carbohydrate source per amount
of diluent. Other continuous reactors include slurry reactors and ebullating bed reactors.
A preferred embodiment of a continuous mode is to use a continuous stirred tank
reactor (CSTR). The use of a CSTR is very suitable for the present process as the diluent in
the CSTR provides an excellent means for diluting the eventual concentration of the
carbohydrate in the CSTR, whereas the feed stream may comprise a high concentration of
carbohydrate. The feed stream to the CSTR may comprise pure carbohydrate. Preferably, the
feed stream is a solution or slurry of the carbohydrate in the diluent. The carbohydrate
concentration in the feed stream can be rather high, since the CSTR contains a reaction
medium that comprises the catalyst system, a mixture of product and carbohydrate source
and diluent. During operation the CSTR is fed with one or more feed streams comprising
carbohydrate source, diluent and optionally some or all of the components of the catalyst
system, and from the CSTR a product stream comprising the alkylene glycol-containing
product mixture, diluent and optionally some or all of the components of the catalyst system is
removed. In addition to the diluent and the carbohydrate source, also additional tungsten
compound can be fed continuously or periodically to make up for any tungsten that is
dissolved in the reaction mixture during the reaction, and subsequently removed from the
reactor. The carbohydrate concentration in the feed stream may be rather high, and be in the
range of 10 to 50 %wt, calculated as amount of carbohydrate source per amount of diluent.
The alkylene glycols that are produced by the reaction of the carbohydrate source provide a
medium wherein tungsten compounds may be dissolved, thereby benefitting the catalytic
activity of the tungsten catalyst component. The present invention therefore also provides for
an embodiment wherein the present process is conducted in a CSTR wherein hydrogen, the
carbohydrate source and the liquid diluent are continuously fed to the CSTR, and wherein
continuously a product mixture comprising alkylene glycol and diluent is removed from the
CSTR.
The process of the present invention allows for embodiments wherein high
concentrations of carbohydrate source in the diluent, e.g. from 4 to 50 %wt, are envisaged.
The high concentration may pose problems vis-a-vis the solubility of the carbohydrate source.
The diluent may comprise an alkylene glycol. The alkylene glycol suitably has 2 to 6 carbon
atoms. Suitable alkylene glycols include 1,6-hexane diol, butylene glycol and propylene
glycol. When butylene glycol is added as extra component to the diluent this butylene diol
needs to be removed from the eventual product mixture. That may require an undesirably
high energy input. Thus, the most preferred alkylene glycol is ethylene glycol. The diluent
further typically includes water as diluent. It also functions as solvent for most of the
carbohydrate sources. The amount of alkylene glycol in the diluent is suitably in the range of
2 to 25 %vol, based on the volume of water and alkylene glycol. The preferred diluent is
therefore a mixture of alkylene glycol, in particular ethylene glycol, and water, wherein the
amount of alkylene glycol ranges from 2 to 25 %vol, based on the volume of water and
alkylene glycol.
In addition, the skilled person may desire to add other compounds to the diluent. Such

other diluents may be selected from the group consisting of sulfoxides, alcohols other than
alkylene glycols, amides and mixtures thereof. A suitable sulfoxide is dimethyl sulfoxide
(DMSO); suitable examples of amides are dimethyl formamide and dimethyl acetamide. The
more preferred organic diluents are the alcohols. The alcohols can be mono-alcohols, in
particular water-miscible mono-alcohols, such as C1-C4 alcohols. The alcohol may also be a
polyol, e.g. glycerol, sorbitol, xylytol or erythritol.
The prior art processes focus on the conversion of hexoses, such as cellulose, starch
and glucose. However, it has been found that it is advantageous to use not only hexose-
containing carbohydrates, but also pentose-containing carbohydrates. Therefore the present
invention also provides a process wherein the carbohydrate source comprises at least one
pentose-containing carbohydrate or, preferably, the carbohydrate source comprises a
combination of at least one pentose-containing carbohydrate and at least one hexose-
containing carbohydrate. The pentose-containing carbohydrate may be a polysaccharide, an
oligosaccharide, a disaccharide or a monosaccharide. The pentose-containing carbohydrate
is suitably a pentosan, for instance xylan or arabinan. In particular, it comprises suitably at
least one of arabinose, ribose, lyxose and xylose moieties. The application of the process
according to the present invention on a combination of hexose- and pentose-containing
carbohydrates has the advantage that the pentose-containing carbohydrate yields both
propylene glycol and ethylene glycol as main products, and the hexose-containing
carbohydrates yield a majority of ethylene glycol. Hence, when propylene glycol is envisaged
as a main by-product, the use of pentose-containing carbohydrate as starting material is
beneficial . It is evident that the carbohydrate source that comprises hexose and pentose units
may be obtained by mixing a separate hexose and a separate pentose fraction. Alternatively,
the carbohydrate source may be the product of a natural source that already contains
pentose and hexose units. It may e.g. be the hydrolysis product of lignocellulosic biomass,
which hydrolysis results in both pentoses and hexoses.
A s indicated above, the ethylene glycol-containing product of the process according to
the present invention generally is a mixture of alkylene glycols. This mixture is suitably
purified, especially when pure ethylene glycol is desired for polymerization purposes. The
azeotrope that is formed with butylene glycol makes it difficult to obtain pure ethylene glycol.
Therefore, an entraining agent is used in accordance with the present invention.
To facilitate the separation process it is advantageous to use also pentose-containing
carbohydrate as starting material. Pentose-containing carbohydrates form hardly any
butylene glycol as by-product. Hence, the proportion of butylene glycol in the reaction product
of a combination of pentose- and hexose-containing carbohydrates will be relatively small.
The purification of such a reaction product in accordance with the invention is therefore
relatively simple. Propylene glycol and ethylene glycol can be easily separated from each
other by means of fractionation. Fractionation of the product of the reaction with a starting
material that comprises both pentose- and hexose-containing carbohydrates will result in pure
ethylene glycol, pure propylene glycol and a relatively small fraction containing butylene
glycol with one or both of the other glycols, which may then be treated with an entraining
agent.
The process for the preparation of ethylene glycol according to the present invention
can be carried out under the process conditions that are known in the art. The conditions
include those that are disclosed in WO 201 4/1 61852. Hence, the reaction temperature is
suitably at least 120 °C, preferably at least 140 °C, more preferably at least 150 °C, most
preferably at least 160 °C. The temperature in the reactor is suitably at most 300 °C,
preferably at most 280 °C, more preferably at most 270 °C, even more preferably at most 250
°C, and most preferably at most 200 °C. The reactor may be brought to a temperature within
these ranges before addition of any starting material and is maintained at a temperature
within the range.
It has been found that the process according to the present invention more
advantageously is carried out at temperatures that are generally somewhat lower than those
used in the prior art processes. It has been found that the formation of butylene glycol is
reduced if relatively low temperatures are employed. The more advantageous temperature
range is from 150 to 225 °C, more preferably from 1 0 to 2 0 °C, and most preferably from
165 to 190 °C. This is contrary to what is taught in US 7,960,594 wherein a reaction
temperature in the range 220 - 250 °C was stated to be most useful.
The process of the present invention takes place in the presence of hydrogen. The
hydrogen can be supplied as substantially pure hydrogen. The total pressure will then be the
hydrogen pressure. Alternatively, the hydrogen may be supplied in the form of a mixture of
hydrogen and an inert gas. The total pressure will then consist of the partial pressures of
hydrogen and this inert gas. The inert gas can suitably be selected from nitrogen, argon,
neon, helium and mixtures thereof. The ratio of hydrogen to the inert gas may vary between
wide ranges. Suitably, the ratio is not very low, since the reaction proceeds well when the
hydrogen partial pressure is sufficiently high. Accordingly, the volume ratio between hydrogen
and the inert gas may be from 1:1 to 1:0.01 . More preferably, only hydrogen is used as gas in
the process according to the invention.
The pressure in the reactor is suitably at least 1 M Pa, preferably at least 2 MPa, more
preferably at least 3 M Pa. The pressure in the reactor is suitably at most 16 MPa, more
preferably at most 12 MPa, more preferably at most 10 MPa. Preferably, the reactor is
pressurized by addition of hydrogen before addition of any starting material. The skilled
person will understand that the pressure at 20 °C will be lower than the actual pressure at the
reaction temperature. The pressure applied in the process is suitably 0.7 to 8 MPa,
determined at 20 °C. The pressure may be applied by hydrogen gas or a hydrogen-containing
gas. When a hydrogen-containing gas is used, the hydrogen content in the hydrogen-
containing gas may be up to 100 vol%, e.g. in the range of 5 to 95 vol%. The balance of the
hydrogen-containing gas may suitably be an inert gas, such as nitrogen, helium neon, argon
or mixtures thereof, as indicated hereinbefore. When the reaction mixture is subsequently
heated the pressure at reaction is suitably in the range of 1 to 16 MPa. As the reaction
proceeds some hydrogen is consumed. Advantageously, the hydrogen partial pressure at
reaction temperature is maintained within the range of 1 to 16 MPa. It is further preferred to
maintain the hydrogen pressure or hydrogen partial pressure within the range during the
entire reaction. Therefore hydrogen or hydrogen-containing gas may be introduced into the
reaction mixture during the reaction.
The process of the present invention may suitably be used as the first step in starting
a continuous process. In such a process the reaction is started with a mixture of
carbohydrate, diluent, catalyst system and hydrogen, wherein the diluent comprises an
alkylene glycol. When the reaction mixture has started to react and the carbohydrate
conversion has resulted in the formation of ethylene glycol, a continuous stream of
carbohydrate, diluent and optionally catalyst components may be fed to the reaction zone and
a continuous stream of alkylene glycol-containing product mixture may be withdrawn from the
reaction zone.
Although in a batch or semi-continuous process there may not be a need for it, it is
possible to add extra catalyst components such as tungsten compound or the hydrogenolysis
metal to the reaction mixture during the course of the reaction. Such may be found desirable
when the reaction is prolonged and the concentration of the catalyst system gets below a
desired level, due to the addition of diluent and/or carbohydrate.
The reaction zone is typically located in a reactor. The reactor in the present invention
may be any suitable reactor known in the art. For a batch process and for the semi-
continuous process the reactor can be a typical batch reactor. That means that it comprises a
pressure vessel, provided with the appropriate number of inlets for the introduction of the
starting material, diluent and catalyst system, as well as an inlet for hydrogen-containing gas.
The vessel is typically provided with a stirring or agitation means. For a continuous process
the reactor may be selected from a variety of reactors, including a trickle flow reactor, a
fluidized bed reactor, a slurry reactor, an ebullating bed reactor, a plug flow reactor and a
continuous stirred tank reactor (CSTR) . The use of a CSTR is very suitable for the present
process as indicated above.
The reaction time in the process according to the present invention may vary. Suitably
the residence time of the carbohydrate source is at least 1 min. Preferably the residence time
is in the range of 5 min to 6 hrs, more preferably from 5 min to 2 hr. In a batch process the
residence time is the time during which the carbohydrate source is contacted with hydrogen
and the catalyst system under reaction conditions. In a continuous process the residence time
is understood to be the quotient of the mass flow rate of the carbohydrate source into the
reaction zone divided by the mass flow rate of the catalyst system in the reaction zone. In
general a continuous process is operated at a weight hourly space velocity (WHSV),
expressed as the mass of carbohydrate source per mass of hydrogenolysis metal, expressed
as metal , per hour, in the range of 0.01 to 100 hr 1 , preferably from 0.05 to 10 hr 1 .
The invention is further illustrated by means of the following Examples.
EXAMPLES
General Procedure
The experiments were conducted according to the following procedure. A n amount of
100 mg of feedstock and 1000 µ Ι of water were added to an 8 ml autoclave reactor. An
amount of hydrogenolysis catalyst and H2W 0 4 as tungsten compound was added to the
reactor. Details of the feedstocks and type and amounts of catalysts are shown in the Tables.
The autoclave was sealed and purged with N2 followed by H2 and finally pressurized to 50 bar
with H2 at room temperature. The autoclave was heated up to 190°C, with constant stirring at
about 900 rpm and kept at temperature for 90 minutes. After 90 minutes, the autoclave was
cooled down to room temperature and liquid product was analyzed using gas
chromatography.
Hydrogenolysis catalysts were prepared by co-impregnation of activated carbon with a
solution of ruthenium nitrate and a salt of another metal (Cu, Ni, Pd, Pt or Sn nitrate, or Ir
acetate) in water. The impregnated support was then dried at room temperature overnight
and at 80 °C for five hours. Subsequently, the dried catalyst thus obtained was reduced in a
flow of H2-containing gas at 250 °C for 2 hours.
EXAMPLE 1
Hydrogenolysis catalysts having the composition as indicated in Table 1 were used,
together with tungstic acid, in the conversion of glucose with hydrogen using the general
procedure as described above. The catalysts contained 0 . 1 or 0.5%wt of promoter metal and
4.9 or 4.5 %wt of ruthenium, respectively, calculated as metal on the hydrogenolysis catalyst.
The total amount of metal was 5%wt for each catalyst. The amounts of hydrogenolysis
catalysts, calculated as milligram metals per liter water, were 0 mg/l; the amount of tungstic
acid in each experiment was 10 mg/l water. The results are shown in Table 1.
The table shows the yields of ethylene glycol (yEG), propylene glycol (yPG) and
butylene glycol (yBG), calculated as the percentage of grams obtained divided by the amount
of grams glucose as starting material.
Table 1

Experiment No. 1 is a comparative experiment. The results show that the use of a
promoter metal increases the yield of ethylene glycol. Comparison between the results of
experiment Nos. 5 and 6 shows that the increase of promoter metal not necessarily increases
the yield.
 EXAMPLE 2
A series experiments were conducted in the same manner as for the experiments of
Example 1, the only difference being that the amounts of hydrogenolysis catalysts, calculated
as milligram metals per liter water, and the amounts of tungstic acid were halved to 5 mg/ml .
The results are shown in Table 2 .
Table 2

The results show that surprisingly the yield of butylene glycol increases when a
smaller amount of catalyst is used in the reaction. In many instances, the yield of ethylene
glycol also increases.

EXAMPLE 3
To show the suitability of the catalysts systems for the conversion of carbohydrates,
other than glucose, a series of experiments was conducted with starch as feedstock, in the
same starting concentration as that of glucose in the other experiments, i.e. 100 mg/l. The
reactions were conducted in accordance with the General Procedure as described above.
The amounts of hydrogenolysis catalysts were in all experiments 5 mg metals/ml water. The
amount of tungstic acid was in each experiment 10 mg/ml.
The catalysts and the results are shown in Table 3 .
 Table 3

The results show that the use of a promoter metal in the catalyst system entails an
increased amount of ethylene glycol and butylene glycol. Comparison of the results of
experiments Nos. 23 to 25 confirms that the increase of the amount of the promoter metal
does not always yield an increased yield of any of the glycols.
 C LA IMS

1. Process for preparing ethylene glycol from a carbohydrate source,

wherein hydrogen, the carbohydrate source, a liquid diluent and a catalyst system are
introduced as reactants into a reaction zone;
wherein the catalyst system comprises a tungsten compound and ruthenium as
hydrogenolysis metal and further at least one promoter metal, selected from transition and
post-transition metals;
wherein the carbohydrate source is reacted with hydrogen in the presence of the
catalyst system to yield a product mixture comprising ethylene glycol and butylene glycol.

2 . Process according to claim 1, wherein butylene glycol is selectively removed from

the product mixture by azeotropic distillation using an entraining agent.

3 . Process according to claim 2 , wherein the entraining agent is selected from the
group of hydrocarbon compounds, preferably consisting of ethyl benzene, p-xylene, n-propyl
benzene, o-diethyl benzene, m-diethyl benzene, m-di-isopropyl benzene, cydopentane,
methyl cyclohexane, 3-meihyi pentane, 2,3-dimethy! butane, heptane, 1-heptene, octane, 1-
octene, 2,3,4-trimethy! pentane, decane, decalin, dicyclo pentadiene, a!pha-pheilandrene,
beta-pinene, myrcene, terpinolene, p-mentha-1 ,5-diene, 3-carene, iimonene and alpha-
terpinene and combinations thereof.

4 . Process according to claim 2 , wherein the entraining agent is selected from the
group consisting of glycerol erythrito!, sorbitol, methyl ethyl ketoxirne and combinations
thereof.

5 . Process according to any one of claims 1 to 4 , wherein the carbohydrate source is

selected from the group consisting of polysaccharides, oligosaccharides, disaccharides, and
monosaccharides.

6 . Process according to any one of claims 1 to 5 , wherein the catalyst system

comprises a tungsten compound has an oxidation state of at least +2.

7 . Process according to any one of claims 1 to 6 , wherein the catalyst system

comprises a tungsten compound selected from the group consisting of tungstic acid (H 2W 0 4) ,
ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate
compounds comprising at least one Group 1 or 2 element, metatungstate compounds
comprising at least one Group 1 or 2 element, paratungstate compounds comprising at least
one Group 1 or 2 element, tungsten oxide (W0 ) , heteropoly compounds of tungsten, and
combinations thereof.

8 . Process according to claim 7 , wherein the catalyst system comprises tungstic acid.

9 . Process according to any one of claims 1 to 8 , wherein the at least one other
transition metal is selected from Cu and the other hydrogenolysis metal from groups 8 , 9 or
10 of the Periodic Table of the Elements.

10 . Process according to claim 9 , wherein the other hydrogenolysis metal from the
groups 8 , 9 or 10 of the Periodic Table of the Elements is selected from the group consisting
of Fe, Ni, Co, Pt, Pd, Rh, Ir, and combinations thereof.

11. Process according to any one of claims 1 to 10 , wherein ruthenium and the at
least one promoter metal are preferably present in the form of a catalyst supported on a
carrier.

12 . Process according to claim 11, wherein the carrier is selected from the group
supports, consisting of activated carbon, silica, alumina, silica-alumina, zirconia, titania,
niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolitic aluminosilicates, titanosilicates,
magnesia, silicon carbide, clays and combinations thereof.

13 . Process according to any one of claims 1 to 12 , wherein the molar ratio of

tungsten to ruthenium is in the range of 1 to 25, preferably from 2 to 20.

14 . Process according to any one of claims 1 to 13 , wherein the concentration of the

tungsten compound is in the range of 1 to 35 %wt, calculated as tungsten and based on the
weight of the carbohydrate source.

15 . Process according to any one of claims 1 to 13 , wherein the amount of ruthenium

as hydrogenolysis metal and the promoter metal or metals ranges from 0.2 to 1.0 %wt,
calculated as the metals and based on the amount of carbohydrate source introduced into the
reaction zone.

16 . Process according to any one of claims 1 to 15 , wherein the carbohydrate source

comprises a combination of at least one pentose-containing carbohydrate and at least one
hexose-containing carbohydrate.
 17 . Process according to any one of claims 1 to 16 , wherein the diluent is a mixture of
alkylene glycol and water, wherein the amount of alkylene glycol ranges from 2 to 25 %vol,
based on the volume of water and alkylene glycol.

18 . Process according to claim 17 , wherein the diluent further comprises one or more
compounds selected from the group consisting of sulfoxides, alcohols other than alkylene
glycols, amides and mixtures thereof.

19 . Process according to any one of claims 1 to 18 , wherein the temperature in the

reaction zone ranges from 120 to 300 °C, preferably from 150 to 225°C, more preferably from
160 to 200 °C.

20. Process according to any one of claims 1 to 19 , wherein the hydrogen partial
pressure in the reaction zone is in the range of 1 to 6 Pa.

2 1. Process according to any one of claims 1 to 20, wherein the average residence
time of the catalyst system in the reaction zone is in the range of 5 min. to 6 hrs.
A . CLASSIFICATION O F SUBJECT MATTER
INV. C07C29/132 C07C31/20
ADD.

According to International Patent Classification (IPC) o r t o both national classification and IPC

B . FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C07C

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data, CHEM ABS Data

C . DOCUMENTS CONSIDERED T O B E RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

CN 102 643 165 B (DALIAN CHEMICAL PHYSICS 1-21

INST) 2 July 2014 (2014-07-02)
Embodiment 3

CN 102 731 255 B (DALIAN CHEMICAL PHYSICS 1-21

INST) 22 October 2014 (2014-10-22)
Embodiment 5

0 2014/173973 Al (SHELL INT RESEARCH 1-21

[NL] ; SHELL OI L CO [US] )
30 October 2014 (2014-10-30)
Tabl e page 13

US 2 360 685 A (PETERSEN JENSEN ERNEST) 1-21

17 October 1944 (1944-10-17)
Tabl e bottom page 1

□ Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :

"T" later document published after the international filing date o r priority
date and not in conflict with the application but cited to understand
"A" document defining the general state of the art which is not considered
the principle o r theory underlying the invention
to be of particular relevance
"E" earlier application o r patent but published o n o r after the international
"X" document of particular relevance; the claimed invention cannot be
filing date considered novel o r cannot b e considered to involve a n inventive
"L" documentwhich may throw doubts o n priority claim(s) orwhich is step when the document is taken alone
cited to establish the publication date of another citation o r other
"Y" document of particular relevance; the claimed invention cannot be
special reason (as specified)
considered to involve a n inventive step when the document is
"O" document referring to a n oral disclosure, use, exhibition o r other combined with one o r more other such documents, such combination
means being obvious to a person skilled in the art
"P" document published prior to the international filing date but later than
the priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

8 June 2016 20/06/2016

Name and mailing address of the ISA/ Authorized officer
European Patent Office, P.B. 5818 Patentlaan 2
N L - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Hacki ng, Mi chi e l
 Patent document Publication Patent family Publication
cited in search report date member(s) date

CN 102643165 02-07-2014 NONE

CN 102731255 B 22- 10--2014 NONE

O 2014173973 Al 30- 10--2014 CN 105121420 A 02 -12 -2015

EP 2989085 Al 02 -03 -2016
US 2016096789 Al 07 -04 -2016
O 2014173973 Al 3 -10 -2014

US 2360685 A 17- 10--1944 NONE