• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    The invention provides a process for the preparation of ethylene glycol and 1,2-propylene glycol from starting material comprising one or more saccharides, the process comprising the steps of: i) supplying the starting material and hydrogen to a first reactor, whose first reactor operates with mixing; ii) reacting said starting material and hydrogen in the first reactor in the presence of solvent and a catalyst system; iii) continuously removing a product stream from the first reactor from the first reactor; iv) supplying at least a portion of the product stream from the first reactor to a second reactor, whose reactor operates essentially in a buffered flow manner; and v) additionally reacting the product stream of the first reactor with hydrogen in the presence of a solvent and optionally a catalyst system in the second reactor.
    公开号:BR112016003939B1
    申请号:R112016003939-4
    申请日:2014-08-22
    公开日:2021-02-23
    发明作者:Evert Van Der Heide；Pieter Huizenga；Govinda Subbanna Wagle
    申请人:Shell Internationale Research Maatschappij B.V.；
    IPC主号:
    专利说明:

    Field of the Invention
    [001] The present invention relates to a process for the preparation of ethylene glycol and polyethylene glycol from a feed containing saccharide. Fundamentals of the Invention
    [002] Ethylene glycol and polyethylene glycol are valuable materials with a multitude of commercial applications, for example as heat transfer media, antifreeze, and precursors for polymers such as PET. Ethylene and polyethylene glycols are typically produced on an industrial scale by hydrolysis of the corresponding alkylene oxides, which are the oxidation products of ethylene and propylene, produced from fossil fuels.
    [003] In recent years, increased efforts have been focused on the production of chemical substances, including glycols, from renewable feed loads, such as sugar-based materials. The conversion of sugars to glycols can be seen as an efficient use of the starting materials with the oxygen atoms remaining intact in the desired product.
    [004] Current methods for converting saccharides to sugars focus on a hydrogenation / hydrogenolysis process as described in Angew. Chem. Int. Ed. 2008, 47, 8510-8513.
    [005] An important objective in this area is to provide a process that is of high yield in desirable products, such as ethylene glycol and polyethylene glycol, and that can be carried out in a commercially viable manner. A preferred methodology for a commercial scale process would be the use of continuous flow technology, in which power is continuously supplied to a reactor and the product is continuously removed from it. By maintaining the feed flow and removing product at the same levels, the reactor contents remain at a more or less constant volume.
    [006] Continuous flow processes for the production of glycols from saccharide-based feed charge are described in US 2011/0313212, CN 102675045A, CN 102643165A, WO 2013/015955 and CN 103731258A. A process for the co-production of biofuels and glycols is described in WO 2012/174087.
    [007] The continuous flow processes can be carried out in a reactor operating essentially in a buffered flow manner. In such a system there is little or no re-mixing. At the start of the reactor there will be a high concentration of reagents. The concentration of starting materials decreases as the material moves along the reactor as a 'buffer' and the reaction continues. Problems occur when the high concentration of reagents causes decomposition and the formation of by-products, resulting in reduced yields of the desired products.
    [008] A continuous flow process with a high degree of re-mixing can also be carried out, for example, in a continuous flow agitated tank reactor. In such a system the concentration of reagents at any point will be very low, avoiding any decomposition due to the high concentrations. However, in such a process, since some of the reaction mixture is continuously removed from the reactor, there will be some material that will not react to completion. This results in a product stream that contains starting material and / or intermediates, reducing the total yield of the process and requiring the separation of the starting material / intermediate from the desired product and its removal or recycling.
    [009] Therefore, it would be advantageous to provide a continuous process for the preparation of ethylene glycol and 1,2-propylene glycol from feeds containing saccharide in which substantially complete conversion of the starting material and / or intermediates is achieved and in which the formation of by-products is reduced. Summary of the Invention
    Consequently, the present invention provides a continuous process for the preparation of ethylene glycol and 1,2-propylene glycol from starting material comprising one or more saccharides, the process comprising the steps of: i) providing the starting material and hydrogen to a first reactor, whose first reactor operates with mixing; ii) reacting said starting material and hydrogen in the first reactor in the presence of solvent and a catalyst system; iii) continuously removing a product stream from the first reactor from the first reactor; iv) supplying at least a portion of the product stream from the first reactor to a second reactor, whose reactor operates essentially in a buffered flow manner; and v) additionally reacting the product stream of the first reactor with hydrogen in the presence of a solvent and optionally a catalyst system in the second reactor. Detailed Description of the Invention
    [0011] Surprisingly, it was found that with the use of a multiple reactor system comprising a reactor with mixing followed by a reactor operating essentially with buffered flow it provides a process in which substantially complete conversion of saccharides can be achieved in the conversion of saccharides in ethylene glycol and 1,2-propylene glycol.
    [0012] The starting material for the present process comprises at least one saccharide selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides. Examples of polysaccharides include cellulose, hemicelluloses, starch, glycogen, chitin and mixtures thereof. If the starting material comprises oligosaccharides or polysaccharides, it is preferable that it be subjected to pretreatment before being fed to the reactor in a form that can be converted in the process of the present invention. Suitable pretreatment methods are known in the art and one or more can be selected from the group including, but not limited to, sizing, drying, grinding, hot water treatment, water vapor treatment, hydrolysis, pyrolysis, heat treatment , chemical treatment, biological treatment.
    [0013] Preferably, the starting material supplied to the first reactor after pretreatment comprises one or more saccharides selected from the group consisting of glucose, sucrose and starch. Said saccharide is suitably present as a solution, a suspension or a slurry in the solvent.
    [0014] The solvent can be water or a C1 to C6 alcohol or mixtures thereof. Preferably, the solvent is water. More solvent can also be added to the reactor in a separate feed stream or can be added to the feed stream containing saccharide before it enters the reactor. Said solvent is also suitably water or a C1 to C6 alcohol or mixtures thereof. Preferably, both solvents are the same. More preferably, both solvents comprise water. With the utmost preference, both solvents are water.
    [0015] In the process of this invention, the starting material is reacted with hydrogen in the presence of a catalyst system in the first reactor. Optionally, a catalyst system can also be present in the second reactor. In one embodiment of the invention, the second reactor is operated in the absence of a catalyst system. In such an embodiment, it is possible that some small amount of catalyst system from the first reactor is present in the second reactor, but no catalyst system is supplied to the second reactor.
    [0016] If a catalyst system is present in the second reactor, the catalyst system used in each of the reactors can be the same or different. Another advantage of the invention is that different catalysts, adapted to the power being supplied to each reactor, can be used in each reactor.
    [0017] Each catalyst system and the components contained therein can be heterogeneous or homogeneous with respect to the solvent or solvents present in the reactors during the process of the present invention.
    [0018] In one embodiment of the present invention, a homogeneous catalyst system is used in the first reactor. In this embodiment, the catalyst system can remain in the product stream of the first reactor and be supplied to the second reactor within that stream. Alternatively, a separation step can be included between the two reactors to allow any catalyst in the product stream from the first reactor to be separated and, optionally, recycled to the first reactor. Another catalyst system, preferably different, can then be present in the second reactor. This other catalyst system may be present in the second reactor as a heterogeneous system or it may be another homogeneous catalyst system added to the second reactor, or to the first reactor product stream before it enters the second reactor. Alternatively, no catalyst system can be present in the second reactor.
    [0019] In another embodiment of the invention, a heterogeneous catalyst system is used in the first reactor. In this embodiment, the second reactor can also contain the same or a different heterogeneous catalyst system or no catalyst system. Alternatively, the catalyst system present in the second reactor can be a homogeneous catalyst system added to the second reactor, or to the product stream of the first reactor before it enters the second reactor.
    [0020] It should be easily understood that each catalyst system can also contain both heterogeneous and homogeneous components.
    [0021] Depending on the physical state of the catalyst systems of any components contained therein, they can be preloaded into the reactors or, if they are in liquid form or present as a solution or slurry in a solvent, they can be fed to the reactor as required in a continuous or discontinuous manner during the process of the present invention.
    [0022] In each reactor, the catalyst system used preferably comprises at least two active catalytic components comprising, as a first active catalytic component, one or more materials selected from transition metals in groups 8, 9 or 10 or their compounds, with catalytic hydrogenation capabilities; and, as a second active catalytic component, one or more materials selected from tungsten, molybdenum and their compounds and complexes.
    [0023] Preferably, the first active catalytic component consists of one or more of the group selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum. This component can be present in elemental form or as a compound. It is also suitable for this component to be present in chemical combination with one or other ingredients in the catalyst system. The first active catalytic component is required to have catalytic hydrogenation capabilities and to be able to catalyze the hydrogenation of material present in the reactor.
    [0024] Preferably, the second active catalytic component comprises one or more compounds, complexes or elementary materials comprising tungsten, molybdenum, vanadium, niobium, chromium, titanium or zirconium. More preferably, the second active catalytic component comprises one or more materials selected from the list consisting of tungstic acid, molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, tungstate compounds comprising at least one Group I or II element, compounds metatungstate compounds comprising at least one Group I or II element, paratungstate compounds comprising at least one Group I or II element, tungsten heteropoly compounds, molybdenum heteropoly compounds, tungsten oxides, molybdenum oxides, vanadium oxides, metavanadates, oxides of chromium, chromium sulfate, titanium ethoxide, zirconium acetate, zirconium carbonate, zirconium hydroxide, niobium oxides, niobium ethoxide, and combinations thereof. The metallic component is in a form other than a carbide, nitride or phosphide. Preferably, the second active catalytic component comprises one or more compounds, complexes or elementary materials selected from those containing tungsten or molybdenum.
    [0025] Preferably, at least one of the active catalytic components is supported on a solid support. In this modality, any other active catalytic component can be present either in heterogeneous or in homogeneous form. Said any other active catalytic component can also be supported on a solid support. In one embodiment, the first active catalytic component is supported on a solid support and the second active catalytic component is supported on a second solid support that can comprise the same or different material. In another embodiment, both active catalytic components are supported on a solid support.
    [0026] Solid supports can be in the form of a powder or in the form of regular or irregular shapes such as spheres, extrudates, pills, globules, tablets, monolithic structures. Alternatively, solid supports can be present as surface coatings, for example on the surfaces of tubes or heat exchangers. Suitable solid support materials are known to the skilled person and include, but are not limited to, aluminas, silicas, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon, activated carbon, zeolites, clays, silica- alumina and its mixtures.
    [0027] Suitably, the ratio between the weight of the first active catalytic component and the weight of the second active catalytic component is in the range of 0.02: 1 to 3000: 1, preferably in the range of 0.1: 1 to 100: 1 , on a metal weight basis present in each component. The weight ratio of the active catalytic components can be varied between the first and second reactors and it can be advantageous to change the composition of the catalyst systems between the reactors to adjust the different supply currents supplied to each reactor.
    [0028] The ratio between the weight of the first active catalytic component (based on the amount of metal in said component) and the weight of sugar is suitably in the range of 1: 100 to 1: 1,000. The ratio between the weight of the second active catalytic component (based on the amount of metal in said component) and the weight of sugar is suitably in the range of 1:10 to 1: 100.
    [0029] The temperature in each of the reactors is suitably at least 130 ° C, preferably at least 150 ° C, more preferably at least 170 ° C, with the most preference at least 190 ° 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. Preferably, the reactor is heated to a temperature within these limits prior to the addition of any starting material and is maintained at such a temperature until the entire reaction is complete.
    [0030] The pressure in each of the reactors is suitably at least 1 MPa, preferably at least 2 MPa, more preferably at least 3 MPa. The pressure in the reactor is suitably at most 12 MPa, preferably at most 10 MPa, most preferably at most 8 MPa. Preferably, the reactor is pressurized to a pressure within these limits by the addition of hydrogen prior to the addition of any starting material and is maintained at such a pressure until the entire reaction is complete by the continuous addition of hydrogen.
    [0031] Again, it can be advantageous to vary the conditions, for example the temperature and pressure, between the first and second reactors. This can result in a more adapted process to adjust the different constituents of the feeds supplied to each reactor.
    [0032] The process of the present invention takes place in the presence of hydrogen. Preferably, the process of the present reaction occurs in the absence of air or oxygen. In order to achieve this, it is preferable that the atmosphere in the reactor is evacuated and replaced with hydrogen repeatedly, after loading any initial contents of the reactor, before the reaction starts.
    [0033] Mixing must take place in the first reactor. Said mixing must be carried out to such an extent that the concentrations of materials in the reactor are relatively consistent from beginning to end. The degree of mixing for a reactor is measured in terms of the number of Péclet. An ideally agitated tank reactor would have a Péclet number of 0. In the first reactor, the Péclet number is preferably at most 0.4, more preferably at most 0.2, even more preferably at most 0.1, with the maximum preferably not more than 0.05.
    [0034] It will be evident to the skilled person, however, that concentrations of any materials can be considerably higher or lower in the immediate vicinity of an inlet to the reactor. Reactors suitable for use as the first reactor include those considered to be a continuous agitated tank reactor that can be used as the first reactor. Examples include slurry reactors, fluidized bed reactors by continuous injection of gas and liquid, jet stream mixing reactors, mechanically agitated reactors, bubbling columns such as bubbling mud columns and reactors with external recycling mesh. The use of these reactors allows the dilution of the reaction mixture to an extent that provides high degrees of selectivity for the desired glycol product (mainly ethylene glycol and polyethylene glycol).
    [0035] In a reactor operating with essentially a buffered flow, the entire supply current moves at the same radially uniform speed and, therefore, has the same residence time. The concentration of reagents in the buffered flow reactor will change as it progresses through the reactor. Although the reaction mixture essentially mixes in a radial direction and preferably does not mix in an axial direction (forward or backward) in practice some mixing in the axial direction (also called feedback) may occur. Suitable reactors operating with essentially buffered flow include, but are not limited to, tubular reactors, tube reactors, descending film reactors, staged reactors, stuffed bed reactors and shell and tube type heat exchangers.
    [0036] The buffered flow reactor can, for example, be operated in a transition area between laminar flow and turbulent flow or in the turbulent flow area, in such a way that a uniform and homogeneous reaction profile is formed.
    [0037] A buffered flow can, for example, be formed in a tubular reactor. It can also be formed in a compartmentalized tubular reactor or in another reactor or in a series of reactors having multiple compartments being transported forward, where preferably each of these compartments is essentially completely mixed. An example of a compartmentalized tubular reactor operated in a buffered flow can be a tubular reactor comprising a thread.
    [0038] Preferably a Péclet number of at least 3, more preferably at least 6, and even more preferably at least 20, with the most preference at least 100 is kept within a buffered flow reactor.
    [0039] Such a reactor typically cannot be applied for converting saccharides to ethylene glycol and polyethylene glycol because the concentration of saccharide at the inlet to the reactor and at the reactor start points would result in an unacceptably high level of sugar degradation and scale under the required reaction conditions.
    [0040] Preferably at least 50% by weight of the starting material undergoes reaction in the first reactor. More preferably at least 70% by weight, even more preferably at least 80% by weight, much more preferably at least 90% by weight, with the most preference at least 95% by weight of the starting material undergoing reaction in the first reactor.
    [0041] The residence time in the first reactor is suitably at least 1 minute, preferably at least 2 minutes, more preferably at least 5 minutes. Suitably, the residence time in the first reactor is not more than 5 hours, preferably not more than 2 hours, more preferably not more than 1 hour.
    [0042] After additionally reacting the product stream of the first reactor with hydrogen in the presence of a solvent and a catalyst system in the second reactor in step (v) of the process of the invention, suitably at least 98% by weight, preferably at least 99 % by weight, more preferably at least 99.5% by weight of the starting material, reacted to completion. The reaction to completion means that the starting material and any unsaturated components such as hydroxyl ketones and hydroxyl aldehydes are no longer present in the reaction mixture.
    [0043] The present invention is further illustrated in the following Examples. Examples Example 1
    [0044] 30 ml of deionized water, 0.300 g of a catalyst consisting of W (10.88) -Ni (3.63) -Pt (0.05) and ZrO2 and 0.300 g of a catalyst consisting of Ru catalyst (1 , 0%) on SiO2 were loaded into a 60 mL autoclave equipped with a gas stirrer and hydrogen supply. The autoclave was closed, the gas phase was replaced by nitrogen, then hydrogen and the autoclave was pressurized to a pressure of 30 bara (3,000 kPa absolute). The autoclave was stirred at 1,450 rpm, heated to 195 ° C in 15 minutes and pressurized with hydrogen to a pressure of 75 bara (7,500 kPa absolute). 5 mL of a 20 wt% glucose solution in water was fed to the reactor. After 5 minutes, a 5 mL sample of liquid is removed from the autoclave. The feeding and sampling process is repeated for another 5 cycles in order to approach the conditions in a continuous flow agitated tank reactor.
    [0045] The reactor was then cooled to room temperature in 15 minutes, depressurized, opened, and the contents of the reactor were filtered. 30 mL of reactor liquid were obtained with an average initial concentration of 12% by weight of glucose. In addition, 30 ml of liquid was obtained from samples combined with an average initial concentration of 8% by weight of glucose. The yields of MEG, MPG and 1,2-butanediol (1,2-BDO) were quantified by GC-FID (gas chromatography-flame ionization detector), applying a CPSil-5 column and can be seen in Table 1. Table 1
    Example 2
    [0046] The reactor liquid (30mL) of Example 1 and 0.300g of a Ru (1.0) / SiO2 catalyst were loaded into a 60 ml autoclave equipped with a gas stirrer and hydrogen supply. The autoclave was closed, and the gas phase was replaced by nitrogen, then hydrogen. The autoclave was then pressurized to 30 bara (3,000 kPa absolute). The autoclave was stirred at 1,450 rpm, heated to 195 ° C in 15 minutes, pressurized to 85 bara (8,500 kPa absolute) and maintained in the reaction conditions for 75 minutes. Such conditions were representative for a buffered flow reactor. The reactor was then cooled to room temperature in 15 minutes, depressurized, opened and a liquid sample was taken for analysis. The yields of MEG, MPG and 1,2-butanediol (1,2-BDO) were quantified by GC-FID, using a CPSil-5 column. The yields are shown in Table 2. Example 3
    [0047] The filtered liquid from combined samples (30mL) of Example 1 and 0.200g of a Ru (1.0) / SiO2 catalyst was loaded into a 60 ml autoclave equipped with a gas stirrer and hydrogen supply . The autoclave was closed, and the gas phase was replaced by nitrogen, then hydrogen. The autoclave was pressurized to 30 bara (3,000 kPa absolute). The autoclave was stirred at 1,450 rpm, heated to 195 ° C in 15 minutes, pressurized to 85 bara (8,500 kPa absolute) and maintained in the reaction conditions for 75 minutes. The reactor was then cooled to room temperature in 15 minutes, depressurized, opened and a liquid sample was taken for analysis. The yields of MEG, MPG and 1,2-butanediol (1,2-BDO) were quantified by GC-FID, using a CPSil-5 column. Yields are shown in Table 2. Table 2
    Example 4
    [0048] 15mL of filtrate from Example 2, 0.350g of a W (10.88) -Ni (3.63) -Pt (0.05) / ZrO2 catalyst and 0.350g of a Ru (1.0 ) / SiO2 were loaded into a 60 mL autoclave equipped with a gas stirrer and hydrogen supply. The autoclave was closed, the gas phase was replaced by nitrogen, then hydrogen, and the autoclave was then pressurized to 30 bara (3,000 kPa absolute). The autoclave was stirred at 1,450 rpm and heated to 195 ° C in 12-15 minutes. The autoclave was maintained at 195 ° C while a solution of 4.2g glucose dissolved in 15mL of deionized water was fed hot to the reactor. The reactor pressure was set to 85 bara (8,500 kPa absolute). The total amount of glucose addition is 6 grams, corresponding to a cumulative concentration of 20% glucose by weight. Samples were removed after 1 minute and 5 minutes of reaction and the reaction was allowed to continue for 75 minutes. The reactor was then cooled to room temperature in 15 minutes, depressurized, opened, a 0.3 mL liquid sample was taken for analysis, the yields of MEG, MPG and 1,2-butanediol (1,2-BDO) were quantified by GC-FID, applying a CPSil-5 column. Yields are shown in Table 3. Table 3
    Example 5
    [0049] 15mL of filtrate from Example 3, 0.400g of a W (10.88) -Ni (3.63) -Pt (0.05) / ZrO2 catalyst and 0.400g of a Ru (1.0 ) / SiO2 were loaded into a 60 mL autoclave equipped with a gas stirrer and hydrogen supply. The autoclave was closed, the gas phase was replaced by nitrogen, then hydrogen and the autoclave was pressurized to 30 bara (3,000 kPa absolute). The autoclave was stirred at 1,450 rpm, heated to 195 ° C in 12-15 minutes. The reaction temperature was maintained at 195 ° C and a solution of 4.8g of glucose dissolved in 15mL of deionized water was fed hot to the reactor. The total amount of glucose addition was 6g, corresponding to a cumulative concentration of 20% by weight of glucose. The reactor pressure was set to 85 bara (8,500 kPa absolute). Samples were removed after 1 minute and 5 minutes of reaction and the reaction was allowed to continue for 75 minutes. The reactor was then cooled to room temperature in 15 minutes, depressurized, opened and a 0.3 mL liquid sample was taken for analysis, the yields of MEG, MPG and 1,2-butanediol (1,2-BDO) were quantified by GC-FID, applying a CPSil-5 column (Table 4). Table 4
    权利要求:
    Claims (9)
    [0001]
    1. Process for the preparation of a compound, the compound being ethylene glycol and 1,2-propylene glycol from starting material comprising one or more saccharides, characterized by the fact that it comprises the steps of: i) supplying the material starting and hydrogen to a first reactor, whose first reactor operates with mixing; ii) reacting the starting material and hydrogen in the first reactor in the presence of solvent and a catalyst system; iii) continuously removing a product stream from the first reactor from the first reactor; iv) supplying at least a portion of the product stream from the first reactor to a second reactor, whose reactor operates essentially in a buffered flow manner; and, v) additionally reacting the product stream of the first reactor with hydrogen in the presence of a solvent and, optionally, a catalyst system in the second reactor.
    [0002]
    Process according to claim 1, characterized in that the catalyst systems present in each of the first and second reactors individually and independently comprise at least two active catalytic components comprising, a first active catalytic component, one or more materials selected from transition metals from groups 8, 9 or 10 or their compounds, with catalytic hydrogenation capacities; and, as a second active catalytic component, one or more materials selected from tungsten, molybdenum, and their compounds and complexes.
    [0003]
    Process according to either of claims 1 or 2, characterized in that the starting material comprises one or more saccharides selected from the group consisting of glucose, sucrose and starch.
    [0004]
    Process according to any one of claims 1 to 3, characterized by the fact that the first reactor is maintained with a maximum number of Péclet 0.4.
    [0005]
    Process according to any one of claims 1 to 4, characterized by the fact that the first reactor is selected from the group consisting of slurry reactors, fluidized bed reactors by continuous injection of gas and liquid, flow mixing reactors jet engines, mechanically agitated reactors, bubbling columns, and reactors with external recycling mesh.
    [0006]
    Process according to any one of claims 1 to 5, characterized in that the second reactor is maintained with a Péclet number of at least 3.
    [0007]
    7. Process according to any one of claims 1 to 6, characterized by the fact that the second reactor is selected from the group consisting of tubular reactors, tube reactors, descending film reactors, stage reactors, stuffed bed reactors and exchangers hull and tube type heat exchangers.
    [0008]
    Process according to any one of claims 1 to 7, characterized in that at least 95% by weight of the starting material undergoes reaction in the first reactor.
    [0009]
    Process according to any one of claims 1 to 8, characterized by the fact that after step v), at least 98% by weight of the starting material has reacted to completion.
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    法律状态:
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13181707|2013-08-26|
    EP13181707.4|2013-08-26|
    PCT/EP2014/067885|WO2015028398A1|2013-08-26|2014-08-22|Process for the preparation of glycols|
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