Patent Application
20230042854
The present invention relates to a process for preparing a mixture of alkylene glycols (e.g. ethylene glycol and/or propylene glycol) from a carbohydrate source by catalytic conversion with hydrogen. More specifically, the catalytic hydrogenolysis process of the invention has a decreased selectivity for larger polyols like sorbitol and erythritol, which larger polyols are obtained generally as a side product in catalytic hydrogenolysis, when viewed in comparison to the selectivity for small alkylene glycols (like ethylene glycol and propylene glycol).
Alkylene glycols such as ethylene glycol and propylene glycol are valuable products or intermediates in chemical industry, as such compounds are used in various chemical processes. Traditionally, alkylene glycols are produced from fossile sources. More recently, there is ongoing research to produce alkylene glycols from renewable sources.
In this connection, CN 102643165 describes a process for producing ethylene glycol and propylene glycol from soluble sugars or starch. Similarly, U.S. Pat. No. 7,960,594 discloses a process in which ethylene glycol is produced from cellulose. In WO 2016/114661 it is stated that ethylene glycol may be obtained from a carbohydrate source by catalytic reaction with hydrogen, which carbohydrate source may be obtained from a variety of sources, such as polysaccharides, oligosaccharides, disaccharides and monosaccharides (which all may be obtained from renewable sources). Suitable examples are stated to be cellulose, hemicellulose, starch, sugars such as sucrose, mannose, arabinose, glucose and mixtures thereof. Only glucose is exemplified as a starting material.
Most references such as US2011/0312488 and WO2017/097839 disclosing processes to obtain alkylene glycols like ethylene glycol or propylene glycol from (renewable) carbohydrates refer in a general sense to whole ranges of carbohydrates as potential starting material, but exemplify often only glucose, starch or cellulose as carbohydrate source.
The processes in the above references and others generally produce ethylene glycol in a selectivity up to 50 to 60%, based on the carbohydrate feed, when glucose is used as a feed, next to a whole range of other components in varying amounts. Next to ethylene glycol, smaller amounts of propylene glycol are obtained in such reactions. Apart from these two desired products, lower alkanols, butanediol (both 1,2- and 1,4-), and polyols like glycerol, erythritol, and sorbitol are formed as side products in the product mix.
US 2011/0046419 discloses a process for producing ethylene glycol in a sealed high-pressure reactor with a catalyst system. The catalyst system includes a first and a second active ingredient. The first active ingredient includes a transition metal of Group 8, 9 or 10 selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum. The second active ingredient includes a metallic state of molybdenum and/or tungsten, or a carbide, nitride, or phosphide thereof.
The world market for ethylene glycol is huge, the market for propylene glycol is smaller but still attractive. After removal of volatiles like lower alkanols, both ethylene glycol and propylene glycol can be obtained in pure form from the reaction mixture easily, as these components can be distilled off without too much problems. Also glycerol and butanediols can be removed, e.g. by distillation. This still leaves erythritol and sorbitol as bottom products, which are also more difficult to separate from eachother. There is a market value for food grade sorbitol, but sorbitol which has been processed in a process with heavy metal catalyst is not so easy to obtain in a food-grade purity. To avoid having to purify a considerable amount of erythritol and sorbitol, it is desired that the amounts in which these products are obtained is preferably as low as possible, whilst obtaining considerable amounts of commercially attractive components which can be obtained easily, like ethylene glycol and propylene glycol. Preferably, such should not be at the expense of total conversion.
Hence, there is a need for a process for preparing alkylene glycols from carbohydrates by reaction with hydrogen, in which reaction there is a decreased selectivity for sorbitol and erythritol, such process still yielding economically attractive amounts of valuable smaller alkane glycols like ethylene glycol and propylene glycol.
It has now been found that the above objective can be met, at least in part, by a process for producing a mixture of 2 to 40% by weight of glycols dissolved in water with a ratio of between 1:5 to 1:100 for the combined selectivity for erythritol and sorbitol:the combined selectivity for ethylene glycol and propylene glycol, of the reaction products produced by said process, which process comprises feeding to a pressurized, continuously stirred tank reactor hydrogen and an aqueous feed solution comprising water and a carbohydrate, wherein the reactor contains a catalyst system which comprises a homogeneous catalyst comprising a tungsten compound and a heterogeneous catalyst comprising a hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements, characterized in that the carbohydrate in the aqueous feed comprises at least 80% of sucrose, by weight based on the total amount of carbohydrate in the aqueous feed.
In other words, it was found that the amount of less desired components such as erythritol and sorbitol (which are produced by hydrogenolysis of carbohydrates using hydrogen and a catalyst system comprising a homogeneous catalyst and a heterogeneous catalyst) can be reduced if one ensures that the feed of carbohydrates comprise a substantial amount of sucrose (e.g. at least 80% on the weight of carbohydrates in the feed). Or put differently, the selectivity for erythritol and sorbitol can be decreased when compared to ethylene glycol and propylene glycol if the carbohydrate feed comprises a substantial amount of sucrose, rather than the more common glucose. The present invention is such that sucrose can directly (i.e. without the need for hydrolysis into the monosaccharides glucose and fructose) be fed to the reactor (in solution).
Depending on the amount of sucrose in the feed and detailed reaction conditions, the selectivity can be pushed further towards preferred products ethylene glycol plus propylene glycol, at the expense of e.g. erythritol and/or sorbitol. Hence, in the present invention it is preferred that the combined selectivity for erythritol and sorbitol:the combined selectivity for ethylene glycol and propylene glycol of the reaction products produced by said process is at least 1:7, preferably at least 1:10, more preferably at least 1:15.
To this end, and also for reasons of easier handling of the feed, it is preferred that the carbohydrate in the aqueous feed comprises at least 90% of sucrose, preferably at least 95% by weight of sucrose, by weight based on the total amount of carbohydrate in the aqueous feed. Most preferably, the feed is only sucrose, but in industrial sucrose minor amounts (e.g. 1-5% by weight) of other carbohydrates can still be present, which are not detrimental to the outcome. The reaction is preferably a continuous process, and the aqueous feed solution comprising water and a carbohydrate in the present process preferably comprises between 5 and 35% by weight of carbohydrate, preferably between 10 and 30% by weight of carbohydrate (by weight on the total feed).
As stated, the carbohydrate source containing sucrose is converted into a product mix comprising ethylene glycol and propylene glycol with hydrogen and a catalyst system which comprises a homogeneous catalyst comprising a tungsten compound and a heterogeneous catalyst comprising a hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements. Concerning the latter, it is preferred that the hydrogenolysis metal from groups 8, 9 or 10 of the Periodic Table of the Elements in this connection is selected from the group consisting of Cu, Fe, Ni, Co, Pd, Pt, Ru, Rh, Ir, Os and combinations thereof. Ruthenium is the preferred metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements in the present invention. It is preferred in the present invention that the amount of the hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements which present in the reactor is preferably present in an amount of between 0.05 and 20 g hydrogenolysis metal/L of reactor volume, more preferably between 0.1 and 12 g g hydrogenolysis metal/L of reactor volume, and most preferably between 0.5 and 8 g hydrogenolysis metal/L of reactor volume.
The hydrogenolysis metal catalyst referred to above can be present as such, but it is preferred that such is present in the form of a catalyst supported on a carrier. Preferred carriers in this case are carriers selected from the group supports, consisting of activated carbon, silica, alumina, silica-alumina, zirconia, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolites, aluminosilicates, titanosilicates, magnesia, silicon carbide, clays and combinations thereof. Activated carbon is a preferred carrier in the present invention, in particular with the hydrogenolysis catalyst being ruthenium.
Next to the metal selected from groups 8, 9 or 10 of the Periodic Table of the Elements (the heterogeneous catalyst part) the catalyst system comprises a homogeneous catalyst part, which is herein a tungsten compound. In the process according to the present invention, it is preferred that the homogeneous catalyst comprising a tungsten compound is selected from the group consisting of tungstic acid (H2WO4), 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 (WO3), heteropoly compounds of tungsten, and combinations thereof. A most preferred homogeneous catalyst in the present reaction comprises tungstic acid and/or a tungstate, e.g. ammonium tungstate, sodium tungstate or potassium tungstate. The homogeneous catalyst comprising a tungsten compound (preferably comprising tungstic acid) in the present invention is preferably dissolved or dispersed in water and/or an alkylene glycol, the latter preferably being ethylene glycol.
The presently claimed process is preferably carried out as a continuous process. To this end, to the reactor are continuously or periodically added: a stream comprising a carbohydrate feed, and the same for pressurized hydrogen gas. Preferably also the homogeneous catalyst comprising a tungsten compound is continuously or periodically added to the reactor. The amount of catalyst in the feed to the reactor is preferably such that the concentration of the homogeneous catalyst comprising a tungsten compound present in the reactor is between 0.05 and 5 wt. %, preferably between 0.1 and 2 wt. % (calculated as tungsten metal).
In the present invention the amount of the homogeneous catalyst comprising a tungsten compound and a heterogeneous catalyst comprising a hydrogenolysis metal selected from the groups 8, 9 or 10 of the Periodic Table of the Elements are present in the reactor in amounts such that the weight ratio of weight of tungsten to the total weight of hydrogenolysis metal, all calculated on metal basis, is between 1:3000 to 50:1 (tungsten metal:transition metal wt:wt).
The process of the present invention is carried out at elevated pressure (i.e. higher than atmospheric). Preferably, the total pressure in the reactor is between 2.0 and 16 MPa, preferably between 4 and 12 MPa, most preferably between 5 and 10 MPa. As hydrogen is key to the present reaction, pressurization is preferably carried out with hydrogen. Furthermore, it is preferred in the present invention that the aqueous feed solution comprising water and a carbohydrate comprises between 40% and 85% of water, between 5 and 35% by weight of carbohydrate, and between 5 to 40% of an alkylene glycol co-solvent (preferably ethylene glycol), all by weight on the total aqueous feed solution.
The reaction is preferably carried out such that the temperature in the reactor is between 150 and 270° C., preferably between 180 and 250° C. The rate of addition of aqueous feed solution comprising water and a carbohydrate into the CSTR is such that WHSV is preferably between 0.01 and 100 hr−1, preferably between 0.05 and 10 hr−1, more preferably between 0.5 and 2 hr−1.
The invention further relates to a process for producing glycols dissolved in water, which process comprises feeding to a pressurized, continuously stirred tank reactor hydrogen an aqueous feed solution comprising water and a carbohydrate, wherein the reactor comprises a catalyst system which comprises a homogeneous catalyst comprising a tungstic acid and a heterogeneous catalyst comprising ruthenium supported on a carrier, characterized in that the carbohydrate in the aqueous feed comprises at least 80% of sucrose, by weight based on the total amount of carbohydrate in the aqueous feed, as it was found that the above objective can be met, at least in part, by this process.
Preferred carriers in this case for the ruthenium are carriers selected from the group supports, consisting of activated carbon, silica, alumina, silica-alumina, zirconia, titania, niobia, iron oxide, tin oxide, zinc oxide, silica-zirconia, zeolites, aluminosilicates, titanosilicates, magnesia, silicon carbide, clays and combinations thereof. Activated carbon is a preferred carrier in the present invention.
The presently claimed process is preferably carried out as a continuous process. To this end, to the reactor are continuously or periodically added: a stream comprising a carbohydrate feed, and the same for pressurized hydrogen gas. Preferably also the homogeneous catalyst comprising a tungsten compound is continuously or periodically added to the reactor. The amount of catalyst in the feed to the reactor is preferably such that the concentration of the homogeneous catalyst comprising tungstic acid present in the reactor is between 0.05 and 5 wt. %, preferably between 0.1 and 2 wt. % calculated as tungsten metal.
It is preferred in the present invention that the amount of ruthenium which present in the reactor is preferably present in an amount of between 0.05 and 20 g ruthenium/L of reactor volume, more preferably between 0.1 and 12 g ruthenium/L of reactor volume, and most preferably between 0.5 and 8 g ruthenium/L of reactor volume. The amount of the homogeneous catalyst comprising tungstic acid and a heterogeneous catalyst comprising ruthenium are present in the reactor in amounts such that the weight ratio of weight of tungsten to the total weight of hydrogenolysis metal, all calculated on metal basis, is between 1:3000 to 50:1 (tungsten metal:transition metal wt:wt).
In the above process, the homogeneous catalyst comprising a tungstic acid is preferably dissolved or dispersed in water and/or an alkylene glycol, the latter preferably being ethylene glycol.
In this process, the carbohydrate in the aqueous feed preferably comprises at least 90% of sucrose, more preferably at least 95% by weight of sucrose, by weight based on the total amount of carbohydrate in the aqueous feed. Furthermore, it is preferred that in the now claimed process the aqueous feed solution comprising water and a carbohydrate preferably comprises between 5 and 35% by weight of carbohydrate, preferably between 10 and 30% by weight of carbohydrate.
The process of the present invention is carried out at elevated pressure (i.e. higher than atmospheric). Preferably, the total pressure in the reactor is between 2.0 and 16 MPa, preferably between 4 and 12 MPa, most preferably between 5 and 10 MPa. As hydrogen is key to the present reaction, pressurization is preferably carried out with hydrogen. Furthermore, it is preferred in the present invention that the aqueous feed solution comprising water and a carbohydrate comprises between 40% and 85% of water, between 5 and 35% by weight of carbohydrate, and between 5 to 40% of an alkylene glycol co-solvent (preferably ethylene glycol), all by weight on the total aqueous feed solution.
The reaction is preferably carried out such that the temperature in the reactor is between 150 and 270° C., preferably between 180 and 250° C. The rate of addition of aqueous feed solution comprising water and a carbohydrate into the CSTR is such that WHSV is preferably between 0.01 and 100 hr−1, preferably between 0.05 and 10 hr−1, more preferably between 0.5 and 2 hr−1.
Hydrogenolysis experiments were carried out in a continuously stirred tank reactor. The amount of liquid in the reactor was about 170 ml. Trials were done with two different residence times:
about 24 minutes residence time (example 1a and comparative 1a) and
about 34 minutes residence time (example 1b and comparative 1b).
The reactor contained as heterogeneous catalyst ruthenium on activated carbon. The amount of ruthenium on activated carbon was about 5 wt % Ru on AC. The total weight of heterogeneous catalyst on carrier was about 7 g Ru+AC for example 1a and comparative 1a, and about 4.3 g for Ru+AC for example 1b and comparative 1b. The reactor was filled with Ru/AC and water before the reactor was heated and pressurized. All of the heterogeneous catalyst remained in the reactor during the reaction.
The carbohydrate feed was prepared by dissolving the sucrose (examples 1a and 1b) and glucose (comparatives 1a and 1b) in a mixture of water and ethylene glycol at a concentration of about 20 wt % on the final feed composition which further contained about 60 wt % water and 20 wt % ethylene glycol. The homogeneous catalyst solution was prepared by dissolving sodium hydroxide and H2WO4 in ethylene glycol, at a molar ratio of 0.7:1, to arrive at a concentration H2WO4 of 0.44 wt %.
The carbohydrate feed solution and homogeneous catalyst solution were mixed prior to use.
The reactor was heated to 220° C. and pressurised with hydrogen gas to 65 bar. Hydrogen gas was entered into the reactor at a flow of 2000 ml/minute.
At the start of the reaction (t=0 minutes) the mixture of carbohydrate feed and homogeneous catalyst solution was pumped into the reactor at a steady flow to obtain the residence times indicated (flow rates added to the reactor at 5 or 7 ml per minute.
Reactions were carried out for about 300 minutes, and from the outlet stream samples were taken at 8-10 times in the interval from 0 to 300 minutes.
The samples obtained were analysed on concentration of polyol (ethylene glycol, propylene glycol, erythritol and sorbitol) using HPLC and from this reaction selectivities were calculated. The results are set out in
From the figures it can be concluded that when using sucrose as a feed much lower selectivities are obtained for both sorbitol and erythritol as opposed to the combined selectivity for ethylene glycol and propylene glycol, when compared to the selectivities for glucose as a feed.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20157690.7 | Feb 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/052949 | 2/8/2021 | WO |
