CATALYST SYSTEM AND PROCESS FOR THE PRODUCTION OF GLYCOLS

Abstract

The invention provides a catalyst system comprising: a) one or more silver tungstate-containing species; and b) one or more catalytic species suitable for hydrogenation, wherein the weight ratio of said one or more silver tungstate-containing species to the one or more catalytic species suitable for hydrogenation is greater than 2.5:1, on the basis of the total weight of the catalyst system; and a process for the preparation of monoethylene glycol from starting material comprising one or more saccharides, by contacting said starting material with hydrogen in a reactor at a reactor temperature in the range of from 145 to 190 C. in the presence of a solvent and said catalyst system.

Claims

1. A catalyst system comprising: a) one or more silver tungstate-containing species; and b) one or more catalytic species suitable for hydrogenation, wherein the weight ratio of said one or more silver tungstate-containing species to the one or more catalytic species suitable for hydrogenation is greater than 2.5:1, on the basis of the total weight of the catalyst system.

2. The catalyst system according to claim 1, wherein the one or more catalytic species suitable for hydrogenation are selected from one or more transition metals from Groups 8, 9 or 10 of the Periodic Table, or compounds thereof.

3. The catalyst system according to claim 1, wherein the one or more catalytic species suitable for hydrogenation are selected from one or more transition metals selected from the group of cobalt, iron, platinum, palladium, ruthenium, rhodium, nickel, iridium, and compounds thereof.

4. The catalyst system according to claim 1, wherein the one or more catalytic species suitable for hydrogenation are solid, unsupported species.

5. The catalyst system according to claim 1, wherein the one or more catalytic species suitable for hydrogenation are on solid catalyst supports.

6. The catalyst system according to claim 5, wherein the solid catalyst support is selected aluminas, silicas, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon, activated carbon, zeolites, clays, silica alumina and mixtures thereof.

7. The catalyst system according to claim 1, wherein the weight ratio of the one or more silver tungstate-containing species to the one or more catalytic species suitable for hydrogenation is greater than 3:1, on the basis of the total weight of the catalyst system.

8. The catalyst system according to claim 1, wherein the weight ratio of the one or more silver tungstate-containing species to the one or more catalytic species suitable for hydrogenation is greater than 4:1, on the basis of the total weight of the catalyst system.

9. The process for the preparation of monoethylene glycol from starting material comprising one or more saccharides, by contacting said starting material with hydrogen in a reactor at a reactor temperature in the range of from 145 to 190 C. in the presence of a solvent and the catalyst system according to claim 1.

10. The process according to claim 9, wherein the saccharides are selected from the group consisting of monosaccharides, disaccharides, oligosaccharides and polysaccharides.

11. The process according to claim 9, wherein the catalytic species suitable for hydrogenolysis in the catalyst system are present in an amount in the range of from 0.005 to 10 wt. %, based on the total weight of the reaction mixture.

12. The process according to claim 9, wherein the reactor temperature is in the range of from 150 to 185 C.

13. The process according to claim 9, wherein the reactor pressure is in the range of from at least 1 to at most 25 MPa.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG. 1 is a schematic diagram of an exemplary, but non-limiting, embodiment of the process of the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0026] In the present invention, there has been surprisingly found a catalyst system which gives rise to advantageous yields of ethylene glycol and propylene glycol from saccharide-containing feedstocks at low reactor temperatures in the range of from 145 to 190 C.

[0027] In particular, the present invention has found that by utilising a catalyst system comprising increased amounts of silver tungstate-containing species to catalyse hydrogenolysis in combination with one or more catalytic species suitable for hydrogenation, it is surprisingly possible to operate at lower reactor temperatures than are typically used in the conversion of saccharide-containing feedstocks to polyols, whilst still achieving advantageous product yields.

[0028] The one or more catalytic species present in the catalyst system which are suitable for hydrogenation of material present in the reactor may be present in elemental form or as one or more compounds. It is also suitable that these one or more catalytic species may be present in chemical combination with one or more other ingredients in the catalyst system.

[0029] The one or more catalytic species which are suitable for the hydrogenation are not limited and may be conveniently selected from one or more transition metals from Groups 8, 9 or 10 of the Periodic Table, and compounds thereof. Preferably, said catalytic species may be one or more transition metals selected from the group of cobalt, iron, platinum, palladium, ruthenium, rhodium, nickel, iridium, and compounds thereof.

[0030] In one embodiment of the present invention, the one or more catalytic species suitable for hydrogenation are solid, unsupported species. Examples of such species include Raney Ni.

[0031] In another embodiment of the present invention, the one or more catalytic species suitable for hydrogenation are in homogeneous form.

[0032] In yet another embodiment of the present invention, the one or more catalytic species suitable for hydrogenation are on one or more solid catalyst supports.

[0033] The solid supports may be in the form of a powder or in the form of regular or irregular shapes such as spheres, extrudates, pills, pellets, tablets, monolithic structures. Alternatively, the solid supports may be present as surface coatings, for examples on the surfaces of tubes or heat exchangers.

[0034] Suitable solid support materials are those known to the skilled person and include, but are not limited to aluminas, silicas, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon, activated carbon, zeolites, clays, silica alumina and mixtures thereof.

[0035] In the catalyst system of the present invention, the one or more silver tungstate-containing species may be present in the catalyst system in unsupported form or, alternatively, may also be present on an inert support. Examples of suitable supports include, but are not limited to aluminas, silicas, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide, carbon, activated carbon, zeolites, clays, silica alumina and mixtures thereof.

[0036] In the catalyst system of the present invention, the weight ratio of the one or more silver tungstate-containing species to the one or more catalytic species suitable for hydrogenation is preferably greater than 3:1, more preferably greater than 4:1 on the basis of the total weight of the catalyst system.

[0037] The present invention further provides a process for the preparation of monoethylene glycol from starting material comprising one or more saccharides, by contacting said starting material with hydrogen in a reactor at a reactor temperature in the range of from 145 to 190 C. in the presence of a solvent and a catalyst system as hereinbefore described.

[0038] In one embodiment of the present invention, the one or more silver tungstate-containing species are present as the catalytic species suitable for hydrogenolysis in the reaction mixture in an amount in the range of from 0.005 to 10 wt. %, preferably in the range of from 0.005 to 8 wt. %, more preferably in the range of from 0.01 to 6 wt. %, based on the total weight of the reaction mixture.

[0039] By reaction mixture in the present invention is meant the total weight of the starting material, catalyst system, hydrogen, solvent present in the reactor. The starting material for use in the process of the present invention comprises one or more saccharides 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, then, optionally, said starting material may be subjected to a pre-treatment before being fed to the reactor in a form that can be more conveniently converted in the process of the present invention. Suitable pre-treatment methods are known in the art and one or more may be selected from the group including, but not limited to, sizing, drying, grinding, hot water treatment, steam treatment, hydrolysis, pyrolysis, thermal treatment, chemical treatment, biological treatment.

[0040] Preferably, the starting material for use in the process of the present invention comprises one or more saccharides selected from the group consisting of glucose, sucrose and starch. Said saccharides are suitably present as a solution, a suspension or a slurry in solvent.

[0041] The solvent present in the reactor may be conveniently selected from water, C.sub.1 to C.sub.6 alcohols, ethers and other suitable organic compounds, and mixtures thereof. Preferably, the solvent is water. If the starting material is provided to the reactor as a solution, suspension or slurry in a solvent, said solvent is also suitably water or a C.sub.1 to C.sub.6 alcohols, ethers and other suitable organic compounds, or mixtures thereof. Preferably, both solvents are the same. More preferably, both solvents comprise water. Most preferably, both solvents are water.

[0042] The temperature in the reactor is generally in the range of from 145 to 190 C., preferably in the range of from 150 to 190 C., more preferably in the range of from 150 to 185 C. and most preferably in the range of from 155 to 185 C.

[0043] Preferably, the reactor is heated to a temperature within these limits before addition of any starting material and is maintained at such a temperature until all reaction is complete.

[0044] The pressure in the reactor is generally at least 1 MPa, preferably at least 2 MPa, more preferably at least 3 MPa. The pressure in the reactor is generally at most 25 MPa, more preferably at most 20MPa, more preferably at most 18 MPa. Preferably, the reactor is pressurised to a pressure within these limits by addition of hydrogen before addition of any starting material and is maintained at such a pressure until all reaction is complete. This can be achieved by subsequent addition of hydrogen.

[0045] The process of the present invention takes place in the presence of hydrogen. Preferably, the process of the present reaction takes place in the absence of air or oxygen. In order to achieve this, it is preferable that the atmosphere in the reactor be evacuated and replaced with hydrogen repeatedly, after loading of any initial reactor contents. It may also be suitable to add further hydrogen to the reactor as the reaction proceeds.

[0046] The reactor in the present invention may be any suitable reactor known in the art.

[0047] The process may be carried out as a batch process or as a continuous flow process.

[0048] In one embodiment of the invention, the process is a batch process. In such a process, the reactor may be loaded with the catalyst system, solvent and one or more saccharides, and the reactor may then be purged and pressurized with hydrogen at room temperature, sealed and heated to the reaction temperature.

[0049] In embodiments of the invention, addition of further portions of starting material may occur in a continuous manner or the portions may be added in a discontinuous manner with time elapsing between the end of the addition of one portion and the start of the addition of the next portion. In the embodiment of the invention wherein the portions are added in a discontinuous manner, the number and size of each portion will be dependent on the scale of the reactor. Preferably, the total number of portions including the first portion is no less than 5, more preferably no less than 8, even more preferably no less than 10. The amount of time over which each portion is added and the time to be elapsed between the end of the addition of one portion and the start of the addition of the next portion will also depend on the scale of the reactor. Preferably, the time to be elapsed between the end of the addition of one portion and the start of the addition of the next portion will be greater than the amount of time over which each portion is added. In embodiments of the invention, wherein the process is a batch process, after addition of all of the portions of the starting material, the reaction may then be allowed to proceed to completion for a further period of time. The reaction product will then be removed from the reactor.

[0050] In embodiments of the invention wherein the process is carried out as a continuous flow process, after initial loading of some or all of the catalysts and, optionally, solvent, the reactor pressurised with hydrogen and heated, and then the first portion of starting material is introduced into the reactor and allowed to react. Further portions of starting material are then provided to the reactor. Reaction product is removed from the reactor in a continuous manner. In some embodiments of the invention, catalysts may be added in a continuous fashion.

[0051] In embodiments of the present invention, the starting material is suitably a saccharide feedstock comprising at least 1 wt. % saccharide as a solution, suspension or slurry in a solvent. Preferably, said saccharide feedstock comprises at least 2 wt. %, more preferably at least 5 wt. %, even more preferably at least 10 wt. %, most preferably at least 20 wt. % saccharide in a solvent. Suitably, the saccharide feedstock contains no more than 50 wt. %, preferably no more than 40 wt. % saccharide in a solvent.

[0052] The weight ratio of the catalyst system to saccharides in the starting material is suitably in the range of from 1:100 to 1:10000.

[0053] FIG. 1 is a schematic diagram of an exemplary, but non-limiting, embodiment of the process of the invention. A feed 101 comprising polysaccharides and solvent is provided to a pre-treatment unit 102 to convert it mainly into glucose, sucrose and/or starch in solvent to form feed 103. The pre-treatment unit 102 may consist of multiple pre-treatment units performing the same or different pre-treatment functions. Pre-treatment is an optional step in case the feed is polysaccharide. Feed 103 is then fed to the main reactor 104 where it undergoes hydrogenation/hydrogenolysis in the presence of catalysts to produce a product stream comprising of MEG 105.

[0054] The process of the present invention is not limited to any particular reactor or flow configurations, and those depicted in FIG. 1 are merely exemplary. Furthermore, the sequence in which various feed components are introduced into the process and their respective points of introduction, as well as the flow connections, may be varied from that depicted in FIG. 1.

[0055] The invention is further illustrated by the following Examples.

EXAMPLES

[0056] 75 ml Hastelloy C batch autoclaves, with magnetic stir bars, were used for the experiments. In typical experiments, known weights of catalysts and feedstocks were added to the autoclaves along with 30 ml of the solvent (typically water). If the catalysts or feedstocks were present as slurries or solutions, the total volume of those as well as the solvent was kept at 30 ml.

Methodology

[0057] In Example 1, 0.3 g of glucose was dissolved in 30 ml of water. The loaded autoclave was then purged three times with nitrogen, followed by hydrogen purge. The hydrogen pressure was then raised to 2000 psig or 14 MPa of hydrogen and the autoclave was sealed and left stirring overnight to do a leak test.

[0058] The next morning the autoclave was de-pressurised to the target hydrogen pressure (1450 psig or 10.1 MPa) at room temperature, and closed. Next the temperature was ramped to the target run temperature either as a fast ramp or in steps.

[0059] In Example 1, there was a fast ramp to temperature. The autoclave was held at the target temperature for known durations of time (75 min), while both the temperature and pressure were monitored. After the required run time had elapsed, the heating was stopped, and the reactor was cooled down to room temperature, de-pressurised, purged with nitrogen and then opened.

[0060] The contents of the autoclave were then analyzed via Gas Chromatography (GC) or High Pressure Liquid Chromatography (HPLC) after being filtered.

[0061] Table 1 provides details on the catalyst systems tested in Example 1.

[0062] Catalyst system B (catalysts B-1 to B-3) is comparative in nature. In addition, catalyst A-1 is also comparative in nature. Catalysts A-2 and A-3 are according to the present invention.

TABLE-US-00001 TABLE 1 Hydrogenation Hydrogenolysis Catalyst (a) Catalyst (b) Catalyst Catalyst Amount W content Amount Ratio System No. Component (g) (g) Component (g) (a):(b) A A-1 Silver tungstate 0.0417 0.017 Raney Ni 2800 0.020 2.1 Silver (comp.) tungstate/ A-2 Silver tungstate 0.0834 0.033 Raney Ni 2800 0.020 4.2 Raney Ni A-3 Silver tungstate 0.1251 0.05 Raney Ni 2800 0.020 6.3 B B-1 Sodium phospho- 0.0150 0.011 Raney Ni 2800 0.010 1.5 Sodium (comp.) tungstate phospho- B-2 Sodium phospho- 0.0450 0.033 Raney Ni 2800 0.010 4.5 tungstate/ (comp.) tungstate Raney Ni B-3 Sodium phospho- 0.0600 0.044 Raney Ni 2800 0.010 6 (comp.) tungstate B-4 Sodium phospho- 0.0900 0.067 Raney Ni 2800 0.010 9 (comp.) tungstate

Results

[0063] In the tables of results herein, MEG=monoethylene glycol, MPG=monopropylene glycol, HA=hydroxyacetone, 1,2-BDO=1,2-butanediol and 1H2BO=1-hydroxy-2-butanone.

Example 1

[0064] Table 2 presents the gas chromatography (GC) results of testing comparative catalyst A-1 at various temperatures.

TABLE-US-00002 TABLE 2 * ** *** Temperature MEG MPG HA 1,2-BDO 1H2BO MEG: C. wt. % wt. % wt. % wt. % wt. % (MPG + HA) 230 39.4 9.5 0.8 6.9 1.4 3.8 195 37.7 6.2 1.0 4.1 1.4 5.2 180 31.2 5.1 0.8 3.3 1.1 5.3 160 18.4 4.5 0.0 1.4 0.7 4.1 * hydroxyacetone ** 1,2-butanediol *** 1-hydroxy-2-butanone

[0065] It is apparent from Table 2 that as the reactor temperature is decreased from 230 to 160 C., the yield of MEG and the total yield of (MEG+MPG) decreases.

Example 2

[0066] Table 3 presents the GC results of testing comparative catalyst B-2 comprising sodium phosphotungstate as the hydrogenolysis catalyst component and Raney Ni as the hydrogenation catalyst component.

TABLE-US-00003 TABLE 3 * ** *** Temperature MEG MPG HA 1,2-BDO 1H2BO MEG: C. wt. % wt. % wt. % wt. % wt. % (MPG + HA) 195 34.9 4.6 2.4 3.1 3.6 5.0 160 9.0 4.3 0.4 0.0 0.8 1.9 * hydroxyacetone ** 1,2-butanediol *** 1-hydroxy-2-butanone

[0067] It is apparent from Table 3 that when comparative catalyst B-2 moved from a reactor temperature of 195 C. to a lower temperature of 160 C., there was a large decrease in the amount of MEG produced and also a significant drop in the ratio of MEG:(MPG+HA).

Example 3

[0068] Table 4 presents the GC results of testing various comparative catalyst systems comprising sodium phosphotungstate as the hydrogenolysis catalyst component and Raney Ni as the hydrogenation catalyst component at 160 C.

[0069] It is apparent that increasing the ratio of sodium phosphotungstate to hydrogenation catalyst in catalyst system B has no positive effect on the catalyst performance. That is to say, the results for catalyst systems B-1, B-2, B-3 and B-4 are all poor at low reactor temperatures of 160 C.

TABLE-US-00004 TABLE 4 Hydrogenolyis Catalyst (a) Hydrogenation * ** W Catalyst (b) MEG MPG HA 1,2- *** MEG: Catalyst Amount content Amount Ratio wt. wt. wt. BDO 1H2BO (MPG + No. Component g g Component g (a):(b) % % % wt. % wt. % HA) B-1 Sodium 0.015 0.011 Raney Ni 0.01 1.5 10.3 4.3 1.1 2.7 1.3 1.9 (comp.) phospho- 2800 tungstate B-2 Sodium 0.045 0.033 Raney Ni 0.01 4.5 9.0 4.3 0.4 0.0 0.8 1.9 (comp.) phospho- 2800 tungstate B-3 Sodium 0.06 0.044 Raney Ni 0.01 6 5.9 4.3 0.0 0.0 0.0 1.4 (comp.) phospho- 2800 tungstate B-4 Sodium 0.09 0.067 Raney Ni 0.01 9 6.8 4.3 0.0 0.0 0.3 1.6 (comp.) phospho- 2800 tungstate * hydroxyacetone ** 1,2-butanediol *** 1-hydroxy-2-butanone

Example 4

[0070] Catalyst system A comprises a combination of silver tungstate as hydrogenolysis catalyst (a) and Raney Ni as hydrogenation catalyst (b), in varying amounts.

[0071] Table 5 presents the results of testing different ratios of said catalyst components in catalyst system A at a temperature of 180 C. for a run time of 75 minutes.

[0072] It is apparent from Table 5 that catalysts A-2 and A-3 perform much better than comparative catalyst A-1 at lower temperatures of 180 C. This clearly shows that by increasing the amount of hydrogenolysis catalyst in the catalyst system, high yields can also be obtained at lower temperatures.

TABLE-US-00005 TABLE 5 ** * 1,2- *** Catalyst Temp. MEG MPG HA BDO 1H2BO MEG: No. C. wt. % wt. % wt. % wt. % wt. % (MPG + HA) A-1 180 31.2 5.1 0.8 3.3 1.1 5.3 (comp.) A-2 180 35.4 5.6 0.9 3.6 1.3 5.5 A-3 180 42.4 7.9 5.0 5.7 7.1 3.3 * hydroxyacetone ** 1,2-butanediol *** 1-hydroxy-2-butanone

Example 5

[0073] Catalyst system A comprises a combination of silver tungstate as hydrogenolysis catalyst (a) and Raney Ni as hydrogenation catalyst (b), in varying amounts.

[0074] Table 6 presents the results of testing different ratios of said catalyst components in catalyst system A at 160 C. for a run time of 75 minutes. Catalyst system A comprises a combination of silver tungstate and Raney Ni in varying amounts.

[0075] It is apparent from Table 6 that catalysts A-2 and A-3 perform much better than comparative catalyst A-1 at lower temperatures of 160 C. Again, this clearly shows that by increasing the amount of hydrogenolysis catalyst in the catalyst system, high yields can also be obtained at lower temperatures.

[0076] Indeed, by comparison of the results in Tables 2 and 6, it is of note that the yield of MEG using catalyst A-3 at 160 C. exceeds the yield of MEG obtained by using catalyst A-1 at a higher temperature of 180 C.

[0077] Furthermore, catalyst A-3 not only shows good yields of MEG in testing runs at 160 C. reactor temperature, but also shows very high C2:C3 ratios (MEG:(MPG+HA)) under said low temperature.

TABLE-US-00006 TABLE 6 ** * 1,2- *** Catalyst Temp. MEG MPG HA BDO 1H2BO MEG: No. C. wt. % wt. % wt. % wt. % wt. % (MPG + HA) A-1 160 18.4 4.5 0.0 1.4 0.7 4.1 (comp.) A-2 160 25.9 4.5 1.4 2.8 1.7 4.4 A-3 160 34.4 4.7 2.2 3.1 3.1 5.0 * hydroxyacetone ** 1,2-butanediol *** 1-hydroxy-2-butanone

Discussion

[0078] Hitherto in the prior art, it has not been possible to obtain high glycol yields at lower temperatures.

[0079] However, it is evident from the results in the Examples herein that in the present invention it has been surprisingly found that by increasing the amount silver tungstate-containing species acting as hydrogenolysis catalyst in a catalyst system comprising said hydrogenolysis catalyst in combination with one or more catalytic species suitable for hydrogenation, the resulting catalyst system displays advantageous results in the preparation of monoethylene glycol from starting material comprising one or more saccharides at low reactor temperatures in the range of from 145 to 190 C. as compared to other catalyst systems.