CA1162567A - Production of ethylene glycol - Google Patents
Production of ethylene glycolInfo
- Publication number
- CA1162567A CA1162567A CA000391126A CA391126A CA1162567A CA 1162567 A CA1162567 A CA 1162567A CA 000391126 A CA000391126 A CA 000391126A CA 391126 A CA391126 A CA 391126A CA 1162567 A CA1162567 A CA 1162567A
- Authority
- CA
- Canada
- Prior art keywords
- platinum
- rhodium
- ethylene glycol
- range
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract Production of Ethylene Glycol Carbon monoxide is reacted with hydrogen to produce ethylene glycol or an ester thereof if a carboxylic acid is present in the presence of a catalyst which comprises rhodium and platinum, suitably as metal carbonyls or mixed metal carbonyls.
Description
~ I 62567 l H.31590 Production of Ethylene Glycol THIS INVENTION relates to ethylene glycol production.
It is known that ethylene glycol may be produced by the reaction of carbon monoxide with hydrogen at elevated pressures in the presence of a rhodium catalyst. However it has been found that if a high concentration of ethylene glycol is to be obtained substantial quantities of methanol are also formed.
Whilst methanol is commercially valuable the costs of the carbon monoxide and hydrogen consumed in producing it together with the costs of compression to the high pressures involved and the additional capital costs involved in constructing a plant to produce it as a by-product are such that it is preferable to reduce theamount of methanol produced relative to ethylene glycol.
We have found that provided that sufficient platinum in the form of a metal carbonyl or mixed metal carbonyl is present the formation of methanol is reduced.
The catalyst system may also be used in the production of ethylene glycol esters if a carboxylic acid is also present.
According to the invention carbon monoxide is reacted with hydrogen to produce ethylene glycol or an ester thereof in ~he presence of a catalyst which comprises rhodium and platinum in a total atomic ratio of at most 8:1, suitably as metal carbonyls or mixed metal carbonyls, and, in the case of an ester, a carboxylic acid which is preferably a monocarboxylic acid having 2 to 10 carbon atoms especially acetic acid.
By "metal carbonyl" or "mixed metal carbonyl" we include any compound of the metal which also comprises carbon monoxide and in particular we include metal hydrocarbonyls. The metal carbonyls are believed to be formed in situ from a wide variety of metal compounds, for example the carboxylates and nitrates, but they may suitably be introduced as such. The reaction is preferabl~
carried out in the substantial absence of compounds of ~ 1 ~2567
It is known that ethylene glycol may be produced by the reaction of carbon monoxide with hydrogen at elevated pressures in the presence of a rhodium catalyst. However it has been found that if a high concentration of ethylene glycol is to be obtained substantial quantities of methanol are also formed.
Whilst methanol is commercially valuable the costs of the carbon monoxide and hydrogen consumed in producing it together with the costs of compression to the high pressures involved and the additional capital costs involved in constructing a plant to produce it as a by-product are such that it is preferable to reduce theamount of methanol produced relative to ethylene glycol.
We have found that provided that sufficient platinum in the form of a metal carbonyl or mixed metal carbonyl is present the formation of methanol is reduced.
The catalyst system may also be used in the production of ethylene glycol esters if a carboxylic acid is also present.
According to the invention carbon monoxide is reacted with hydrogen to produce ethylene glycol or an ester thereof in ~he presence of a catalyst which comprises rhodium and platinum in a total atomic ratio of at most 8:1, suitably as metal carbonyls or mixed metal carbonyls, and, in the case of an ester, a carboxylic acid which is preferably a monocarboxylic acid having 2 to 10 carbon atoms especially acetic acid.
By "metal carbonyl" or "mixed metal carbonyl" we include any compound of the metal which also comprises carbon monoxide and in particular we include metal hydrocarbonyls. The metal carbonyls are believed to be formed in situ from a wide variety of metal compounds, for example the carboxylates and nitrates, but they may suitably be introduced as such. The reaction is preferabl~
carried out in the substantial absence of compounds of ~ 1 ~2567
2 H.31590 phosphorus, arsenic, sulphur and antimony.
The reaction is preferably carried out a-t a pressure in the range 200 to 5000 and more preferably 500 to 1200 bars. A reaction temperature in the range 100 to 400C and preferably 150 to 300C may be employed.
The catalyst may be introduced as a solution in a polar solvent which preferably contains no hydroxy groups, e.g. Me0(C2H40)4Me and/or N~methylpyrrolidone. rf desired the catàlyst may be provided on a support, for example an alpha alumina, activated charcoal, silica or aluminosilicate support. In the latter case a solvent for ethylene glycol is suitably provided to ena~le the product to migrate from the catalytic sites after formation.
When the catalyst is provided as a solution it is preferred that the rhodium concentration should be in the range 1 to 100 and preferably 20 to 40 milligram atoms per litre and that the platinum concentration should be in the range 0.1 to 50 and preferably 4 to 10 milligram atoms per litre. The atomic ratio of rhodium to platinum is suitably in the range 6:1 to 1:1.
The molar ratio of carbon monoxide to hydrogen fed to the process may be varied widely, though it is preferably in the range 5:1 to 1:5.
25 ~ Ethylene glycol esters may if desired be hydrolysed to ethylene glycol or cracked to ethylene oxide in the case of the mono-ester or vinyl acetate in the case of the diester by known means.
A 100 ml stainless steel autoclave was charged with a solution of [NBu~ 2 ~Rhl2(CO)3~ (0.43 g compound, 2 milligram atoms Rh) and [NBu4]2 [Ptl2(CO)24~ ( compound, 0.4 milligram atoms Pt) (Bu means n-butyl) in N-methylpyrrolidone (10 mls) and tetraethylene glycol dimethyl ether (40 mls) and the vessel was sealed.
Hydrogen and carbon monoxide in 1:1 ratio were introduced to a total pressure of 6000 psig and the vessel was heated to give a temperature of 220~C. The solution was J ~ B2567
The reaction is preferably carried out a-t a pressure in the range 200 to 5000 and more preferably 500 to 1200 bars. A reaction temperature in the range 100 to 400C and preferably 150 to 300C may be employed.
The catalyst may be introduced as a solution in a polar solvent which preferably contains no hydroxy groups, e.g. Me0(C2H40)4Me and/or N~methylpyrrolidone. rf desired the catàlyst may be provided on a support, for example an alpha alumina, activated charcoal, silica or aluminosilicate support. In the latter case a solvent for ethylene glycol is suitably provided to ena~le the product to migrate from the catalytic sites after formation.
When the catalyst is provided as a solution it is preferred that the rhodium concentration should be in the range 1 to 100 and preferably 20 to 40 milligram atoms per litre and that the platinum concentration should be in the range 0.1 to 50 and preferably 4 to 10 milligram atoms per litre. The atomic ratio of rhodium to platinum is suitably in the range 6:1 to 1:1.
The molar ratio of carbon monoxide to hydrogen fed to the process may be varied widely, though it is preferably in the range 5:1 to 1:5.
25 ~ Ethylene glycol esters may if desired be hydrolysed to ethylene glycol or cracked to ethylene oxide in the case of the mono-ester or vinyl acetate in the case of the diester by known means.
A 100 ml stainless steel autoclave was charged with a solution of [NBu~ 2 ~Rhl2(CO)3~ (0.43 g compound, 2 milligram atoms Rh) and [NBu4]2 [Ptl2(CO)24~ ( compound, 0.4 milligram atoms Pt) (Bu means n-butyl) in N-methylpyrrolidone (10 mls) and tetraethylene glycol dimethyl ether (40 mls) and the vessel was sealed.
Hydrogen and carbon monoxide in 1:1 ratio were introduced to a total pressure of 6000 psig and the vessel was heated to give a temperature of 220~C. The solution was J ~ B2567
3 H.31590 agitated. Further hydrogen and carbon monoxide were added to increase the pressure to 12500 psig. The reaction was continued for four hours, the pressure being maintained at 12500 psig by periodic re-pressurisations.
After this time the vessel was cooled to room temperature, the gases vented and the liquid contents collected. The liquid reaction product was analysed by gas chromatography.
By way of comparison Example 1 was repeated, except that the~NBu4~2 LPt12(C0)24]
EXAMPLE ~
Example 1 was repeated, except that ~NBu~ 2 [ 12( )3~ and [NBU412 LPtl2(C0)24] were omitted and Pt~Rhl2(CO)3~ (0.30 ~ 2 milligram atoms Rh) was added instead.
By way of comparison, Example 1 was repeated except that [NBu4~ [Rhl2(C0)3~ and [NBu~ 2 [Ptl2(C0)24~
were omitted and Rh4(C0)12 (0.37 g, 2 milligram atoms Rh) was added instead.
Example 4 was repeated, except that ~NBu4]2 [Ptl2(C0)24] (0.29 g, 1 milligram atom Pt) was added.
25Example 4 was repeated, except that NBu~ 2 [Ptl2(C0)24] (0.15 g, 0.5 milligram atom Pt) was added.
Example 4 was repeated except that [NBu4~2 ~Ptl2(C0)24] (0.12 g 0.4 milligram atom Pt) was added.
Example 4 was repeated except that [NBu~ 2 [Ptl2(C0)24~ (0.072 g, o.25 milligram atom pt) was added.
Example 1 was repeated except that [NBu~ 2 [ 12 301 ~ 4~2 [Ptl2(C)2~ were omitted and U4~ rRh5Pt(CO)15~ ~0.875 mg atoms Rh) was added.
The NBu4 groups in ~he above examples may be replaced for example by alkali metal ions.
~ ~ 62567
After this time the vessel was cooled to room temperature, the gases vented and the liquid contents collected. The liquid reaction product was analysed by gas chromatography.
By way of comparison Example 1 was repeated, except that the~NBu4~2 LPt12(C0)24]
EXAMPLE ~
Example 1 was repeated, except that ~NBu~ 2 [ 12( )3~ and [NBU412 LPtl2(C0)24] were omitted and Pt~Rhl2(CO)3~ (0.30 ~ 2 milligram atoms Rh) was added instead.
By way of comparison, Example 1 was repeated except that [NBu4~ [Rhl2(C0)3~ and [NBu~ 2 [Ptl2(C0)24~
were omitted and Rh4(C0)12 (0.37 g, 2 milligram atoms Rh) was added instead.
Example 4 was repeated, except that ~NBu4]2 [Ptl2(C0)24] (0.29 g, 1 milligram atom Pt) was added.
25Example 4 was repeated, except that NBu~ 2 [Ptl2(C0)24] (0.15 g, 0.5 milligram atom Pt) was added.
Example 4 was repeated except that [NBu4~2 ~Ptl2(C0)24] (0.12 g 0.4 milligram atom Pt) was added.
Example 4 was repeated except that [NBu~ 2 [Ptl2(C0)24~ (0.072 g, o.25 milligram atom pt) was added.
Example 1 was repeated except that [NBu~ 2 [ 12 301 ~ 4~2 [Ptl2(C)2~ were omitted and U4~ rRh5Pt(CO)15~ ~0.875 mg atoms Rh) was added.
The NBu4 groups in ~he above examples may be replaced for example by alkali metal ions.
~ ~ 62567
4 H.31590 The results are shown in the Table below:-TABLE
Glycol MeOH Selectivity *
Example (mol/1/hr) (mol/l/hr) (o~) 1 0.5 0.17 75 2 0.54 0.40 57 3 0.46 0.26 63 4 0.43 0.32 57 0.31 0.13 70 6 0.34 0.14 71 7 0.37 0.15 71 8 0.40 0.20 66 9 0.48 0.17 74 * Selectivity = Glycol Glycol + MeOH x lOO
A 100 ml silver-lined stirred autoclave was charged with rhodium trisacetylacetonate (0.80 g, 2.0 milligram atoms Rh), platinum bisacetylacetonate (0.157 g, 0.40 milligram atom Pt), and cesium carbonate (0.130 g) and acetic acid (50 ml). The pressure and temperature were raised to lOOO atm using CO:H2 (l:l) at 230C. The reaction was continued ~or 4 hours under these conditions with regular top-up of gas to maintain a steady pressure. Analysis of the liquid on discharge from the reactor showed the production of methyl acetate, ethyl acetate, and ethylene glycol diacetate at rates of 0.120,0.011 and 0.066 mole/l/h respectively.
psig means pounds per square inch gauge.
Glycol MeOH Selectivity *
Example (mol/1/hr) (mol/l/hr) (o~) 1 0.5 0.17 75 2 0.54 0.40 57 3 0.46 0.26 63 4 0.43 0.32 57 0.31 0.13 70 6 0.34 0.14 71 7 0.37 0.15 71 8 0.40 0.20 66 9 0.48 0.17 74 * Selectivity = Glycol Glycol + MeOH x lOO
A 100 ml silver-lined stirred autoclave was charged with rhodium trisacetylacetonate (0.80 g, 2.0 milligram atoms Rh), platinum bisacetylacetonate (0.157 g, 0.40 milligram atom Pt), and cesium carbonate (0.130 g) and acetic acid (50 ml). The pressure and temperature were raised to lOOO atm using CO:H2 (l:l) at 230C. The reaction was continued ~or 4 hours under these conditions with regular top-up of gas to maintain a steady pressure. Analysis of the liquid on discharge from the reactor showed the production of methyl acetate, ethyl acetate, and ethylene glycol diacetate at rates of 0.120,0.011 and 0.066 mole/l/h respectively.
psig means pounds per square inch gauge.
Claims (10)
1. A process in which ethylene glycol or an ester thereof is produced by reacting carbon monoxide with hydrogen and when an ester is to be produced a carboxylic acid in the presence of a catalytic amount of rhodium together with platinum in an amount of at least one atom of platinum per eight atoms of rhodium to decrease methanol production.
2. A process as claimed in Claim 1 in which ethylene glycol is produced by reacting carbon monoxide with hydrogen and in the presence of a catalyst which comprises rhodium and platinum in a total atomic ratio of at most 8:1.
3. A process as claimed in Claim 1 in which an acetate of ethylene glycol is produced by the reaction of carbon monoxide, hydrogen and acetic acid.
4. A process as claimed in Claim 1 in which the rhodium and platinum are supplied as metal carbonyls or mixed metal carbonyls.
5. A process as claimed in Claim 1 which is carried out at a pressure in the range 500 to 1200 bars.
6. A process as claimed in Claim 1 which is carried out at a temperature in the range 150 to 300°C.
7. A process as claimed in Claim 1 in which the catalyst is introduced as a solution in a polar solvent which contains no hydroxy groups.
8. A process as claimed in Claim 7 in which the rhodium concentration is in the range 1 to 100 milligram atoms per litre and the platinum concentration is in the range 0.1 to 50 milligram atoms per litre.
9. A process as claimed in Claim 1 in which the atomic ratio of rhodium to platinum is in the range 6:1 to 1:1.
10. A process as claimed in Claim 1 in which the molar ratio of carbon monoxide to hydrogen fed to the process is in the range 5:1 to 1:5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8038002 | 1980-11-27 | ||
| GB8038002 | 1980-11-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162567A true CA1162567A (en) | 1984-02-21 |
Family
ID=10517586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000391126A Expired CA1162567A (en) | 1980-11-27 | 1981-11-27 | Production of ethylene glycol |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU7792981A (en) |
| CA (1) | CA1162567A (en) |
| ZA (1) | ZA818127B (en) |
-
1981
- 1981-11-23 ZA ZA818127A patent/ZA818127B/en unknown
- 1981-11-26 AU AU77929/81A patent/AU7792981A/en not_active Abandoned
- 1981-11-27 CA CA000391126A patent/CA1162567A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ZA818127B (en) | 1982-10-27 |
| AU7792981A (en) | 1982-06-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |