GB2087392A - Process for the production of acetaldehyde dimethyl acetal - Google Patents
Process for the production of acetaldehyde dimethyl acetal Download PDFInfo
- Publication number
- GB2087392A GB2087392A GB8133370A GB8133370A GB2087392A GB 2087392 A GB2087392 A GB 2087392A GB 8133370 A GB8133370 A GB 8133370A GB 8133370 A GB8133370 A GB 8133370A GB 2087392 A GB2087392 A GB 2087392A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- weight
- cobalt
- reaction
- methanol
- 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.)
- Granted
Links
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000003426 co-catalyst Substances 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002739 metals Chemical class 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000004820 halides Chemical class 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 claims abstract description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- MYCXIDKAJBXPCZ-UHFFFAOYSA-N 1-ethoxy-1-methoxyethane Chemical compound CCOC(C)OC MYCXIDKAJBXPCZ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- -1 acetaldehyde, ethers Chemical class 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical class [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
- C07C43/303—Compounds having groups having acetal carbon atoms bound to acyclic carbon atoms
Abstract
A process for the production of acetaldehyde dimethyl acetal comprises reacting methanol with carbon dioxide and hydrogen at an elevated temperature and pressure in the presence of (i) a promoter comprising a halogen and/or a halide, (ii) a cobalt catalyst and (iii) either a co-catalyst comprising nickel together with a compound of trivalent arsenic and/or antimony or one or more of the metals molybdenum, tungsten, uranium, chromium, vanadium, titanium and iron together with a compound of trivalent phosphorous, arsenic and/or antimony as ligand. The reaction is effected using a ratio of carbon monoxide to hydrogen of between 2:1 and 1:3; up to 1% by weight of cobalt and up to 5% by weight of the above-mentioned metals, based on the methanol used, is used; the molar ratio of ligand to co-catalyst is from 5:1 to 1:5.
Description
SPECIFICATION
Process for the production of an acetal
This invention relates to a process for the production of an acetal and, more particularly, to the production of acetaldehyde dimethyl acetal by reacting methanol with carbon monoxide and hydrogen at an elevated temperature and pressure in the presence of a catalyst.
United Kingdom Patent Application No. 80 10023 (German Application No. P 29 1 3 677.4) relates to a process for the production of acetaldehyde dimethyl acetal by the cobaltcatalysed reaction of methanol with carbon monoxide and hydrogen in the presence of halogen and/or halide as promoter at an elevated temperature and pressure. In addition to cobalt, nickel in the form of its compounds or in the form of finely divided metal is used as co-catalyst together with a compound of trivalent phosphorous as ligand. This was the first disclosure of a two-metal catalyst system for the production of acetaldehyde dimethyl acetal which has advantages over the use of cobalt alone.Although it had previously been proposed to use ruthenium in addition to cobalt in the homologisation of methanol, this was done to promote the hydrogenation reaction in addition to the homologisation reaction and hence to promote the formation of ethanol and to suppress the formation of secondary products, for example acetaldehyde, ethers and esters, (US-PS No.
4,1 33,966).
It has now been found that, instead of nickel, other metals may also be successfully added as co-catalyst to the cobalt and, irrespective of the metal used, compounds of trivalent phosphorus, arsenic and/or antimony may be used as ligand. Accordingly, the present invention provides a process for the production of acetaldehyde dimethyl acetal by the cobalt-catalysed reaction of methanol with carbon monoxide and hydrogen in the presence of halogen and/or halogen compounds as promoter at elevated temperatures and pressures, characterised in that, in addition to cobalt, nickel together with compounds of trivalent arsenic and/or antimony is used as co-catalyst or one or more of the metals molybdenum, tungsten, uranium, chromium, vanadium, titanium and iron together with compounds of trivalent phosphorus, arsenic or antimony as ligands is/are used as co-catalyst, the ratio of carbon monoxide to hydrogen being from 2:1 to 1:3, up to 1% by weight of cobalt and up to 5% by weight of the abovementioned metals, based on the methanol used, being used and the molar ratio of ligand to co-catalyst used being from 5:1 to 1:5.
Accordingly, it has been found that not only does the use of nickel as co-catalyst in addition to cobalt promote the reaction of methanol to form acetal-dehyde dimethyl acetal, the new principle of two-metal catalysts may be applied in a surprisingly broad scope.
It is advantageous to carry out the reaction in the liquid phase with the catalyst dissolved.
However, the catalyst may also be used in insoluble form, for example in the form of finely divided metal or on a support. The reaction may also be carried out in the gaseous phase. Although solvents are not necessary for the reaction according to the invention, they may be used. Examples of suitable solvents are hydrocarbons, such as heptane, cyclohexane, toluene or oxygen-containing solvents.
The catalyst, cobalt, and the above-mentioned co-catalysts are advantageously used in the form of metal carbonyls or in the form of suitable salts, for example bromides, iodides, acetates, formates or propionates, and other compounds which form carbonyl or hydrocarbonyl complexes with carbon monoxide or with carbon monoxide and hydrogen.
The cobalt is used in a quantity of up to 1% by weight and preferably in a quantity of from 0.01 to 0.5% by weight, based on the methanol used, whilst the co-catalyst is used in a quantity of up to 5% by weight and preferably in a quantity of from 0.01 to 3% by weight, based on the methanol used.
The ligands used are, in particular, compounds of trivalent phosphorous corresponding to the following formula:
in which R1, R2 and R3 may represent for example alkyl, aryl or aralkyl groups. However, many other compounds, such as bicyclic compounds, in which P is incorporated as a hetero atom, phenoxy or alkoxy groups, are also suitable for the reaction. It has proved to be advantageous to use triphenyl phosphine for example. With all co-catalyst systems, it is also possible to use the corresponding compounds of trivalent arsenic or antimony. Surprisingly, none of the disadvantages of intensified aldol condensation (EPA 0 010 373) attending the use of catalysts containing cobalt only were observed where the two-metal catalysts were used.
Suitable promoters for the reaction are halides, particularly hydrogen iodide or bromide, and also metal bromides and ioldides, methyl iodide or bromide, phosphonium iodides as well as elemental iodine or bromine and mixtures thereof.
The molar ratio of iodine and/or bromine, based on the co-catalyst, is generally from 0.1 to 5. The reaction is carried out at a temperature in the range from 1 80 to 230"C and under a pressure in the range from 200 to 500 bars, although it may be advantageous to apply higher pressures. Preferred raction conditions are temperatures in the range from 190 to 210"C and pressures in the range from 230 to 320 bars. The ratios of carbon monoxide to hydrogen are in the range from 2:1 to 1:3, the preferred ratio being 1:1. The yield of acetaldehyde dimethyl acetal is not adversely affected if inert constituents, such as CO2, N2 or C H4, are present in the starting gas. Accordingly, synthesis gas of standard quality may be used.
In the process according to the invention, the residence times of longer than 30 hours which are required in known processes may generally be reduced to less than two hours.
The preferred residence times are between 5 hours and 2 hours, depending on whether the process is carried out continuously or in batches.
The reaction product contains only small quantities of secondary products and may be worked up by distillation in the usual way.
The invention is illustrated by the following
Examples.
EXAMPLE 1 A stirrer-equipped autoclave was charged with 39.8g (1.24 moles) of methanol, 1 60 mg of Co(acetate)2. 4H20, 429 mg of 57% aqueous hydrogen iodide solution, 674 mg of triphenyl phosphine and 450 mg of tungsten hexacarbonyl. A mixture of carbon monoxide and hydrogen (ratio by volume 1:1) was introduced under pressure in a quantity such that, after the temperature had reached 200 C, the pressure amounted to 300 bars. Synthesis gas was introduced during the 1-hour reaction to maintain that pressure. After cooling and working up, it was found that 56.0% by weight of the methanol used had reacted.
Selectivities of 85.5% of acetaldehyde dimethyl acetal, 6.6% of acetaldehyde, 0.7% of acetaldehyde methyl ethyl acetal, 1.0% of ethanol, 4.9% of methyl acetate and 1.3% of products with C > 2 were obtained for the organic products. Repetition of the test using 61 2 mg of triphenyl arsine instead of triphenyl phosphine and a reaction time of 45 minutes produced a conversion of 56.4% by weight for a selectivity of 84.1 % of acetaldehyde dimethyl acetal.
EXAMPLE 2
The reaction was carried out in the same way as described in Example 1, except that 338 mg of molybdenum heacarbonyl were used instead of the tungsten carbonyl.
The conversion amounted to 69.1% by weight of the methanol used. The selectivities amounted to 66.6% of acetaldehyde dimethyl acetal, 15.1% of acetaldehyde, 5.0% of acetaldehyde methyl ethyl acetal, 4.0% of ethanol, 5.3'iSo of methyl acetate and 4.0% of products with C > 2. Repetition of the test using 495 mg of tributyl phosphine produced a methanol conversion of 64.2% by weight for a selectivity of 68.4% of acetaldehyde dimethyl acetal.
EXAMPLE 3
The reaction was carried out in the same way as described in Example 1 except that 450 mg of chromium (acetylacetonate)3 and 336 mg of triphenyl phosphine were added as the two-metal catalyst system. The methanol conversion amounted to 68.2% by weight for a selectivity of 69.9% of acetaldehyde dimethyl acetal. Repetition of the test using 225 mg of chromium (acetylacetonate)3 produced corresponding values of 68.6% and 66.8%.
EXAMPLE 4
The reaction was carried out in the same way as described in Example 1 but with 336 mg of triphenyl phosphine and with 446 and 223 mg of vanadium (acetylacetonate)3. The methanol ccnversion amounted to 66.7% and 69.1% by weight for acetaldehyde dimethyl acetal selectivities of 56.9% and 64.2% respectively.
EXAMPLE 5
The reaction was carried out in the same way as described in Example 1 but with 336 mg of triphenyl phosphine and 1 68 mg of titanium (acetyl acetonate)2. A methanol conversion of 63.4% by weight was obtained for an acetaldehyde dimethyl acetal selectivity of 63.8%. Repetition of the test with 168 mg of triphenyl phosphine produced corresponding values of 65. 1% and 62.1%.
Claims (7)
1. A process for the production of acetaldehyde dimethyl acetal which comprises reacting methanol with carbon monoxide and hydrogen in the presence of (i) a promoter comprising halogen and/or a halide; (ii) a catalyst comprising cobalt and (iii) a co-catalyst comprising nickel together with a com- 4 pound of trivalent arsenic and/or antimony or one or more of the metals molybdenum, tungsten, uranium, chromium, vanadium, titanium and iron together with a compound of trivalent phosphorus, arsenic and/or antimony as ligand; the reaction being effected at a temperature in the range from 1 80 to 230on and under pressure of at least 200 bars with a ratio of carbon monoxide to hydrogen of between 2:1 and 1:3, up to 1% by weight of cobalt and up to 5% by weight of the abovementioned metals, based on the methanol used, being used and the molar ratio of ligand to co-catalyst used being from 5:1 to 1:5.
2. A process as claimed in Claim 1, wherein the reaction is effected under a pressure of from 200 to 500 bars.
3. A process as claimed in Claim 1 or 2,
wherein salts of cobalt and of the co-catalyst
which are soluble in the reaction medium are
used.
4. A process as claimed in any of Claims
1 to 3, wherein from 0.01 to 0.5% by weight
of cobalt, based on the methanol used, is
used.
5. A process as claimed in any of Claims
1 to 4, wherein from 0.01 to 3% by weight
of co-catalyst, based on the methanol used, is used.
6. A process as claimed in any of Claims
1 to 5, wherein the reaction is effected at a
temperature in the range of from 1 90 to 210"C and pressure in the range from 230 to
320 bars.
7. A process as claimed in Claim 1, sub
stantially as herein described with reference to
the specific Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3042633A DE3042633C2 (en) | 1980-11-12 | 1980-11-12 | Process for the preparation of acetaldehyde dimethyl acetal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2087392A true GB2087392A (en) | 1982-05-26 |
| GB2087392B GB2087392B (en) | 1984-05-10 |
Family
ID=6116580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8133370A Expired GB2087392B (en) | 1980-11-12 | 1981-11-05 | Process for the production of acetaldehyde dimethyl acetal |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS57158734A (en) |
| BE (1) | BE890964R (en) |
| DE (1) | DE3042633C2 (en) |
| FR (1) | FR2493835B2 (en) |
| GB (1) | GB2087392B (en) |
| IT (1) | IT1172053B (en) |
| NL (1) | NL8104804A (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2036739B (en) * | 1978-11-21 | 1983-02-09 | British Petroleum Co | Use of group viii metals as co-cata-lysts in the homologation of methanol |
| DE2913677C2 (en) * | 1979-04-05 | 1983-03-03 | Union Rheinische Braunkohlen Kraftstoff AG, 5000 Köln | Process for the preparation of acetaldehyde dimethyl acetal |
-
1980
- 1980-11-12 DE DE3042633A patent/DE3042633C2/en not_active Expired
-
1981
- 1981-10-23 NL NL8104804A patent/NL8104804A/en not_active Application Discontinuation
- 1981-11-03 BE BE0/206422A patent/BE890964R/en active
- 1981-11-05 GB GB8133370A patent/GB2087392B/en not_active Expired
- 1981-11-10 IT IT49668/81A patent/IT1172053B/en active
- 1981-11-12 FR FR818121174A patent/FR2493835B2/en not_active Expired
- 1981-11-12 JP JP56180449A patent/JPS57158734A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2493835A2 (en) | 1982-05-14 |
| IT8149668A0 (en) | 1981-11-10 |
| DE3042633C2 (en) | 1983-03-24 |
| FR2493835B2 (en) | 1985-07-26 |
| IT1172053B (en) | 1987-06-18 |
| NL8104804A (en) | 1982-06-01 |
| DE3042633A1 (en) | 1982-06-03 |
| GB2087392B (en) | 1984-05-10 |
| BE890964R (en) | 1982-03-01 |
| JPS57158734A (en) | 1982-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4133966A (en) | Selective formation of ethanol from methanol, hydrogen and carbon monoxide | |
| US4239924A (en) | Ethanol from methanol | |
| US4321414A (en) | Catalytic hydrogenation of glycolaldehyde to produce ethylene glycol | |
| EP0029723A1 (en) | Process for the production of ethanol and/or acetaldehyde in the presence of metal complex catalyst systems | |
| US4193943A (en) | Hydroformylation catalysts | |
| EP0030434B1 (en) | Methanol homologation using cobalt-ruthenium catalysts | |
| US4317946A (en) | Process for producing ethylene glycol via catalytic hydrogenation of glycolaldehyde | |
| US4138420A (en) | Hydroformylation catalysts | |
| JPS5984838A (en) | Manufacture of carboxylic acid, carboxylic anhydride and carboxylic acid ester and catalyst therefor | |
| US4239705A (en) | Process for producing acetaldehyde | |
| US4400551A (en) | Process for the production of acetaldehyde and ethanol | |
| US4278819A (en) | Process for the production of acetaldehyde dimethyl acetal | |
| EP0001936B1 (en) | Process for the production of acetaldehyde by the reaction of methanol with synthesis gas | |
| US4239925A (en) | Ethanol from methanol | |
| CA1156258A (en) | Methanol homologation using iron-cobalt catalyst | |
| US4357480A (en) | Process for the production of ethanol by the liquid phase hydrocarbonylation of methanol | |
| EP0055887A2 (en) | Novel catalyst system and process for producing ethanol using said novel catalyst system | |
| EP0037586A1 (en) | Process for the selective hydroformylation of methanol to acetaldehyde | |
| EP0013464A1 (en) | Selective formation of ethanol from methanol, hydrogen and carbon monoxide | |
| EP1392709B1 (en) | One-step production of 1,3-propanediol from ethylene oxide and syngas with a catalyst with a phospholanoalkane ligand | |
| US3725438A (en) | Production of cyclic acetals | |
| US4536597A (en) | Selective hydrocarboxylation of propylene to isobutyric acid | |
| EP0171802A1 (en) | Production of carboxylic anhydrides from methyl carboxylates using rhodium complex catalysts | |
| GB2087392A (en) | Process for the production of acetaldehyde dimethyl acetal | |
| CA1181734A (en) | Preparation of carboxylic acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |