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US4552976A
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Process for oxidative dicarbonylation of butadiene
Assignee: Huntsman Corp
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Filing: 1984-08-27
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Granted: 1985-11-12
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Expires: 2004-08-27
Abstract
Abstract This invention relates to the carbonylation of olefins. More particularly it involves the carbonylation of aliphatic conjugated diolefins such as 1,3-butadiene to form adipic acid precursors such as, for example, dimethyl hex-3-ene-1,6-dioate by a process comprising reacting said 1,3-butadiene with carbon monoxide and oxygen in the presence of a hetergeneous palladium catalyst, a copper-containing compound and a lithium-containing compound.
Inventors
- 👤 Jiang-Jen Lin
- 👤 John F. Knifton
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 20:11
CPC Classifications
C; C07; C07C; C07C67/00; C07C67/36; C07C67/38
Claims Analysis
Total Claims: 10
Claim 1
Independent Claim
177 words
A process for oxidative carbonylation of aliphatic conjugated diolefins containing 4 to 12 carbon atoms per molecule of the formula: ##STR6## wherein each carbon is bonded either to hydrogen or a hydrocarbyl group, by reaction with carbon monoxide and oxygen in the presence of an alkanol coreactant containing 1 to 20 carbon atoms per molecule, to form an aliphatic dicarboxylic acid ester having the formula: ##STR7## wherein R is a saturated alkyl group, said process being conducted in the presence of a heterogeneous supported palladium catalyst, a copper-containing cocatalyst and a lithium-containing cocatalyst, at a temperature of 80° C. to 150° C. and a pressure of from 500 psi to 1800 psi to effect the desired carbonylation reaction, wherein the carbon monoxide to oxygen ratio is from 5:1 to 20:1, the palladium catalyst is deposited on said support in a concentration range of 0.1 to 20 wt %, the concentration of copper-containing cocatalyst is between 0.1 wt % and 50 wt % and the concentration of lithium-containing cocatalyst is between 0.0001 wt % and 1.0 wt %.
Claim 2
Dependent Claim
177 words
A process for oxidative carbonylation of aliphatic conjugated diolefins containing 4 to 12 carbon atoms per molecule of the formula: ##STR6## wherein each carbon is bonded either to hydrogen or a hydrocarbyl group, by reaction with carbon monoxide and oxygen in the presence of an alkanol coreactant containing 1 to 20 carbon atoms per molecule, to form an aliphatic dicarboxylic acid ester having the formula: ##STR7## wherein R is a saturated alkyl group, said process being conducted in the presence of a heterogeneous supported palladium catalyst, a copper-containing cocatalyst and a lithium-containing cocatalyst, at a temperature of 80° C. to 150° C. and a pressure of from 500 psi to 1800 psi to effect the desired carbonylation reaction, wherein the carbon monoxide to oxygen ratio is from 5:1 to 20:1, the palladium catalyst is deposited on said support in a concentration range of 0.1 to 20 wt %, the concentration of copper-containing cocatalyst is between 0.1 wt % and 50 wt % and the concentration of lithium-containing cocatalyst is between 0.0001 wt % and 1.0 wt %.
Claim 3
Dependent Claim
103 words
A process according to claim 1 wherein the conjugated diolefin is 1,3-butadiene, the alkanol coreactant is methanol coreactant, the supported palladium catalyst comprises 1% palladium on graphite; the copper-containing cocatalyst comprise a copper salt from the group consisting of cupric chloride, cuprous bromide and cuprous chloride hydrate; the lithium-containing cocatalyst comprises a lithium salt from the group consisting of lithium iodide, lithium bromide and lithium chloride; the temperature is at least 25° C.; the carbon monoxide pressure is least 50 psi and the carbon monoxide to oxygen ratio is initially between 1:1 and 100:1 and the primary aliphatic dicarboxylic acid ester is hex-3-ene-1,6-dioate.
Claim 4
Dependent Claim
23 words
A process according to claim 2 further comprising producing adipic acid by subjecting the dimethyl hex-3-ene-1,6-dioate product obtained to reduction followed by hydrolysis.
Claim 5
Dependent Claim
29 words
A process according to claim 1 wherein the copper-containing cocatalyst comprises a copper salt from the group consisting of cupric chloride, cupric bromide, cupric iodide and cuprous chloride hydrate.
Claim 6
Dependent Claim
18 words
A process according to claim 1 wherein the lithium-containing cocatalyst comprises a lithium salt which is lithium chloride.
Claim 7
Dependent Claim
15 words
A process according to claim 1 wherein the support for the palladium catalyst is graphite.
Claim 8
Dependent Claim
20 words
A process according to claim 2 wherein said dimethyl hexe-3-ene-1,6-dioate product is separated from said palladium catalyst system by filtration.
Claim 9
Dependent Claim
131 words
A process for oxidative carbonylation of 1,3-butadiene, which comprises reacting 1,3-butadiene with carbon monoxide and oxygen in the presence of methanol over a heterogeneous supported palladium catalyst comprising 1% palladium graphite, in the presence of a copper-containing cocatalyst comprising a copper salt from the group consisting of cupric chloride, cuprous bromide and cuprous chloride hydrate and a lithium-containing cocatalyst from the group consisting of lithium iodide, lithium bromide and lithium chloride wherein the ratio of palladium catalyst-to copper-to lithium-containing cocatalyst is about 0.01:1.0:0.005, at a temperature of 80° C. to 150° C. and a pressure of 500 psi to 1800 psi to form dimethyl hex-3-ene-1, 6-dioate, and thereafter separating said dimethyl-hex-3-ene-1, 6 dioate from said supported catalyst by filtration, wherein the carbon monoxide to oxygen ratio is from 5:1 to 20:1.
Claim 10
Dependent Claim
131 words
A process for oxidative carbonylation of 1,3-butadiene, which comprises reacting 1,3-butadiene with carbon monoxide and oxygen in the presence of methanol over a heterogeneous supported palladium catalyst comprising 1% palladium graphite, in the presence of a copper-containing cocatalyst comprising a copper salt from the group consisting of cupric chloride, cuprous bromide and cuprous chloride hydrate and a lithium-containing cocatalyst from the group consisting of lithium iodide, lithium bromide and lithium chloride wherein the ratio of palladium catalyst-to copper-to lithium-containing cocatalyst is about 0.01:1.0:0.005, at a temperature of 80° C. to 150° C. and a pressure of 500 psi to 1800 psi to form dimethyl hex-3-ene-1, 6-dioate, and thereafter separating said dimethyl-hex-3-ene-1, 6 dioate from said supported catalyst by filtration, wherein the carbon monoxide to oxygen ratio is from 5:1 to 20:1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-11-11 | 1989-05-13 | 1989-11-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-11-11 | 1993-05-13 | 1993-11-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-11-11 | 1997-05-13 | 1997-11-12 | $7700.00 | Window Closed / Lapsed |