US4473705A
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Process for producing oxalate diester
Assignee: Mitsubishi Gas Chemical Co Inc
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Filing: 1982-12-21
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Granted: 1984-09-25
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Expires: 2002-12-21
Abstract
Abstract A process for producing an oxalate diester is provided. The oxalate diester is produced by reacting an aliphatic alcohol, carbon monoxide and molecular oxygen at an elevated temperature and under pressure in the presence of a catalyst comprising (1) metallic palladium or a palladium compound, (2) a heteropoly-acid and (3) at least one nitrogen compound selected from the group consisting of nitric acid, nitrogen oxides and esters of nitrous acid.
Inventors
- 👤 Hiroshi Miyamori
- 👤 Tadashi Simomura
- 👤 Mituo Miura
- 👤 Katsushige Hayashi
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 13:07
CPC Classifications
B; B01; B01J; B01J27/00; B01J27/14; B01J27/186; B01J23/00; B01J23/38; B01J23/54; B01J27/02; B01J27/057; B01J27/0576
Claims Analysis
Total Claims: 20
Claim 1
Independent Claim
177 words
A process for producing an oxalate diester which comprises reacting an aliphatic alcohol, carbon monoxide and molecular oxygen at an elevated temperature and under pressure in the presence of a catalyst consisting essentially of (1) metallic palladium or a palladium compound, (2) a heteropoly-acid represented by the following formula: Hn [LxMyOz]mH.sub.2 O wherein L represents a hetero atom selected from the group consisting of P, As, Ti, Si, Ge, Sn, Zr, Th, Ce, B, I, Te, Fe, Cr, Al, Co, Ni, Rh, Cu, Mn, Se and Y; M represents at least one metal selected from the group consisting of Mo, W, V, Nb, Ta and Re; n depends on the valence number of L; m is mol number of H 2 O involved; x is 1 or 2 and y is an integer to bring the ratio of y/x to within the range of from 6 to 12; and z is an integer of 24-56 and (3) at least one nitrogen compound selected from the group consisting of nitric acid, nitrogen oxides and esters of nitrous acid.
Claim 2
Dependent Claim
177 words
A process for producing an oxalate diester which comprises reacting an aliphatic alcohol, carbon monoxide and molecular oxygen at an elevated temperature and under pressure in the presence of a catalyst consisting essentially of (1) metallic palladium or a palladium compound, (2) a heteropoly-acid represented by the following formula: Hn [LxMyOz]mH.sub.2 O wherein L represents a hetero atom selected from the group consisting of P, As, Ti, Si, Ge, Sn, Zr, Th, Ce, B, I, Te, Fe, Cr, Al, Co, Ni, Rh, Cu, Mn, Se and Y; M represents at least one metal selected from the group consisting of Mo, W, V, Nb, Ta and Re; n depends on the valence number of L; m is mol number of H 2 O involved; x is 1 or 2 and y is an integer to bring the ratio of y/x to within the range of from 6 to 12; and z is an integer of 24-56 and (3) at least one nitrogen compound selected from the group consisting of nitric acid, nitrogen oxides and esters of nitrous acid.
Claim 3
Dependent Claim
30 words
The process as claimed in claim 1, wherein component (1) of the catalyst is selected from the group consisting of metallic palladium nitrate, palladium sulfate, palladium halide and palladium acetate.
Claim 4
Dependent Claim
18 words
The process as claimed in claim 1, wherein component (1) of the catalyst is supported on a carrier.
Claim 5
Dependent Claim
25 words
The process as claimed in claim 3, wherein the carrier is selected from the group consisting of alumina, silicagel, carbon, activated carbon and diatomaceous earth.
Claim 6
Dependent Claim
27 words
The process as claimed in claim 1, wherein the hetero atom is selected from the group consisting of P and Si, and the metal, M, is Mo.
Claim 7
Dependent Claim
68 words
The process as claimed in claim 1, wherein component (2) of the catalyst is selected from the group consisting of the compounds represented by the following formulas: H.sub.8-n [LMo.sub.12 O.sub.40 ].mH.sub.2 O and H.sub.12-n [LMo.sub.12 O.sub.42 ].mH.sub.2 O wherein L is selected from the group consisting of P and Si; n is the valence number of L; and m is a mol number of H 2 O involved.
Claim 8
Dependent Claim
35 words
The process as claimed in claim 1, wherein component (2) of the catalyst is selected from the group consisting of the compounds having the following formulas: H.sub.3 [PMo.sub.12 O.sub.40 ], and H.sub.4 [SiMo.sub.12 O.sub.40 ].
Claim 9
Dependent Claim
39 words
The process as claimed in claim 1, wherein component (3) is selected from the group consisting of fuming nitric acid, nitrogen monoxide, nitrogen dioxide, dinitrogen trioxide, dinitrogen tetraoxide, dinitrogen pentaoxide, and nitrous acid esters of monohydric saturated aliphatic alcohols.
Claim 10
Dependent Claim
16 words
The process as claimed in claim 1, wherein the aliphatic alcohol is a saturated monohydric alcohol.
Claim 11
Dependent Claim
30 words
The process as claimed in claim 9, wherein the saturated monohydric alcohol is selected from the group consisting of linear, branched and cyclic aliphatic alcohols which may include a substituent.
Claim 12
Dependent Claim
29 words
The process as claimed in claim 1, wherein the molecular oxygen is introduced in the form of pure oxygen gas, oxygen enriched gas or air into the reaction system.
Claim 13
Dependent Claim
21 words
The process as claimed in claim 1, wherein the reaction is carried out in the presence of an inert organic solvent.
Claim 14
Dependent Claim
26 words
The process as claimed in claim 12, wherein the inert organic solvent is selected from the group consisting of aromatic hydrocarbons, carbonates, esters, ethers and ketones.
Claim 15
Dependent Claim
30 words
The process as claimed in claim 12, wherein the inert organic solvent is used in a volume from 1 to 15 times as great as that of the alcohol feed.
Claim 16
Dependent Claim
37 words
The process as claimed in claim 1, wherein component (1) is used in an amount ranging from 0.01 to 100 mg atom, calculated as metallic palladium, per 1 liter of the alcohol employed as a starting material.
Claim 17
Dependent Claim
49 words
The process as claimed in claim 1, wherein component (2) is used in an amount ranging from 1×10 -8 mol to 1 mol per 1 l of the alcohol employed as a starting material or per 1 l of the total amount of the alcohol and an inert solvent.
Claim 18
Dependent Claim
48 words
The process as claimed in claim 1, wherein component (3) is used in an amount ranging from 0.01 mol to 0.5 mol per 1 l of the alcohol employed as a starting material or per 1 l of the total amount of the alcohol and an inert solvent.
Claim 19
Dependent Claim
33 words
The process as claimed in claim 1, wherein the reaction is carried out at a partial pressure of carbon monoxide in the range of 50 kg/cm 2 (gauge) to 150 kg/cm 2 (gauge).
Claim 20
Dependent Claim
22 words
The process as claimed in claim 1, wherein the reaction is carried out at a temperature between 30° C. and 200° C.
References Cited (Backward Citations)
US3393136A
Cited
US4229589A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-09-25 | 1988-03-26 | 1988-09-25 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-09-25 | 1992-03-26 | 1992-09-25 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-09-25 | 1996-03-26 | 1996-09-25 | $7700.00 | Window Closed / Lapsed |