Organic compounds -- part of the class 532-570 series – Organic compounds – Phosphorus acids or salts thereof
Reexamination Certificate
2000-12-21
2003-07-01
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Phosphorus acids or salts thereof
Reexamination Certificate
active
06586621
ABSTRACT:
FIELD OF THE INVENTION
This invention generally relates to liquid phase oxidation processes using a carbon-supported, noble-metal-containing catalyst (particularly a deeply reduced catalyst) in conjunction with a supplemental promoter (e.g., bismuth or tellurium). In an especially preferred embodiment, this invention relates to such a process wherein N-(phosphonomethyl)iminodiacetic acid (“PMIDA”) or a salt thereof is oxidized to form N-(phosphonomethyl)glycine (also known in the agricultural chemical industry as “glyphosate”) or a salt thereof. This invention also generally relates to enhancing the activity, selectivity, and/or stability of a carbon-supported, noble-metal-containing catalyst (particularly a deeply reduced catalyst) using a supplemental promoter.
BACKGROUND OF THE INVENTION
N-(phosphonomethyl)glycine is described in Franz, U.S. Pat. No. 3,799,758. N-(phosphonomethyl)glycine and its salts are conveniently applied as a post-emergent herbicide in an aqueous formulation. Glyphosate is a highly effective and commercially important broad-spectrum herbicide useful in killing or controlling the growth of a wide variety of plants, including germinating seeds, emerging seedlings, maturing and established woody and herbaceous vegetation, and aquatic plants.
Various methods for making N-(phosphonomethyl)glycine are known in the art. Franz (U.S. Pat. No. 3,950,402) discloses that N-(phosphonomethyl)glycine may be prepared by the liquid phase oxidative cleavage of PMIDA with oxygen in the presence of a catalyst comprising a noble metal deposited on the surface of an activated carbon support:
Other by-products also typically form, such as formic acid (HCO
2
H), which is formed by the oxidation of the formaldehyde by-product; and aminomethylphosphonic acid (“AMPA”), which is formed by the oxidation of N-(phosphonomethyl)glycine. Even though the Franz method produces an acceptable yield and purity of N-(phosphonomethyl)glycine, high losses of the costly noble metal into the reaction solution (i.e., “leaching”) result because, under the oxidation conditions of the reaction, some of the noble metal is oxidized into a more soluble form, and both PMIDA and N-(phosphonomethyl)glycine act as ligands which solubilize the noble metal.
In U.S. Pat. No. 3,969,398, Hershman discloses that activated carbon alone, without the presence of a noble metal, may be used to effect the oxidative cleavage of PMIDA to form N-(phosphonomethyl)glycine. In U.S. Pat. No. 4,624,937, Chou further discloses that the activity of the carbon catalyst disclosed by Hershman may be increased by removing the oxides from the surface of the carbon catalyst before using it in the oxidation reaction. See also, U.S. Pat. No. 4,696,772, which provides a separate discussion by Chou regarding increasing the activity of the carbon catalyst by removing oxides from the surface of the carbon catalyst. Although these processes obviously do not suffer from noble metal leaching, they do tend to produce greater concentrations of formic acid and formaldehyde by-product when used to effect the oxidative cleavage of N-phosphonomethyliminodiacetic acid. These byproducts are particularly undesirable because they react with N-(phosphonomethyl)glycine to produce unwanted by-products (mainly N-methyl-N-(phosphonomethyl)glycine, sometimes referred to as “NMG”) which reduce the N-(phosphonomethyl)glycine yield. In addition, the formaldehyde by-product itself is undesirable because of its potential toxicity. See Smith, U.S. Pat. No. 5,606,107.
Optimally, therefore, it has been suggested that the formic acid and formaldehyde be simultaneously oxidized to carbon dioxide and water as the PMIDA is oxidized to N-(phosphonomethyl)glycine in a single reactor, thus giving the following net reaction:
As the above references suggest, such a process requires the presence of both carbon (which primarily effects the oxidation of PMIDA to form N-(phosphonomethyl)glycine and formaldehyde) and a noble metal (which primarily effects the oxidation of formaldehyde and formic acid to form carbon dioxide and water). Previous attempts to develop a stable catalyst for such an oxidation process, however, have not been entirely satisfactory.
Like Franz, Ramon et al. (U.S. Pat. No. 5,179,228) disclose using a noble metal deposited on the surface of a carbon support. To reduce the problem of leaching (which Ramon et al. report to be as great as 30% noble metal loss per cycle), however, Ramon et al. disclose flushing the reaction mixture with nitrogen under pressure after the oxidation reaction is completed to cause re-deposition of the noble metal onto the surface of the carbon support. According to Ramon et al., nitrogen flushing reduces the noble metal loss to less than 1%. Still, the amount of noble metal loss incurred with this method is unacceptable. In addition, re-depositing the noble metal can lead to loss of noble metal surface area which, in turn, decreases the activity of the catalyst.
Using a different approach, Felthouse (U.S. Pat. No. 4,582,650) discloses using two catalysts: (i) an activated carbon to effect the oxidation of PMIDA into N-(phosphonomethyl)glycine, and (ii) a co-catalyst to concurrently effect the oxidation of formaldehyde into carbon dioxide and water. The co-catalyst consists of an aluminosilicate support having a noble metal located within its pores. The pores are sized to exclude N-(phosphonomethyl)glycine and thereby prevent the noble metal of the co-catalyst from being poisoned by N-(phosphonomethyl)glycine. According to Felthouse, use of these two catalysts together allows for the simultaneous oxidation of PMIDA to N-(phosphonomethyl)glycine and of formaldehyde to carbon dioxide and water. This approach, however, suffers from several disadvantages: (1) it is difficult to recover the costly noble metal from the aluminosilicate support for re-use; (2) it is difficult to design the two catalysts so that the rates between them are matched; and (3) the carbon support, which has no noble metal deposited on its surface, tends to deactivate at a rate which can exceed 10% per cycle.
In PCT/US99/03402, Ebner et al. disclose a reaction process for making N-(phosphonomethyl)glycine compounds from PMIDA compounds using a deeply reduced, carbon-supported, noble metal catalyst which exhibits improved resistance to noble metal leaching and increased destruction of undesirable byproducts (e.g., formaldehyde). Still, this reaction process typically does not eliminate all the formaldehyde and formic acid byproduct, and, consequently, also does not eliminate all the N-methyl-N-(phosphonomethyl)glycine byproduct.
Thus, a need continues to exist for an improved reaction process for oxidizing PMIDA to N-(phosphonomethyl)glycine using a catalyst which exhibits resistance to noble metal leaching and increased oxidation of formic acid and formaldehyde into carbon dioxide and water (i.e., increased formic acid and formaldehyde activity).
SUMMARY OF THE INVENTION
This invention provides, in part, for an improved process for oxidizing PMIDA, salts of PMIDA, and esters of PMIDA to form N-(phosphonomethyl)glycine, salts of N-(phosphonomethyl)glycine, and esters of N-(phosphonomethyl)glycine, particularly such a process which uses a catalyst (or catalyst system) that (a) exhibits resistance to noble metal leaching, and (b) exhibits increased oxidation of formic acid and/or formaldehyde, and consequent decreased formation of NMG; an improved process for oxidizing a substrate in general wherein the activity, selectivity, and/or stability of a carbon-supported, noble-metal-containing catalyst used to catalyze the oxidation is enhanced by merely mixing the catalyst with a supplemental promoter (rather than using a catalyst which already contains the promoter, and, consequently, is more costly to manufacture); an improved process for making an oxidation catalyst system (particularly an oxidation catalyst system for oxidizing PMIDA compounds) having enhanced activity, selectivity, and/or stability; and an oxidation catalyst system (particularly an oxidation cataly
Ebner Jerry R.
Leiber Mark A.
Rogers Peter
Wan Kam-To
Woods Anthony
Monsanto Technology LLC
Schaper Joseph A.
Senniger Powers Leavitt & Roedel
Vollano Jean F.
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