OXIDATIVE PREPARATION OF MALEIC ACID

Abstract

The invention is directed to a process for the preparation of maleic acid or a derivative thereof. Said process comprising an electrochemical oxidation of a furoic acid compound into maleic acid in an electrolyte solution; and optionally further comprising a step of reacting the maleic acid to the derivative thereof. In an alternative embodiment, said process comprising a first step comprising an electrochemical oxidation in an electrolyte solution of a furanic compound into one or more intermediates; followed by a second step comprising a chemo-catalytic oxidation of said intermediates to provide maleic acid or a derivative thereof.

Claims

1. Process for the preparation of maleic acid or a derivative thereof, said process comprising a first step comprising an electrochemical oxidation in an electrolyte solution of a furanic compound into one or more intermediates; wherein said furanic compound is a compound according to formula I of which R.sup.1 is H, CH.sub.2OH, CO.sub.2H or CHO and R.sup.2 is H, OH, C.sub.1-C.sub.6 alkyl or O(C.sub.1-C.sub.6 alkyl), or esters, ethers, amides, acid halides, anhydrides, carboximidates, nitriles, and salts thereof; ##STR00007## which first step is followed by a second step comprising a chemo-catalytic oxidation of said intermediates to provide maleic acid or a derivative thereof.

2. Process according to claim 1, wherein said one or more intermediates comprise 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid. ##STR00008##

3. Process according to claim 1, wherein the electrolyte solution is essentially free of a mediator.

4. Process according to claim 1, wherein the chemo-catalytic oxidation is carried out by using oxygen as an oxidation agent in the presence of a catalyst.

5. Process according to claim 1, further comprising an extraction of said intermediates with an organic solvent and preferably carrying out said second step in said organic solvent.

6. Process according to claim 1, wherein said second step directly provides maleic anhydride. ##STR00009##

7. Process according to claim 1, wherein said first step comprises photoelectrochemical oxidation.

8. Process for the preparation of maleic acid or a derivative thereof, said process comprising a one-step electrochemical oxidation of a furanic compound into maleic acid, which electrochemical oxidation is carried out in an electrolyte solution comprising a mediator; wherein said furanic compound is a compound according to formula I ##STR00010## wherein R.sup.1 is H, CH.sub.2OH, CO.sub.2H or CHO and R.sup.2 is H, OH, C.sub.1-C.sub.6 alkyl or O(C.sub.1-C.sub.6 alkyl), or esters, ethers, amides, acid halides, anhydrides, carboximidates, nitriles, and salts thereof; which process optionally further comprising a step of reacting the maleic acid to the derivative thereof.

9. Process according to claim 8, wherein the mediator comprises one or more of vanadates, vanadium oxides (e.g. V.sub.2O.sub.5, VO.sub.2), molybdates (MoO.sub.4.sup.2−), chromates (CrO.sub.4.sup.2−), dichromates (Cr.sub.2O.sub.7.sup.2−), permanganates (MnO.sub.4.sup.−) manganates (MnO.sub.4.sup.2−), manganese salts (Mn.sup.2+), tungstates (WO.sub.4.sup.2−), iodates (IO.sub.3.sup.−), chlorates (ClO.sup.−), chloride-chlorine couple (Cl.sup.−/Cl.sub.2), bromates (BrO.sup.−), bromide-bromine couple Br.sup.−/Br.sub.2, peroxydisulfates (S.sub.2O.sub.8.sup.2−) ozone (O.sub.3), cobalt salts (Co.sup.2+/Co.sup.3+), cerium salts (Ce.sup.3+/Ce.sup.4+), and the like, most preferably a mediator comprising vanadium oxide, sodium molybdate, and/or potassium dichromate.

10. Process according to claim 8, wherein said mediator is immobilized, preferably immobilized on the surface of the electrode.

11. Process according to claim 1, wherein said electrolyte solution is an aqueous electrolyte solution.

12. Process according to claim 1, wherein the derivative of maleic acid is one or more selected from the group consisting of maleic anhydride, fumaric acid, succinic acid, succinonitrile, putrescine, malic acid, and salts, anhydrides, amide, imides or esters of any of these compounds.

13. Process according to claim 1, wherein the electrolyte solution comprises an acid.

14. Process according to claim 1, wherein the electrochemical oxidation is carried out at a pH of less than 4.

15. Process according to claim 1, wherein the electrochemical oxidation is carried out at an initial concentration of the furanic compound in the electrolyte solution in the range of 0.01 to 5 mol/L.

16. Process according to claim 1, wherein the chemo-catalytic oxidation is carried out at a temperature in the range of 20 to 150° C.

17. Process according to claim 1, wherein said electrochemical oxidation is carried out with one or more working electrodes comprising lead oxide, for instance PbO.sub.2, and/or boron doped diamond (BDD).

18. Process according to claim 1, further comprising a step of isolating the maleic acid or the derivative thereof to provide the isolated maleic acid or derivative thereof and a used electrolyte solution.

19. Process according to claim 1, which process is a continuous process which is carried out in a continuous reactor system.

20. Process according to claim 1, wherein at the start of the process, the electrolyte solution essentially consists of only water, the furanic compound, the acid in accordance with claim 13 and optionally an inorganic salt.

21. Process comprising a step of chemo-catalytic oxidation of 5-hydroxy-2(5H)-furanone and/or cis-β-formylacrylic acid to maleic acid or a derivative thereof, which chemo-catalytic oxidation is carried out in accordance with claim 1.

Description

EXAMPLE 1: CONVERSION OF METHYL 2-FUROATE TO MALEIC ACID

[0057] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 10 mM of methyl furoate and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 mL of 0.5 M aqueous sulfuric acid. A 22 cm.sup.2 PbO.sub.2 electrode was activated by cyclic voltammetry (CV) between 0.8-2.4V against standard hydrogen electrode (SHE). The reference and working electrodes were made ready, then a potential of 1.75V vs. reversible hydrogen electrode (RHE) was applied across the cell. Analysis after 6 hours shows ˜42% yield on maleic acid, with residual methyl furoate and reaction intermediate formyl-acrylic acid both present.

EXAMPLE 2: CONVERSION OF 2-FUROIC ACID TO MALEIC ACID —VANADIUM PENTOXIDE MEDIATOR

[0058] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 20 mM of 2-furoic acid and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2.1V against SHE. The reference and working electrodes were made ready then a potential of 1.6V vs. saturated calomel electrode SCE was applied across the cell. Analysis after 7 hours shows 15:4:1 ratio of the reaction intermediate formyl-acrylic acid:maleic acid:2-furoic acid present.

EXAMPLE 3: CONVERSION OF 2-FUROIC ACID TO MALEIC ACID —VANADIUM PENTOXIDE MEDIATOR AND INCREASED CONCENTRATION

[0059] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 50 mM of 2-furoic acid and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.8-2.1V against SHE. The reference and working electrodes were made ready, then a galvanostatic current of 0.2 A was applied. Analysis after 15 hours shows ˜2:3 ratio of the reaction intermediate formyl-acrylic acid:maleic acid present.

EXAMPLE 4: CONVERSION OF 2-FUROIC ACID TO MALEIC ACID —VANADIUM PENTOXIDE MEDIATOR, INCREASED CONCENTRATION, AND HEATED

[0060] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 50 mM of 2-furoic acid and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.8-2.1V against SHE. The reference and working electrodes were made ready, then the contents of the cells were heated to 35° C. A galvanostatic current of 0.2 A was then applied. Analysis after 12 hours shows ˜9:11 ratio of the reaction intermediate formyl-acrylic acid:maleic acid being present.

EXAMPLE 5: CONVERSION OF 2-FUROIC ACID TO MALEIC ACID—NO MEDIATOR

[0061] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 20 mM of 2-furoic acid. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2.1V against SHE. The reference and working electrodes were made ready, then a potential of 1.84 V vs. SCE was applied across the cell. Analysis after 19 hours shows 25:74:1 ratio of the reaction intermediate formyl-acrylic acid:maleic acid:2-furoic acid being present.

EXAMPLE 6: CONVERSION OF FURFURAL TO MALEIC ACID —VANADIUM PENTOXIDE MEDIATOR

[0062] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 20 mM of furfural and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2,1V against SHE. The reference and working electrodes were made ready then a potential of 1.6 V vs. SCE was applied across the cell. Analysis after 19 hours shows ˜5:1 ratio of the reaction intermediate formyl-acrylic acid:maleic acid present.

EXAMPLE 7: CONVERSION OF FURFURAL TO MALEIC ACID —VANADIUM PENTOXIDE MEDIATOR

[0063] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 40 mM of furfural and 20 mM of vanadium pentoxide. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2,1V against SHE. The reference and working electrodes were made ready then a potential of 1.9 V vs. SCE was applied across the cell. Analysis after 12 hours shows ˜80% yield of maleic acid present.

EXAMPLE 8: CONVERSION OF FURFURAL TO 5-HYDROXY-2(5H)-FURANONE

[0064] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 50 mM of furfural. Conversion at 20° C. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2,1V against SHE. The reference and working electrodes were made ready then a potential of 1.85 V vs. SCE was applied across the cell. Analysis after 7 hours shows ˜2:1 ratio of the reaction intermediate formyl-acrylic acid:maleic acid present, and ˜9:1 after 20 hours. The maximum total yield of the product (maleic acid and 5-hydroxy-2(5H)-furanone is ˜80%).

EXAMPLE 9: CONVERSION OF FURFURAL TO 5-HYDROXY-2(5H)-FURANONE

[0065] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 50 mM of furfural. Conversion at 35° C. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2,1V against SHE. The reference and working electrodes were made ready then a potential of 1.85 V vs. SCE was applied across the cell. Analysis after 7 hours shows ˜1:2 ratio of the reaction intermediate formyl-acrylic acid:maleic acid present, and ˜1:10 after 20 hours. The maximum total yield of the product (maleic acid and 5-hydroxy-2(5H)-furanone is ˜70%).

EXAMPLE 10: CONVERSION OF FURFURAL TO 5-HYDROXY-2(5H)-FURANONE

[0066] The anode compartment of an H-cell was charged with 100 mL of 0.5 M aqueous sulfuric acid containing 50 mM of furfural. Conversion at 50° C. The cathode compartment of the H-cell was charged 100 ml of 0.5 M aqueous sulfuric acid. A 10 cm.sup.2 PbO.sub.2 electrode was activated by CV between 0.5-2,1V against SHE. The reference and working electrodes were made ready then a potential of 1.85 V vs. SCE was applied across the cell. Analysis after 7 hours shows ˜1:34 ratio of the reaction intermediate formyl-acrylic acid:maleic acid present.

EXAMPLE 11: EXTRACTION OF CIS-β-FORMYLACRYLIC ACID/5-HYDROXY-2(5H)-FURANONE AND MALEIC ACID FROM ELECTROLYTE

[0067] An equal volume of the electrolyte from Example 9 and an organic solvent (Ethyl acetate, Dichloromethane, Toluene, 2-Methyltetrahydrofuran, Diethyl Ether) were mixed together intensely and then left to phase separate. Both the aqueous and organics phases were then analysed by HPLC to determine the relative levels of cis-ß-formylacrylic acid/5-hydroxy-2(5H)-furanone and maleic acid in each of the phases:

TABLE-US-00001 Aqueous Phase Organic Phase Maleic Maleic Furanone Acid Furanone Acid Ethyl Acetate 8.3% 54.8% 91.7 45.2% Dichloromethane 99.1%  100%  0.9%   0% Toluene 99.1%  100%  0.9%   0% 2-MethylTHF 41.3% 26.4% 58.7% 73.6% Diethyl Ether 65.9% 63.2% 34.1% 36.6%

[0068] The conditions using ethyl acetate were scaled up, with the organic phase being separated from the aqueous, dried over sodium sulfate, then concentrated in vacuo to yield a white solid product (400 mg). This was analyzed by NMR and confirmed to be a ˜2.7:1 ratio of cis-ß-formylacrylic acid/5-hydroxy-2(5H)-furanone:maleic acid.

EXAMPLE 12: OXIDATION OF CIS-β-FORMYLACRYLIC ACID/5-HYDROXY-2(5H)-FURANONE TO MALEIC ACID/ANHYDRIDE

[0069] To two separate reactors were charged the cis-ß-formylacrylic acid/5-hydroxy-2(5H)-furanone:maleic acid mixture isolated in Example 11 (50 mg), 5% palladium on carbon (25 mg), and solvent (350 μL—either 0.5 M aqueous sulfuric acid, pH 7 aqueous buffer solution of monopotassium phosphate and dipotassium phosphate). The reactors were then heated to 70° C. with stirring and oxygen was bubbled through the mixture. After 2 hours, the reactions were cooled to room temperature and analyzed by HPLC. In both cases, conversion of cis-ß-formylacrylic acid/5-hydroxy-2(5H)-furanone to maleic acid.

EXAMPLE 14: SOLVENTS FOR THE OXIDATION OF HFO TO MALEIC ACID

[0070] An autoclave (10 ml) was charged with HFO, solvent (1 ml) and 10% Pd/C according to the Table 1 below.

[0071] The reactor was sealed then flushed with nitrogen. The reactor was then charged to 10 bar of pressure with pure oxygen. The reactor was then heated to 85° C. and stirred for 15 hours. After cooling to ambient temperature, the pressure was released and the reactor flushed with nitrogen. The product solutions were then filtered to remove catalyst, then analyzed by high-performance liquid chromatography (HPLC), with the yield of maleic acid compiled in Table 1.

TABLE-US-00002 TABLE 1 Solvent HFO (mg) Pd/C (mg) TOF/sec for MA* Water 10.0 5.7 0 0.5M Sulfuric Acid 8.3 4.1 0 Ethyl Acetate 7.0 9.1 155 Methylisobutylketone 5.5 4.4 265 Methyl-t-butyl ether 5.8 5.1 321 2-MeTHF 7.1 4.4 790 Dichloromethane 6.6 8.5 0 Acetic Acid 6.5 7.3 10 n-Heptane 6.0 3.7 276 Toluene 4.6 4.4 738 Acetonitrile 5.3 12.0 43 Acetone 4.6 12.0 108 Dimethyl Carbonate 5.4 4.1 115 Nitromethane 5.3 4.7 86 *TOF/sec for MA means turnover frequency of the catalyst for MA under those conditions

EXAMPLE 15: CATALYSTS FOR THE OXIDATION OF HFO TO MALEIC ACID IN TOLUENE

[0072] An autoclave (10 ml) was charged with HFO (10.6 mg), toluene (1 ml) and catalyst according to the Table 2. The reactor was sealed then flushed with nitrogen. The reactor was then charged to 10 bar of pressure with pure oxygen. The reactor was then heated to 111° C. and stirred for 14 hours. After cooling to ambient temperature, the pressure was released and the reactor flushed with nitrogen. The product solutions were then filtered to remove catalyst, then analyzed by HPLC, with the results compiled in Table 2.

TABLE-US-00003 TABLE 2 Solvent Catalyst (mg) TOF/sec for MA No Catalyst — 0 Au/SiO2 94 3279 Pd/C 6.0 309 Pt/C 13 82 Ru/C 11 1464 * TOF/sec for MA means turnover frequency of the catalyst for MA under those conditions