Process for the preparation of a purified acid composition

Abstract

A purified acid composition including 2,5-furandicarboxylic acid is prepared by a process including a) providing an acid composition solution of a crude acid composition in a polar solvent, the crude acid composition including 2,5-furandicarboxylic acid (FDCA) and 2-formyl-furan-5-carboxylic acid (FFCA); b) contacting the acid composition solution with hydrogen in the presence of a hydrogenation catalyst to hydrogenate FFCA to hydrogenation products, such that the hydrogenation products contain a minor amount of 2-methyl-furan-5-carboxylic acid (MFA) or no MFA, yielding a hydrogenated solution; c) separating at least a portion of the FDCA from the hydrogenated solution by crystallization.

Claims

1. A process for the preparation of a purified acid composition comprising 2,5-furandicarboxylic acid, comprising: a) providing an acid composition solution of a crude acid composition in a polar solvent having a polarity sufficient to dissolve the crude acid composition, the crude acid composition comprising 2,5-furandicarboxylic acid (FDCA) and 2-formyl-furan-5-carboxylic acid (FFCA); b) contacting the acid composition solution with hydrogen in the presence of a hydrogenation catalyst to hydrogenate FFCA to hydrogenation products, such that the hydrogenation products contain up to a minor amount of 2-methyl-furan-5-carboxylic acid (MFA), yielding a hydrogenated solution; and c) separating a portion or all of the FDCA from the hydrogenated solution by crystallization, wherein the acid composition solution is contacted with hydrogen at a temperature in the range of 150 to 200 C. and a contact time with the hydrogenation catalyst in the range of 5 seconds to at most 10 min.

2. The process according to claim 1, wherein the hydrogenation catalyst comprises palladium on carbon.

3. The process according to claim 1, wherein the pressure is in the range of 1 to 80 bar.

4. The process according to claim 1, wherein the hydrogen partial pressure is in the range of 0.5 to 40 bar.

5. The process according to claim 1, which is conducted as a continuous process.

6. The process according to claim 1, wherein the polar solvent is selected from the group consisting of water, alcohols, acids and mixtures thereof.

7. A process for the preparation of a purified acid composition comprising 2,5-furandicarboxylic acid, comprising: (i) oxidizing a feedstock containing 5-alkoxymethylfurfural to an oxidation product comprising FDCA, FFCA, and esters of FDCA and, optionally, esters of FFCA; (ii) optionally, dissolving part or all of the oxidation product in a polar solvent having a polarity sufficient to dissolve the oxidation product to obtain a solution of the oxidation product, comprising FDCA, FFCA and esters of FDCA and FFCA; (iii) hydrolyzing part or all of the oxidation product in the presence of water, thereby hydrolyzing part or all of esters of FDCA and, optionally, of FFCA to obtain an aqueous solution of an acid composition; (iv) contacting a solution of the acid composition obtained in step (iii) with hydrogen in the presence of a hydrogenation catalyst to hydrogenate FFCA to hydrogenation products, yielding a hydrogenated solution; and (v) separating a portion or all of the FDCA from part or all of the hydrogenated solution by crystallization, wherein the acid composition solution is contacted with hydrogen at a temperature in the range of 150 to 200 C. and a contact time with the hydrogenation catalyst in the range of 5 seconds to at most 10 min.

8. The process according to claim 7, wherein in step (iv) FFCA is hydrogenated such that the hydrogenation products contain up to a minor amount of 2-methyl-furan-5-carboxylic acid (MFA).

9. The process according to claim 7, wherein in step (i) the feedstock is oxidized by means of an oxygen-containing gas in the presence of a catalyst comprising cobalt and manganese.

10. The process according to claim 9, wherein the catalyst comprises cobalt and manganese, and further comprises bromine.

11. The process according to claim 7, wherein the feedstock is oxidized at a temperature of from 60 to 220 C., at a pressure of from 5 to 100 bar and at a residence time of from 0.1 to 48 hours.

12. The process according to claim 7, wherein in step (ii) the part or all of the oxidation product is hydrolyzed by contacting the part or all of the oxidation product with water in the presence of a hydrolysis catalyst.

13. The process according to claim 7, wherein in step (ii) the part or all of the oxidation product is hydrolyzed by contacting the part or all of the oxidation product with water in the absence of a hydrolysis catalyst.

14. The process according to claim 7, wherein in step (ii) the part or all of the oxidation product is hydrolyzed by contacting the part or all of the oxidation product with water at a temperature of 120 to 200 C. and a pressure of 5 to 80 bar.

15. The process according to claim 7, wherein in step (iv) the pressure is in the range of 1 to 80 bar.

16. The process according to claim 7, wherein the polar solvent is selected from the group consisting of water, alcohols, acids and mixtures thereof.

17. The process according to claim 7, which is conducted as a continuous process.

18. The process according to claim 7, wherein steps (iii) and (iv) are carried out in a single reactor, comprising a hydrolysis zone and a hydrogenation zone.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a schematic process scheme of a suitable manner to carry out the process of hydrolysis and hydrogenation according to the present invention.

(2) FIG. 2 shows another embodiment of such a process.

DETAILED DESCRIPTION OF THE INVENTION

(3) FIG. 1 shows a stream (1) containing primarily methoxymethyl furfural (MMF) that is combined with a recycled acetic acid rich stream (2) and a water rich stream (3) also containing recycled catalyst. The streams are combined into a stream (4) that is fed to an oxidation reactor (5). Oxygen-containing gas, such as air, is passed via a compressor (not shown) to the oxidation reactor (5) via a line (6). Make-up catalyst, typically comprising Co and Mn, and optionally Br, is fed into the oxidation reactor (5) via a line (7). It is understood that other oxidation catalysts may also be used. In the oxidation reactor MMF is oxidized to FDCA with the oxygen-containing gas in the presence of a catalyst that e.g. comprises Co, Mn, in acetic acid as solvent. FIG. 1 shows one reactor. The skilled person will realize that two or more reactors in series may also be used. Excess oxygen is discharged from the oxidation reactor (5) via a line 31. Oxidized product is withdrawn from the oxidation reactor via a line (29) and fed into a crystallization vessel (8). The crystallization may be conducted as an evaporative cooling crystallizer. Any acetic acid and/or water that are freed in the evaporative crystallization may be discharged from the crystallization vessel (8) via a line (32). A slurry of crude FDCA, that contains some FFCA, methyl ester of FDCA and catalyst, is fed via a line (33) to a filtration equipment (9), where the slurry is separated into an acetic acid-containing mother liquor stream (10) and a solid crude product that is passed via a line (34) to a washing unit (12). The acetic acid-containing mother liquor stream (10) is combined with a stream of make-up acetic acid, supplied via a line (11) to form the stream (2) that is combined with the MMF in stream (1) and water in stream (3). In some embodiments at least a part of the evaporated acetic acid and/or water in the line (8) is combined with the stream (10) (not shown). In such cases any water in stream (8) will typically be separated from the acetic acid, and the acetic acid will be combined with the compounds in the stream (10).

(4) In the washing unit (12) the solid crude FDCA acid composition is washed with water that is supplied via a line (13). The water takes up acetic acid and the catalyst. The resulting liquid is discharged via a line (14) and fed to a distillation column (15). In the distillation column (15) some water is distilled off and removed overhead via a line (38). The bottom product of the distillation column (15) contains water, acetic acid and catalyst and is withdrawn as stream (3) that is combined with the MMF in stream (1) and acetic acid in stream (2). The figure shows the filtration and washing unit as two separate pieces of equipment. The skilled person will realize that the filtration and washing steps may be combined in one piece of equipment. In such a case the filtration will generate a filter cake, and the filter cake will be subjected to a washing treatment with water.

(5) The solid crude FDCA acid composition obtained after washing is withdrawn via a line 39 and combined with some water from a line (35) and from another line (30) and as a combined stream (16) passed to a hydrolysis reactor (17). The residence time in the hydrolysis reactor (17) is selected such that the esters are all hydrolyzed to methanol and FDCA. As indicated above, the hydrolysis reactor may be loaded with a bed of an acidic zeolite or ion exchange resin to catalyze the hydrolysis. The hydrolysis reactor may be operated at a temperature of about 160 C. The hydrolysis product comprising FDCA, water and methanol, is withdrawn via a line (18) and fed to an hydrogenation reactor (20). The hydrogenation reactor (20) contains a bed of hydrogenation catalyst. Hydrogen that is fed into the hydrogenation reactor (20) via a line (19) reacts with FFCA to HMFA as main hydrogenation product, and the hydrogenation product, together with FDCA, water and some methanol, is removed from the reactor and via a line (21) fed into a second crystallizer (22).

(6) As indicated above, it is also possible to combine hydrolysis reactor (17) and hydrogenation reactor (20) into one combined reactor. The combined stream (16) and hydrogen stream (19) may then be fed into the combined reactor in the upper part of this combined reactor. The stream (16) is maintained in a hydrolysis zone of the reactor and the combination of the thus hydrolyzed product and hydrogen is passed over a bed of hydrogenation catalyst, contained in the lower part of the combined reactor. The hydrogenation product is withdrawn at the bottom of the combined reactor. When the hydrogenation product contains any gas, such as excess hydrogen, such gas may be separated via a flash column (not shown). The remaining liquid stream, being the hydrogenation product that contains FDCA, water and methanol, is passed via the line 21 to the second crystallizer (22).

(7) The crystallizer (22) is an evaporative cooling crystallizer wherein some water and methanol are liberated and withdrawn via a line (23). The water and methanol in line (23) may be separated and be re-used in the process. Methanol can for instance be recycled to the step wherein a carbohydrate with methanol is converted to MMF. Water that is separated from the mixture in line (23) can be used as wash water in one of the washing steps in the present process.

(8) The solid FDCA that is obtained in the crystallizer (22) is passed as a slurry in a line (36) to a filtration equipment (24) where wet FDCA is separated from a mother liquor. The mother liquor contains water, optionally some methanol, HMFA, and optionally some other compounds that result from the hydrogenation of FFCA. The mother liquor is withdrawn from the filtration equipment (24) via a line (25). The line (25) is split into the line (35) to facilitate the transport of the crude solid FDCA acid composition from the washing unit (12) and into the line (13) that is used to wash the solid crude FDCA acid composition. As indicated above, the washing liquid is withdrawn via the line (14). Any HMFA that is contained in the liquid in the line (13) will be withdrawn in the line (14), and via the distillation column (15) and the bottom product thereof in the line (3) will be recycled to the oxidation reactor. In this way no valuable product is lost.

(9) The purified solid FDCA obtained in the filtration equipment (24) is passed through a line (37) to a washing unit (26) where it is washed with water, supplied via a line (27). The washing water is recovered via the line (30) and re-used. The washed purified FDCA acid composition is recovered from the washing unit (26) as the product stream (28).

(10) As indicated above, the filtration equipment and washing unit can be combined into one piece of equipment. The skilled person will further realize that the crystallizer (22) can consist of one or more crystallizers. In such a case the second or subsequent crystallizer may be used to re-crystallize the product to obtain an even purer product.

(11) FIG. 2 shows a different embodiment of the process according to the invention. In FIG. 2 some streams have been given the same number as corresponding streams in FIG. 1.

(12) MMF in stream (1) is combined with an acetic acid stream (2) and a water/catalyst stream (3) to a stream (4), which is passed to an oxidation reactor (5). In reactor (5) air that via a compressor through a line (6) is fed into the reactor (5), and catalyst, provided via a line (7), are combined with the MMF and allowed to react to yield a crude FDCA-containing acid composition. Excess oxygen is vented via a line (31). The crude FDCA-containing acid composition is passed via a line (29) to a first crystallizer (101). In crystallizer (101) only part of the crude acid composition is crystallized, yielding relatively pure FDCA. Crystallizer (101) is an evaporative cooling crystallizer, yielding a stream of acetic acid and water, discharged via a line (32), and a stream (120) comprising a slurry of the FDCA-containing acid composition and acetic acid. The FDCA-rich and acetic acid-rich slurry is passed to a filtration equipment (102) via the line (120). In the filtration equipment (102), acetic acid-containing mother liquor (still containing a substantial amount of the methyl ester of FDCA and most of FFCA) is separated from the crystallized FDCA and withdrawn via a line (104). The filtered solid FDCA is passed via a line (121) to a washing unit (103) where it is washed with water supplied via a line (13). The used wash water containing acetic acid and catalyst is withdrawn via a line (122). The washed FDCA is withdrawn via a line (111).

(13) The acetic acid-containing mother liquor in the line (104) is passed to a second evaporative crystallizer (105). Further acetic acid and water is vented via a line (123). Via a line (124) a slurry of crystallized FDCA, containing FFCA and the methyl ester of FDCA, is fed into a filtration equipment (106) where the solid material is separated from a mother liquor. The mother liquor comprises acetic acid and is withdrawn via a line (10). The streams (32) and (123) may be combined with the stream (10), optionally after separation of at least part of the water contained in the streams (32) and (123). The combined stream (10) is supplemented with make-up acetic acid from a line (11) and the combined stream is passed as stream (2) to the MMF feedstock in stream (1) and to the oxidation reactor (5).

(14) The crude FDCA-containing acid composition that is recovered as filter cake is passed via a line (125) to a washing unit (107) where it is washed with water, supplied via a line (108). The wash water is recovered as stream (126). The stream (126) and (122) are combined to form a stream (14) which is passed to a distillation column (15) to separate water, discharged via a line (16), from the bottom product comprising water, acetic acid and oxidation catalyst, withdrawn via the line (3) that is combined with MMF and acetic acid, and recycled to the oxidation reactor.

(15) The crude acid composition that is recovered in the washing unit (107) contains an amount of the monomethyl ester of FDCA, i.e. FDCA-ME. Therefore it is passed to a hydrolysis reactor (110) via a line (127). A stream of recycled water is fed into the line (127) through a line (109) to facilitate the transport of the acid composition. The hydrolysis reactor may be provided with a bed of heterogeneous catalyst to facilitate the hydrolysis. It is observed that the hydrolysis reactor can be smaller than in the process according to FIG. 1, as a smaller stream is passed through the hydrolysis reactor.

(16) The hydrolysis product comprising FDCA, water, methanol and some FFCA, is withdrawn from the hydrolysis reactor (110) through a line 128 and added to an aqueous stream in a line (112). The aqueous stream in the line (112) is combined with washed FDCA in the line (111) to form a stream (113), which is passed to a hydrogenation reactor (20). Hydrogen, supplied to the hydrogenation reactor (20) via a line (19), is reacted with FFCA supplied together with FDCA by the line (113), over a bed of a hydrogenation catalyst. The hydrogenated product, comprising HMFA, is passed via a line (129) to an evaporative cooling crystallizer (22), wherein some water and methanol are liberated and withdrawn via a line (23). The methanol and water may be re-used in the process as described above.

(17) Via a line (36) a slurry of crystallized purified FDCA is passed to a filtration equipment (24) where wet purified FDCA is separated from a mother liquor that comprises water and HMFA. The mother liquor is withdrawn via a line (114). The wet purified FDCA is recovered through a line (37) and fed to a washing unit (26), where it is washed with water, supplied via a line (27). The wash water is withdrawn via a stream (115) to which the stream in the line (114) is added. The stream in the line (115) is split into the streams in the lines (112), (109), (108) and (13). Via the lines (115), (13), (122), (14), and (3) HMFA is recycled to the oxidation reactor (5) where it can be oxidized to FDCA. If needed, the amount of water in the line (115) can be supplemented by make-up water that can be supplied via a line (130).

(18) Washed purified FDCA acid composition is recovered from the washing unit (26) as the product stream (28). Optionally, the purified acid composition can be further dried in a drying unit.

(19) The process schemes of FIGS. 1 and 2 are schematic. Auxiliary equipment, such as pumps, heating or cooling means, compressors or expanders have not been shown in the Figures.

(20) The invention will be further illustrated by means of the following examples.

EXAMPLES

(21) The following experiments were conducted in a stainless steel reactor wherein a bed of solid catalyst was placed. The catalyst bed was kept at the same temperature. Feedstock containing FDCA and FFCA was fed over the bed of catalyst. The feedstock was an aqueous stream containing 0.5% wt of crude FDCA composition. The crude FDCA composition consisted of 98.0% wt of FDCA, 1.0% wt of FFCA, and about 1.0% wt of the monomethyl ester of FDCA (FDCA-ME). The composition further contained some ppm of the components of the oxidation catalyst, viz. cobalt, manganese and bromine.

(22) Hydrogen-containing gas, consisting of 10% vol hydrogen and 90% vol nitrogen, was used for the hydrogenation.

(23) The catalysts used were Catalyst 1, comprising 5% wt palladium on carbon and Catalyst 2, comprising 0.43% wt palladium on carbon.

(24) The experiments were conducted as follows. The reactor was charged with a desired load of the desired catalyst. The bed of catalyst was vented several times with hydrogen to remove any oxygen. Unless otherwise indicated, the reactor was subsequently pressurized with the hydrogen-containing gas to a pressure of 15 bar (at 20 C.) and heated to the desired reaction temperature before the feedstock was passed over the bed of catalyst with the desired space velocity, expressed as weight hourly space velocity (WHSV) in grams of feedstock per gram of catalyst per hour. The Tables may also contain the contact time or residence time.

Example 1

(25) In order to show the influence of the reaction temperature on the conversion of the FFCA to HMFA and MFA Catalysts 1 and 2 were used in experiments wherein the above feedstock was passed over beds of the two catalysts with different space velocities and at different reaction temperatures. From the reactor effluent the amounts of FFCA, HMFA and MFA were determined. The results are shown in Table 1. The amounts of FFCA, HMFA and MFA are expressed as mass %, based on the amount of FFCA in the feedstock.

(26) TABLE-US-00001 TABLE 1 Exp. Contact time, Temp., FFCA, HMFA, MFA, No. Catalyst min C. mass % mass % mass % 1 1 0.15 160 0 72 17 2 2 0.15 160 4 85 6 3 1 3.0 160 0 0 10 4 2 3.0 160 0 0 20 5 1 0.12 170 0 75 18 6 2 0.15 170 10 70 7 7 1 3.0 170 0 0 9 8 2 3.0 170 0 5 10 9 1 0.12 180 0 62 20 10 1 3.0 180 0 0 8 11 2 3.0 180 0 0 5 12 1 0.12 190 15 58 12 13 1 0.23 190 0 50 25 14 1 1.0 190 0 0 15 15 2 1.0 190 0 0 5

Example 2

(27) To show the catalytic effect of the hydrogenation catalyst on the hydrolysis reaction Catalysts 1 and 2 were tested at different hydrogenation conditions as to space velocity and temperature. In addition, blank experiments were conducted at the same conditions, but in the presence of inert ceramic particles instead of catalyst particles. The feedstock was similar to that described in Example 1. The amount of FDCA-ME was measured for the each of the effluents, and expressed as weight percent of the total liquid effluent. The results are shown in Table 2.

(28) TABLE-US-00002 TABLE 2 Experiment WHSV, Contact Temperature, FDCA- No. Catalyst hr.sup.1 time, min C. ME, % wt 16 Blank 160 0.75 17 1 267 0.22 160 0.60 18 2 267 0.22 160 0.65 19 Blank 160 0.75 20 1 160 0.37 160 0.60 21 2 160 0.37 160 0.60 22 Blank 160 0.75 23 1 40 1.5 160 0.40 24 2 40 1.5 160 0.18 25 Blank 160 0.75 26 1 20 3.0 160 0.25 27 2 20 3.0 160 0.0 28 Blank 190 1.10 29 1 267 0.22 190 0.90 30 2 267 0.22 190 0.90 31 Blank 190 1.10 32 1 160 0.37 190 0.80 33 2 160 0.37 190 0.82 34 Blank 190 1.10 35 1 40 1.5 190 0.30 36 2 40 1.5 190 0.17 37 Blank 190 1.10 38 1 20 3.0 190 0.17 39 2 20 3.0 190 0.0

Example 3

(29) To show the difficulties of separating FDCA from the hydrogenation products of FFCA the following experiments were conducted.

(30) Pure FDCA was mixed with a pure contaminant in an amount of up to 2% wt, based on the amount of FDCA. The mixture was dissolved in water to a concentration of about 4% wt of FDCA by heating. FDCA was crystallized by cooling the solution under controlled cooling rates. The FDCA crystals were filtered at 80, 50 and 20 C. and the levels of each contaminant in the wet crystals were determined. The results are shown in Table 3 below. The levels are shown as percentages of the amounts of the contaminants that were added to the pure FDCA.

(31) The results show that many compounds that may be produced in the hydrogenation of FFCA are difficult to separate from FDCA. The best separation can be obtained with HMFA.

(32) TABLE-US-00003 TABLE 3 Contaminant % @ 20 C. % @ 50 C. % @ 80 C. 5-hydroxymethyl furan-2- 8 4 4 carboxylic acid (HMFA) furan-2-carboxylic acid (FCA) 45 45 44 5-methyl-furan-2-carboxylic 22 17 14 acid (MFA) 5-formyl-furan-2-carboxylic 65 58 54 acid (FFCA) monomethyl ester of 88 87 85 2,5-furandicarboxylic acid (FDCA-ME)

Example 4

(33) To show the efficacy of the present process on more concentrated solutions of FDCA solutions of up to 30% wt, based on the total solution, were tested. The solutions were prepared by dissolving 10, 20 or 30% wt of crude FDCA in water. The crude FDCA (cFDCA) contained 98.0% wt of FDCA, 1.0% wt of FFCA, and about 0.9% wt of the monomethyl ester of FDCA (FDCA-ME) and 0.1% wt of FCA (furan carboxylic acid). The solutions were contacted with a slurry of catalyst, comprising 0.43% wt palladium on carbon at different temperatures and at different space velocities. The space velocities were expressed as weight hourly space velocity (as gr cFDCA/gr catalyst/hour). The hydrogenated solutions were analyzed for the presence of hydrogenation products. For the hydrogenated solutions the percentage of FDCA recovered was determined.

(34) In Tables 4 to 6 the results of the hydrogenation experiments are shown at 160 C., at 180 C., and 190 C., whilst the pressure at room temperature of the hydrogen-containing gas (10 vol % H.sub.2/90 vol % N.sub.2) was 5 bar, 10 bar and 15 bar, respectively. The amounts of FFCA, HMFA and MFA are shown as analyzed from the hydrogenated solutions. In addition, the amounts of FCA, which may be formed as the result of the decarboxylation of the starting material, as well as the amounts of FDCA-ME, have been determined. The amounts of FDCA shown have been calculated as the percentage of the amount of FDCA that was passed to the catalyst bed.

(35) TABLE-US-00004 TABLE 4 Hydrogenation of 10% wt crude FDCA solution at 160 C./5 bar pressure Exp. WHSV, FFCA, HMFA, MFA, FCA, FDCA- FDCA, No. h.sup.1 ppmw ppmw ppmw % wt ME, % wt % wt 40 5 0 294 93 0.1 0.8 99 41 10 0 445 98 0.1 0.9 99 42 95 221 667 16 0.1 0.9 99

(36) TABLE-US-00005 TABLE 5 Hydrogenation of 20% wt crude FDCA solution at 180 C./10 bar pressure Exp. WHSV, FFCA, HMFA, MFA, FCA, FDCA- FDCA, No. h.sup.1 ppmw ppmw ppmw % wt ME, % wt % wt 43 10 0 0 11 0.5 0.4 99 44 20 0 0 0 0.4 0.4 99 45 44 0 24 0 0.4 0.4 99 46 92 160 49 0 0.4 0.4 99

(37) TABLE-US-00006 TABLE 6 Hydrogenation of 30% wt crude FDCA solution at 190 C./15 bar pressure Exp. WHSV, FFCA, HMFA, MFA, FCA, FDCA- FDCA, No. h.sup.1 ppmw ppmw ppmw % wt ME, % wt % wt 47 15 0 0 0 0.6 0.4 99 48 30 0 0 0 0.6 0.4 99 49 56 0 0 0 0.7 0.4 99 50 125 193 0 0 0.5 0.4 99

(38) The above results show that the formation of undesired MFA by-product can substantially be avoided by subjecting the crude FDCA compositions to hydrogenation at various temperatures and at high WHSV values.