Continuous method for producing muconic acid from aldaric acid

Abstract

According to an example aspect of the present invention, there is provided a continuous method of producing muconic acid from aldaric acid in the presence of a solid heterogeneous catalyst and an alcohol solvent with short reaction time. Another aspect of the present invention is the use of a non-expensive solid heterogenous catalyst, which is automatically separated from the product.

Claims

1. A continuous method of producing muconic acid from an aldaric acid comprising passing the aldaric acid in a solvent through a pressurized reactor at temperature of 120 to 140 C. with a solid heterogenous rhenium-based catalyst at weight hourly space velocity of 0.1-10 h.sup.1 during a pre-determined reaction time.

2. The method according to claim 1, wherein the aldaric acid is galactaric acid or glucaric acid, either in free acid or ester form.

3. The method according to claim 1, wherein the solvent is an alcohol solvent selected from monovalent or polyvalent C.sub.1-C.sub.6 alcohols, or any combination thereof.

4. The method according to claim 1, wherein the solvent is methanol or butanol.

5. The method according to claim 1, wherein the catalyst is ammonium perrhenate, which is fixed in a packed bed inside of the reactor.

6. The method according to claim 1, wherein the reactor is pressurized into 500-2000 kPa with hydrogen, argon or nitrogen gas flow through the reactor.

7. The method according to claim 1, wherein the catalyst is activated by heat at temperature of 120 to 130 C. for at least an hour before passing the aldaric acid feed through the reactor.

8. The method according to claim 1, wherein the weight hourly space velocity is 0.2-5 h.sup.1, more preferably about 0.2 h.sup.1.

9. The method according to claim 1, wherein the reaction time is 1 to 6 hours.

10. Use of muconic acid and esters as an intermediate in the production of industrial chemicals and pharmaceutical building blocks wherein the muconic acid and esters are produced by a continuous method of producing muconic acid from an aldaric acid comprising passing the aldaric acid in a solvent through a pressurized reactor at temperature of 120 to 140 C. with a solid heterogenous rhenium-based catalyst at weight hourly space velocity of 0.1-10 h.sup.1 during a pre-determined reaction time.

11. Use of muconic acid and esters as an intermediate in the production of chemicals selected form the group consisting of: adipic acid, terephthalic acid, hexamethylenediamine, caprolactone, caprolactam, polyamides and nylons, wherein the muconic acid and esters are produced by a continuous method of producing muconic acid from an aldaric acid comprising passing the aldaric acid in a solvent through a pressurized reactor at temperature of 120 to 140 C. with a solid heterogenous rhenium-based catalyst at weight hourly space velocity of 0.1-10 h.sup.1 during a pre-determined reaction time.

Description

EXAMPLES

[0041] The reactor used to study the continuous process is sulphuric free tube reactor. The reactor is 30 cm long and has a diameter of 12 mm. The catalyst bed held with-in the reactor, is supported by a metal rod.

Experiment Set Up

[0042] Raw material in solution is drawn into the system with HPLC pump with the mass flow rate monitored using a balance under the raw material vessel. Before the reactor, raw material flows through pre-heater vaporizer and is mixed with the gas flow. The system is capable of using hydrogen, nitrogen and argon gases. Volumetric flow of the gases is controlled with flow controllers. The reactor heating is done using two 230 V ceramic electronic ovens. The reactor temperature is measured with thermocouple which measures temperature from three points in the reactor. After the reactor, the products enter the pressurized sampling vessel, where the products can be collected under pressure. The products then enter the pressure controller and after that the sampling vessel. In this work, the products were collected using the second sampling vessel. The both sampling vessels are cooled down using a cryostat. The used gas continues from the sampling vessel and to FTIR or an air conditioner. The reactor system diagram is illustrated in FIG. 1.

Chemicals

[0043] All the chemicals were supplied by Sigma-Aldrich, except galactaric acid butyl ester, coarse silicon carbide and quartz wool. Silicon carbide was supplied by Alfa Aesar, quartz wool by Roth and galactaric acid butyl ester was produced in house by the VTT. During the project, more the raw material, galactaric acid butyl ester, had to be synthesised with esterification of D-Saccharic acid potassium salt and n-butanol in the presence of H.sub.2SO.sub.4. The product was oily galactaric acid butyl ester and solid material which had to be filtered with porosity 3 glass filter. GC-FID and GC-MS analysis showed the solid material to be unreacted D-Saccharic acid potassium salt.

Continuous Experiments Method

[0044] The experimental conditions were decided using similar conditions to batch reactor experiments. Due to mucic acid being highly insoluble, a 0.1 g/ml galactaric acid butyl ester in n-butanol solution was used instead as a raw material. The catalyst was changed from MTO to ammonium perrhenate, due to significantly lower catalyst cost and more material required for the continuous reactor. The catalyst bed also consisted of inert silicon carbide to spread the bed to increase the bed height. Changing the solvent from n-butanol to methanol was studied, since it would decrease the process costs and make the process a truly petrochemical free route for muconic acid production. Initially in methanol test, galactaric acid methyl ester was to be used as a raw material, but it was not soluble enough in methanol, whereby butyl ester from had to be used.

Method

[0045] Catalyst bed, consisting of ammonium perrhenate (0.83 g) and coarse silicon carbide (2.49 g) between quartz wool layers (1 g), was placed into the reactor which was then attached into the process system. The reactor ovens were then left to heat up to 140 to 155 C. and the reactor to about 120-130 C. After the heating was complete, the reactor was pressure tested with argon gas by increasing system pressure into 500 to 1000 kPa. The reactor was then pressurized into 500 kPa with hydrogen and hydrogen flow through the reactor was set to 5 l/h. The experiment was started by setting pump raw material feed to 15 g/h and the heating of pre-heater to 115 C. A sample was collected from the product trap every hour. The reactor was stopped by after 6 hours by closing the pump, the hydrogen feed and heating. The reactor was then depressurised and it was set to have 50 l/h nitrogen flow thought it. The end sample was collected about 15 h later.

[0046] The method was described for the test 1:15 g/h raw material flow. The other experiments that were performed are shown on table 1.

TABLE-US-00001 TABLE 1 Continuous reactor experiments Test # Aim 1 Raw material flow rate 15 g/h 2 Raw material flow rate 30 g/h. Sampling was done every 30 min. 3 Raw material flow rate 60 g/h. Sampling was done every 15 min. 4 Raw material flow rate 7 g/h 5 The catalyst changed from ammonium perrhenate to MTO (0.77 g) and P-TSA (0.53 g). 6 Solvent changed to methanol. Pressure increased into 1000 kPa, due to volatility of methanol. Reactor heating was decreased into 135 C. 7 Recycling system. The products were collected to raw material vessel and was left to run for 24 h. 8 Catalyst loading increased: ammonium perrhenate (8.3 g) and coarse silicon carbide (20.75 g)

Analysis

[0047] Sample of the reaction material (0.4 ml) was syringed into a glass vial. Pyridine (0.4 ml) was added into the vial and then BSTFA (0.2 ml). The vial was then heated in block heater to 60 C. for 30 min.

[0048] GC-FID analyses were carried out using an Agilent 6890 equipped with a FID: Column & length: HP-5 5% Phenyl Methyl Siloxane, 30 m, 0.32 mm, 0.25 um film, carrier gas: He, injector temperature: 250 C., FID temperature: 300 C., oven temperatures: Initial temp: 30 C., Initial time: 1.00 min, Ramp: 13 C./min to 300 C., final time 15 min. GC results were compared to reference standards, which were used to accurately determine the products obtained in the experiments.

Results

[0049] Test 1: Raw material flow rate 15 g/h
GC-FID results can be seen in table 2.

TABLE-US-00002 TABLE 2 GC-FID results of continuous reactor test 1 Component concentrations (g/l) Test 1 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 0 5.4 2.1 1.4 5.6 1 5.6 2.5 8.9 5.2 2 4.3 2.4 12.3 7.0 3 4.2 2.3 11.4 7.0 4 4.2 2.3 10.6 6.7 5 4.0 2.3 10.5 7.0
Test 2: Raw material flow rate 30 g/h
GC-FID results can be seen in table 3.

TABLE-US-00003 TABLE 3 GC-FID results of continuous reactor test 2 Component concentrations (g/l) Test 2 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 0 5.4 2.1 1.4 5.6 1 2.2 2.4 9.2 6.4 2 1.6 2.2 7.4 6.5 3 2.2 2.2 7.8 6.4 4 2.2 2.2 8.3 6.6 5 2.4 2.3 8.8 6.8 6 3.4 2.4 8.7 6.7
Test 3: Raw material flow rate 60 g/h
GC-FID results can be seen in table 4.

TABLE-US-00004 TABLE 4 GC-FID results of continuous reactor test 3 Component concentrations (g/l) Test 3 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 0 5.4 2.1 1.4 5.6 1 3.5 2.7 13.0 7.5 2 2.1 2.4 10.2 7.5 3 2.2 2.3 7.9 7.0 4 2.8 2.4 8.4 7.1 5 2.3 2.4 8.7 7.3 6 2.7 2.4 8.8 7.0
Test 4: Raw material flow rate 7 g/h
GC-FID results can be seen in table 5.

TABLE-US-00005 TABLE 5 GC-FID results of continuous reactor test 4 Component concentrations (g/l) Test 4 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 0 5.4 2.1 1.4 5.6 1 3.2 1.2 2.9 2.4 2 7.1 2.5 15.3 7.2 3 8.3 2.7 15.2 7.8 4 8.5 2.5 15.3 7.4 5 8.1 2.6 12.8 7.1
Test 5: Catalyst changed to MTO
GC-FID results can be seen in table 6.

TABLE-US-00006 TABLE 6 GC-FID results of continuous reactor test 5 Component concentrations (g/l) Test 5 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 0 5.4 2.1 1.4 5.6 1 2.5 1.6 23.3 18.5 2 1.9 2.2 21.8 9.1 3 1.7 2.1 13.1 6.7 4 2.1 2.1 7.7 6.5 5 3.3 2.3 6.4 6.8 6 4.4 2.2 4.9 6.3
Test 6: Solvent changed to methanol
GC-FID results can be seen in table 7.

TABLE-US-00007 TABLE 7 GC-FID results of continuous reactor test 6 Component concentrations (g/l) Test 6 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid methyl ester 1 0.0 0.4 6.8 0.5 2 1.9 2.2 19.8 1.9 3 2.8 2.7 19.0 1.9 4 5.5 3.9 19.0 1.9
Test 7: Recycling reactor
GC-FID results can be seen in table 8.

TABLE-US-00008 TABLE 8 GC-FID results of continuous reactor test 7 Component concentrations (g/l) Test 7 Galactaric acid Muconic acid Time/h butyl ester Mucic acid Muconic acid butyl ester 2.5 8.7 3.7 13.4 4.6 18 9.2 4.1 18.8 5.7 26 9.6 4.2 21.0 6.7
Test 8: Catalyst amount increase
GC-FID results can be seen in table 9.

TABLE-US-00009 TABLE 9 GC-FID results of continuous reactor test 8 Component concentrations (g/l) Test 8 Galactaric acid butyl Mucic Muconic Muconic acid butyl Time/h ester acid acid ester 1 2.9 0.1 2.6 1.2 2 15.0 3.7 8.2 3.0 3 16.6 4.2 8.6 3.3 4 17.1 4.2 8.3 3.1

CITATION LIST

Patent Literature

[0050] U.S. Pat. No. 4,355,107 [0051] WO 2015/189481

Non Patent Literature

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