PROCESS FOR MAKING BIOBASED PROPYLENE GLYCOL FROM LACTIC ACID ESTERS

Abstract

A process is described for making a biobased propylene glycol product at least in part from a carbohydrate-derived feed, wherein a feed comprised of a lactic acid ester is reacted with hydrogen in the presence of a catalyst, in a nonaqueous solvent in which lactide may be essentially wholly solubilized at the conditions under which the reaction is carried out, so that lactide does not precipitate out to an extent whereby plugging of the reactor or fouling of the hydrogenation catalyst is observed.

Claims

1. A process for making a biobased propylene glycol product at least in part from a carbohydrate-derived feed, wherein a feed comprised of a lactic acid ester is reacted in a liquid phase reaction in the presence of a catalyst with hydrogen, in a nonaqueous solvent in which lactide may be essentially wholly solubilized at the conditions under which the reaction is carried out.

2. A process according to claim 1, wherein the feed consists of one or more esters of lactic acid and a selected alcohol.

3. A process according to claim 2, wherein the alcohol is propylene glycol, ethanol, propyl alcohol, or butyl alcohol.

4. A process according to claim 3, wherein the alcohol is propylene glycol.

5. A process according to claim 1 or claim 4, wherein the feed comprises both of glycerol and a lactic acid ester.

6. A process according to claim 5, wherein the nonaqueous solvent is propylene glycol.

7. A process according to any of claims 1-4, wherein the nonaqueous solvent is propylene glycol.

8. A process according to claim 6, wherein the propylene glycol comprises a recycle portion of biobased propylene glycol formed by the process.

9. A process according to claim 5, wherein the propylene glycol solvent accounts for substantially all of the liquid phase in which the reaction is conducted.

10. A process according to claim 1, wherein the propylene glycol solvent accounts for substantially all of the liquid phase in which the reaction is conducted.

11. A process according to claim 1, wherein the catalyst is a copper-containing catalyst.

12. A process according to claim 1, wherein the catalyst is a copper alloy-based sponge metal catalyst.

13. A process according to claim 12, wherein the catalyst is a Raney copper catalyst.

Description

DESCRIPTION OF EMBODIMENTS

[0021] In a preferred embodiment, a process for obtaining a biobased propylene glycol product at least in part from a carbohydrate-derived renewable feed comprises reacting a lactic acid ester, such as may be obtained by the fermentation of dextrose to produce lactic acid and then the esterification of the lactic acid by reaction with an alcohol according to well-known and commercially practiced methods, in the liquid phase with hydrogen in the presence of a heterogeneous hydrogenation catalyst, using a nonaqueous solvent in which any lactide that is formed from the lactic acid under elevated temperature conditions may be solubilized, and not precipitate out to an extent whereby plugging of the reactor or fouling of the hydrogenation catalyst may be observed.

[0022] In one embodiment, the nonaqueous solvent is propylene glycol, especially a recycle portion of the biobased propylene glycol made by the process of the present invention. In another embodiment, the propylene glycol solvent forms substantially all of the liquid phase in which the process is conducted.

[0023] In an embodiment, the heterogeneous hydrogenation catalyst is a copper-containing catalyst. In other embodiments, the catalyst can be a copper alloy-based sponge metal catalyst, especially, a Raney copper catalyst prepared from an alloy comprising copper and aluminum and optionally further comprising a promoter such as zinc.

[0024] In a particular embodiment the catalyst selected is also useful, under the same reaction conditions as employed for the hydrogenation of the lactic acid ester, for the hydrogenolysis of glycerol to provide a biobased propylene glycol, so that a process for making a biobased propylene glycol product is contemplated from a combined feed including both a lactic acid ester and glycerol. The glycerol can comprise a greater or lesser part of such a combined feed in relation to the lactic acid ester portion of the combined feed, and the respective amounts of glycerol and lactic acid ester that can be used in the feed may be substantial both on an individual feed component basis and collectively, being practically limited only by solubility limits in the nonaqueous solvent.

[0025] A variety of lactic acid esters may be used, but those lactic acid esters that are highly soluble in propylene glycol under mild temperature conditions are particularly preferred, for example, propylene glycol lactate, ethyl lactate, propyl lactate and butyl lactate. As demonstrated by the examples which follow, such lactic acid esters may be fed to a fixed bed reactor in substantial concentrations in propylene glycol as a solvent, and readily react with hydrogen under mild temperature conditions and in the presence of a copper-containing catalyst (in the form of a Raney copper catalyst) to provide both a biobased propylene glycol product and to regenerate the alcohol from which the lactic acid ester had been formed originally (e.g., propylene glycol, ethanol, propanol or butanol) for recycle and reuse if desired.

[0026] Some propanol can additionally be expected by dehydration of propylene glycol, but the amount of propanol formed will be small, especially under the preferred mild temperature conditions, and the propanol will, with the ethanol, propanol or butanol from ethyl, propyl or butyl lactate feeds, respectively, be easy to separate by simple distillation from the propylene glycol product and solvent. Where propylene glycol lactate is employed as the feed for the process, of course, lactic acid can be combined with propylene glycol in a first step to form the propylene glycol lactate, and then additional propylene glycol can be added as appropriate to achieve a desired lactic acid ester feed concentration going into the second, lactic acid ester hydrogenation step. Propylene glycol is in any event formed by the hydrogenation step at high selectivity and with high conversion of the lactic acid esters, with no leaching observed from the catalyst.

[0027] Solutions of a lactic acid ester in propylene glycol which may be fed to the inventive process can be at least at a concentration of 10 percent by weight, but preferably will be at a concentration of at least 20 percent and more preferably will be at a concentration of at least 40 percent. Liquid hourly space velocities for the inventive process can be from 0.3 hr.sup.−1, preferably from 0.5 hr.sup.−1, and more preferably can be from 1.0 hr.sup.−1 up to 3.0 hr.sup.−1.

[0028] While the use of lactic acid esters as a starting material rather than lactic acid and while the use of a nonaqueous solvent in the substantial absence of water according to preferred embodiments will each have the benefit of reducing opportunities for corrosion within the reactor and also reduce opportunity for leaching of the catalyst, preferably mild temperature conditions and modest hydrogen pressures are employed for carrying out the hydrogenation. For example, reaction temperatures of not more than 250 degrees Celsius, preferably not more than 220 degrees Celsius and more preferably not more than 210 degrees Celsius can be employed with hydrogen pressures less than 17.2 MPa (2500 pounds per square inch), preferably less than 15.2 MPa (2200 pounds per square inch) and more preferably less than 14.5 MPa (2100 pounds per square inch).

[0029] The process of the present invention can be conducted in a batchwise, semi-batch or continuous manner, but preferably will be conducted continuously in a fluidized or especially a fixed bed reactor system.

[0030] The present invention is further demonstrated by the examples that follow:

EXAMPLES

Example 1

[0031] Lactide (417 g) purchased from NatureWorks LLC, Minnetonka, Minn. was combined with propylene glycol (1000 g), and the combination was heated to 125 degrees Celsius with stirring under low vacuum (300-500 torr) overnight, in a stirred batch reactor. The mixture was then cooled to room temperature to precipitate out any unreacted lactide. Conversion of the lactide was found to be greater than 96 percent, with the product mixture predominantly comprising propylene glycol dilactate, with smaller amounts of propylene glycol lactate, propylene glycol tetralactate and free lactic acid.

Example 2

[0032] A 180 cubic centimeter stainless steel, jacketed tubular reactor was loaded with a Raney copper catalyst. The reactor temperature was maintained by adjusting the temperature of the oil flowing through the jacket. An Isco dual piston pump and mass flow controllers were used to supply the lactate ester and hydrogen feeds to the reactor, with a condenser maintained at 0 degrees Celsius being used to collect the products from the reactor. Reactor pressure was controlled using a dome loaded back pressure regulator. A propylene glycol lactic acid ester feed prepared from lactide and propylene glycol in the manner of Example 1 was fed into the reactor as a 40 percent solution by weight in a propylene glycol solvent, at an LHSV of 0.5 hr.sup.−1. Hydrogen was supplied concurrently in a hydrogen:ester feed ratio of 20:1 using 11.0 MPa (1600 psi) hydrogen, and reacted with the propylene glycol lactic acid ester feed at a reaction temperature of 210 degrees Celsius in the presence of the Raney copper catalyst. Conversion of the lactic acid esters was greater than 99 percent, with a selectivity to propylene glycol of greater than 96 percent. Propanol (in the form of 2-propanol) was produced as a minor byproduct, by the dehydration of propylene glycol.

Examples 3-13

[0033] The same 180 cubic centimeter reactor was used as in Example 2, to process a mixed feed comprised of equal parts of 20 percent each of refined glycerol and of the lactide-derived lactic acid ester feed used in Example 2, in the remainder of propylene glycol as a solvent. At 210 degrees Celsius, using 12.4 MPa (1800 psi) hydrogen and various liquid hourly space velocities, in the presence of a Raney copper catalyst the product mixtures were produced as shown below in Table 1, at the indicated product percent selectivities as determined by liquid chromatographic analysis. Propanol would be again obtained by the dehydration of propylene glycol, while minor amounts of ethylene glycol are also produced from the presumed hydrogenolysis of glycerol in the feed:

TABLE-US-00001 TABLE 1 Lactic Example LHSV EG PG 2-propanol 1-propanol acid 3 0.8 0.164 93.218 0.259 0.912 0 4 0.6 0.138 91.103 0.37 1.175 0 5 0.6 0.152 91.361 0.399 1.247 0 6 0.6 0.134 91.55 0.376 1.21 0 7 0.6 0.141 89.302 0.363 1.133 0 8 0.6 0.162 91.268 0.516 1.412 0 9 0.3 0.185 86.341 0.713 2.237 0 10 0.3 0.2 85.711 0.794 2.428 0 11 0.3 0.171 79.579 0.861 2.484 0 12 0.3 0.125 83.668 1 2.864 0 13 0.3 0.243 77.715 0.354 2.458 0

Example 14

[0034] An ethyl lactate ester feed was produced in the manner of Example 1, using ethanol rather than propylene glycol for the reactant with the lactide. A 40% solution of this ethyl lactate ester feed in propylene glycol was then converted as in previous examples, using 11.0 MPa (1600 psi) hydrogen, an LHSV of 1 hr.sup.−1, a hydrogen:ester feed ratio of 20:1, a reaction temperature of 180 degrees Celsius and a Raney copper catalyst. Conversion of the lactic acid esters was again greater than 99 percent, with a selectivity to propylene glycol of 98.5 percent. Ethanol and propanol were produced as minor components.

Example 15

[0035] A butyl lactate ester feed was produced in the manner of Example 1, using butanol rather than propylene glycol for the reactant with the lactide. A 40% solution of this butyl lactate ester feed in propylene glycol was then converted as in previous examples, using 11.0 MPa (1600 psi) hydrogen, an LHSV of 1 hr.sup.−1, a hydrogen:ester feed ratio of 20:1, a reaction temperature of 190 degrees Celsius and a Raney copper catalyst. Conversion of the lactic acid esters was again greater than 99 percent, with a selectivity to propylene glycol of 97 percent. Butanol and propanol were produced as minor components.

Example 16

[0036] A propyl lactate ester feed was produced in the manner of Example 1, using n-propanol (1-propanol) rather than propylene glycol for the reactant with the lactide. A 40% solution of this propyl lactate ester feed in propylene glycol was then converted as in previous examples, using 12.4 MPa (1800 psi) hydrogen, an LHSV of 1 hr.sup.−1, a hydrogen:ester feed ratio of 20:1, a reaction temperature of 185 degrees Celsius and a Raney copper catalyst. Conversion of the lactic acid esters was again greater than 99 percent, with a selectivity to propylene glycol of 81.3 percent. Isopropyl and n-propyl alcohols were produced at 16.4 percent combined.