CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Patent Application No.

15/783,358, filed on October 13, 2017, and claims the benefit of U.S. Provisional

Application No. 62/532,340 filed on July 13, 2017, the entire disclosures of which are incorporated herein by reference.

FIELD OF INVENTION

This invention relates to a process for oxidizing a polystyrene-containing polymer to benzoic acid.

BACKGROUND OF INVENTION

Polystyrene is a high volume polymer with many uses as a foamed product, as an injected product, and as a copolymer with other materials. Recycle and reuse of polystyrene is limited, however, due to costs of collection, purification, reformation, and reuse versus use of the virgin material. In addition, the slow biodegradation behavior of polystyrene-containing polymers results in high waste disposal costs.

Oxidation of polystyrene to benzoic acid using acetic acid is described in U.S. Patent No. 6,958,373 to Partenheimer.

It has now been found that waste polystyrene can be efficiently converted to benzoic acid, a commercially useful compound by oxidation at elevated temperature and pressure.

SUMMARY OF INVENTION

A polystyrene-containing polymer is converted into benzoic acid by selective liquid phase oxidation of the polystyrene with water and carbon dioxide as byproducts. The produced benzoic acid is removed by evaporation and reaction product separation is achieved utilizing heat of the reaction. The physical properties of benzoic acid permit use of polystyrene-containing feedstocks containing impurities such as other polymers because the resulting oxidation products other than benzoic acid differ considerably from benzoic acid in volatility and other physical properties, thereby facilitating separation.

The conversion process comprises the steps of providing as a feedstock to an oxidizing reactor a polystyrene-containing polymer, introducing into the reactor an oxidant together with an oxidation catalyst so as to produce a reactant admixture, agitating the reactant admixture at a reactor temperature in the range of about 125°C. to about 300°C, preferably about 180°C. to about 230°C, and a reactor pressure in the range of about 1 to about 30 atmospheres for a time sufficient to convert polystyrene to benzoic acid, recovering from the reactor benzoic acid and water by evaporation, and condensing the recovered benzoic acid and water. Optionally, a portion of the recovered benzoic acid and a portion of the recovered water can be recycled to the reactor to maintain a substantially constant benzoic acid-water mol ratio in the reactant admixture.

The oxidant is an oxygen-containing gas, preferably air.

The catalyst preferably is a heavy metal catalyst. The catalyst can be soluble or insoluble in the reactant admixture.

The present polystyrene conversion process is useful for transforming polystyrene waste into benzoic acid, a compound useful as a food preservative, for treatment of fungal skin diseases, as a precursor to plasticizers, insect repellents, artificial flavors.

BRIEF DESCRIPTION OF DRAWINGS

In the drawings,

FIGURE 1 is a schematic process flow diagram of a preferred embodiment of the present invention; and

FIGURE 2 is a schematic process flow diagram of another preferred embodiment of the present invention.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present conversion process can be carried out as a batch, semi-continuous, or continuous process. The oxidation reactor can be a continuously stirred tank reactor (CSTR), or a plug flow reactor. A CSTR is preferred. The feedstock for the present polystyrene conversion process can utilize waste polystyrene-containing polymers which include polystyrene as well as polystyrene- polybutadiene copolymers, polystyrene-poly(acrylic acid) block copolymers, polystyrene- polyethylene glycol) block copolymers, 2-poly(vinyl)pyridine copolymerized with styrene, and the like. The term "polystyrene" as used herein and in the appended claims means a polymer having at least two styrene units, preferably three to about 1,000 styrene units in the molecule.

Solvent for the polystyrene-containing polymers is optional and can be benzoic acid or an aromatic solvent such as toluene, and the like. The amount of solvent present in the feedstock usually is the minimum amount necessary to totally dissolve the polystyrene at the process temperature. Optionally, when using toluene as solvent, the toluene solution containing polystyrene can be fed to an overhead region of the reactor, rather than directly into the liquid phase, so that contact with hot exit gasses will cause a substantial portion of the toluene to evaporate and flow out of the reactor with the hot exit gasses. The much less volatile liquid phase polystyrene will flow into the reactor where the desired reaction will occur. The vaporized toluene can be condensed and recycled to dissolve additional polystyrene feedstock. The reactor overhead for feeding the toluene solution of polystyrene can be anywhere that provides sufficient residence time and gas heat capacity to volatilize at least a portion of the toluene while providing a pathway for the polystyrene to the reactor. The weight ratio of polystyrene-to-solvent in the feedstock preferably is in the range of about 2 to about 0.2.

A relatively small amount of water in the reactant admixture is desirable. Water can be introduced in the reactant admixture as part of the feedstock, which upon introduction into the reactor, will flash into vapor phase and will strip (steam distill) some of the produced benzoic acid from the liquid to the vapor. The amount of water recycled to the reactor is a variable that can be utilized to remove benzoic acid from the reactor in this manner. The amount of water fed to the reactor can be up to 5 times the weight of the polystyrene fed. The water content in the reactant admixture at reaction conditions can be up to about 6 percent by weight of the reactant admixture, preferably about 0.1 to about 3 weight percent. A suitable oxidation catalyst is a heavy metal catalyst, preferably one soluble in the liquid reactant admixture. Typically, the oxidation catalyst includes at least one heavy metal component, i.e., a metal having atomic weight in the range of about 23 to about 200. Such metals include cobalt, manganese, vanadium, molybdenum, chromium, iron, nickel, zirconium, cerium, hafnium, platinum and the like. A particularly preferred homogeneous oxidation catalyst is a cobalt-manganese-bromide catalyst which contains ionic cobalt, manganese, and a bromide in cobalt-to-manganese molar ratios in the range of about 0.001 to 1000 and metal-to-bromide molar ratios in the range of about 10 to 0.1.

The oxidation catalyst can be introduced directly into the oxidation reactor as a solution or slurry or by premixing with the polystyrene-containing feedstock.

Use of heterogeneous oxidation catalyst containing manganese oxide or platinum on zirconia provides a processing advantage inasmuch as such catalysts are not volatile and would remain in the oxidation reactor while the produced benzoic acid is recovered from the oxidation reactor by evaporation.

The amount of the oxidation catalyst present in the liquid reactant admixture can be in the range of about 0.01 to about 5 weight percent, based on weight of the liquid reactant admixture in the oxidation reactor.

The gaseous oxidant is an oxygen containing gas such as air or a mixture of oxygen with another inert gas such as nitrogen or argon. Introduction of the gaseous oxidant into the oxidation reactor under pressure by sparging or the like can provide the necessary agitation of the liquid reactant admixture. If more intense agitation is desired, mechanical stirring can be utilized as well in lieu of, or in addition to, sparging. The gaseous oxidant is introduced into the reactor at a rate adequate to provide at least 2 mols of oxygen per unit of styrene in the polystyrene fed to the reactor. Preferably, oxygen concentration in the head space of the oxidation reactor is maintained at no more than about 10% by volume.

Conversion of polystyrene to benzoic acid can be achieved by continuous air oxidation in the process flow diagram illustrated in FIGURE 1.

As shown in Figure 1, polystyrene-containing feedstock is fed from feedstock source 11 to continuous stirred tank reactor (CSTR) 10 via conduit 12 and oxidizing catalyst solution or slurry is fed from catalyst source 13 to CSTR 10 via conduit 14 to provide a liquid reactant admixture 16 in CSTR 10.

When the solvent in the polystyrene feedstock is toluene, it is preferable to introduce the feedstock into the reactor overhead, i.e., above the liquid level in the reactor so as to minimize oxidation of the toluene. In this manner, most of the introduced toluene is evaporated before oxidation, and leaves the reactor together with the reactor off-gas via conduit 20.

Gaseous oxidant such as compressed air or other oxygen-containing gas is introduced into liquid reactant mixture 16 via conduit 18 from oxidant source 19 below the liquid level of reactant admixture 16. Oxygen by itself can be used as well. The oxidation reaction that takes place in CSTR 10 is exothermic, and the released heat is utilized to drive the reaction and to vaporize benzoic acid and water present in CSTR 10. Benzoic acid vapor together with water vapor, residual oxygen, solvent, and inert gases leave CSTR 10 as reactor off-gas via conduit 20 and enter flash column 22 (which may be a series of columns if separation of lights is desired) where crude molten benzoic acid is removed, usually at or below the reactor pressure as a bottoms stream via conduit 24 and water, together with light process byproducts. Solvent, and residual gases are removed as a vapor stream via conduit 26 which leads to condenser 34 for process heat recovery, condensation, or additional separation if desired. An additional distillation column or columns may be inserted upstream of condenser 34 if separation of the off-gas components (i.e., if a solvent like toluene is used) is desired. Water and light byproduct condensate is received in condensate tank 38 equipped with vent 46 for venting residual oxygen and insert gases, and subsequent treatment to meet environmental standards, if necessary. Separation and recycle of toluene, if used, can also be conducted on the mixed condensate by methods known to those skilled in the art— including taking advantage of the phase separation between water and toluene.

A portion of crude benzoic acid in the bottoms stream is returned to CSTR 10 via conduit 28 while the rest of the bottoms stream is received in crude benzoic acid storage tank 32 for further purification, if desired. A portion of the condensed water together with any light product condensate that may be present is recycled to CSTR 10 via conduit 39, pump 41 and conduit 40, preferably together with gaseous oxidant via conduit 18. In this manner plugging at the point of gaseous oxidant entry may be avoided. Additional water, if needed, is supplied to CSTR 10 via conduit 45. The rest of the water and light condensate is removed via conduit 42.

Recycling of a portion of recovered benzoic acid and a portion of the recovered water to CSTR 10 is optional, but preferred so as to maintain a substantially constant benzoic acid-water mol ratio in the reactant admixture in CSTR 10.

Purge conduit 44 is provided from CSTR 10 for catalyst recovery and removal of heavy byproducts that may accumulate in the oxidation reactor.

Another embodiment of the invention is illustrated in FIGURE 2. In this particular embodiment, benzoic acid is recovered from the reactor at a pressure below reactor pressure. Polystyrene-containing polymer is fed to continuous stirred tank reactor (CSTR) 50 from feedstock source 51 via conduit 52. Heavy metal catalyst dissolved or slurried in benzoic acid or another suitable solvent, including water, is fed into CSTR 50 via conduit 54. Air is fed into CSTR 50 from oxidant source 59 via conduit 58. During the resulting oxidation reaction the reactant admixture is agitated by mechanical or non-mechanical stirring while benzoic acid and water vapors leave CSTR 50 via conduit 60. A liquid effluent stream leaves CSTR via conduit 61. Conduits 60 and 61 are equipped with respective back pressure control valves 63 and 65 which maintain the desired pressure in CSTR 50 while providing a relatively lower pressure downstream, usually in the range of about 1 atm to about 5 atm. The liquid effluent leaving CSTR 50 via conduit 61 will be partially flashed as it passes through back pressure control valve 65 and into flash column 62. As a result, benzoic acid and water liquids and vapors are fed into flash column 62.

Crude benzoic acid admixed with catalyst and heavy byproducts leaves the flash column 62 as a bottoms stream via conduit 64 and pump 67 and a portion thereof is returned to CSTR 50. The rest of the bottoms stream is a purge stream removed via conduit 84. If desired, the purge stream can be subjected to a separate catalyst recovery process.

Crude benzoic acid without admixed catalyst and heavy byproducts is drawn off at an intermediate stage of flash column 62 via conduit 70 to storage tank 72. Heat recovery and attendant condensation of water and light byproducts is achieved by condenser 74 in conduit 66. The water and light product condensed from condenser 74 is received in condensate tank 78 equipped with vent 79. Effluent from vent 79 can be subjected to off-gas treatment before release in the ambient surroundings, if necessary.

A portion of condensed water and light byproduct condensate is returned via conduit 71 to flash column 62 as reflux and a portion via conduit 80 and pump 83 to CSTR 50, preferably together with gaseous oxidant stream in conduit 58. The rest of condensed water and light byproduct condensate are purged from the system via conduit 82. If additional water is needed in CSTR 50, such additional water is supplied via conduit 85.

The foregoing description and the process flow diagrams are illustrative and are not to be taken as limiting. Still other variants of the described process are possible and will readily present themselves to those skilled in the art.