Mechanocatalytic Depolymerization of Plastics

Abstract

Systems and methods for recycling polymers are provided. One embodiment provides a method for recycling synthetic polymers by combining the polymers with a solid depolymerizing catalyst in a vessel, mechanically shearing the combined polymers and the solid depolymerizing catalyst against each other to produce monomers from the polymers; and collecting the monomers. In some embodiments the solid depolymerizing catalyst is solid sodium hydroxide. In some embodiments collecting the monomers is achieved by contacting the sheared polymer and catalyst with a recyclable volatile solvent to dissolve the monomers. In some embodiments, the method includes purifying the collected monomers for repolymerization. In some embodiments purifying the monomers is achieved using nanofiltration membrane technology, cyclic fixed bed adsorption, simulated moving-bed adsorption or a combination thereof.

Claims

1. A method comprising: combining polymer products with a depolymerizing catalyst; and producing a slurry from depolymerized polymers , water and alcohol.

2. The method of claim 1 further comprising: mechanically shearing the combined polymer products and the depolymerizing catalyst against each other to produce monomers; and collecting the monomers; wherein the slurry is produced from the monomers, water and alcohol.

3. The method of claim 2, wherein collecting the monomers comprises contacting the sheared combined polymer products and the depolymerizing catalyst with a recyclable volatile solvent.

4. The method of claim 2 further comprising purifying the collected monomers for repolymerization.

5. The method of claim 4, wherein purifying is selected from the group consisting of purifying via nanofiltration membrane technology, cyclic fixed bed adsorption, simulated moving-bed adsorption and a combination thereof.

6. The method of claim 2, wherein mechanically shearing comprises milling the combined polymer products and the depolymerizing catalyst with a grinding ball.

7. The method of claim 1, wherein combining comprises milling the polymer products and the depolymerizing catalyst in a milling vessel with a grinding ball; wherein the polymer products are synthetic polymer products that are depolymerized into monomers; and wherein producing comprises introducing vaporized water and the alcohol into the milling vessel to produce the slurry .

8. The method of claim 7, wherein the synthetic polymer products comprise polyethylene terephthalate (PET).

9. The method of claim 7, wherein the depolymerizing catalyst comprises solid depolymerizing catalyst particles that can be recovered magnetically.

10. The method of claim 7, wherein the depolymerizing catalyst comprises surface-functionalized iron oxide nanoparticles.

11. The method of claim 7 further comprising separating synthetic polymer product monomers and non-polymer monomers from the slurry .

12. The method of claim 7 further comprising recovering the depolymerizing catalyst and unreacted or partially reacted synthetic polymer products from the slurry .

13. The method of claim 12, wherein recovering comprises nanofiltration membrane technology to recycle high molecular weight catalyst and unreacted or partially reacted synthetic polymer products; and wherein the nanofiltration membrane technology is selected from the group consisting of graphene oxide nanofiltration, polyethersulfone nanofiltration, and polyvinylidene fluoride nanofiltration.

14. The method of claim 11, wherein separating comprises at least one of: contacting the slurry with a recyclable volatile solvent to dissolve the monomers; evaporative crystallization to concentrate the slurry, recover volatile solvent, and crystallize monomers, wherein different monomers crystallize at different concentrations and temperatures; cyclic fixed bed adsorption; and simulated moving-bed adsorption.

15. (canceled)

16. A method for depolymerizing synthetic polymers comprising: milling synthetic polymers, methanol and a catalyst, wherein the synthetic polymers are depolymerized into soluble monomer products; recovering at least a portion of the solid fraction; introducing at least a portion of the recovered solid fraction into water, wherein the catalyst and soluble monomer products are dissolved into the water producing a liquid comprising dissolved catalyst and soluble monomer products; and precipitating at least a portion of the soluble monomer products from the liquid.

17. (canceled)

18. The method of claim 16 further comprising purifying at least a portion of the soluble monomer products.

19. A system for recycling synthetic polymers according to the method of claim 7 comprising: a mechanochemical reactor; a mixing tank downstream of and in liquid communication with the mechanochemical reactor; a nanofiltration system downstream of and in liquid communication with the mixing tank; solvent dryers in liquid communication with both the mixing tank and the nanofiltration system, and optionally in liquid communication with the mechanochemical reactor; a crystallizer, chromatography column, or both downstream of and in liquid communication with the nanofiltration system; and a distillation unit downstream of and in liquid communication with the crystallizer, chromatography column, or both.

20-23. (canceled)

24. A method for recycling synthetic polymers from solid mixed textile waste comprising: combining a solid mixed textile waste feedstock with a solid depolymerizing catalyst in a vessel; mechanically shearing the combined solid mixed textile waste feedstock and the solid depolymerizing catalyst against each other to produce monomers from polymers present in the solid mixed waste feedstock; collecting at least a portion of the monomers; purifying at least a portion of the collected monomers; and repolymerizing at least a portion of the purified monomers into synthetic polymers for repurposing; wherein the monomers are selected from the group consisting of adipic acid, sebacic acid, dodecanedoic acid, terphthalic acid, isophtalic acid, tetramethylene diamine, hexamethylene diamine, 1,9-diaminononane, 2-methyl pentamethylene diamine, trimethyl hexamethylene diamine, m-xylylene diamine, and 1,5-pentanediamine.

25-29. (canceled)

30. A method comprising: milling polymer products and a solid catalyst, wherein at least a portion of the polymer products are depolymerized into monomers; recovering at least a portion of the solid catalyst and unreacted or partially reacted polymer products; and purifying at least a portion of the polymer product monomers and non-polymer monomers.

31. The method of claim 30 further comprising: producing a slurry; and separating at least a portion of the polymer product monomers and non-polymer monomers from the slurry; wherein the solid catalyst is a solid depolymerizing catalyst; wherein the milling comprises milling in a milling vessel; wherein producing the slurry comprises introducing vaporized water and alcohol to the milling vessel; and wherein purifying is after separating.

32. The method of claim 31, wherein one or more: at least a portion of the recovered solid depolymerizing catalyst is configured to be used again in another cycle of recycling; at least a portion of the unreacted or partially reacted polymer products are configured to be used again in another cycle of recycling; and at least a portion of the purified polymer product monomers are configured to be used as products or by-products to produce new polymer products.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG. 1A is a photograph of an industrial ball mill for cement production. FIG. 1B is a line graph for mechanocatalytic lignin depolymeration. FIG. 1C is an exemplary lab-scale mill system.

[0015] FIG. 2 shows an exemplary base case continuous process flowsheet for mixed-waste PET recycling by mechnocatalyic depolymerization and product separations.

[0016] FIG. 3 shows a representative flowsheet superstructure including potential alternative steps.

DETAILED DESCRIPTION OF THE INVENTION

[0017] One embodiment provides a continuous process combining a mechanocatalytic reactor with separation processes based mainly upon membranes and crystallization is provided. The objectives will have a significant concurrency due to the integral approach pursued. The “base case” process flowsheet (FIG. 2), defines a “superstructure” of process integration alternatives, refine the “best” alternative via technoeconomic metrics and optimization.

[0018] In some embodiments a mechanocatalytic process can be used to depolymerize PET into monomers. For this purpose, PET will be processed in shaker ball mill (FIG. 1C) with solid acid catalysts (e.g., iron oxide nanoparticles' or surface-functionalized iron oxide nanoparticles which can be recovered magnetically) and milling balls made from stainless steel or other hard materials. There is one previous report using iron oxide nanoparticles to depolymerize PET, but in the absence of mechanical forces (Bartolome, L., et al.., Green Chemistry, 16, 279-286 (2014)). Co-reactants (water/alcohols/ethylene glycol) can be provided as vapors in a carrier gas stream, because excessive liquid would buffer the mechanical impact of collisions. Due to the high melting points of the monomers (DMT:141° C., BHET:106° C., PTA:427° C.), depolymerization will result in catalyst particles coated with mostly solid products. Other monomers such as ethylene glycol (from PET) and hexamethylenediamine (from nylon) would likely be in liquid form, so that the product can be generally assumed to be a concentrated slurry. This “solid”/“slurry” phase depolymerization with minimal liquid products is attractive for scalability, since it creates a strong potential of directly using existing continuous ball mill technology. The process can will be performed in batch mode in a shaker ball mill, but other types of mills would be used for eventual scale-up and continuous operation. The compositions of liquid or soluble reaction products will be quantified by NMR spectroscopy or chromatography (GC/HPLC). Targeting nanoparticles can be used with the addition of different types and concentrations of Bronsted and/or Lewis acid sites by design.

[0019] In one embodiment the following classes of components can be present in the product mixture: (1) catalysts, (2) unreacted/partially reacted feedstock, (3) PET monomers, and (4) non-PET monomers (amines, adipic/other alkanoic dicarboxylic acids, glucose). Additionally, an easily recyclable (volatile) green solvent (e.g., ethanol, ethyl acetate) can be added in minimum required quantity to the product slurry after it exits the ball mill, to dissolve the monomers and enable separations processes (FIG. 2). As shown, classes (1) and (2) would be recovered and recycled to the reactor, and classes (3) and (4) would be purified as desired products/byproducts. The added solvent would be recovered and recycled. A robust graphene oxide (GO) nanofiltration membrane technology can be used to recycle high-molecular weight classes (1) and (2), with a dryer included for residual solvent removal. These GO membranes are stable in extreme chemical environments, with molecular weight cutoffs (MWCOs) tunable from about 1000 Da to about 100 Da, and much lower fouling than polymeric membranes. They were originally developed for fractionating kraft black liquor, which is a high-solids byproduct of biomass depolymerization and contains a similar species distribution (polymers, oligomers, monomers). In some embodiments, magnetic stirrers can be used. Next, the clarified permeate stream from the membrane is separated by evaporative crystallizers to concentrate the solution, recover additional volatile solvent, and crystallize the dicarboxylic acids (terephthalic from PET, and alkanoic from nylon) and diamines (from nylon) at different operating concentrations/temperatures. Since the crystallizers are operating with a volatile organic solvent (low heat of vaporization), energy consumption is expected to be much lower than for monomer crystallizations from aqueous solvents in biological depolymerizations. The crystallization processes can be demonstrated using simple rotary evaporators (rotovaps). The stream exiting the final crystallization step will contain ethylene glycol and volatile solvent, which will be separated by a final distillation step. Again, this is expected to have a low cost due to the large volatility difference between the two components. In one embodiment, an alternative to crystallizers is to use adsorption processes — either cyclic fixed bed or continuous simulated moving bed (SMB) - for recovering monomers.

[0020] Two major challenges towards the development of an integrated process flowsheet are: (1) a systems-level analysis of critical decisions and linking variables across process units and (2) integration of different fidelity models using a combination of physics-based and data-driven reduced-order models. This work involves close collaboration between the modeling and experimental groups. All the experimental data and known physics-based models of reactors and separators can be combined and translated into a series of integrated base-case process flowsheets. The model detail can be sufficient to capture the limits of each unit, but maintain tractability of the systems-level process synthesis optimization problem. For example, the final distillation step is easily modeled through established mass-balance and equilibrium equations, whereas the mechanocatalytic reactor model will consist of data-driven correlations/kinetic models developed using the obtained data. This hybrid physics-based and data-driven approach” can accelerate process development even without “full fundamental knowledge” of each process unit.

[0021] FIG. 3 describes still another embodiment that includes all process alternatives and potential stream connections (i.e., a combination of all of possible base-case flowsheets). This model, coupled with Mixed-Integer Nonlinear Programming (i.e., the introduction of yes/no decision variables that select/deactivate a process step) can be used to identify the optimal process alternative for typical compositions of solid plastic feedstocks and different objectives and constraints. This framework can be used to answer important questions, e.g., (a) Which process configuration is most robust to feed variations while satisfying product specifications; (b) Is a different optimal process configuration favored when an economic/cost objective versus an energy efficiency objective is enforced.

[0022] While in the foregoing specification this invention has been described in relation to certain embodiments thereof, and many details have been put forth for the purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.

[0023] All references cited herein are incorporated by reference in their entirety. The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and, accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.