Every year, scores of billions of plastic water and soda bottles are purchased and used in the United States alone. Plastic water and soda bottles are often comprised of polyethylene terepthalate (PET), or plastic #1. PET is reported to have a recycling rate of approximately 25 percent; indeed, recycling programs for PET products are relatively ubiquitous. However, nearly every one of those water bottles includes a plastic cap. The caps are typically comprised of polypropylene (PP), or plastic #5. The two plastics cannot generally be recycled together—PP melts at a temperature of nearly 160 degrees Fahrenheit higher than PET. If a cap gets mixed in with bottles, the entire batch may be ruined because there is un-melted plastic in the mix. Therefore, many municipalities do not accept the caps for recycling, or PP products in general.
PP products are, thus, often simply discarded. PP products are not limited to bottle caps. For example, PP products include, for example, common packaging used in containers for cottage cheese, yogurt, cream cheese, ricotta cheese, margarine, hummus, medicine bottles, some plastic ice cream containers, food storage and take-out containers, as well as flip caps on tubes and food product bottles (e.g., condiments), jar lids (e.g., peanut butter), and laundry detergent lids. At best, when not recycled, these PP products end up in landfills. Too often, PP products such as bottle caps end up as litter, where they pose a significant hazard to wildlife and the environment.
Not only do discarded PP products present an environmental risk, but they also represent lost opportunity. Polypropylene is a hydrocarbon, as are gaseous and liquid fuels and oils. Proper decomposition of PP products should yield useful hydrocarbon products. Thus, methods and systems are needed to decompose waste PP products into useful hydrocarbon products, including fuels.
In one embodiment, a method is provided for recovering at least one organic decomposition product from a polypropylene-containing product, the method comprising: placing the polypropylene-containing product in a reduction zone of a material recovery system; flowing an inert gas through the reduction zone from a reduction inlet to a reduction outlet to purge the reduction zone and maintain a positive pressure therein; applying electromagnetic wave energy from an electromagnetic wave generator to the reduction zone via a bifurcated waveguide assembly, while maintaining the polypropylene-containing product in a stationary position for at least a portion of the applying, to yield at least one gaseous organic decomposition product; and exhausting the at least one gaseous organic decomposition product from the reduction zone along with the inert gas through the reduction outlet.
In another embodiment, a method is provided for recovering at least one organic decomposition product from a source substance comprising at least one of crushed, ground, or shredded polypropylene-containing bottle caps, the method comprising: contacting the crushed, ground, or shredded polypropylene-containing bottle caps with a substance which is more absorptive of electromagnetic wave energy than polypropylene, such as activated carbon; placing the crushed, ground, or shredded polypropylene-containing bottle caps and the activated carbon in a reduction zone of a microwave applicator; flowing an inert gas through the reduction zone from a reduction inlet to a reduction outlet to purge the reduction zone and maintain a positive pressure therein; applying electromagnetic wave energy from an electromagnetic wave generator to the reduction zone via a bifurcated waveguide assembly, while maintaining the crushed, ground, or shredded polypropylene-containing bottle caps and the activated carbon in a stationary position for at least a portion of the applying, to yield at least one gaseous organic decomposition product; and exhausting the at least one gaseous organic decomposition product from the reduction zone along with the inert gas through the reduction outlet.
In another embodiment, a material recovery system is provided, the material recovery system comprising: a housing adapted to receive a predominately polypropylene product in a reduction zone, the housing including an inert gas inlet and a reduction outlet in operative communication with the reduction zone; wherein the inert gas inlet is configured to permit purging of the reduction zone and maintaining of a positive pressure therein, and wherein the reduction outlet is configured to exhaust an initial gaseous content of the reduction zone during the purging, and to exhaust at least some of an inert gas during the maintaining of the positive pressure; an electromagnetic wave generator in operative communication with the housing and adapted to apply electromagnetic wave energy to the reduction zone via a bifurcated waveguide assembly to reduce the polypropylene product in the reduction zone to at least one gaseous organic decomposition product, the at least one gaseous organic decomposition product being exhausted with the inert gas via the reduction outlet during the maintaining of the positive pressure; and wherein the reduction zone is configured such that the predominately polypropylene product is stationary in the reduction zone during at least a portion of application of the electromagnetic wave energy.
In the accompanying figures, diagrams, charts, and experimental data are given that, together with the detailed description provided below, describe example embodiments of the claimed invention.
Methods and systems are provided for recovering at least one organic decomposition product from a polypropylene-containing product.
As shown in
Material recovery system 100 may further comprise a controller 190. Controller 190 may be in operative communication with electromagnetic wave generator 160 to control application and removal of the electromagnetic wave energy to reduction zone 120. Controller 190 may also permit the power level, frequency, or other parameters of the electromagnetic wave energy to be adjusted. In other embodiments, controller 190 may control inert gas supply 150 for purging and maintaining of the positive pressure within reduction zone 120.
Thus, in one embodiment, shown in
The polypropylene-containing product may be any polypropylene-containing item which may be at least one of crushed, ground, shredded, or otherwise sized and able to be placed within reduction zone 120. For example, suitable polypropylene containing products may include bottle caps, containers for cottage cheese, yogurt, cream cheese, ricotta cheese, margarine, hummus, medicine bottles, plastic ice cream containers, food storage and take-out containers, as well as flip caps on tubes and food product bottles (e.g., condiments), jar lids (e.g., peanut butter), and laundry detergent lids.
The electromagnetic wave energy may be at a select ultra-high frequency (UHF) (i.e., 300-3,000 MHz), such as 915 MHz or 2,450 MHz. Other UHF frequencies may also be selected for the electromagnetic waves. The electromagnetic wave energy may also be referred to as microwave energy.
In some embodiments, bifurcated waveguide assembly (e.g., waveguide assembly 170) is configured to divide the electromagnetic wave energy into a first electromagnetic wave energy and a second electromagnetic wave energy, wherein the first electromagnetic wave energy is 90 degrees out of phase with the second electromagnetic wave energy.
In some embodiments, the polypropylene-containing product may be contacted with a substance that is more absorptive of microwave energy than polypropylene. For example, activated carbon recovered from subjecting crushed, ground, shredded, or otherwise sized tires to the systems and methods disclosed in U.S. patent application Ser. No. 11/955,830 may be useful to mix with crushed, ground, shredded, or otherwise sized polypropylene. Thus, in one embodiment, shown in
With continued reference to
Second collection vessel 475 may be in fluid communication with a condenser, e.g., a coil reflux condenser 485, wherein various carbon-rich waxes may be collected. Uncondensed exhaust gas may be routed from coil reflux condenser 485 through tempered glass tubing to a third collection vessel 490. As shown
The following examples demonstrate that the systems and methods described herein are useful to recover carbonaceous material, including fuels, from polypropylene-containing products.
Certain embodiments are described below in the form of examples. It is impossible to depict every potential application of the invention. Thus, while the embodiments are described in considerable detail, it is not the intention to restrict or in any way limit the scope of the appended claims to such detail, or to any particular embodiment.
A 429.1 g mixture of polypropylene-containing bottle caps and polypropylene-containing bottles, shredded into pieces between one eighth and one quarter inch, was mixed with 200 g of activated carbon (acquired from microwaving shredded tires as disclosed in U.S. patent application Ser. No. 11/955,830), and placed in a 500 mL beaker lined with insulating material. The beaker was placed in a 4 L vessel. The vessel was sealed with high temperature gasket material. The vessel was placed in a Panasonic® NE-3280 microwave oven modified with an inert gas inlet tube and process gas outlet tube. The tubes were connected to corresponding connections on the vessel.
Inert gas was introduced into the vessel from an argon tank system and regulator. The vessel was purged with argon for about 3 min.
After the purge was completed, microwave energy was applied to the feedstock inside the vessel. Specifically, microwave energy was applied from both the top and the bottom of the microwave at a rate of 1600 W in 2 min intervals for 20 min. At the end of each 2 min interval, the microwave was opened to check the vessel's seals for leaks.
Gray colored fuel gas entered the tempered glass tubing from the process gas outlet tube. The fuel gas, having an approximate temperature of 260° C., was routed through the tempered glass tubing to a Graham condenser (see, e.g.,
Details of the GC-MS are as follows. An Agilent 7890A GC, equipped with an HP-5MS column (30 m×250 μm×0.25 μm, constant flow 0.9 mL/min,) and a 7693 autosampler, injecting 5 μL of sample into a split injector held at 300° C. with a 200:1 split ratio, and 5975C VL quadrupole (150° C.) mass selective detector (MSD) with electron ionization (EI at 230° C.) operating in the 5-550 m/z range using default settings generated by a daily autotune, was used. The oven was operated at 40° C. for 5 min, then heated at 5° C./min to 300° C. and held for 5 min. The total ion chromatograph (TIC) was obtained and auto integration and identification (NIST mass spectra library, U+A: 1, Flag Threshold: 1%, Min Est Purity: 50%, with tilting) was completed using Enhanced MSD ChemStation® E.02.01.1177.
The gas chromatographic analyses of liquids were performed using a Shimadzu GC-MS QP5050A equipped with a capillary column Petrocol™ DH 24160-U (100 m length, 0.25 mm diameter, 0.5 μm stationary phase), using a 1:30 split ratio and a quadruple mass (MS) detector with electron ionization, operating in the mass range 40-450 m/z. The oven operated at 298 K for 15 min, was heated at 2.5 K/min up to 523 K, and was kept at this temperature for 15 min. The total ion chromatography (TIC) was obtained with a signal-noise ratio of five, and the area percentage was reported without any response factors correction. The compounds were identified using the NIST mass spectra library.
The yellow liquid was analyzed neat. The carbonaceous content of the yellow liquid is shown in tabular form in
Solid products are unable to be directly introduced into the GC-MS. Thus, with respect to the wax, pentane and m-xylene were chosen as solvents. Pentane allowed for an analysis of non-polar compounds. The carbonaceous content of the wax dissolved in pentane is shown in tabular form in
The gray colored fuel gas that did not condense continued into a second flat bottom flask bathed in a −75° C. dry ice/acetone bath (see
With respect to the wax, pentane and m-xylene were again chosen as solvents. The carbonaceous content of the wax dissolved in pentane is shown in tabular form in
Generally speaking, carbonaceous products produced from polypropylene chips had carbon counts normally distributed from C5 to C25, centered at C15. 80% of the product is comprised of alkanes (paraffins), 13% alkenes (olefins), and 6% aromatics, with the balance being alcohols.
At 15 min, the gray colored fuel gas became a clear fuel gas. This continued until the end of the run at 20 min. After the vessel cooled it was removed from the microwave and opened. The shredded polypropylene had been reduced to carbon.
To the extent that the term “includes” or “including” is used in the specification or the claims, it is intended to be inclusive in a manner similar to the term “comprising” as that term is interpreted when employed as a transitional word in a claim. Furthermore, to the extent that the term “or” is employed (e.g., A or B) it is intended to mean “A or B or both.” When the applicants intend to indicate “only A or B but not both” then the term “only A or B but not both” will be employed. Thus, use of the term “or” herein is the inclusive, and not the exclusive use. See Bryan A. Garner, A Dictionary of Modern Legal Usage 624 (2d. Ed. 1995). Also, to the extent that the terms “in” or “into” are used in the specification or the claims, it is intended to additionally mean “on” or “onto.” Finally, where the term “about” is used in conjunction with a number, it is intended to include ±10% of the number. In other words, “about 10” may mean from 9 to 11.
As stated above, while the present application has been illustrated by the description of embodiments thereof, and while the embodiments have been described in considerable detail, it is not the intention of the applicants to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. Therefore, the application, in its broader aspects, is not limited to the specific details, illustrative examples shown, or any apparatus referred to. Departures may be made from such details, examples, and apparatuses without departing from the spirit or scope of the general inventive concept.
This application is a continuation-in-part application of U.S. patent application Ser. No. 11/955,830, filed on Dec. 13, 2007, and which claims priority to U.S. Provisional Patent Application Ser. No. 60/874,852, filed on Dec. 14, 2006. Both of these related applications are incorporated by reference herein in their entireties.
Number | Name | Date | Kind |
---|---|---|---|
3449213 | Knapp et al. | Jun 1969 | A |
3560347 | Knapp et al. | Feb 1971 | A |
3843457 | Grannen et al. | Oct 1974 | A |
3849332 | Bailey et al. | Nov 1974 | A |
4055001 | Forster et al. | Oct 1977 | A |
4065361 | Hanson | Dec 1977 | A |
4153533 | Kirkbride | May 1979 | A |
4250158 | Solbakken et al. | Feb 1981 | A |
4252487 | Jeppson | Feb 1981 | A |
4282066 | Wagener et al. | Aug 1981 | A |
4319856 | Jeppson | Mar 1982 | A |
4376034 | Wall | Mar 1983 | A |
4412841 | Du Broff et al. | Nov 1983 | A |
4567340 | Latchum, Jr. | Jan 1986 | A |
4592291 | Sullivan, III | Jun 1986 | A |
4759300 | Hansen et al. | Jul 1988 | A |
4776936 | Smith et al. | Oct 1988 | A |
5084140 | Holland | Jan 1992 | A |
5084141 | Holland | Jan 1992 | A |
5105563 | Fingerson et al. | Apr 1992 | A |
5152074 | Kishi | Oct 1992 | A |
5237755 | Lowe | Aug 1993 | A |
5304962 | Bobadilla et al. | Apr 1994 | A |
5330623 | Holland | Jul 1994 | A |
5366595 | Padgett et al. | Nov 1994 | A |
5373646 | Wosnitza et al. | Dec 1994 | A |
5387321 | Holland | Feb 1995 | A |
5507927 | Emery | Apr 1996 | A |
5536477 | Cha et al. | Jul 1996 | A |
5634281 | Nugent | Jun 1997 | A |
5864964 | Barragan | Feb 1999 | A |
5877395 | Emery | Mar 1999 | A |
5899630 | Brock | May 1999 | A |
5950325 | Mehdizadeh et al. | Sep 1999 | A |
5974687 | Gante et al. | Nov 1999 | A |
6008750 | Cottle et al. | Dec 1999 | A |
6133500 | Emery | Oct 2000 | A |
6152306 | Miller | Nov 2000 | A |
6184427 | Klepfer et al. | Feb 2001 | B1 |
6187988 | Cha | Feb 2001 | B1 |
6233841 | Beach | May 2001 | B1 |
6534754 | Schulz et al. | Mar 2003 | B2 |
6618957 | Novak et al. | Sep 2003 | B2 |
6864757 | Du Toit et al. | Mar 2005 | B2 |
7028623 | Pearson | Apr 2006 | B1 |
7101464 | Pringle | Sep 2006 | B1 |
7133584 | Dawes | Nov 2006 | B2 |
7361303 | Kantor | Apr 2008 | B2 |
7607860 | Novak | Oct 2009 | B2 |
7629497 | Pringle | Dec 2009 | B2 |
7767187 | Hong | Aug 2010 | B2 |
7927465 | Novak | Apr 2011 | B2 |
8378161 | Hemmings et al. | Feb 2013 | B1 |
8466332 | Hemmings et al. | Jun 2013 | B1 |
8476480 | Brown | Jul 2013 | B1 |
20020046474 | Novak et al. | Apr 2002 | A1 |
20020090268 | Haller | Jul 2002 | A1 |
20020150425 | Bodish | Oct 2002 | A1 |
20030070912 | Holzschuh et al. | Apr 2003 | A1 |
20070102279 | Novak | May 2007 | A1 |
20070131591 | Pringle | Jun 2007 | A1 |
20070135877 | Pringle | Jun 2007 | A1 |
20080179177 | Cha | Jul 2008 | A1 |
20080277388 | Carr | Nov 2008 | A1 |
20110132902 | Novak | Jun 2011 | A1 |
20110215092 | Novak | Sep 2011 | A1 |
Number | Date | Country |
---|---|---|
4026800 | Feb 1991 | DE |
9103281 | Mar 1991 | WO |
9202598 | Feb 1992 | WO |
9314821 | Aug 1993 | WO |
0103473 | Jan 2001 | WO |
0214764 | Feb 2002 | WO |
Entry |
---|
Condensers, The Lab Depot, Apr. 3, 2004 (date obtained using Google search tools), available online at: http://www.labdepotinc.com/c-26-glass-condenser.php. |
“How is tempered glass made?”, Scientific American, Feb. 1, 2001 (date obtained using Google search tools), available online at: https://www.scientificamerican.com/article/how-is-tempered-glass-mad/. |
Complaint for Injunctive Relief and Damages, dated Aug. 13, 2010, in Novak, et al. v. Farneman, et al., United States District Court for the Southern District of Ohio, Eastern Division, Case No. 2:10-cv-00768. |
Defendants' [Farneman, et al.] Post-Hearing Brief in Opposition to Plaintiffs' [Novak, et al.] Motion for Preliminary injunction, dated Oct. 22, 2010, in Novak, et al. v. Farneman, et al., United States District Court for the Southern District of Ohio, Eastern Division, Case No. 2:10-cv-00768. |
Introducing the EnviroWave Process, www.envirowave.com/index.html, printed on Nov. 7, 2007, The Envirowave Corporation (2007), Fredericktown, OH 1 page. |
Drying and Treating Bio-solids with Microwaves, www.envirowave/com/biosolids.html, printed on Nov. 7, 2007, The Envirowave Corporation, Fredericktown, OH 3 pages. |
Opinion and Other Denying Plaintiffs' [Novak, et al.] Motion for Preliminary Injunction, dated Nov. 9, 2010, in Novak, et al. v. Farneman, et al., United States District Court for the Southern District of Ohio, Eastern Division, Case No. 2:10-cv-00768. |
Gaines et al., “Discarded Tires: Energy Conservation Through Alternative Uses,” Argonne National Laboratory, ANL/CNSV-5, Dec. 1979, pp. 1, 16, 19, and 22. |
Advanced Microwave Technology, “An energy storage device,” www.antmicrowave.com/resonant_cav.htm, printed Jan. 14, 2012, NSW 2500, Australia, 2 pages. |
Bebb, “Chemistry of Rubber Processing and Disposal.” Environmental Health Perspectives, vol. 17, pp. 95-102, Oct. 1976. |
Waddell et al., “Pneumatic Tire Compounding,” The Goodyear Tire & Rubber Company, pp. 596-611. |
Rubber Manufactures Association, “Pyrolysis.” www.rma.org/scraptire.html. May 2002, 1 page. |
Rubber Manufactures Association, “Tire—Petroleum Energy Comparison.” www.rma.org, 1 page. |
Dodds et al., “Scrap Tires: A Resource and Technology Evaluation of Tire Pyrolysis and Other Selected Alternative Technologies.” EG&G, EGG-2241, Nov. 1983, pp. 1, 4, 18-20. |
CalRecovery, Inc., “Appendix Table D-4. Selected Compounds in Tire-Derived Oil.” Environmental Factors of Waste Tire Pyrolysis, Final Report, Jul. 1995, p. D-4. |
Zelibor et al., “Recycling Scrap Tires Into New Tires.” Scrap Tire Management Council; Rubber Manufacturers Association, p. 1 and 4-6. |
Int'l App. No. PCT/US07/87399, International Search Report, dated May 7, 2008, 4 pages. (31126-04004). |
Int'l App. No. PCT/US07/87399, Written Opinion of the International Search Authority, dated May 7, 2008, 5 pages. (31126.04004). |
Remediation of PCB's and Other Organic Contaminants, www.envirowave.com/organics.htm, printed on Nov. 7, 2007, The Envirowave Corporation, Fredericktown, OH, 3 pages. |
The EnviroWave Process and Waste Tire Reduction, www.envirowave.com/scraptirereduction.htm, printed on Nov. 7, 2007, The Envirowave Corporation, Fredericktown, OH, 3 pages. |
Frequently Asked Questions About the EnviroWave Microwave Process, www.envirowave.com/faq. htm, printed on Nov. 7, 2007, The Envirowave Corporation, Fredericktown, OH, 3 pages. |
$25 Million Fraud Litigation Action Against Exxadon, Environmental Waste Management Corporation, http://findarticles.com/p/articles/mi_m0EIN/is_196_July_25/ai_18519643, printed Apr. 23, 2007, Business Wire (Jul. 25, 1996), 4 pages. |
Brahic, Giant microwave turns plastic back to oil, http://environment.newscientist.com/article.ns?id=dn12141&print=true, printed Feb. 14, 2008, NewScientist Environment (Jun. 26, 2007), 2 pages. |
New Scientist Magazine Features Global Resource Corp.'s HAWK 10 Emission-Free Recycling Machine, press release by Global Resource Corporation, West Berlin, NJ (Jun. 28, 2007), 2 pages. |
Environmental Waste International Inc.—Complete Profile, http://strategis.ic.gc.ca/app/ccc/search/navigate.do?language=eng&portal=1&subPortal . . . , printed Apr. 23, 2007, Industry Canada, Ottawa, Ontario, Canada, 5 pages. |
Molecular Waste Technologies, Inc. Introduces you to the 21st Century in Waste Disposal, www.molecularwastetech.com, printed Apr. 23, 2007, Molecular Waste Technologies, Inc., Marietta, GA (2006), 5 pages. |
About EnviroWave Corporation, www.envirowave.com/aboutenvirowave.htm, printed Nov. 7, 2007, The Envirowave Corporation, Fredericktown, OH, 3 pages. |
Microwave Reduction of Medical Waste and Tires, Ontario Centre for Environmental Technology Advancement (OCETA) Environmental Technology Profiles, CAT. #06-008 / 08-023 / 09-028, www.oceta.ca/profiles/ewi/ewi_tech.html, printed Apr. 23, 2007, OCETA, Mississauga, Ontario, Canada (Jul. 2000), 6 pages. |
Number | Date | Country | |
---|---|---|---|
20130144095 A1 | Jun 2013 | US |
Number | Date | Country | |
---|---|---|---|
60874852 | Dec 2006 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 11955830 | Dec 2007 | US |
Child | 13753251 | US |