Abstract: I’m going to make a pitch for incinerating plastic. Yes, it will indeed produce CO2. But as we go merrily down the reduced carbon footprint path, I think it is reasonable to exempt certain activities from stringent reduction. One of them is incineration of waste. It can be done efficiently while generating electrical power and can be put to use in getting rid of BTU-laden waste combustibles like plastic.
Synthetic polymers, i.e. plastics, long ago rose to a high level of production due to demand. In particular, plastics like polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polyurethanes, polymethylmethacrylate (PMMA), various polyamides and adhesives are produced at incomprehensible scale. Within several of these major polymer varieties are their copolymers. LDPE is a good example. Low density polyethylene is a copolymer of ethylene and alpha-olefins like 1-butene, 1-hexene, and 1-octene. Placing the olefin group (C=C) exclusively at the 1-position requires some large-scale wizardry as internal olefins are thermodynamically more stable. Generally, commodity scale alpha-olefins have the terminal olefin put in place as they are made, not afterwards. These comonomers interfere with crystal formation within the bulk polymer. This has a large effect on many things including melt temperature, melt strength, stiffness, glass transition temperature, puncture resistance, tensile strength and lower density.
||| Side Note: Alpha olefins have other uses besides polymer manufacture. They are a crucial raw material for plasticisers, soaps/detergents, lubricants and oilfield chemicals. Interestingly, ethylene is a ripening hormone used by fruit.
The low unit price of plastic products like films, food packaging and medical packaging along with steady marketing has conditioned the consumer to expect such goods as disposable. And the plastics industry is happy to fill that expectation. Single use applications fill homes, businesses, hospitals … everywhere. Single use plastic waste also fills landfills, the countryside, waterways, and increasingly the oceans.
Recycling of plastic waste is complicated. Plastics may be made of just the pure homopolymer with only a single repeat monomer or along with a copolymer. A blend of mixed polymer waste may also contain a dog’s lunch of pigments, soot, intumescent additives, plasticizers, glue residues or labels, multiple layers of different polymers and UV blockers- components that you are unlikely to want to transfer into the final product. Even if you neglect the additive problem, there is always the immiscibility of different polymers. Yes, mixed polymers do not always form a homogeneous melt. This is a problem for everyone down the value chain.
Making polymers
While the end-use consumer is the final customer of the producer’s polymer, it is the converters who order the resin pellets directly from the polymer producers or wholesalers. Those who design the plastic article may or may not do a deep dive into the exact brand and grade of plastic to be used. Certainly there many articles (toys) that can be made from a variety of plastic brands and specifications where buyer input may be unknowledgeable or minimal. For many buyers of finished plastic goods, like everything price is likely to be the major parameter.
Users of performance polymers for demanding applications requiring particular polymer specifications will be more specific in their requirements.
The converters blow continuous films or do the injection or blow molding for those who set the final product specs. The converters buy their raw polymer on the basis of specified properties. One measure of the suitability of a particular polymer grade relates to the torque required to produce the maximum number of widgets per hour from the extruder. The converter’s business economics depend on throughput. A polymer that is otherwise wondrous to behold but its melt is too viscous will be problematic for the converter if it requires considerable torque from the extrusion equipment.
Make no mistake, retailers like Home Depot or Menard’s neither know or care about polymer specifications, nor do the end users. The companies who distribute wholesale products are specialists in warehousing and shipping and are unlikely to know polyurethane from HDPE because they don’t need to. The engineers who design and specify properties for the manufacturer are the key decision makers in the value chain.
The plastic manufacturer produces a polymer to give a set of particular physical properties. The converter takes the polymer pellets and combines them with additives, if any, to meet particular specifications. Polymer properties depend to a large extent on their thermal history. Once melted and cooled a polymer’s physical properties can change. Heating and cooling can lead to new phase transitions not present in the pellets. One change could be the glass transition temperature where the rigidity of a polymer changes from glassy to rubbery. Imagine a plastic coffee cup with a glass transition temperature of 75 oC trying to hold 87 oC coffee. Such a cup sags when the coffee is poured in. This is no good. The phase changes like glass transition temperature or melting temperatures can be identified with Differential Scanning Calorimetry (DSC).
Synthetic polymers such as PE are everywhere in our lives. These polymers are made from crude oil or, especially in the US, natural gas feedstocks. Collectively we consume and throw away massive amounts of polymer waste. The effort to recycle plastic in the US has largely been a failure due in part to insufficient segregation and cleaning. Closing the loop with a strong demand for recycled plastics has also faltered. Apart from recycling, what else can be done with it?
Plastics as fuel
Sending a metric ton of polyethylene plastic to the landfill produced the same energy as sending a ton of gasoline or diesel to the landfill in terms of potential energy. Synthetic polymers are either entirely hydrocarbon in composition or mostly so with some oxygen, nitrogen or chlorine thrown in. The fundamental fact is that these polymers are high in BTU content. The downside is that they ignite poorly due to the lack of volatiles. The polymers have to be thermally “cracked” or depolymerized to form volatile components that have a lower flash point. This cracking requires higher ignition temperatures than liquid or gas fuels.
Specific energy density refers to the amount of chemical energy per kilogram of material. In the table below the top three listings are pure hydrocarbons. Coal contains hydrocarbons but also minerals that do not contribute to overall combustion energy.
| Substance | Specific Energy (MJ/kg) |
| Diesel Fuel | 45.6 |
| Methane | 55.6 |
| Polyethylene (PE) | 46.3 |
| Coal, Bituminous | 24 – 35 |
In liquid combustion, it is the vapor above the liquid that burns. All liquids have a certain fraction of substance in gas phase at equilibrium above it at a given temperature. The flash point is the temperature in which the vapor can sustain combustion. Here is the official definition-
The flash point of a material is the “lowest liquid temperature at which, under certain standardized conditions, a liquid gives produces vapors in a quantity such as to be capable of forming an ignitable vapor/air mixture”. (EN 60079-10-1)
Source: Wikipedia.
In normal use, flashpoint (Fp) is used to gauge the ease of ignition of a substance when exposed to air. The Fp allows us to partition high hazard from lower hazard combustible materials high flashpoint liquids like motor oil pose less of a fire risk than does gasoline or propane. In the Globally Harmonized System (GHS) of Classification and Labeling of Chemicals,-
Flammable liquids are categorized by flammability, from Category 1 with a flash point < 23 °C and initial boiling point < 35 °C to Category 4 with flash point > 60 °C and < 93 °C.
Naturally, in the US we do it a bit differently with categories Flammable and Combustible–
Flammable– Flash point < 100 oF (38 oC), e.g. gasoline, methanol, acetone, natural gas
Combustible– Flash point > 100 oF (38 oC), e.g., paper, organic dusts, cooking oils
The US system is easier to remember than is the GHS but is perhaps a bit imprecise.
Plastic combustion
Why all of this vapor pressure stuff? It turns out that most plastics like polyethylene or polyethylene terephthalate (PET) have insignificant vapor pressures at room temperature. This is due to the extremely long chain lengths of the polymer and its subsequent high molecular weight. Considerable energy is needed to loosen these polymers from the liquid phase into the gas phase. So, the trick is the use pyrolysis to crack the long chains into shorter and more volatile pieces. This can be called destructive distillation like the process used for making coal gas. But this requires an input of energy to raise the temperature high enough to do the cracking.
Plastic pyrolysis is conducted at temperatures between 300 oC and 1000 oC with residence times between 0.5 seconds to 100 minutes, depending on the temperature. YouTube has videos of people using homemade pyrolysis reactors to produce a diesel-like composition. The thermally cracked polymer produces vapors that are condensed and recovered. There are a few examples of homebrew crackers that vent the exhaust subsurface into water to condense the vapors. Seems clever until you realize that when the cracker begins to cool, the fluid in the condenser tank will siphon back into the still hot cracker and flash explosively into vapor. An inline trap could easily prevent this.
In 2007, EPA compared waste-to-energy emissions between 1990 and 2005; it found decreases of 24 percent in nitrogen oxide, 88 percent in sulfur dioxide, 99 percent in dioxins and 96 percent in mercury.
In addition to heat for steam production to drive electrical generators, pyrolysis of plastics will indeed produce CO2, hydrochloric acid (from PVC) as well as ash and char. Properly done, the ash, char and hydrochloric acid can be effectively scrubbed. Some thought will have to be given to the ultimate disposition of solid residues which will contain what remains of the mineral additives found in some plastics. Some may not be friendly.
It is hard for me to imagine the world completely shutting down petroleum-based energy resources. CO2 emissions do not need to be totally extinguished. A sustainable CO2 output has been put forward by James Hansen, et al., and at Columbia University’s Earth Institute. They suggest that an initial target of CO2 levels below 350 ppm would likely be sustainable. The caveat is that continued research to refine a sustainable level.
By merely existing on Earth, humans will continue to produce air, water and soil pollution. We’ll continue to burn fossil fuels to some extent and continue to belch combustion gases into the air. I think this is a given. Humans will continue to collect raw materials for manufacturing. A mass movement to live a more modest, low consumption zero carbon footprint life is unlikely to occur. But, how about just a lower carbon footprint?
The point of this little pyrolysis excursion is that plastics are a potential energy resource that we wantonly toss into the landfill or in the street. Pyrolysis always produces solid waste residues which must be disposed of, so waste is still being produced, but a smaller volume than the plastic waste. As usual, the costs and benefits of the process depend on the balance of input costs vs output value.
As of March 2024, the CO2 level is a 425 ppm. We should remember that we do not have to drop the atmospheric CO2 to the level of the year 1800, just below some value like 350 ppm according to Columbia University. What we can do now is to begin living a somewhat lower consumption life. Instead of driving 5 miles to 7-Eleven in your F-150 to buy Miller Lite, cigarettes and lottery tickets, consider making all of your purchases next time you gas up. Consider backing off just a bit on plastic consumption.
Oh, and shut off the damned lights when you vacate a room. Unplug “wall-wart” device chargers that are not in use. They draw a trickle charge even when not in use. Have an “instant-on” TV or stereo not in use? Unplug it. The instant-on feature uses electricity to stay instantly ready for you. If it doesn’t “click” or it switches on/off by remote, it is likely an instant-on device. There. I’m finished now.
Lamentations on Chemistry 
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