Plastics and the Ocean. Группа авторов

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Figure 1.9 Classification of plastics according to inherent biodegradability.

In evaluating the merits of substituting conventional petrochemicals with bio‐based feedstocks, close attention must be paid to the scope of the relevant life‐cycle analyses (LCA). Bishop (2020), in a review of 44 studies comparing bio‐based with conventional feedstock for plastics, found that 84% of them did not account for additives in the inventories used in their analyses and most did not adopt a broad enough domain of impacts. For instance, using either sugar beet or wheat, yields a biomass yield of 73 T/ha and 8.6 T/ha, respectively, but the crop needed per ton of PE was 23.9 T and 6.84 T, respectively. On an area cultivated basis, sugar beet yielded a benefit in reducing climate change, that was at least two times greater than that by wheat bran biomass, underling the complexities of selecting the proper biomass source for feedstock (Belboom and Léonard 2016). The bio‐based and biodegradable plastic PLA, is often used in food‐service items. A “cradle‐to‐grave” comparison of PLA, PP, and PET for the fabrication of beverage cups found that PLA was superior (by 40–50%) to PP and PET, both in terms of climate change impacts as well as fossil fuel conservation (Moretti et al. 2021). But, in other impact categories such as eutrophication, acidification, particulates, and photochemical ozone formation, PLA was found to be worse than both conventional plastics. Mainly due to the lack of harmonization, it is difficult to compare different LCA studies on biobased resins (Cheroennet et al. 2017; Papong et al. 2014; Simon et al. 2016) with each other. Spierling et al. (2018), in their review of LCA on bio‐based plastics, concluded them to significantly contribute to environmental sustainability, potentially eliminating the emission of 240–315 MMT of carbon equivalents at a 65.8% substitution of conventional plastics in use. As with using any material in a given application, there are environmental and economic trade‐offs to be considered when using bio‐based resins as well. A full environmental assessment of the candidate bio‐plastic, based on LCA for the particular application, is a prerequisite for their adoption.

1.5 Plastic Manufacturing

      Plastics manufacturing is too broad a subject to be discussed in any detail here, and the following is a minimal introduction to allow readers who are not familiar with plastics to better appreciate the following chapters. Feedstock for polyolefin production are gaseous chemicals, called monomers, that are derived from oil, natural gas, or coal. Generally, a distilled fraction of oil, such as naphtha, is thermally cracked into these olefin monomers. Hydrocarbons in natural gas can also be converted to olefins; alternatively, biomass‐derived ethanol can also be converted into ethylene for use as a monomer. The ethylene made by any of these processes is polymerized using specialized catalyst systems,such as the Ziegler‐Natta or metallocene catalysts, to obtain olefin polymers with closely controlled molecular weight, chain geometry, and crystallinity. Pressure and temperature are the key variables that determine the structure and properties of the resin formed. The reaction is a catalyzed free‐radical polymerization, but several different reactor technologies, such as autoclaves, tubular reactors, stirred tanks, and fluidized bed reactors, are generally used in the manufacture of polyolefin resins. Mostly the same types of reactors are used in the manufacture of PP as well. Styrene monomer used in the manufacture of PS by free‐radical polymerization is a liquid, allowing emulsion polymerization in the liquid phase. The result of this resin manufacturing process are the virgin plastic pellets used by processors who convert these into useful plastic products.

      An important part of this latter operation is ‘compounding’, where the plastic is melted and intimately mixed with chemical compounds called additives, meant to improve the properties of the plastics to obtain their best performance in the intended product (see Chapter 2). Mixing can be conveniently carried out in a compounding extruder at a temperature high enough to melt the plastic. The compounded plastic is then used to mold products by one of many techniques, the ones popular with thermoplastics being injection molding, extrusion, and blow molding. These approaches do not work well with thermoset plastics that need to be compression molded.

Figure 1.10 A plot of the GWP (kg CO₂‐e) versus Embodied Energy (GJ) per 1000 kg of common plastics. Ranges of values for non‐plastic materials are indicated by shaded rectangles, for comparison.

The energy expended and the greenhouse gases such as CO₂ emitted (expressed as the global warming potential, GWP (kgCO₂‐e)) in producing common plastics, estimated in 2011 by Franklin Associates (for the American Chemical Council), is given in Figure 1.10 and compared with that for copper, alumina ceramic, paperboard, and thermoplastic rigid foams. Similar data for other plastics such as composites, metals such as nickel or aluminum, and for materials such as wood, clay, and stone lie outside the scale of this diagram. These estimates depend on several variables, including the feedstock used, the mix of energy employed in the process, the reaction engineering employed, and the specific grade of the resin produced. Estimates will therefore vary from location to location and even temporally. Still, the figure provides a general appreciation for the magnitude of energy and emissions associated with manufacturing different materials. Most of this energy is expended in extracting and purifying the feedstock rather than in polymerizing the monomer.

Individual plastics cannot be “ranked” for environmental desirability based on the figure, as many other externalities are associated with manufacturing resins. Acidic emissions that potentially acidify the oceans, nitrogen release that can result in eutrophication, ozone‐depleting gases that affect the stratospheric ozone layer, and ground‐level smog‐forming emissions are some of these. A detailed life cycle (LCA) analysis based on reliable inventory data is needed to evaluate the impact of these on the environment. Estimated impacts were recently reported for three classes of polyethylenes (Table 1.4). Again, the impacts will vary with the location as well as the process employed in the manufacture.

Table 1.4 Estimated environmental impacts of plastic manufacture (per 1000 kg) of plastic.

Plastic	Water (L)	Acidification (kg SO2‐e)	Eutrophication (kg N‐e)	Ozone Depletn. (kg CFC‐11‐e)	Smog (kgO3‐e)
HDPE	8143	5.22	0.26	12 × 106	129
LDPE	11553	6.54	0.30	1.3 × 106	148
LLDPE	7383	4.69	0.25	1.2 × 106	125