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<title>Thermal depolymerization</title>

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Thermal depolymerization

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Thermal depolymerization (TDP) is the process of converting a <a href="Polymer" title="Polymer">polymer</a> into a <a href="Monomer" title="Monomer">monomer</a> or a mixture of monomers,<a href="#cite_note-1">[1]</a> by predominantly thermal means. It may be <a href="Catalysis" title="Catalysis">catalyzed</a> or un-catalyzed and is distinct from other forms of <a href="Depolymerisation" class="mw-redirect" title="Depolymerisation">depolymerization</a> which may rely on the use of chemicals or biological action. This process is associated with an increase in <a href="Entropy" title="Entropy">entropy</a>.

For most polymers, thermal depolymerization is chaotic process, giving a mixture of <a href="Volatility_(chemistry)" title="Volatility (chemistry)">volatile</a> compounds. Materials may be depolymerized in this way during <a href="Waste_management" title="Waste management">waste management</a>, with the volatile components produced being burnt as a form of <a href="Synthetic_fuel" title="Synthetic fuel">synthetic fuel</a> in a <a href="Waste-to-energy" title="Waste-to-energy">waste-to-energy</a> process. For other polymers, thermal depolymerization is an ordered process giving a single product, or limited range of products; these transformations are usually more valuable and form the basis of some <a href="Plastic_recycling" title="Plastic recycling">plastic recycling</a> technologies.<a href="#cite_note-Thiounn2020-2">[2]</a>

<div class="mw-heading mw-heading2"><h2 id="Disordered_depolymerization">Disordered depolymerization</h2></div>

For most polymeric materials, thermal depolymerization proceeds in a disordered manner, with random <a href="Chain_scission" title="Chain scission">chain scission</a> giving a mixture of volatile compounds. The result is broadly akin to <a href="Pyrolysis" title="Pyrolysis">pyrolysis</a>, although at higher temperatures <a href="Gasification" title="Gasification">gasification</a> takes place. These reactions can be seen during <a href="Waste_management" title="Waste management">waste management</a>, with the products being burnt as synthetic fuel in a <a href="Waste-to-energy" title="Waste-to-energy">waste-to-energy</a> process. In comparison to simply <a href="Incinerating" class="mw-redirect" title="Incinerating">incinerating</a> the starting polymer, depolymerization gives a material with a higher <a href="Heating_value" class="mw-redirect" title="Heating value">heating value</a>, which can be burnt more efficiently and may also be sold. Incineration can also produce harmful <a href="Dioxins_and_dioxin-like_compounds" title="Dioxins and dioxin-like compounds">dioxins and dioxin-like compounds</a> and requires specially designed reactors and emission control systems in order to be performed safely. As the depolymerization step requires heat, it is energy-consuming; thus, the ultimate balance of <a href="Thermal_efficiency" title="Thermal efficiency">energy efficiency</a> compared to straight incineration can be very tight and has been the subject of criticism.<a href="#cite_note-3">[3]</a>

<div class="mw-heading mw-heading3"><h3 id="Biomass">Biomass</h3></div>

Many agricultural and animal wastes can be processed, but these are often already used as <a href="Fertilizer" title="Fertilizer">fertilizer</a>, animal feed, and, in some cases, as feedstocks for <a href="Paper_mill" title="Paper mill">paper mills</a> or as low-quality <a href="Boiler" title="Boiler">boiler</a> fuel. Thermal depolymerization can convert these into more economically valuable materials. Numerous <a href="Biomass_to_liquid" title="Biomass to liquid">biomass to liquid</a> technologies have been developed. In general, <a href="Biochemical" class="mw-redirect" title="Biochemical">biochemicals</a> contain oxygen atoms, which are retained during pyrolysis, giving liquid products rich in <a href="Phenol" title="Phenol">phenols</a> and <a href="Furan" title="Furan">furans</a>.<a href="#cite_note-4">[4]</a> These can be viewed as partially oxidized and make for low-grade fuels. <a href="Hydrothermal_liquefaction" title="Hydrothermal liquefaction">Hydrothermal liquefaction</a> technologies dehydrate the biomass during thermal processing to produce a more energy-rich product stream.<a href="#cite_note-5">[5]</a> Similarly, <a href="Gasification" title="Gasification">gasification</a> produces hydrogen, a very high-energy fuel.

<div class="mw-heading mw-heading3"><h3 id="Plastics">Plastics</h3></div>

<a href="Plastic_waste" class="mw-redirect" title="Plastic waste">Plastic waste</a> consists mostly of <a href="Commodity_plastics" title="Commodity plastics">commodity plastics</a> and may be actively <a href="Waste_sorting" title="Waste sorting">sorted</a> from <a href="Municipal_waste" class="mw-redirect" title="Municipal waste">municipal waste</a>. Pyrolysis of mixed plastics can give a fairly broad mix of chemical products (between about 1 and 15 carbon atoms), including gases and aromatic liquids.<a href="#cite_note-6">[6]</a> Catalysts can give a better-defined product with a higher value.<a href="#cite_note-7">[7]</a> Likewise, <a href="Hydrocracking" class="mw-redirect" title="Hydrocracking">hydrocracking</a> can be employed to give <a href="Liquefied_petroleum_gas" title="Liquefied petroleum gas">LPG</a> products. The presence of <a href="PVC" class="mw-redirect" title="PVC">PVC</a> can be problematic, as its thermal depolymerization generates large amounts of <a href="Hydrogen_chloride" title="Hydrogen chloride">HCl</a>, which can corrode equipment and cause undesirable chlorination of the products. It must be either excluded or compensated for by installing dechlorination technologies.<a href="#cite_note-8">[8]</a> <a href="Polyethylene" title="Polyethylene">Polyethylene</a> and <a href="Polypropylene" title="Polypropylene">polypropylene</a> account for just less than half of global plastic production and, being pure <a href="Hydrocarbons" class="mw-redirect" title="Hydrocarbons">hydrocarbons</a>, have a higher potential for conversion to fuel.<a href="#cite_note-2011CommercialRev-9">[9]</a> Plastic-to-fuel technologies have historically struggled to be economically viable due to the costs of collecting and sorting the plastic and the relatively low value of the fuel produced.<a href="#cite_note-2011CommercialRev-9">[9]</a> Large plants are seen as being more economical than smaller ones,<a href="#cite_note-10">[10]</a><a href="#cite_note-11">[11]</a> but require more investment to build.

The method can, however, result in a mild net-decrease in <a href="Greenhouse_gas" title="Greenhouse gas">greenhouse gas</a> emissions,<a href="#cite_note-12">[12]</a> though other studies dispute this. For example, a 2020 study released by Renolds on their own Hefty EnergyBag program shows net greenhouse gas emissions. The study showed then when all cradle-to-grave energy costs are tallied, burning in a cement kiln was far superior. Cement kiln fuel scored a −61.1 kg CO2 equivalents compared to +905 kg CO2 eq. It also fared far worse in terms of landfill reduction vs. kiln fuel.<a href="#cite_note-Table_ES.1_–_End_of_Life_GWP_Summary_Table-13">[13]</a> Other studies have confirmed that plastics pyrolysis to fuel programs are also more energy intensive.<a href="#cite_note-14">[14]</a><a href="#cite_note-15">[15]</a>

For tire waste management, <a href="Tire_recycling#Tire_pyrolysis" title="Tire recycling">tire pyrolysis</a> is also an option. Oil derived from tire rubber pyrolysis contains high sulfur content, which gives it high potential as a pollutant and requires <a href="Hydrodesulfurization" title="Hydrodesulfurization">hydrodesulfurization</a> before use.<a href="#cite_note-16">[16]</a><a href="#cite_note-17">[17]</a> The area faces legislative, economic, and marketing obstacles.<a href="#cite_note-j.rser.2013.02.038-18">[18]</a> In most cases, tires are simply incinerated as <a href="Tire-derived_fuel" title="Tire-derived fuel">tire-derived fuel</a>.

<div class="mw-heading mw-heading3"><h3 id="Municipal_waste">Municipal waste</h3></div>

Thermal treatment of <a href="Municipal_waste" class="mw-redirect" title="Municipal waste">municipal waste</a> can involve the depolymerization of a very wide range of compounds, including plastics and biomass. Technologies can include simple incineration as well as pyrolysis, <a href="Gasification" title="Gasification">gasification</a>, and <a href="Plasma_gasification" title="Plasma gasification">plasma gasification</a>. All of these are able to accommodate mixed and contaminated feedstocks. The main advantage is the reduction in volume of the waste, particularly in densely populated areas lacking suitable sites for new <a href="Landfill" title="Landfill">landfills</a>. In many countries, incineration with energy recovery remains the most common method, with more advanced technologies being hindered by technical and cost hurdles.<a href="#cite_note-19">[19]</a><a href="#cite_note-20">[20]</a>

<div class="mw-heading mw-heading2"><h2 id="Ordered_depolymerization">Ordered depolymerization</h2></div>

Some materials thermally decompose in an ordered manner to give a single or limited range of products. By virtue of being pure materials, they are usually more valuable than the mixtures produced by disordered thermal depolymerization. For plastics this is usually the starting <a href="Monomer" title="Monomer">monomer</a>, and when this is recycled back into fresh polymer, it is called feedstock recycling. In practice, not all depolymerization reactions are completely efficient, and some competitive pyrolysis is often observed.

<div class="mw-heading mw-heading3"><h3 id="Biomass_2">Biomass</h3></div>

<a href="Biorefinery" title="Biorefinery">Biorefineries</a> convert low-value agricultural and animal waste into useful chemicals. The industrial production of <a href="Furfural" title="Furfural">furfural</a> by the acid-catalyzed thermal treatment of <a href="Hemicellulose" title="Hemicellulose">hemicellulose</a> has been in operation for over a century. <a href="Lignin" title="Lignin">Lignin</a> has been the subject of significant research for the potential production of <a href="BTX_(chemistry)" title="BTX (chemistry)">BTX</a> and other aromatic compounds,<a href="#cite_note-21">[21]</a> although such processes have not yet been commercialized with any lasting success.<a href="#cite_note-22">[22]</a>

<div class="mw-heading mw-heading3"><h3 id="Plastics_2">Plastics</h3></div>

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</style><div role="note" class="hatnote navigation-not-searchable">Main article: <a href="Plastic_recycling" title="Plastic recycling">Plastic recycling</a></div>

Certain polymers like <a href="PTFE" class="mw-redirect" title="PTFE">PTFE</a>, <a href="Nylon_6" title="Nylon 6">Nylon 6</a>, <a href="Polystyrene" title="Polystyrene">polystyrene</a>, and <a href="Polymethylmethacrylate" class="mw-redirect" title="Polymethylmethacrylate">PMMA</a><a href="#cite_note-23">[23]</a> undergo <a href="Depolymerization" title="Depolymerization">depolymerization</a> to give their starting <a href="Monomers" class="mw-redirect" title="Monomers">monomers</a>. These can be converted back into new plastic, a process called chemical or feedstock recycling.<a href="#cite_note-24">[24]</a><a href="#cite_note-25">[25]</a><a href="#cite_note-26">[26]</a> In theory, this offers infinite recyclability, but it is also more expensive and has a higher <a href="Carbon_footprint" title="Carbon footprint">carbon footprint</a> than other forms of plastic recycling; however, in practice, this still yields an inferior product at higher energy costs than virgin polymer production in the real world because of contamination.

<div class="mw-heading mw-heading2"><h2 id="Related_processes">Related processes</h2></div>

Although rarely employed presently, <a href="Coal_gasification" title="Coal gasification">coal gasification</a> has historically been performed on a large scale. Thermal depolymerization is similar to other processes which use <a href="Superheated_water" title="Superheated water">superheated water</a> as a major phase to produce fuels, such as direct <a href="Hydrothermal_liquefaction" title="Hydrothermal liquefaction">hydrothermal liquefaction</a>.<a href="#cite_note-27">[27]</a> These are distinct from processes using dry materials to depolymerize, such as <a href="Pyrolysis" title="Pyrolysis">pyrolysis</a>. The term thermochemical conversion (TCC) has also been used for conversion of biomass to oils, using superheated water, although it is more usually applied to fuel production via pyrolysis.<a href="#cite_note-28">[28]</a><a href="#cite_note-29">[29]</a> A demonstration plant due to start up in the Netherlands is said to be capable of processing 64 tons of biomass (<a href="Dry_basis" title="Dry basis">dry basis</a>) per day into oil.<a href="#cite_note-30">[30]</a> Thermal depolymerization differs in that it contains a hydrous process followed by an anhydrous cracking / distillation process.

<a href="Condensation" title="Condensation">Condensation</a> polymers bearing cleavable groups such as <a href="Ester" title="Ester">esters</a> and <a href="Amides" class="mw-redirect" title="Amides">amides</a> can also be completely depolymerized by <a href="Hydrolysis" title="Hydrolysis">hydrolysis</a> or <a href="Solvolysis" title="Solvolysis">solvolysis</a>; this can be a purely chemical process but may also be promoted by enzymes.<a href="#cite_note-31">[31]</a> Such technologies are less well developed than those of thermal depolymerization but have the potential for lower energy costs. Thus far, <a href="Polyethylene_terephthalate" title="Polyethylene terephthalate">polyethylene terephthalate</a> has been the most heavily studied polymer.<a href="#cite_note-32">[32]</a> It has been suggested that waste plastic could be converted into other valuable chemicals (not necessarily monomers) by microbial action,<a href="#cite_note-33">[33]</a><a href="#cite_note-34">[34]</a> but such technology is still in its infancy.

<ul><li><a href="Thermal_treatment" title="Thermal treatment">Thermal treatment</a></li>

<li><a href="Mechanical_heat_treatment" title="Mechanical heat treatment">Mechanical heat treatment</a></li>

<li><a href="Wet_oxidation" title="Wet oxidation">Wet oxidation</a></li>

<li><a href="Staged_reforming" title="Staged reforming">Staged reforming</a></li></ul>

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</style><div id="Bioenergy240" style="font-size:114%;margin:0 4em"><a href="Bioenergy" title="Bioenergy">Bioenergy</a></div></th></tr><tr><th scope="row" class="navbox-group" style="width:1%"><a href="Biofuel" title="Biofuel">Biofuels</a></th><td class="navbox-list-with-group navbox-list navbox-odd" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Alcohol_fuel" title="Alcohol fuel">Alcohol</a></li>

<li><a href="Algae_fuel" title="Algae fuel">Algae</a></li>

<li><a href="Babassu_oil" title="Babassu oil">Babassu oil</a></li>

<li><a href="Bagasse" title="Bagasse">Bagasse</a></li>

<li><a href="Butanol_fuel" title="Butanol fuel">Biobutanol</a></li>

<li><a href="Biodiesel" title="Biodiesel">Biodiesel</a></li>

<li><a href="Biogas" title="Biogas">Biogas</a></li>

<li><a href="Biogasoline" title="Biogasoline">Biogasoline</a></li>

<li><a href="Bioliquids" title="Bioliquids">Bioliquids</a></li>

<li><a href="Biomass_(energy)" title="Biomass (energy)">Biomass</a></li>

<li><a href="Cooking_oil" title="Cooking oil">Cooking oil</a>

<ul><li><a href="Vegetable_oil_fuel" title="Vegetable oil fuel">vegetable oil</a></li></ul></li>

<li><a href="Ethanol_fuel" title="Ethanol fuel">Ethanol</a>

<ul><li><a href="Cellulosic_ethanol" title="Cellulosic ethanol">cellulosic</a></li>

<li><a href="Common_ethanol_fuel_mixtures" title="Common ethanol fuel mixtures">mixtures</a></li></ul></li>

<li><a href="Methanol_fuel" title="Methanol fuel">Methanol</a></li>

<li><a href="Stover" title="Stover">Stover</a>

<li><a href="Straw" title="Straw">Straw</a></li>

<li><a href="Pontederia_crassipes#Bioenergy" title="Pontederia crassipes">Water hyacinth</a></li>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%"><a href="Energy_crop" title="Energy crop">Energy from foodstock</a></th><td class="navbox-list-with-group navbox-list navbox-even" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Camelina_sativa#Biodiesel_and_jet_fuel" title="Camelina sativa">Camelina sativa</a></li>

<li><a href="Cassava" title="Cassava">Cassava</a></li>

<li><a href="Coconut_oil#Industry" title="Coconut oil">Coconut oil</a></li>

<li><a href="Grape" title="Grape">Grape</a></li>

<li><a href="Maize" title="Maize">Maize</a></li>

<li><a href="Potato" title="Potato">Potato</a></li>

<li><a href="Rapeseed" title="Rapeseed">Rapeseed</a></li>

<li><a href="Sorghum" title="Sorghum">Sorghum</a></li>

<li><a href="Soybean" title="Soybean">Soybean</a></li>

<li><a href="Sugar_beet" title="Sugar beet">Sugar beet</a></li>

<li><a href="Sugarcane" title="Sugarcane">Sugarcane</a></li>

<li><a href="Common_sunflower" title="Common sunflower">Sunflower</a></li>

<li><a href="Wheat" title="Wheat">Wheat</a></li>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%"><a href="Nonfood_crop" title="Nonfood crop">Non-food energy crops</a></th><td class="navbox-list-with-group navbox-list navbox-odd" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Arundo" title="Arundo">Arundo</a></li>

<li><a href="Andropogon_gerardi" title="Andropogon gerardi">Big bluestem</a></li>

<li><a href="Camelina" title="Camelina">Camelina</a></li>

<li><a href="Triadica_sebifera" title="Triadica sebifera">Chinese tallow</a></li>

<li><a href="Lemnoideae" title="Lemnoideae">Duckweed</a></li>

<li><a href="Jatropha_curcas" title="Jatropha curcas">Jatropha curcas</a></li>

<li><a href="Miscanthus_%C3%97_giganteus" title="Miscanthus × giganteus">Miscanthus × giganteus</a></li>

<li><a href="Pongamia" title="Pongamia">Pongamia pinnata</a></li>

<li><a href="Salicornia#Industrial_use" title="Salicornia">Salicornia</a></li>

<li><a href="Panicum_virgatum" title="Panicum virgatum">Switchgrass</a></li>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%">Technology</th><td class="navbox-list-with-group navbox-list navbox-even" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Bioconversion_of_biomass_to_mixed_alcohol_fuels" title="Bioconversion of biomass to mixed alcohol fuels">Bioconversion of biomass to mixed alcohol fuels</a></li>

<li><a href="Bioenergy_with_carbon_capture_and_storage" title="Bioenergy with carbon capture and storage">Bioenergy with carbon capture and storage</a></li>

<li><a href="Biomass_heating_system" title="Biomass heating system">Biomass heating systems</a></li>

<li><a href="Biorefinery" title="Biorefinery">Biorefinery</a></li>

<li><a href="Fischer%E2%80%93Tropsch_process" title="Fischer–Tropsch process">Fischer–Tropsch process</a></li>

<li><a href="Industrial_biotechnology" class="mw-redirect" title="Industrial biotechnology">Industrial biotechnology</a></li>

<li><a href="Pellet_fuel" title="Pellet fuel">Pellet fuel</a>

<li><a href="Pellet_stove" title="Pellet stove">stove</a></li></ul></li>

<li><a href="Sabatier_reaction" title="Sabatier reaction">Sabatier reaction</a></li>

</ul>

</div></td></tr><tr><th scope="row" class="navbox-group" style="width:1%">Concepts</th><td class="navbox-list-with-group navbox-list navbox-odd" style="width:100%;padding:0"><div style="padding:0 0.25em">

<ul><li><a href="Agflation" title="Agflation">Agflation</a></li>

<li><a href="Cellulosic_ethanol_commercialization" class="mw-redirect" title="Cellulosic ethanol commercialization">Cellulosic ethanol commercialization</a></li>

<li><a href="Energy_content_of_biofuel" title="Energy content of biofuel">Energy content of biofuel</a></li>

<li><a href="Energy_crop" title="Energy crop">Energy crop</a></li>

<li><a href="Energy_forestry" title="Energy forestry">Energy forestry</a></li>

<li><a href="Energy_return_on_investment" title="Energy return on investment">Energy return on investment</a></li>

<li><a href="Issues_relating_to_biofuels" title="Issues relating to biofuels">Issues relating to biofuels</a></li>

<li><a href="Sustainable_biofuel" title="Sustainable biofuel">Sustainable biofuel</a></li></ul>

</div></td></tr><tr><td class="navbox-abovebelow" colspan="2"><div>

<ul><li> Category</li></ul>

</div></td></tr></tbody></table></div>

<div class="mw-heading mw-heading2"><h2 id="References">References</h2></div>

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