Thermal depolymerization (TDP) is a depolymerization process using hydrous pyrolysis for the reduction of complex organic materials (usually waste products of various sorts, often biomass and plastic) into light crude oil and methane gas. It mimics the natural geological processes thought to be involved in the production of fossil fuels. Under pressure and heat, long chain
polymers of hydrogen, oxygen, and carbon decompose into short-chain petroleum hydrocarbons with a maximum length of around 18 carbons.
Thermal depolymerisation is similar to other processes which use superheated water as a major step to produce fuels, such as direct Hydrothermal Liquefaction. These are distinct from processes using dry materials to depolymerize, such as pyrolysis. 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. The Hydro Thermal Upgrading (HTU) process uses superheated water to produce oil from domestic waste. Thermal depolymerisation differs in that it contains a hydrous process followed by an anhydrous cracking / distillation process.
Thermal depolymerization is similar to the geological processes that produced the fossil fuels used today, except that the technological process occurs in a timeframe measured in hours. Until recently, the human-designed processes were not efficient enough to serve as a practical source of fuel more energy was required than was produced.
The first industrial process to obtain gas, diesel fuels and other petroleum products through pyrolysis of coal, tar or biomass was designed and patented in the late 1920s by Fischer-Tropsch. In U. S. patent 2,177,557, issued in 1939, Bergstrom and Cederquist discuss a method for obtaining oil from wood in which the wood is heated under pressure in water with a significant amount of calcium hydroxide added to the mixture. In the early 1970s Herbert R. Appell and coworkers worked with hydrous pyrolysis methods, as exemplified by U. S. patent 3,733,255 (issued in 1973), which discusses the production of oil from sewer sludge and municipal refuse by heating the material in water, under pressure, and in the presence of carbon monoxide.
An approach that exceeded break-even was developed by Illinois microbiologist Paul Baskis in the 1980s and refined over the next 15 years (see U. S. patent 5,269,947, issued in 1993). The technology was finally developed for commercial use in 1996 by Changing World Technologies (CWT). Brian S. Appel (CEO of CWT) took the technology in 2001 and expanded and changed it into what is now referred to as TCP (Thermal Conversion Process), and has applied for and obtained several patents (see, for example, published patent 8,003,833, issued August 23, 2011). A Thermal Depolymerization demonstration plant was completed in 1999 in Philadelphia by Thermal Depolymerization, LLC, and the first full-scale commercial plant was constructed in Carthage, Missouri, about 100 yards (91 m) from ConAgra Foods' massive Butterball turkey plant, where it is expected to process about 200 tons of turkey waste into 500 barrels (79 m3) of oil per day.
Theory and process
In the method used by CWT, the water improves the heating process and contributes hydrogen to the reactions.
In the Changing World Technologies (CWT) process, the feedstock material is first ground into small chunks, and mixed with water if it is especially dry. It is then fed into a pressure vessel reaction chamber where it is heated at constant volume to around 250C. Similar to a pressure cooker (except at much higher pressure), steam naturally raises the pressure to 600 psi (4 MPa) (near the point of saturated water). These conditions are held for approximately 15 minutes to fully heat the mixture, after which the pressure is rapidly released to boil off most of the water (see: Flash evaporation). The result is a mix of crude hydrocarbons and solid minerals. The minerals are removed, and the hydrocarbons are sent to a second-stage reactor where they are heated to 500C, further breaking down the longer hydrocarbon chains. The hydrocarbons are then sorted by fractional distillation, in a process similar to conventional oil refining.
The CWT company claims that 15 to 20% of feedstock energy is used to provide energy for the plant. The remaining energy is available in the converted product. Working with turkey offal as the feedstock, the process proved to have yield efficiencies of approximately 85%; in other words, the energy contained in the end products of the process is 85% of the energy contained in the inputs to the process (most notably the energy content of the feedstock, but also including electricity for pumps and natural gas or woodgas for heating). If one considers the energy content of the feedstock to be free (i.e., waste material from some other process), then 85 units of energy are made available for every 15 units of energy consumed in process heat and electricity. This means the "Energy Returned on Energy Invested" (EROEI) is (6.67), which is comparable to other energy harvesting processes. Higher efficiencies may be possible with drier and more carbon-rich feedstocks, such as waste plastic.
By comparison, the current processes used to produce ethanol and biodiesel from agricultural sources have EROEI in the 4.2 range, when the energy used to produce the feedstocks is accounted for (in this case, usually sugar cane, corn, soybeans and the like). These EROEI values are not directly comparable, because these EROEI calculations include the energy cost to produce the feedstock, whereas the above EROEI calculation for thermal depolymerization process (TDP) does not.
The process breaks down almost all materials that are fed into it. TDP even efficiently breaks down many types of hazardous materials, such as poisons and difficult-to-destroy biological agents such as prions.
Feedstocks and outputs with thermal depolymerization
Average TDP Feedstock Outputs
||Solids (mostly carbon based)
(Note: Paper/cellulose contains at least 1% minerals, which was probably grouped under carbon solids.)
Carthage plant products
As reported on 04/02/2006 by Discover Magazine, a Carthage, Missouri plant was producing 500 barrels per day (79 m3/d) of oil made from 270 tons of turkey entrails and 20 tons of hog lard. This represents an oil yield of 22.3 percent. The Carthage plant produces API 40+, a high value crude oil. It contains light and heavy naphthas, a kerosene, and a gas oil fraction, with essentially no heavy fuel oils, tars, asphaltenes or waxes. It can be further refined to produce No. 2 and No. 4 fuel oils.
TDP-40 Oil Classification by D-5443 PONA method
||% by Weight
The fixed carbon solids produced by the TDP process have multiple uses as a filter, a fuel source and a fertilizer. It can be used as activated carbon in wastewater treatment, as a fertilizer, or as a fuel similar to coal.
The process can break down organic poisons, due to breaking chemical bonds and destroying the molecular shape needed for the poison's activity. It is likely to be highly effective at killing pathogens, including prions. It can also safely remove heavy metals from the samples by converting them from their ionized or organometallic forms to their stable oxides which can be safely separated from the other products.
Along with similar processes, it is a method of recycling the energy content of organic materials without first removing the water. It can produce liquid fuel, which separates from the water physically without need for drying. Other methods to recover energy often require pre-drying (e.g. burning, pyrolysis) or produce gaseous products (e.g. anaerobic digestion).
The process only breaks long molecular chains into shorter ones, so small molecules such as carbon dioxide or methane cannot be converted to oil through this process. However, the methane in the feedstock is recovered and burned to heat the water that is an essential part of the process. In addition, the gas can be burned in a combined heat and power plant, consisting of a gas turbine which drives a generator to create electricity, and a heat exchanger to heat the process input water from the exhaust gas. The electricity can be sold to the power grid, for example under a feed-in tariff scheme. This also increases the overall efficiency of the process (already said to be over 85% of feedstock energy content).
Another option is to sell the methane product as biogas. For example, biogas can be compressed, much like natural gas, and used to power motor vehicles.
Many agricultural and animal wastes could be processed, but many of these are already used as fertilizer, animal feed, and, in some cases, as feedstocks for paper mills or as boiler fuel. Energy crops constitute another potentially large feedstock for thermal depolymerization.