Thermal De polymerization process

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Thermal depolymerizationFrom Wikipedia, the free encyclopedia

It has been suggested that this article be mergedinto

Hydrothermal liquefaction.(Discuss) Proposed since November

2013.

Thermal depolymerization(TDP) is a depolymerizationprocess using hydrous pyrolysisfor thereduction of complex organic materials(usuallywasteproducts of various sorts, often biomassand

plastic) into light crude oil. It mimics the natural geologicalprocesses thought to be involved in the

production of fossil fuels. Under pressure and heat, long chain polymersof hydrogen, oxygen, and

carbondecompose into short-chain petroleumhydrocarbonswith a maximum length of around 18

carbons.

Contents [hide]

1 Similar Processes

2 History

3 Theory and process

4 Feedstocksand outputs with thermal depolymerization

4.1Carthage plant products

5 Advantages

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6 Potential sources of waste inputs

7 Limitations

8 Current status

8.1 Company expansion

8.2 Smell complaints

8.3 Status as of February 2009

8.4 Similar technologies9 See also

10 References

11 Further reading

Similar Processes [edit]

Thermal depolymerisation is similar to other processes which use superheated wateras a majorstep to produce fuels, such as direct Hydrothermal Liquefaction.[1]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.[2][3]Other commercial scale

processes include the "SlurryCarb" process operated by EnerTech, which uses similar technology

to decarboxylate wet solid biowaste, which can then be physically dewatered and used as a solid

fuel called E-Fuel. The plant was designed to Rialtoto process 683 tons of waste per day.

However, it failed to perform to design standards and was closed down. The Rialto facility

defaulted on its bond payments and is in the process of being liquidated. [4]The Hydro Thermal

Upgrading (HTU) process uses superheated water to produce oil from domestic waste.[5]A

demonstration plant is due to start up in The Netherlands said to be capable of processing 64 tons

of biomass (dry basis) per day into oil.[6]Thermal depolymerisation differs in that it contains a

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hydrous process followed by an anhydrous cracking / distillation process.

History [edit]

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 sourceof fuelmore energywas required than was produced.

The first industrial process to obtain gas, diesel fuelsand 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 hydroxideadded 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 sludgeand municipal refuse by

heating the material in water, under pressure, and in the presence of carbon monoxide.

An approach that exceeded break-evenwas developed by IllinoismicrobiologistPaul Baskisin 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 itinto 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 Philadelphiaby

Thermal Depolymerization, LLC, and the first full-scale commercial plant was constructed in

Carthage, Missouri, about 100 yards (91 m) from ConAgra Foods' massive Butterballturkey plant,

where it is expected to process about 200 tonsof turkeywaste into 500 barrels (79 m3) of oil per
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day.

Theory and process [edit]

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,[7]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 volumeto around 250 C. 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 areremoved, and the hydrocarbons are sent to a second-stage reactor where they are heated to 500

C, 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 offalas 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 orwoodgasfor 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
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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 ethanoland biodieselfrom 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, soybeansand 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 poisonsand difficult-to-destroy biological agents such

as prions.[citation needed]

Feedstocks and outputs with thermal depolymerization [edit]

Ave rage TDP Feedstock Outputs[8]

Fe edstock Oils Gases Solids (mostly carbon based) Wate r (Steam)

Plastic bottles 70% 16% 6% 8%

Medical waste 65% 10% 5% 20%

Tires 44% 10% 42% 4%

Turkey offal 39% 6% 5% 50%

Sewage sludge 26% 9% 8% 57%

Paper (cellulose) 8% 48% 24% 20%

(Note: Paper/cellulose contains at least 1% minerals, which was probably grouped under carbon
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solids.)

Carthage plant products [edit]

As reported on 04/02/2006 by Discover Magazine, a Carthage, Missouriplant 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 oilfraction, 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[9]

Output Material % by Weight

Paraffins 22%

Olefins 14%

Naphthenes 3%

Aromatics 6%

C14/C14+ 55%

100%

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 inwastewatertreatment, as a fertilizer, or as a

fuel similar to coal.
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Advantages [edit]

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.[citation needed]It can also safely remove heavy metalsfrom 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).

Potential sources of waste inputs [edit]The United States Environmental Protection Agencyestimates that in 2006 there were 251 million

tons of municipal solidwaste, or 4.6 pounds generated per day per person in the USA.[10]Much of

this mass is considered unsuitable for oil conversion.

Limitations [edit]

The process only breaks long molecular chains into shorter ones, so small molecules such ascarbon dioxideor methanecannot 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 tariffscheme. This also increases the overall efficiency of the process (already said to be
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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 millsor as boilerfuel. Energy

cropsconstitute another potentially large feedstock for thermal depolymerization.

Current status [edit]

Reports in 2004 claimed that the Carthage facility was selling products at 10% below the price of

equivalent oil, but its production costs were low enough that it produced a profit. At the time it was

paying for turkey waste (see also below).

The plant then consumed 270 tons of turkey offal (the full output of the turkey processing plant)and 20 tons of egg production waste daily. In February 2005,[11]the Carthage plant was producing

about 400 barrels per day (64 m3/d) of crude oil.

In April 2005 the plant was reported to be running at a loss. Further 2005 reports summarized

some economic setbacks which the Carthage plant encountered since its planning stages. It was

thought that concern over mad cow disease would prevent the use of turkey waste and other

animal products as cattle feed, and thus this waste would be free. As it turned out, turkey wastemay still be used as feed in the United States, so that the facility must purchase that feed stock at

a cost of $30 to $40 per ton, adding $15 to $20 per barrel to the cost of the oil. Final cost, as of

January 2005, was $80/barrel ($1.90/gal).

The above cost of production also excludes the operating cost of the thermal oxidizer and

scrubber added in May 2005 in response to odor complaints (see below).
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A biofuel tax credit of roughly $1 per US gallon (26 /L) on production costs was not available

because the oil produced did not meet the definition of "biodiesel" according to the relevant

American tax legislation. The Energy Policy Act of 2005specifically added thermal

depolymerization to a $1 renewable diesel credit, which became effective at the end of 2005,

allowing a profit of $4/barrel of output oil.

Company expansion [edit]

The company has explored expansion in California, Pennsylvania, and Virginia, and is presently

examining projects in Europe, where animal products cannot be used as cattle feed. TDP is also

being considered as an alternative means for sewage treatment in the United States.[12]

Smell complaints [edit]

The pilot plant in Carthage was temporarily shut down due to smell complaints. It was soonrestarted when it was discovered that few of the odors were generated by the plant.[13]

Furthermore, the plant agreed to install an enhanced thermal oxidizer and to upgrade its air

scrubbersystem under a court order.[14]Since the plant is located only four blocks from the

tourist-attracting town center, this has strained relations with the mayor and citizens of Carthage.

According to a company spokeswoman, the plant has received complaints even on days when it is

not operating. She also contended that the odors may not have been produced by their facility,

which is located near several other agricultural processing plants.[15]

On December 29, 2005, the plant was ordered by the state governor to shut down once again

over allegations of foul odors as reported by MSNBC.[16]

As of March 7, 2006, the plant has begun limited test runs to validate it has resolved the odor

issue.[17]
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As of August 24, 2006, the last lawsuit connected with the odor issue has been dismissed and the

problem is acknowledged as fixed.[18]In late November, however, another complaint was filed over

bad smells.[19]This complaint was closed on January 11 of 2007 with no fines assessed.[20]

Status as of February 2009 [edit]

A May 2003 article in Discover magazine stated, "Appel has lined up federal grant money to help

build demonstration plants to process chicken offal and manure in Alabama and crop residuals

and grease in Nevada. Also in the works are plants to process turkey waste and manure in

Colorado and pork and cheese waste in Italy. He says the first generation of depolymerization

centers will be up and running in 2005. By then it should be clear whether the technology is as

miraculous as its backers claim."[21]

However, as of August 2008, the only operational plant listed at the company's website is the initial

one in Carthage, Missouri.[22]

Changing World Technology applied for an IPOon August 12; 2008, hoping to raise $100

million.[23]

The unusual Dutch Auctiontype IPO failed possibly because CWT has lost nearly $20 million with

very little revenue.[24][25]

CWT, the parent company of Renewable Energy Solutions, filed for Chapter 11bankruptcy. No

details on plans for the Carthage plant have been released.[26]

In April 2013, CWT was acquired by a Canadian firm, Ridgeline Energy Services, based in

Calgary.[27]

Similar technologies [edit]

Plasma Convertersuse powerful electric arcs to reduce and extract energy from waste.
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See also [edit]

Staged reforming

References [edit]

1. ^"Biomass Program, direct Hydrothermal Liquefaction" . US Department of Energy. EnergyEfficiency and Renewable Energy. 2005-10-13. Retrieved 2008-01-12.

2. ^Demirba, Ayhan (2005-10-07). "Thermochemical Conversion of Biomass to Liquid Products in the

Aqueous Medium" . Energy Sources(Taylor Francis) 27(13): 12351243.

doi:10.1080/009083190519357 . Retrieved 2008-02-05.

3. ^Zhang, Yuanhui; Gerald Riskowski and Ted Funk (1999). Thermochemical Conversion of Swine

Manure to Produce Fuel and Reduce Waste . University of Illinois. Retrieved 2008-02-05.

4. ^Sforza, Teri (2007-03-14). "New plan replaces sewage sludge fiasco" . Orange county register.

Retrieved 2008-01-27.

5. ^de Swaan Arons, Jakob; H. van derKooi and Wei Feng. "Hydrothermal Upgrading of Biomass" .

University of Delft. Retrieved 2008-02-05.

6. ^Goudriaan, Frans; Naber, Jaap and van den Berg, Ed. "Conversion of Biomass Residues to

Transportation Fuels with th HTU Process" . Retrieved 2008-01-12.

7. ^The description of the operation of the process, including temperatures, pressures, and time, has

been adapted from the description inBrad Lemley (May 2003). Anything Into Oil. Discover. See

also the description of the operation of the process in Appel et al., published U. S. patent application

US 2004/0192980 , publication date September 30, 2004.

8. ^The data on the outputs for the various feedstocks, except for cellulose, is taken fromBrad

Lemley (May 2003). Anything Into Oil. Discover. The same data, with additional data for cellulose,

is found in Appel et al., published U. S. patent application US 2004/0192980 , published

September 30, 2004.
http://pdfcrowd.com/http://pdfcrowd.com/redirect/?url=http%3a%2f%2fen.wikipedia.org%2fwiki%2fThermal_depolymerization&id=ma-140802170413-64213e12http://pdfcrowd.com/customize/http://pdfcrowd.com/html-to-pdf-api/?ref=pdfhttp://en.wikipedia.org/w/index.php?title=Thermal_depolymerization&action=edit&section=14http://en.wikipedia.org/w/index.php?title=Thermal_depolymerization&action=edit&section=15http://en.wikipedia.org/wiki/Staged_reforminghttp://www1.eere.energy.gov/biomass/pyrolysis.html#thermalhttp://www.ingentaconnect.com/content/tandf/ueso/2005/00000027/00000013/art00005http://en.wikipedia.org/wiki/Digital_object_identifierhttp://dx.doi.org/10.1080%2F009083190519357http://www.age.uiuc.edu/bee/RESEARCH/tcc/tccpaper3.htmhttp://www.ocregister.com/ocregister/news/local/article_1620010.phphttp://www.dct.tudelft.nl/ttf/biomass.htmhttp://www.nvrd.nl/nvrd/proceedings/downloadProceedings.asp?filename=618085%20Paper.pdf&filesize=85441http://discovermagazine.com/2003/may/featoil/http://www.google.com/patents?id=VrGfAAAAEBAJhttp://discovermagazine.com/2003/may/featoil/http://www.google.com/patents?id=VrGfAAAAEBAJ


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9. ^"A PONA classif ication of the TDP 40 oil is shown below in Table 2.[. .] The oil classif ication is

useful for predicting fuel performance when used in combustion, e.g. as a diesel fuel replacement.

The classification is also a useful prediction for fuel refiners or blenders in determining product

distribution in a refinery or specialty chemical plant." Converting turkey offal into bio-derived

hydrocarbons oil (pdf) (Accessed January 7, 2008)

10. ^Municipal Solid Waste - Basic Facts

11. ^Spragins, Elyn (1 February 2005). "A Turkey in your Tank" . Fortune Magazine(Time Inc.).Retrieved 2008-10-15.

12. ^Kantor, Andrew (2004-01-23). "Killing germs, reducing waste, making oil: TDP might be the next

big thing" . USA Today. Retrieved 2007-02-21. "The City of Philadelphia currently turns a lot of its

sewage sludge into landfill. (All together now: Eww.) But working with Changing World, the city is

planning a TDP project to divert that sludge and whatever pathogens are living in it away from

the land and into oil."

13. ^Reported by the Kansas City Star, April 12, 2005. The Kansas City Star website has since

archived this article: Kansas City: Search results

14. ^In the circuit court of Jasper country, Missouri, at Carthage

"The company said it has finished installation of a thermal oxidizer and upgraded odor scrubber

system that were ordered as part of a consent agreement with the city and the Missouri attorney

general's office." City questions RES

15. ^"A plant spokeswoman, Julie Gelfand, tells the Pitch that repeated odor complaints have been

lodged on days when the plant wasn't in operation or when wind conditions were inconsistent with

the complaints." Fowl & Crude16. ^"A foul-smelling plant that turns turkey byproducts into fuel oil was ordered closed by the governor

Wednesday until the company finds a way to clear the air. " Turkey-oil plant closed due to foul

odors.

17. ^"An experimental plant that turns turkey byproducts into fuel oil can resume normal operations for

15 days to test whether new equipment solves a problem with bad smells that prompted the state to

shut it down in December.Kansascity.com
http://pdfcrowd.com/http://pdfcrowd.com/redirect/?url=http%3a%2f%2fen.wikipedia.org%2fwiki%2fThermal_depolymerization&id=ma-140802170413-64213e12http://pdfcrowd.com/customize/http://pdfcrowd.com/html-to-pdf-api/?ref=pdfhttp://en.wikipedia.org/wiki/Chemical_planthttp://ergosphere.files.wordpress.com/2007/04/cwt_genconflasvegas3_3_04.pdfhttp://www.epa.gov/epaoswer/non-hw/muncpl/facts.htmhttp://money.cnn.com/magazines/fsb/fsb_archive/2005/02/01/8250633/index.htmhttp://www.usatoday.com/tech/columnist/andrewkantor/2004-01-22-kantor_x.htmhttp://en.wikipedia.org/wiki/USA_Todayhttp://nl.newsbank.com/nl-search/we/Archives?s_dispstring=(turkey-to-oil)%20AND%20date(2005)http://www.ago.mo.gov/lawsuits/2005/050605rescarthage.pdfhttp://www.joplinglobe.com/story.php?story_id=188739&c=87http://www.pitch.com/Issues/2005-11-24/news/feature_4.htmlhttp://www.msnbc.msn.com/id/10636943http://www.kansascity.com/mld/kansascity/news/local/14040813.htm


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18. ^"The last lawsuit left from a dispute over odors from a plant that converts turkey waste into fuel oil

was dismissed Thursday after the facility fixed its odor problems. " Last lawsuit dropped in Carthage

turkey plant odor case

19. ^Belleville.com

20. ^News Release 012 - MoDNR

21. Ânything Into Oil. Discover magazine

22. ^Changingworldtech.com23. ^News.Cnet.com

24. Êarth2tech.com , changing world IPO is a no go

25. ÛK.reuters.com

26. ^"Breaking News: RES parent company files for bankruptcy" . Carthagepress.com. Retrieved

2009-03-07.

27. ^"Canadian firm acquires Carthage RES plant" . Carthage Press. 2013-04-13. Retrieved 2013-04-

23.

Further reading [edit]

Brad Lemley (May 2003). Anything Into Oil Discover.

Peter Fairley (November 2008). Go Green This Thanksgiving: Turn Turkey Guts Into Oil.

(Update) Discover.

Yuanhui Zhang, Ph.D., P.E. (PI), Gerald Riskowski, Ph.D., P.E., Ted Funk, Ph.D., P.E. (1999).

Thermochemical Conversion of Swine Manure to Produce Fuel and Reduce Waste.

University of Illinois.

Stefan Lovgren (July 2, 2004) Pig Manure Converted to Crude Oil National Geographic News

write up about the above paper.

Andrew Kantor (January 22, 2004). CyberSpeak: Killing germs, reducing waste, making oil.

USA Today.
http://pdfcrowd.com/http://pdfcrowd.com/redirect/?url=http%3a%2f%2fen.wikipedia.org%2fwiki%2fThermal_depolymerization&id=ma-140802170413-64213e12http://pdfcrowd.com/customize/http://pdfcrowd.com/html-to-pdf-api/?ref=pdfhttp://en.wikipedia.org/w/index.php?title=Thermal_depolymerization&action=edit&section=16http://www.dfw.com/mld/dfw/business/15352930.htmhttp://www.belleville.com/mld/belleville/news/state/16029275.htmhttp://www.dnr.mo.gov/newsrel/nr07_012.htmhttp://discovermagazine.com/2003/may/featoil/http://www.changingworldtech.com/where/index.asphttp://news.cnet.com/8301-11128_3-10017027-54.html?tag=nefd.tophttp://earth2tech.com/2009/02/13/changing-world-ipo-is-a-no-go/http://uk.reuters.com/article/governmentFilingsNews/idUKN0130987720090201http://www.carthagepress.com/news/x1362397575/BREAKING-NEWS-RES-parent-company-files-for-bankruptcyhttp://www.carthagepress.com/article/20130416/NEWS/130419181/1001/NEWS?rssfeed=truehttp://discovermagazine.com/2003/may/featoilhttp://discovermagazine.com/2008/nov/25-anything-into-oil/http://www.age.uiuc.edu/bee/RESEARCH/tcc/tccpaper3.htmhttp://en.wikipedia.org/wiki/University_of_Illinoishttp://news.nationalgeographic.com/news/2004/07/0701_040702_pigoil.htmlhttp://en.wikipedia.org/wiki/National_Geographic_Newshttp://www.usatoday.com/tech/columnist/andrewkantor/2004-01-22-kantor_x.htmhttp://en.wikipedia.org/wiki/USA_Todayhttp://home.everestkc.net/tasir/CWT/Depolymerization.htm


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[hide]VTE

Theo Asir (December 1, 2003). Depolymerization Field Observation Report (observation of

Carthage, Missouri plant).

Thermal depolymerization process

Fortune Magazine Article (February 2005) update on the Changing World Technologies

plant.

Bioenergy

Biofuels

Alcohol Algae fuel Bagasse Babassu oil Biobutanol Biodiesel

Biogas Biogasoline Corn s tover Ethanol(cellulosic mixtures)

Methanol Stover Straw Vegetable oil Wood gas

Energy from

foodstock

Barley Cassava Grape Hemp Maize Oat Palm oil Potato

Rapeseed Rice Sorghum bicolor Soybean Sugarcane

Sugar beet Sunflower Wheat Yam

Non-food

energy crops

Arundo Big bluestem Camelina Chinese tallow DuckweedJatropha curcas Millettia pinnata Miscanthus giganteus

Switchgrass Wood fuel

Technology

Bioconversion Biomass heating systems Biorefinery

FischerTropsch process Industrial biotechnology Pellets(mill

stove) Thermal depolymerization

Concepts

Cellulosic ethanol commercialization Energy content of biofuel

Energy crop Energy forestry EROEI Food vs. fuel

Sustainable biofuel

Categories: Pyrolysis Energy development Industrial processes

Biodegradable waste management Thermal treatment Petroleum technology

Plastic recycling
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