ISIS Report 29/11/05
Waste Plastics into Oil
What if the mountains of plastic wastes that blight our
landscapes and beaches spewing poisons from incinerators and landfills could
be transformed overnight into combustible gas and diesel oil. Dr.
Mae-Wan Ho
A fully referenced version
of this paper is posted on ISIS members’ website. Details here
As the price of oil and gas soar, alternative energy sources are rapidly becoming
cost-effective by comparison. One attractive option that has emerged is diesel
oil from waste plastics.
Chinese oil refinery used waste plastics
The first report of turning plastic wastes into oil came in 2001 from the People’s
Daily, China’s English language newspaper [1]. An oil refinery in
Hunan province had succeeded in processing 30 000 tonnes of plastic wastes into
20 000 tonnes of gasoline and diesel oil that satisfied the provincial standards.
Wang Xu, who built the refinery in 1999, started experimenting with waste plastic
processing in the 1980s, and later teamed up with Hunan University doctoral
tutor Zeng Guangming who gave him scientific advice on decomposing plastic wastes.
This may be one reason why China has been importing enormous amounts of plastic
wastes (“Redemption from the plastic
wasteland”, this series).
Although no details were given on the technology used, it is most likely based
on thermal depolymerization, a process for breaking down organic wastes under
heat and pressure into light crude oil, which has been studied in the West since
the 1970s [2]. It mimics the natural geological processes thought to be involved
in producing fossil fuels. Under high pressure and heat, long chain polymers
of carbon, hydrogen and oxygen decompose into short-chain petroleum hydrocarbons
in a matter of hours. Until quite recently, however, the artificial process
was far from energy-efficient, as more energy had to be put in than was produced,
and the product, a crude oil, was also full of impurities.
In the 1980s, Illinois microbiologist Paul Baskis in the United States modified
the process to produce a lighter, cleaner oil, but failed to convince investors
until 1996, when a company called Changing World Technologies began development
with Baskis to make the process commercially viable [3].
Changing World Technologies opened a demonstration plant in Philadelphia, Pennsylvania,
and in 2001, the first full-scale plant was built in Carthage, Missouri, and
the company applied to patent a “thermal conversion process” (TCP) for converting
organic wastes, such as pig manure, into oil and other products.
Turkey offal into diesel oil and fertilizer
The first pilot TCP plant was built to treat turkey offal, which it succeeded
in converting to diesel fuel, along with fertilizer and absorbent carbon. The
full-scale plant, located in Carthage, Missouri, can process up to 191 tonnes
of turkey wastes a day [4].
(The TCP plant looks like a small refinery operation, and it is likely that,
given the earlier report from China, existing oil refineries could easily be
converted into TCP plants.)
Processing is divided into two main stages. In the first stage, the turkey
waste is pulped into a slurry and heated at a pressure of 40 bar (1 bar ~ 1
atmosphere) to 200-300C. The solids are separated and the liquid is ‘flashed’
to a lower pressure to separate the oil from water. The oil is then heated in
a second stage reactor to a higher temperature around 500C to ‘crack’ it into
light hydrocarbon oil, leaving a solid product. Recovered from the first stage
are solid minerals and a liquid concentrate rich in nitrogen and other nutrients.
From the second stage, fuel gas, carbon, and diesel oil are recovered. The fuel
gas produced is a mixture of methane, carbon monoxide, carbon dioxide and low
molecular weight hydrocarbons. The oil contains predominantly straight chain
hydrocarbons with a chain length between 15 and 20.
One advantage of TCP is that it claims to break down the prion proteins associated
with mad cow disease - which survives normal boiling or autoclaving - and is
therefore suitable for treating slaughterhouse wastes, disinfecting the wastes
at the same time that biodiesel, gas fuels and fertilizers are produced. However,
no evidence was presented for this claim.
The process also appears to be energy efficient and environmentally friendly
in a lifecycle audit [5]. The audit did not include energy and carbon emission
costs involved in building the TCP plant, however.
From an input of 191 tonnes of wet turkey offal per day (50 percent moisture)
plus 3.0 tonnes of sulphuric acid and 91.2MJ of grid electricity, the output
are 2506 GJ of diesel oil, 274GJ fuel gas, 30.6 tonnes liquid nitrogen fertilizer,
7.5 tonnes mineral fertilizer, 6.1 tonnes of carbon and 79.9 m3 waste water.
There are no discharges to the atmosphere from the plant during the processing.
The only gaseous product is the medium to high heat-content fuel-gas (heating
values between 9 and 19 MJ/m3) used for
heat in processing, or as fuel for a boiler or turbine. Emissions from the turbine
have been independently verified to be in compliance with the Clean Air Act.
The oil product is typically a light hydrocarbon similar to diesel fuel that
could be used as heating oil or converted into higher value products.
There are two types of fertilizers/soil amendments produced by the TCP: Res
minerals and Res liquid concentrate [6]. Both are produced from food and agricultural
wastes such as turkey offal, feathers, bones, pig manure, used cooking oil and
slaughterhouse waste. Res minerals consist of N, P K, and Ca, representing nearly
30 percent of the total fertilizer, the rest is made up of organic material
such as carbohydrates, amino acids, fatty acids and moisture (40 percent).
The Res liquid concentrate is a mixture rich in nitrogen that also contains
phosphorus, potassium, sulphur and trace minerals, similar to a fish emulsion,
and is rich in amino acids and derivatives.
The products leave the unit at about 100C after heat recovery. With full heat
recovery, the overall energy efficiency could be above 85 percent based on the
heating value of the products and the dry weight of the feedstock. In other
words, it generates 467 percent more energy than it takes to produce it; except
that this figure leaves out energy needed to construct the TCP plant.
For comparison, biofuel from maize crops, according to the latest study, generates
at best only 35 percent more energy than it takes to produce [7], and has the
added disadvantage that growing crops for biofuels uses up valuable agricultural
land that could produce food.
Each tonne wet weight of turkey wastes processed was estimated to save more
than a tonne of carbon dioxide equivalents in green house gas emissions, largely
on account of the savings due to substituting for diesel.
There were various setbacks experienced by the Carthage plant [3]. The plant
was shut down for a period due to reported noxious smell, though it could not
be confirmed to have come from the plant. In addition, the oil produced by the
plant did not qualify as a biofuel for tax purposes, and so the plant did not
qualify for the $42 per barrel of No. 2 oil in tax credits. But the definitions
have since been changed to allow explicitly for diesel generated from thermal
depolymerization process, taking effect at the end of 2005.
Despite the setbacks, the process appears cost effective. In January 2005,
the Carthage plant was producing refined No. 2 oil (used for diesel and gasoline)
for about $80/barrel, compared to the on-highway prices for diesel in the US
at $101/barrel or $2.40/gallon (8 August 2005), which is likely to continue
to rise.
Bench pilot for plastic wastes
Changing World Technologies aims to tackle plastic wastes next [7]. A major
source of plastic wastes comes from some 15 million cars that are de-registered
in the US each year, 95 percent shredded to recover metals, leaving a ‘shredder
residue’ of fluff 25 percent by weight that’s buried in landfills. Most of this
two million tonnes of shredder residue is plastic: polyurethane foams and rubber.
In a pilot bench experiment, the company demonstrated the conversion of two
different mixtures of shredder residue (see Table 1) into a variety of products
including light hydrocarbon oil. The two mixtures of shredder residues differed
both in their composition of solids and in the amount of moisture. They were
first screened to remove a small portion of the inorganic material (mainly iron
oxides and small pieces of glass and rocks) that would not fit in the bench-scale
reactor.
Table 1. Average composition of shredder residue (SR) #1 and #2
| Content (weight %) |
SR #1 |
SR #2 |
Moisture
|
10.0 |
34.0 |
Solids
Plastics
Foams
Rubber & Elastomeres
Fabric
Wires
Fines
Miscellaneous
|
90.0
28.4
6.9
32.3
10.6
7.6
3.8
19.4
|
66.0
3.3
9.8
17.4
8.6
1.6
43.5
15.8
|
The bench reactors were capable of operating at temperatures above 900C and
pressures above 138 atmospheres.
In SR #1 the polymers that make up the rubber and plastics were mostly transformed
into the hydrocarbon oil, which is similar to diesel, with a small fraction
going to the 2nd stage gas. The first stage gas was primarily carbon
dioxide. But the second stage was rich in hydrocarbons and would support combustion.
It had a heating value of approximately 80 percent that of natural gas. The
yield of hydrocarbon oil was 41.9 percent of the total input mass or 65 percent
of the initial weight of solids. Less than 20 percent of the solids went into
the carbon matrix.
For SR #2, which contained more water, oil yield was 29.8 percent of overall
mass, or 52.7 percent of the initial solid matter. The carbon matrix yield was
32 percent of the solids.
The two samples of fuel gas were quite similar, as were the diesel oil obtained.
Shredder residue is often contaminated with toxic chemicals such as PCB (polychlorinated
biphenyls) and heavy metals. The samples treated were spiked with water containing
PCB. The PCB was largely degraded in the process. The heavy metals arsenic,
barium cadmium, chromium, copper, lead, mercury, silver and zinc were detected,
mainly concentrated in the carbon matrix. Selenium was not detected. Small amounts
of zinc were detected in the oil from SR #1, and zinc, chromium and lead in
oil from SR #2. Practically no bromine (from polybrominated flame retardant)
were found in oils, but ended up in the water and the carbon matrix.
TCP and similar processes look promising both for extending the use of oil
by recycling mixed plastics wastes and for turning food and agricultural wastes
into renewable fuel and saving on greenhouse gas emissions, though certain questions
remains unanswered.
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