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Legal Aspects of Incident Investigation

 Suzanne Shelley
Guest Columnist and Freelance Technical Writer
Suzanne Shelley is a Manhattan-based freelance technical writer specializing in
science, engineering and technology (Email: suzanneashelley at yahoo.com). A 16-year
veteran and former Managing Editor of Chemical Engineering magazine, Suzanne no
w writes about a broad array of engineering and business topics related to the c
hemical, petroleum refining, pharmaceutical and related industries, for both cor
porate clients and technical trade magazines. She currently serves as Contributi
ng Editor to several magazines, including Chemical Engineering, Chemical Enginee
ring Progress, Turbomachinery International, and Pharmaceutical Commerce. Suzann
e holds a B.S. in geology (honors) from Colgate University, and an M.S. in geolo
gy from the University of South Carolina (Columbia).
Published: January 8, 2008
Biodiesel: The Road Ahead
Market drivers
The benefits of biodiesel
Improving air quality
Technology innovations
World-class facilities
Advanced reactor designs
Novel catalysts
Pursing non-traditional feedstocks
Sidebar: Converting a glut of glycerin into propylene glycol
In the U.S. alone, biodiesel capacity has grown more than seven-fold since 2004.
Today, growing demand for this renewable transportation fuel is helping to driv
e a flurry of grassroots expansions and technology innovations worldwide, includ
ing advanced reactor designs, novel catalysts, and other process improvements.
Market Drivers
With concern over greenhouse gas emissions and global warming reaching a fever p
itch, crude oil prices expected to average $75/barrel throughout 2008, and much
of the world s crude oil still coming from geopolitically unstable regions of the
globe, it s no surprise that worldwide demand for, and production of, the biofuels
ethanol and biodiesel have been on the rise, as cleaner-burning alternatives to
traditional petroleum-derived transportation fuels.
Compared with ethanol, biodiesel is currently produced and used on a far smaller
scale worldwide. However, if recent market and technological activity around bi
odiesel are any indication, biodiesel is clearly poised to occupy an increasingl
y larger portion of the renewable barrel in the years to come.
For instance, to meet growing demand, biodiesel capacity in the U.S. has grown m
ore than seven-fold in recent years, and European capacity (which already tops U
.S. capacity) has been also been rising steadily.
In 2004, just 22 plants in the U.S. were producing biodiesel at a rate of roughl
y 157 million gallons per year. By June 2007, the number of plants had grown to
105, bringing U.S. nameplate capacity to 1.4 billion gallons per year, according
to the National Biodiesel Board (NBB; Jefferson City, Mo.; www.biodiesel.org),
the industry trade group representing U.S. biodiesel producers.
In addition, according to NBB s June 2007
industry update, an additional 97 facilities are currently under construction i
n the U.S. (representing both new capacity and capacity expansions). Should all
of these facilities ultimately come to fruition, they could result in an additio
nal 1.9 billion gallons per year of U.S. biodiesel capacity over the next two ye
ars.
(For comparison, as of mid-2007, there were 119 ethanol plants in the U.S., with
a combined production capacity of more than 6.2 billion gallons/year, according
to the Renewable Fuels Association (RFA; Washington, D.C.; www.ethanolrfa.org),
the trade association for the U.S. ethanol industry. An additional 86 ethanol r
efineries or expansions are under construction, representing another 6.4 billion
gallons/yr of new capacity that is anticipated to come online by 2009. Worldwid
e, 2006 ethanol capacity (including the U.S.) was 13.5 billion gal/yr, according
to RFA.)
In 2006, conventional diesel fuel made up roughly 22% of the ground transportati
on fuel pool used in the U.S., and

Download maps of existing biodiesel facilities and new construction.

"diesel makes up 22% of the ground transportation fuel in the U.S., and biodiese
l made up just 0.5% of the highway diesel fuel consumed in the U.S. in 2006", ac
cording to Kreido Biofuels (Camarillo, Calif.; www.kreido.com).
biodiesel made up just 0.5% of the highway diesel fuel used, according to Kreido
Biofuels (Camarillo, Calif.; www.kreido.com). However, that figure is on the ri
se, driven in part by the U.S. Energy Policy Act of 2005, which mandates an incr
ease in renewable fuel use to 7.5 billion gallons/yr by 2012 (up from 4 billion
gallons/year in 2006). The bill supports the alternative fuel industry with vari
ous production incentives, such as tax credits and other government subsidies.
As noted earlier, European biodiesel production has also been growing a swift cl
ip. For instance, in 2005, the biodiesel production capacity among the so-called
EU-25 countries was 960 million gallons./yr a 65% increase over the 2004 total
of 570 million gallons/yr, according to trade group The European Biodiesel Board
(EBB; Brussels, Belgium; www.ebb-eu.org). By 2006, European capacity for biodie
sel had grown to 1,832 million gallons/yr. According to EBB, most of the biodi
esel production can be attributed to the leading EU-15 member countries, but the
number of EU countries with a biodiesel industry has nearly doubled in recent y
ears, from 11 in 2005, to 20 in 2006.
In Europe, strong growth in biodiesel production is being driven in part by the
2003 European Biofuels Directive concerning biofuels (2003/30/EC Article 3(1)),
which aims to replace:
· 5.75% of the overall motor fuel (diesel and gasoline) pool in Europe with biofue
ls by 2010 (creating estimated demand for 4.2-5.4 billion gallons/yr of biofuels
)
· 10% by 2020 (creating estimated biofuel demand of 11.4 billion gallons/yr)
· 25% by 2030, (creating estimated biofuel demand of 22.5 billion gallons/yr)
These goals will spur significant growth, considering that in 2007, biofuel use
(including both ethanol and biodiesel) in Europe accounted for less than 2% of t
he current 300-million-m.t./yr transportation fuel consumed.
The Benefits of Biodiesel (Back to Top)
As an alternative to conventional petroleum-derived diesel fuel, biodiesel is co
mprised of fatty acid methyl esters (FAME), which are produced via the catalytic
transesterification of various renewable feedstocks, ranging from vegetable oil
s (including soybean, canola, palm, rapeseed and other vegetable oils) to variou
s types of animal fats (even recycled

Biodiesel is produced via the catalytic transesterification of various renewable

feedstocks, most commonly vegetable oils and animals fats. Soybean crops (shown
here) are one of the most widely used feedstocks.
Source: U.S. Dept. of Agriculture
cooking grease). Biodiesel is produced by reacting the triglycerides in these re
newable feedstocks with an alcohol (typically methanol or ethanol), in the prese
nce of an alkaline catalyst (most often sodium hydroxide or sodium methylate, al
though several novel alternatives are discussed below). The reaction yields meth
yl esters (biodiesel) and byproduct glycerin.
Byproduct glycerin is widely used during the manufacture of soaps, cosmetics, ph
armaceuticals and other products. Today, the rapid expansion in biodiesel produc
tion worldwide has saturated the glycerin market and the anticipated glut of gly
cerin has spurred parallel technological innovation among a growing number of ch
emical companies, who are racing to commercialize routes to convert byproduct gl
ycerin into the widely used commodity chemical propylene glycol (as a renewable
alternative to the traditional petroleum-derived feedstock propylene glycol).
For more on this, see the sidebar box.
Biodiesel is biodegradable and non-toxic, is essentially free of sulfur and arom
atic compounds, and burns more cleanly than its fossil-fuel-derived counterpart,
according to the NBB. It can be blended (in any amount) with traditional diesel
, or used on its own, in existing diesel (compression-ignition) engines with lit
tle or no modifications. Biodiesel blends are denoted as BXX, with the XX repres
enting the percentage of biodiesel in the blend. Today, most biodiesel sold in t
he U.S. is B20 (a blend of 20% biodiesel and 80% conventional diesel fuel).
In addition to its favorable environmental profile compared to traditional petro
leum-derived diesel fuel (discussed in greater detail below, in the section call
ed improving Air

Quality), biodiesel offers some other positive performance attributes, as well.

These include increased cetane (the measure of the combustion quality of the fue
l), higher fuel lubricity (which lowers engine friction), higher oxygen content,
and the highest Btu content of any alternative fuel, which makes it a "preferre
d blending stock to produce ultraclean diesel," according to the NBB. A 2000 rep
ort produced for the U.S. Department of Energy (DOE) by the National Renewable E
nergy Laboratory (Golden, Colo.; www.nrel.gov), entitled "Biodiesel: the Clean,
Green Fuel for Diesel Engines," (DOE/GO-102000-1048, May 2000; http://www.ott.do
e.gov/biofuels/environment.html), shows that even 1% biodiesel blends can improv
e lubricity by up to 30%, thereby reducing engine wear and tear and enabling eng
ine components to be used longer.
As for cetane numbers, the International Energy Agency (IEA; Paris; www.iea.org)
, says that in the U.S., typical petroleum-derived #2 diesel fuel has cetane num
bers in the range of 40-45, while for #1 diesel, cetane numbers of 48-42 are typ
ical. By comparison, biodiesel from vegetable oils can have cetane numbers rangi
ng from 46-52, while animal-fat-derived biodiesel can have cetane numbers as hig
h a 56-60, according to a 216-page report published in 2004 by the International
Energy Agency ("Biofuels for Transport: An International Perspective;" http://w
ww.iea.org/textbase/nppdf/free/2004/biofuels2004.pdf; page 110).
Similarly, biodiesel has the highest energy balance of any liquid fuel currently
produced. For instance, for every unit of energy used to make biodiesel, 3.24 u
nits are gained, according to the U.S Dept. of Energy (DOE; Washington, D.C.; ww
w.doe.gov).
The NBB emphasizes that despite lingering confusion to the contrary biodiesel is
"not an experimental fuel." Rather, the group notes that biodiesel "has been pr
oven to perform similarly to diesel in more than 50 million successful road mile
s in virtually all types of diesel engines, countless off-road miles and marine
hours." And today, in the U.S. alone, more than 600 major fleets (ranging from s
chool buses and commercial vehicles to government and military fleets) now use d
iesel blends that incorporate the cleaner-burning fuel. Through all of this expe
rience, B20 has demonstrated similar fuel consumption, horsepower, torque, and h
aulage rates as conventional diesel fuel.
One potential downside is that pure biodiesel (B100) has a solvent effect, which
can lead to the release of deposits that may have accumulated on tank walls, pi
pes and engine components. To keep such sludge from clogging filters, the NBB re
commends that precautions should be taken to replace fuel filters until such bui
ldup is eliminated, but notes that this issue is less prevalent with B20 blends,
and says that there is no evidence that lower-level blends (such as B2) have ex
perienced filter pluggage.
This solvency effect has also been shown to soften and degrade certain types of
incompatible elastomers and natural rubber compounds over time (i.e., those used
for certain fuel hoses and fuel pump seals), although this effect is lessened a
s the biodiesel blend level is reduced. The group notes that extensive experienc
e with B20 has found that no changes to gaskets or hoses are necessary, and note
s that many OEMs have switched to components that are more compatible with biodi
esel.
Improving Air Quality (Back to Top)
As a petroleum-free transportation fuel, biodiesel is less toxic than table salt,
and biodegrades as fast as sugar according to the NBB. The trade group notes tha
t today, biodiesel is the only alternative fuel to have fully completed the Tier
I and Tier II health-effects testing requirements of the 1990 Clean Air Act Ame
ndments. Because it contains no sulfur or aromatic compounds, tailpipe exhaust
from diesel engines firing biodiesel contains no sulfate emissions, and has redu
ced levels of unburned hydrocarbons, carbon monoxide and particulate matter, com
pared to diesel-fired exhaust.
In its 2002 report, entitled A Comprehensive Analysis of Biodiesel Impacts on Exh
aust Emissions, can be found at www.epa.gov/otaq/models/analysis/biodsl/p02001.pd
f), the U.S. Environmental Protection Agency (EPA; Washington, D.C.; www.epa.gov
) surveyed a large body of biodiesel emissions studies and compiled average stat
istics related to both regulated and non-regulated air pollutants. These average
values (in terms of emissions reductions compared to petroleum-derived diesel),
are shown in Table 1.
Table 1: Average Biodiesel Emissions Compared to Conventional Diesel
Emission Type
B100 (100% Biodiesel)
B20 (20% Biodiesel)
Regulated
Total unburned hydrocarbons -67% -20%
Carbon Monoxide -48% -12%
Particulate matter -47% -12%
NOx +10% +2% to -2%
Unregulated
Sulfates -100% -20% *
PAH
(polycyclic aromatic hydrocarbons) ** -80% -13%
nPAH (nitrated PAHs) ** -90% -50% ***
Ozone potential of speciated HCs -50% -10%
Notes:
* Estimated from B100 results
** Average reduction across all compounds measured
*** 2-nitroflourine results were within test method variability
Source: EPA's 2002 report entitled "A Comprehensive Analysis of Biodiesel Impact
s on Exhaust Emissions,"
www.epa.gov/otaq/models/analysis/biodsl/p02001.pdf as posted on the Biodisel Boa
rd's website (http://www.biodiesel.org/pdf_files/fuelfactsheets/emissions.pdf)
While EPA s 2002 analysis showed that NOx emissions in tailpipe emissions can some
times increase with biodiesel use (depending on the engine family and testing pr
ocedures), the fact that biodiesel contains no sulfur allows a variety of cataly
tic NOx-control technologies to be used, without the poisoning threat that fuel-
borne sulfur can pose. Similarly, a number of companies have developed additives
to reduce NOx emissions in biodiesel blends, according to NBB.
As for carbon dioxide (CO2) and other greenhouse gas (GHG) emissions, a variety
of studies shown that net GHG emissions reductions from rapeseed-derived biodies
el range from 40% to 60% compared to conventional diesel fuel in light-duty comp
ression-ignition engines, according to the 216-page IEA report (p. 63) cited ear
lier.
In addition to its potential to improve air quality, the increased use of biodie
sel is also expected to provide some advantages for the economy. For instance, i
n the U.S. alone, the biodiesel industry is expected to add $24 billion to the U
.S. economy between 2005 and 2015, and create more than 40,000 jobs, according t
o Joe Jobe, CEO of the NBB (in remarks made before the U.S. House Small Business
Committee on May 3, 2007). That group s stated goal is to have biodiesel make up
5% of the U.S. diesel fuel market by 2015. Says Jobe: That may not sound like a l
ot, but if 5% biodiesel were added to all of today s on-road diesel in the U.S., i
t would displace 1.85 billion gallons of petroleum-derived diesel.
Technology Innovations (Back to Top)
As noted earlier, commercial-scale processes to produce biodiesel react any numb
er of renewable feedstocks based on vegetable oils and animal fats with ethanol
or methanol in the presence of a catalyst. In the U.S., fuel-grade biodiesel mus
t be produced in compliance with strict industry specifications (ASTM D6751), to
ensure proper performance. While the processes for producing biodiesel are prov
en, the biodiesel industry is always looking toward the next-generation of biodi
esel production routes. For instance, today, a
Growing worldwide demand for biodiesel has spurred numerous grassroots expansion
s, and is driving a number of reactor and catalyst innovations, and other proces
s advances.
Source: National Biodiesel Board
number of novel catalysts and advanced reactor designs and non-traditional feeds
tocks are being investigated and commercialized, to enable greater feedstock fle
xibility, increase conversion rates and biodiesel yield, allow the reactions to
be carried out under increasingly mild operating conditions (i.e., at lower pres
sures and temperatures), and reduce capital and operating costs.
Many of these promising new advances are discussed later in this article. As wit
h most burgeoning technologies, costs tend to fall as additional facilities are
built, technologies are proven and optimized, and economies of scale are exploit
ed.
Speaking for the entire industry at the NextEnergy Biodiesel Summit held in Detr
oit in March 2007, Donnell Rehagen, NBB s chief operations officer said: Our goals
for next generation biodiesel are to optimize biodiesel s fatty acid profile for c
old flow and stability, optimize agriculture for higher production of oils and f
ats from traditional crops, and develop additional, non-traditional crops such a
s micro-algae for biodiesel, and even crops that can be grown on marginal land o
r Brownfield sites.
World-class Facilities (Back to Top)
While it is not possible to profile all of the many grassroots plants that are u
nder development today, a variety of world-class deals are discussed here. Many
of these are pushing the envelope in terms of nameplate capacity, and incorporat
ing newer (so-called second-generation) biodiesel technologies.
Lurgi AG (Frankfurt, Germany; www.lurgi.com) has built what it claims is the wor
ld s largest biodiesel plant (although larger pending plants are discussed below)
in Piesteritz, (East) Germany, for Neckermann-Renewables GmbH (Wittenberg, Germa
ny), and parent company Global Alternative Energy (GATE) GmbH. The facility, whi
ch started up in June 2007, is producing 200,000 tons/yr of biodiesel from rapes
eed oil, plus 20,000 tons/yr of pharmaceutical-grade glycerin, and 300,000 tons/
year of colza meal.
According to Lurgi, the plant is the first in Germany to integrate field-to-fuel
-pump biodiesel production (including seed processing, pressing and oil extracti
on, processing the crude rapeseed oil, and producing biodiesel). In Europe, Neck
ermann runs several biodiesel plants with total capacity of more than 350,000 to
ns/year.
Lurgi is also constructing an even-bigger two-train biodiesel plant in the port
of Rotterdam for biodiesel producer Biopetrol Industries AG (Zug, Switzerland, w
ww.biopetrol-ind.com). Once online in the third quarter of 2007, annual capacity
will be 400,000 tons/yr of biodiesel (with anticipated scale up to 650,000 m.t.
/yr), plus 60,000 tons/yr of pharmaceutical-grade glycerin and 60,000 ton/yr of
fatty acids for re-esterification. This plant will be the third biodiesel plant
for Biopetrol (the other two are in Brandenburg, Germany, and Rostock, Germany),
bringing its total biodiesel capacity to 750,000 tons/yr of biodiesel in 2007,
and 1 million tons/yr by 2008.
Lurgi is also building a 200,000-m.t./yr biodiesel plant for The Victoria Group
(Novi Sad, Serbia), to be located in Sid, near Belgrade. The plant is slated for
startup in 2007.
Since July 2005, Lurgi has been awarded nine biodiesel contracts, for a total ca
pacity of 1 million m.t./yr. Once these facilities all come online, the company
claims that 60-70% of global biodiesel output will be produced using Lurgi techn
ology.
When it came online in May 2007, the 170,000-m.t./year biodiesel plant at Neste
Oil s petroleum refinery in Porvoo, Finland, became the first commercial-scale fac
ility to use the company s proprietary NExBTL (for next-generation biomass-to-liqui
d ) process. A second, identical facility is under construction at the refinery, a
nd is slated to come online in 2008 .
Source Neste Oil Corp.
The scale of these world-class facilities continues to grow. For instance, speci
alty and intermediate chemical company Ineos Enterprises (Hampshire, U.K.; www.i
neos.com) is in the process of building a new 500,000-ton/yr biodiesel plant at
its petroleum refinery in Grangemouth, Scotland (startup is slated for 2008). Th
e company is also in the process of doubling the output of its biodiesel plant a
t Baleycourt (France), which has been producing biodiesel for more than 10 years
, and it is building a new biodiesel facility at its site at Zwijndrecht, in the
Port of Antwerp (Belgium). That facility will have a capacity of 500,000 m.t./y
r once it starts up in 2009. The company s stated goal is to achieve at least 1.2
million m.t./yr of biodiesel by 2020, and 2 million m.t./yr by 2012.
In May 2007, Neste Oil Corp. (Helsinki, Finland; www.nesteoil.com) brought onlin
e a 170,000-m.t./yr biodiesel plant at its Porvoo, Finland, petroleum refinery.
That facility marks the commercial debut of the company s proprietary NExBTL for ne
xt generation biomass-to-liquid process, which can use a flexible mix of vegetabl
e oil and animal fat to produce premium biodiesel, says the company. A second,
identical plant is being built alongside the original facility at Porvoo, and it
is slated for completion by late 2008. To ensure a captive supply of rapeseed o
il for the Porvoo facility, Neste also signed a contract in mid-2007 with Raisio
plc (Raisio, Finland; www.raisio.com) to buy 10,000 tons/yr of that renewable f
eedstock.
Meanwhile, following the signing of a Memorandum of Understanding (MOU) in July
2005, Neste Oil and Total S.A. (France; www.total.com) are evaluating the possib
ility of jointly building a large-scale biodiesel facility at one of Total s petro
leum refineries. The proposed facility, which is being given a target startup da
te of 2008, would also use the Neste s NExBTL process.
In April 2007, ConocoPhillips LP (CP; Houston, Tex.; www.conocophillips.com) and
Tyson Foods (Springdale, Ark.; www.tyson.com) which claims to be the world s larg
est producer and marketer of chicken, beef and pork, and produces large volumes
of various types and grades of animal fats announced a strategic alliance to com
mercialize a proprietary thermal depolymerization process (developed by CP) that
produces a product called renewable diesel (RD), using a mix of beef, pork and po
ultry fats supplied by Tyson s rendering plants and traditional hydrocarbon feedst
ocks.
According to CP, renewable diesel and biodiesel are not the same. While they are
produced from similar feedstocks, they are produced using different processing
methods that yield chemically different products. Because RD is chemically equiv
alent to conventional diesel, CP says it can be shipped via conventional pipelin
es, along with other fuels.
CP s thermal depolymerization process using animal fats has been successfully test
ed at the company s Whitegate Refinery in Cork, Ireland (which has also been produ
cing 1,000 barrels per day 150,000 liters of renewable diesel from soybean oil s
ince late 2006).
Commercial-scale production of renewable diesel from animal fats is expected to
be carried out at several CP refineries by the end of 2007, and could reach 175
million gallons/year by mid-2009, says the company. The company s goal is to have
renewable diesel ultimately comprise 3 vol.% of its total biodiesel production.
Meanwhile, in June 2007, Tyson also announced a 50/50 joint venture with Syntrol
eum (Tulsa, Okla.; www.syntroleum.com). The new venture, dubbed Dynamic Fuels LL
C, will produce a range of synthetic fuels, including renewable diesel, using Sy
ntroleum s patented Biofining process. The first facility (at a yet-to-be-decided
site in south-central U.S.) will produce about 75 million gallons/yr of syntheti
c fuel, with startup slated for 2010.
Similarly, UOP LLC (Des Plaines, Ill.; www.uop.com) and Eni S.p.A. (Milan, Italy
) have jointly developed a process to produce what they call Green Diesel, a prem
ium, high-cetane diesel blending component for refineries from various vegetable
oils such as soybean, palm or rapeseed oil. The process developers christened th
eir product Green Diesel to distinguish it from biodiesel, which is obtained by re
acting vegetable oil with methanol (the Green Diesel process is described below)
.
According to UOP, Green Diesel has cetane values of 70-90 (by comparison, conven
tional petroleum-derived diesel and biodiesel blends found at the pump today hav
e cetane values ranging from 40-60), providing significant blending benefits for r
efiners seeking to enhance existing diesel fuels and expand the diesel pool.
As reported by Chemical Engineering magazine (May 2007), the Green Diesel produc
t is produced by reacting vegetable oils with hydrogen to remove oxygen from the
oil via decarboxylation and hydrodeoxygenation. The reactions occur simultaneou
sly, at roughly 300 deg C and 400-600 psi, over a proprietary fixed-bed catalyst
.
All of the olefinic bonds are saturated, so that the product consists only of no
rmal paraffins, plus about 5% byproduct propane. In a second step, the paraffins
are hydroisomerized to obtain isoparaffins and produce a fuel with good cold-fl
ow properties. This step also produces a small amount of naphtha. The Green Dies
el yield is 86-98%, and hydrogen consumption is 1.5-3.8 wt.%, according to the p
rocess developers.
UOP and Eni have tested the process, which UOP says integrates seamlessly into ex
isting refinery operations, and they offer it for license.
In June 2007, UOP and Eni announced that Eni will build a production facility in
Livorno, Italy, which will produce 6,500 barrels per day of Green Diesel using
UOP s Ecofining (catalytic hydroprocessing) technology. It is expected to come onlin
e in 2009.
Meanwhile, in late 2006, Uhde GmbH (Dortmund, Germany; www.uhde.biz) was awarded
a contract from Thai Oleochemicals Co. (Bangkok, Thailand) and Thai Fatty Alcoh
ols Company Ltd. for the construction of an integrated biodiesel plant, slated f
or startup from late 2007 to early 2008. It will produce 200,000-m.t./year of bi
odiesel, 100,000 m.t fatty alcohols and 30,000 m.t./yr of glycerin from a variet
y of vegetable oils. To be located in Map Ta Phut, Thailand, it will be that cou
ntry s first biodiesel plant, and its first to make refined fatty alcohols. The fee
dstock-flexible facility will use process technology licensed from AT-Agrar-Techn
ik GmbH & Co. KG (Schlaitdorf, Germany; www.biodieselanglangenbau.de) to transes
terify the feedstocks with methanol at room temperature using a potassium hydrox
ide catalyst.
In 2006, Chevron USA (San Ramon, Calif.; www.chevron.com) created a new biofuels
business unit. One of its first initiatives, through its Chevron Technology Ven
tures division, was to acquire a 22% interest in a large biodiesel facility in G
alveston, Tex. The facility, operated by BioSelect Fuels LLC (Houston; www.biose
lectfuels.com) started up in May 2007, with 20-million-gallons/year, but is expe
cted to undergo expansion to 110 million gallons/yr by 2010, says the company.
Advanced Reactors (Back to Top)
As for advanced reactor designs, Kreido Biofuels (Camarillo, Calif.; www.kreido.
com) has developed a new, high-shear reactor, whose commercial debut is being ma
de in the production of biodiesel. The company claims that its STT (for spinning
tube-in-tube ) process intensification reactor can speed chemical reaction rates b
y up to three orders of magnitude.
The patented Shock Wave Power Reactor (SPR) from Hydro Dynamics is said to cut t
he residence time required for the transesterification of vegetable oils and ani
mal fats from hours to seconds, using what the company calls process intensificat
ion through controlled cavitation. It made its commercial debut in 2007 at a gras
sroots biodiesel plant operated by Memphis Biofuels LLC
Source: Hydro Dynamics
Biodiesel producer Foothills Bio-Energies (Lenoir, N.C.; www.foothillsbio-energi
es.com) is currently using Kreido s STT reactor to add one million gal/yr of capac
ity to its existing 1-million-gal/yr capacity (which it produces by transesterif
ying vegetable oil using a sodium hydroxide catalyst).
Kreido's patented STT reactor consists of a 4.5-in-dia. cylindrical vessel (whic
h functions as a stator tube), and an inner rotating cylinder (which functions a
s the rotor) that is driven at up to 5,000 rpm by a variable-speed motor. Reacta
nts are fed into the narrow annulus between the rotor and stator at one end of t
he reactor, and exit at the other end, with a residence time of less than 1 seco
nd. According to its inventor, the STT reactor not only accelerates chemical rea
ction rates (especially those processes that have mass transfer, temperature con
trol, viscosity or solids issues), but can also increase selectivity, conversion
rate and yield.
The novel reactor is said to achieve these advantages by inducing faster, more-u
niform mixing in the narrow annual gap between the stationary stator and the rap
idly rotating, concentric, internal rotor, so the reactants move as a coherent t
hin film in a high-shear field. The equipment is available at working volumes fr
om 1.5 milliliters to 1 liter. A 1-liter system can produce as much as 50 millio
n pounds/year, says the company, with larger production capacities available thr
ough the use of parallel STT reactors.
Similarly, Hydro Dynamics (Rome, Ga.; www.advancedbiofuel.net) has developed the
patented ShockWave Power Reactor (SPR), which, according to the company, cuts t
he residence time required for the transesterification of vegetable oil or anima
l fats from more than an hour to just several seconds through process intensific
ation.
The company claims to have harnessed the destructive force of hydrodynamic cavita
tion, and applied it for useful purposes, after years of intensive research. Insi
de the reactor is a cylinder that contains numerous cavities, and rotates at abo
ut 3,600 rpm. As the liquids pass through the SPR, tiny bubbles continuously for
m and collapse generating shockwaves. This controlled cavitation breaks the fluids
into microscopic droplets (thereby increasing the overall surface area of the l
iquids and achieving higher mass-transfer rates, and more-efficient mixing and h
eating compared to traditional reactors that rely on bladed or impeller designs,
says the company). Faster reaction times also help to reduce unwanted saponific
ation and emulsification during the transesterification of vegetable oils and an
imal fats, according to Hydro Dynamics.
The SPR is making its commercial debut at a grassroots biodiesel plant that was
started up in 2007 by Memphis Biofuels LLC (Memphis, Tenn.; www.memphisbiofuels.
com). Using the new reactor, Memphis Biofuels is able to drive the transesterifi
cation reaction used to produce biodiesel in a matter of seconds. The 50-million
-gallon/year facility is currently using a 3-gallon SPR to produce 100 gallons/m
inute of biodiesel. In general, the SPR can be used in either batch or continuou
s mode, to produce up to 150-million gallons/yr of biodiesel, according to its m
anufacturer.
Novel Catalysts (Back to Top)
In an attempt to improve yield and allow for more favorable processing condition
s, a variety of process developers are pursuing (and commercializing) advanced p
rocesses based on novel catalysts. For instance, in late 2006, engineering and c
onstruction firm Technip (Paris; www.technip.com) was awarded two contracts by P
aris-based Diester Industrie S.A. for two new biodiesel plants in France. The fi
rst is for a new production unit near Bordeaux. The second will double the capac
ity at Diester s existing facility near Rouen. Each facility will have a capacity
of 250,000-m.t./year, and both are slated to go online by the end of 2007. Both
facilities will use process technology from Axens (Rueil-Malmaison France; www.a
xens.com), and vegetable oil as the feedstock.
Technip has already built three other biodiesel units for Diester in France (at
Rouen, Séte and Compiegne), and is currently constructing another 250,000-m.t./yr
unit, in Montoir-de-Bretagne (France), which is also slated for startup in 2007.
The 160,000-m.t./yr facility at Séte is the first commercial plant to use the newE
sterfip-H biodiesel process, which was initially developed by the Institut Françai
s du Pétrole (IFP; Rueil-Malmaison, France; www.ifp.fr), and commercialized by Axe
ns. The Esterfip-H process is a fixed-bed process that is based on a heterogeneo
us catalyst, rather than the traditional Esterfip process, which uses a homogene
ous catalyst and has been in commercial use since 1992 (the first commercial app
lication of the traditional, homogeneous-catalyzed Esterfip process is at Dieste
r Industrie s Venette, France, site).
The newer heterogeneous catalyst in use at Diester s Séte location is a spinel mixed
oxide of two non-noble metals, as reported in Chemical Engineering magazine (Oc
tober 2004). According to Axens, the continuous Esterfip-H process carries out t
he transesterification reaction at a higher temperature than that used by the ho
mogenous-catalyzed process, with an excess of methanol, which is later removed b
y vaporization and recycled to the process. The use of the solid, heterogeneous
catalyst enables a significant reduction in waste streams compared to other proce
sses, says the company. This is possible by eliminating the need for catalyst rec
overy and aqueous neutralization and washing steps (and the waste streams associ
ated with them) that are required when biodiesel is produced using conventional
homogeneous catalysts (most often sodium hydroxide or sodium methylate).
In addition, Axens says the methyl ester purity exceeds 99%, with yields close t
o 100%, the glycerin byproduct that is produced using the Esterfip-H process has
a purity on the order of 98%, compared to about 80% using the homogenous-cataly
st routes.
Perstorp Oxo (Perstorp, Sweden; www.perstorp.com) has also selected Axens Esterfi
p-H biodiesel technology for a 160,000-ton/year plant it is building in Stenungs
und, Sweden (about 50 km north of Gothenburg). That facility is slated to come o
nline by late 2007.
As noted earlier, when it comes to biodiesel production, the desired fatty acid
methyl esters (FAME) are typically made by the transesterification of vegetable
oils with an alkaline catalyst. As an alternative, Kansai Chemical Engineering C
o. (Amagasaki, Japan; www.kce.co.jp/English/En-index.html), in cooperation with
Japan s Kobe University, has developed a process that uses whole-cell biocatalysis
for the transesterification of vegetable oils. The novel process, as reported i
n Chemical Engineering (March 2005), is said to be simpler and more cost-effecti
ve than the traditional catalytic approach to biodiesel production, because it d
oes not generate the large volumes of wastewater that are typically produced usi
ng traditional alkali-catalyzed routes. Because no free acids or catalyst residu
e remains, no purification process is required for the product FAME or the glyce
rin byproduct, according to the process developer.
Other novel catalysts are also being pursued. For instance, according to reporti
ng in the December 2005 issue of Chemical Engineering magazine, Toshikuni Yonemo
to, professor of chemical engineering at Tokohu University (Sendai, Japan) says
that to sidestep the need to remove alkaline catalysts from co-product glycerin,
and treat alkali-laden wastewater prior to disposal, biodiesel routes based on
supercritical alcohol or enzymes have been attempted but not successfully deploy
ed, mainly because of difficulties that arise from the need for high-pressure/te
mperature equipment or highly stable and active enzymes.
Yonemoto s research group has developed an alternative catalytic process for biodi
esel is said to eliminate the problems associated with alkali catalysts, while o
perating at mild (50 deg C and 1 atm) conditions. In the new process, a mixture
of vegetable oil, animal fat, and alcohol (ethanol or methanol) is fed to a fixe
d-bed reactor that is packed with a cation-exchange resin, which serves as the c
atalyst to esterify the free fatty acids.
According to the magazine, the product is then pumped to a second fixed-bed reac
tor that is packed with an anion-exchange resin, which catalyzes the transesteri
fication of the triglycerides. The transesterification is carried out in a pair
of reactors, which alternate in either reactor mode or catalyst-regeneration mod
e. The catalyst, once contaminated by byproduct glycerin, is regenerated by rins
ing with an organic acid solution and then an alkaline solution. The researchers
are optimizing the process and working to commercialize it.
Meanwhile, in October 2006, Verenium (formerly Diversa Corp.; San Diego, Calif.;
www.verenium.com), announced that its Purifine enzyme had received EPA approval
for use in non-food applications, including its use to increase the efficiency
of oilseed processing during the production of biodiesel fuel. According to the
company, enzymes have not been widely used in the vegetable-oil-refining process
es. However, Verenium s new enzyme is said to reduce the need for harsh chemicals
to remove unwanted oil phospholipids (to de-gum the oil). This improves biodiesel
yield and quality without requiring major changes to conventional processing con
ditions, says the company.
In August 2007, Chemical Engineering reported another catalyst breakthrough rela
ted to biodiesel fuel production. The new catalyst, developed by Victor Lin, a c
hemistry professor at Iowa State University (Ames, Iowa; www.iastate.edu) was de
veloped as an alternative to the soluble, sodium methoxide catalyst that is now
widely used for the transesterification of oils during biodiesel manufacture.
Lin s catalyst consists of 1-micrometer-dia. honeycomb spheres of mixed oxides, wh
ich incorporate both acid and base sites. According to the magazine, the acidic
sites convert the free fatty acids to biodiesel by esterification, and the base
sites convert oil to fuel by transesterification.
The catalyst is said to be preferable for animal fats (which tend to be consider
ably less costly than vegetable oils), and because it is a solid, it can be recy
cled (whereas sodium methoxide is dissolved in the process fluid). Production of
the catalyst is being scaled up by Catilin Inc. (www.catilin.com