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BUSINESS

LATER THIS MONTH, a new Dutch com-pany called BioMCN plans to open a large-scale facility that will convert glycerin into methanol. The first of its kind, the plant is intended to take advantage of a surplus of glycerin in Europe and the rest of the world.

This global excess is the result of the ex-plosive growth of biodiesel as a renewable alternative to traditional diesel fuel. For ev-ery 10 gal of biodiesel manufactured from vegetable oil, 1 gal of glycerin is produced on the side.

Although making chemicals out of glyc-erin looked like a sure thing a few years ago, today it seems anything but. Even though the surplus is real and growing, glycerin has proven to be a volatile commodity that experiences huge price swings. At least one big glycerin-based chemical project has been shelved and two others are signifi-cantly delayed. Perhaps more ominously, questions are emerging about glycerin’s long-term supply security.

In the U.S., the biodiesel boom began in 2004, when then-president George W. Bush signed a jobs creation law that includ-ed a generous tax incentive to companies

that produce biodiesel. According to the National Biodiesel Board, U.S. biodiesel output tripled from 2004 to 2005 to 75 mil-lion gal. It continued to skyrocket for the next three years, reaching 700 million gal in 2008.

Government mandates and incentives in Europe and Southeast Asia spawned similar biodiesel run-ups. Depending on the region, the raw material was soybean oil, rapeseed oil, or palm oil. But the result was the same: React more and more veg-etable oil with methanol to create biodiesel and you get increasing amounts of coprod-uct glycerin.

Darol Brown, U.S. head of the oleo-chemicals consulting firm HBI, has been in the glycerin business since 1985. When he started, glycerin was a fairly staid by-product of making soap and oleochemicals. Today, Brown says, close to two-thirds of world glycerin production comes from biodiesel. Combined U.S. and European output last year was 1.2 million metric tons, almost triple what it was in 2004.

Around 2005, chemical companies began eyeing glycerin’s three-carbon back-bone and wondering what they could do

with it. In 2006, both Dow Chemi-cal and Solvay announced plans to use glycerin as a raw material for

epichlorohydrin, an epoxy raw material that is now derived from propylene via a somewhat inefficient multistep process.

Only months later, Dow and other com-panies, including Archer Daniels Midland and a joint venture between Cargill and Ashland, started revealing plans to make propylene glycol from glycerin instead of the petrochemical propylene oxide.

Other companies began researching glycerin-based chemistry. The Brazilian pet-rochemical maker Quattor announced that it would make propylene out of glycerin. France’s Arkema proposed generating acryl-ic acid and acrolein from glycerin. Hunts-man Corp. developed glycerin carbonate to complement its line of alkylene carbonates. And the industrial gases producer Linde an-nounced a pilot plant to generate hydrogen using glycerin as the source.

Start-up companies also got into the fray. Senergy Chemical was created by a group of propylene glycol consumers to commercialize glycerin-to-propylene gly-col technology developed by researchers at the University of Missouri. Glycos Biotech-nologies was formed around glycerin con-version technology from Rice University.

AS WOULD BE EXPECTED from the bio-diesel explosion, glycerin prices fell, bot-toming out in March 2007 at 32 cents per lb for refined glycerin in the U.S. But in mid-2007, a jump in rapeseed oil prices sud-denly rendered Europe’s biodiesel industry uncompetitive, and plants started shutting down. Glycerin shot up around the world in response. According to HBI’s quarterly market report, the U.S. price of refined glycerin hit 90 cents per lb in March 2008 and stayed there for several months.

Cargill and Ashland got cold feet. In a financial report issued in April of last year, Ashland disclosed that the partners had suspended their plan to build a plant in Eu-rope to convert glycerin into 65,000 metric tons per year of propylene glycol. The reason, according to Ashland, was “persis-tently high glycerin input costs.”

Other projects also stumbled. Senergy’s website hasn’t been updated in years. The company doesn’t provide a phone num-ber, and an e-mail requesting information bounced back as undeliverable.

GLYCERIN GAMBITMaking chemicals from the

BIODIESEL BY-PRODUCT proves challengingMICHAEL MCCOY, C&EN NORTHEAST NEWS BUREAU

RENEWABLES DEBUT BioMCN’s glycerin-to-methanol plant starts up this month.

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For more C&EN coverage of chemical sustainability, go to www.cen-online.org/sustainability/sustainability.html.

GOING GREEN

17WWW.CEN-ONLINE.ORG JUNE 1, 2009

Dow hatched plans to make propylene glycol from glycerin by contracting with its Dow Haltermann Custom Processing subsidiary to carry out the conversion at a facility in Houston. Dow called the product PGR, for propylene glycol renewable, and predicted that it would help customers reduce their use of fossil fuels and other finite resources.

But although Dow still has PGR for sale, the company has stopped producing it because of glycerin volatility and other economic aspects of the technology. Dow says it is evaluating ways to improve the cost picture, even though no decisions have been made.

Likewise, Dow and Solvay have pushed back their plans for glycerin-to-epichlo-rohydrin facilities. As recently as last Oc-tober, Dow said it was on target to build a 150,000-metric-ton plant in China’s Shanghai Chemical Industry Park by 2011. The project is now on hold. “Dow made this decision in light of the economic downturn and the significant drop in forecasted market demand,” a spokesman says. The company says it is “firmly commit-ted to this project” but won’t say when it will be revived.

And Solvay says its facility, a 100,000-metric-ton plant originally set for Thailand by the end of this year, is now being targeted for comple-tion in the second half of 2011.

Although Dow and Solvay cite market conditions for their delays, Brown says glycerin’s price swings concern many companies. Even Solvay acknowledges that “glycerin price volatility is going to stay and represents a risk for our investment.”

With the exception of one small Dow plant in Europe, all glycerin is a by-product of other processes. Its main source, bio-diesel production, is subject to the vagaries of government renewable fuel policies and is a slave to vegetable oil prices. “People come to me all the time and ask what I think the price of glycerin will be in one year,” Brown says. “It’s a hard question.”

Yet some glycerin chemistry projects are proceeding. ADM is advancing a plan to

make propylene glycol and ethylene glycol out of glycerin and sorbitol, a corn-derived polyol. The company affirms to C&EN that it is building a 100,000-metric-ton plant in Decatur, Ill. Start-up is set for the third quarter.

And Rob Voncken, chief executive offi-cer of BioMCN, reports that his company’s facility in Delfzijl, the Netherlands—a ret-rofitted conventional methanol plant—is on target to open this month. At full capac-ity the plant will be able to make 200,000 metric tons of methanol per year, requiring about 250,000 metric tons of glycerin.

UNLIKE FIRMS such as Dow and ADM that are preserving glycerin’s carbon structure, BioMCN is gasifying glycerin and using the individual carbons to make methanol. The economics look better than they did

a year ago. The price of refined glycerin has dropped by 50% since last summer, although it is still above the lows it reached in early 2007.

BioMCN’s facility can consume crude glycerin, which sells for about 12 cents per lb in Europe. That’s still more than the Eu-ropean methanol price of about 9 cents per lb, but thanks to biofuel-use targets in the European Union’s Renewable Energy Di-rective, Voncken says that he can price his biomethanol on par with more expensive bioethanol.

And just getting off the ground as a developer of glycerin-derived chemicals is Glycos, the Rice spin-off. The Houston-based firm was launched last year to com-mercialize technology developed in the lab of Ramon Gonzalez, a professor of chemi-

cal and biomolecular engineering. Accord-ing to the company, Gonzalez’ microbes can convert glycerin to lactic acid, succinic acid, 1,2-propanediol, 1,4-butanediol, etha-nol, and other chemicals.

Richard Cilento, an entrepreneur who joined Glycos two months ago as chairman, acknowledges that glycerin can be a volatile commodity. But he points out that Glycos is able to start with cheap, bottom-of-the-barrel glycerin that is contaminated with sugars, methanol, or solids. “Our bugs and fermentation can deal with that,” he says.

According to Cilento, Glycos is in ne-gotiations with several biodiesel facilities looking to upgrade their by-product glyc-erin into environmentally friendly chemi-cals. “They’ll make biodiesel just to make the glycerin to make the green chemical,” he predicts. “We hope to be in production

next year.”HBI’s Brown

acknowledges that biodiesel producers typically have excess glycerin on their hands, but he isn’t con-vinced that this state of affairs will remain. “I would argue that bio-diesel in the long haul is probably not the fuel of the future,” he says. “It is probably an interim fuel that will be replaced by more ef-ficient fuels.”

Already in the U.S., the big meat company Tyson Foods is work-ing with a technology

partner to turn fats into a renewable fuel with advantages over biodiesel, including the absence of glycerin. In Europe, the world’s largest biodiesel production cen-ter, the fuel is coming under scrutiny in the food-versus-fuel debate. And in Southeast Asia, the burning of rain forests to plant biodiesel-yielding crops has created an outcry.

For now, though, even with the bad economy, glycerin-based chemistry is a tantalizing prospect. Unrefined glycerin from biodiesel plants, Brown says, is often sold as animal feed or burned for its fuel value. And even when refined, it’s still cheaper than many other chemical raw materials out there. That’s a reality that en-terprising chemical executives can’t seem to pass up. ■

OH

HO HO

Glycerin

OH

O

OO

Glycerin carbonate

O

OH

Acrylic acid

O

Cl

Epichlorohydrin

OH

HO

Propylene glycol

Propylene

Hydrogen

H2Methanol

CH3OH

ADMDowAshland/Cargill

Quattor

Linde

BioMCN

Huntsman

ArkemaDowSolvay

BRANCHING OUT Glycerin is a potentially versatile chemical feedstock.