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UOP looking to biomass catalytic pyrolysis to expand volumes of renewable hydrocarbon fuels

21 July 2012

Honeywell’s UOP—a major international supplier and licensor of technology for petroleum refining, gas processing, petrochemical production and major manufacturing industries—has also been an early leader in developing technologies for the production of renewable drop-in hydrocarbon fuels.

The company currently has three major initiatives in that area: the commercialization of the hydrotreating UOP/Eni Ecofining process to convert fats, greases and non-edible, second-generation natural oils to Honeywell Green Diesel (earlier post); Green Jet Fuel (earlier post); and its joint venture with Ensyn Corporation, Envergent Technologies, for the pyrolytic conversion of forest and agricultural waste residues to a liquid renewable oil and subsequent upgrading (earlier post). It’s the last initiative that UOP currently believes has a good opportunity for delivering high volumes of renewable liquid hydrocarbon fuels, according to Jim Rekoske, vice president and general manager of Honeywell’s UOP Renewable Energy and Chemicals business unit.

Fats and greases and inedible oils are opportunity feedstocks, but the US supply of fats and greases is probably on the order of less than 10 million barrels, closer to 1-2 million barrels on an annual basis. That’s a big sum. But in the context of worldwide demand it’s nowhere near what we need. When you sit down and think about how to scale, if that doesn’t scale to the full extent that we want it to, what does? So we looked at solid biomass. That’s really why we were driven to it. We recognize the need to expand the feedstock pool. There’s not a single silver bullet.

—Jim Rekoske

Green Diesel. The hydroprocessing technology used in the Green Diesel process—and also used for Green Jet—is relatively mature, Rekoske noted. UOP is moving faster commercially on the Green Diesel side, with the Diamond Green project with Darling International and Valero Energy nearly complete. (Earlier post.) That plant, in Norco, Louisiana, will have the capacity to produce more than 9,300 barrels per day of renewable diesel product.

Hydroprocessing
In a review of hydroprocessing technologies published in a new paper in the ACS journal Energy & Fuels, Mustafa Al-Sabawi and Jinwen Chen of CanmetENERGY, Natural Resources Canada, note that:
“Hydroprocessing of oils, whether petroleum- or biomass- derived, entails hydrotreating and/or hydrocracking technologies. The primary objective of conventional hydrotreating is to remove impurities present in petroleum feedstocks, such as sulfur and nitrogen, via the addition of hydrogen. In the case of biomass-derived feedstocks, hydrotreating would also be used to remove the high content of oxygen impurities found in such feedstocks.”
“Hydrocracking, on the other hand, is a process that combines catalytic cracking and hydrogenation, wherein hydrocarbon feedstocks are cracked in the presence of hydrogen to produce lighter fuel products. Hydrocracking typically employs different types of catalysts than hydrotreating, as well as more severe operating conditions (higher temperatures and pressures).”
—Al-Sabawi and Chen (2012)

UOP also has licensed plants in Italy and Portugal to use the EcoFining technology.

More recently, UOP signed an agreement to license technology to Emerald Biofuels LLC to produce Honeywell Green Diesel at another facility in Louisiana. (Earlier post.) Emerald is expected to use the UOP/Eni Ecofining process technology to produce 85 million gallons per year of Honeywell Green Diesel from non-edible, second-generation oils and animal fats.

Under the current set of prices and slate of feedstocks available, you can produce Green Diesel fuels from renewable fats and greases at a price competitive with petroleum diesel—provided you get feedstock at the price needed. The refining technology is probably about $4-5/barrel more expensive to make renewable diesel out of fats and greases...there’s not a lot of extra cost on the refining technology. Really the question is can the feedstocks be procured at a price competitive to petroleum oil.

Obviously, we want to make the window of circumstances as wide open as possible. We are working on the catalysts to make the process as inherently efficient as possible. On the diesel side, that’s going to be hard to do. There are two drivers to the cost of production: the feedstock cost and the yield of product. Our technology produces about 90 to 95 gallons [of renewable diesel] for every 100 gallons of raw feedstock that comes in. It’s pretty doggone efficient; it’s hard to make dramatic changes in overall efficiency of that process.

—Jim Rekoske

Another area of refining cost is the hydrogen consumption, which is required for taking the oxygen out of the natural feedstocks. Lowering hydrogen costs would thus lower production costs. However, right now in North America, Rekoske noted, it’s pretty inexpensive, since the majority of hydrogen is produced from natural gas and natural gas prices are low.

We think that [making hydrogen] is a better use of natural gas, instead of worrying about CNG and LNG vehicles. We see it as a great enabler to allow us to revitalize the chemical industry and the renewable fuel industry in the US.

—Jim Rekoske

RIMPAC and Green Fleet demo
The US Navy’s Great Green Fleet demonstration, currently underway as part of RIMPAC 2012, will consume 700,000 gallons of hydro-treated renewable diesel fuel (HRD76) and 200,000 gallons of hydro-treated renewable aviation fuel (HRJ5)—both fuels a 50/50 blend of traditional petroleum-based fuel and biofuel comprising of a mix of waste cooking oil and algae oil.
Held every two years by Commander, US Pacific Fleet (PACFLT), Rim of the Pacific (RIMPAC) is a multinational maritime exercise that takes place in and around the Hawaiian Islands.
The RIMPAC 2012 exercise, the 23rd in the series that began in 1971, is scheduled from 27 June 27 to 7 August. Twenty-two nations, 40 surface ships, 6 submarines, more than 200 aircraft and 25,000 personnel will participate.
Units from Australia, Canada, Chile, France, Japan, Mexico, New Zealand, Republic of Korea, Russia, Singapore, and the United States will participate. Military personnel from Colombia, India, Indonesia, Malaysia, Netherlands, Norway, Peru, Republic of Philippines, Thailand, Tonga and the United Kingdom will also participate.
The Great Green Fleet demo, part of RIMPAC 2012, is designed to show that the Navy can operate with a reduced reliance on conventional petroleum.
The US Navy aircraft carrier USS Nimitz (CVN 68) will use some 200,000 gallons of renewable aviation fuel (HRJ5), and the guided-missile cruiser USS Princeton (CG 59) and destroyers USS Chung-Hoon (DDG 93) and USS Chaffee (DDG 90) will use some 700,000 gallons of renewable diesel (HRD76).
One question is the role of the military in [renewable drop-in fuels]. I don’t think the military should be owners of refineries—why make it when you can buy it. That said, it is important to realize that someone has to step up and create a market and buy. And when it comes to jet fuel in particular, an airline is not sufficiently sound to offer that commitment. It’s not a bankable guarantee. Having a AAA-rated entity like the US government to create a market is very valuable and is extremely appropriate for what the government needs to do to move forward.
—Jim Rekoske

Envergent. Envergent Technologies uses Ensyn’s Rapid Thermal Processing (RTP) to produce bio-oil from biomass. RTP rapidly heats biomass feedstocks to approximately 500 °C in the absence of oxygen using a circulating transported fluidized bed reactor system similar to the one used in the UOP Fluid Catalytic Cracking (FCC) technology. The result is a bio-oil that—depending upon the feedstock—delivers up to 8,680 Btu per pound.

Something like 85-90% of energy process is retained in the pyrolysis liquid. It’s just a way to densify and to move the biomass into a convenient format that we know how to handle in refining technology.

—Jim Rekoske

Although bio-oil (or pyrolysis oil, or pyrolysis liquid) has the potential to be co-processed with petroleum-derived feedstocks, it presents processing challenges. It is highly viscous, corrosive, and relatively unstable. It also contains significant amounts of oxygenated compounds, including acids, aldehydes, ketones, alcohols, esters, ethers, glycols, and phenols. Upgrading thus is essential for use as a transportation fuel or blendstock.

Upgrading of bio-oil produced from biomass for various applications can be accomplished by catalytic hydroprocessing. Catalytic hydroprocessing has several advantages over other processes, such as fermentation, pyrolysis, and trans-esterification...catalytic hydroprocessing is one of the most viable options for downstream upgrading of bio-oil.

...The hydroprocessing of pyrolysis bio-oils is a very important step because upgrading pyrolysis oils often leads to the formation of significant amounts of tars, chars, and coke and to irreversible catalyst deactivation due to the high oxygen content in the feed. The elimination of oxygen compounds by hydrotreating results in hydrodeoxygenation (HDO) material that is cleaner and easier to co-process with conventional petroleum-derived vacuum gas oil (VGO) in downstream processes.

—Al-Sabawi and Chen (2012)

Challenges for the upgrading of pyrolysis oil include contiguous carbon chain length in biomass, carbon efficient condensation chemistry, and ways to avoid polymerization.

In August 2011, UOP began construction in Hawaii of a demonstration unit that will convert forest residuals, algae and other cellulosic biomass into renewable drop-in transportation fuels via a rapid pyrolysis process integrated with a catalytic upgrading process. (Earlier post.)

The Integrated Biorefinery will utilize rapid thermal processing (RTP) technology to convert biomass into a pourable, liquid bio-oil which will then be upgraded to gasoline, jet and diesel fuels using catalytic hydroprocessing technology being developed by UOP.

On the pyrolysis side, we have done the work necessary at the pilot scale to optimize the process. Simultaneously, we are building the plant in Hawaii with the help of the DOE grant. We expect that demo plant fully up and working in 2013—at that point, we will be ready for commercial sale of the technology. The end product is more like a mixture of 50% gasoline, 40% distillates, 10% LPG, and potentially C4 chemicals, things like that. It’s a really good mix and a good split of refining capacity.

We are only at the pilot scale—too early to talk about costing. We feel very confident that with biomass available at prevailing prices, we will be able to make gasoline and distillates at parity with the cost of production of gasoline and diesel at $80/barrel—cost competitive without subsidy.

This is a young field; we’ve been at this in UOP for about 6 years—that’s a very short period of time in the world of new process development, and a very short time in the world of fuels. We’re in it for the long run, we don’t expect miracles to occur. We are very happy with the progress made thus far; the combination of technology development and business development has been very encouraging for us. We’re excited to see how the industry is progressing. Yes, there are challenges, but there were challenges for last 6 years, and will be for the next 20 as well.

—Jim Rekoske

Resources

  • Mustafa Al-Sabawi and Jinwen Chen (2012) Hydroprocessing of Biomass-Derived Oils and Their Blends with Petroleum Feedstocks: A Review. Energy & Fuels doi: 10.1021/ef3006405

July 21, 2012 in Aviation, Bio-hydrocarbons, Biomass, Diesel | Permalink | Comments (2) | TrackBack (0)

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Comments

We think that [making hydrogen] is a better use of natural gas, instead of worrying about CNG and LNG vehicles. We see it as a great enabler to allow us to revitalize the chemical industry and the renewable fuel industry in the US.

At least, it's where they make their money.

Perhaps some advance like fast pyrolysis in a methane atmosphere can break the cost barrier that's keeping cellulosic biofuels in the nosebleed price realm.  It'll take something that simple to get costs down.  I don't see hydrogen qua hydrogen doing it.

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