October 2021 - Ethanol Producer Magazine by BBI International

OCTOBER 2021

BLENDS THAT CAN BEAT EVS How Mid-Levels Might Match Up PAGE 12

PLUS

Spectroscopy’s Actionable Insight PAGE 18

ACE Conference Review PAGE 24

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Contents

NUVU FUELS

SPECSHELL

ACE/ZIMMCOMM

OCTOBER 2021 VOLUME 27 ISSUE 10

DEPARTMENTS 6

EDITOR'S NOTE America's EV Future Might Be Delayed by Reality

FEATURES 12 BLENDS

Matching for More

AD INDEX/EVENTS CALENDAR

VIEW FROM THE HILL Choosing America’s Farm Fields Over OPEC Oil Fields

By Melissa Anderson

GLOBAL SCENE As Nations Seek Carbon Neutrality, Demonstrating Ethanol’s Role Is Vital BUSINESS BRIEFS

MARKETPLACE

Instant Intel

By Tom Bryan

By Brian Healy

By Jennifer Starner

PROCESS

Inline spectroscopy offers real-time feedback

By Geoff Cooper

Investigating the Effectiveness of Antibiotic Combinations Utilized in Fuel Ethanol Production

Aligning blending practices and engine tech for growth

By Tom Bryan

CONTRIBUTIONS 28 BACTERIAL CONTROL

ACE conference affirms ethanol’s ability to compete By Anna Simet

Understanding CIP Additive Packages for Ethanol Production By Lance Renfrow

EVENT

No Better Time than Now

CLEANING

SPOTLIGHTS 36 EUROFINS

Next-Level Grain Grading for Ethanol’s Next Stage By Tom Bryan

ENERTECH SOLUTIONS Lab Products Tailored for Precision By Tom Bryan

ON THE COVER In the sweet spot between E15 and E85, mid-level ethanol blends might provide a critical pathway for liquid fuels to stay competitive with electric vehicles for decades to come. Proponents of E30 believe the blend is compatible with existing engines, but flex-fuel labels are still required.

Ethanol Producer Magazine: (USPS No. 023-974) October 2021, Vol. 27, Issue 10. Ethanol Producer Magazine is published monthly by BBI International. Principal Office: 308 Second Ave. N., Suite 304, Grand Forks, ND 58203. Periodicals Postage Paid at Grand Forks, North Dakota and additional mailing offices. POSTMASTER: Send address changes to Ethanol Producer Magazine/Subscriptions, 308 Second Ave. N., Suite 304, Grand Forks, North Dakota 58203. ETHANOLPRODUCER.COM | 5

Editor's Note

America’s EV Future Might Be Delayed by Reality As clear-minded people continue asking fair questions about electric vehicles—starting with where all the green power will come from—the ironies of climate change and the realities of auto buying trends offer, at best, an inconsistent picture of the impending EV takeover. As I wrote this column in early September, General Motors had announced a multi-week shutdown of its factories— save a few—due to that outrageous microchip shortage we’ve all been hearing about. GM kept four factories running in order to not further short the already scarce inventory of American-made pickups able to tow 5,000-pound surf boats, SUVs big enough for half a soccer team, and Corvettes able to go zero to whatever in five seconds. Apparently, EV manufacturing didn’t make the cut as vehicles with throaty, liquid-fueled engines are what people actually want. At the same time, as power outages hit Louisiana and Mississippi in the wake of Hurricane Ida—which of course produced equally devastating torrential rains in the Northeast—more real-world EV concerns surfaced. As Forbes reported in a Sept. 5 piece titled "Electric Vehicles Powerless During Hurricanes," if there were any EV owners among the more than 1 million people that lost power after the storm, they may have been immobilized for days. Ida was yet another reminder of the ironic vulnerability of our electric grid in the era of climate change. It is fair to wonder, now, if the Biden administration’s call for a 50% transition to EV manufacturing by 2030 was responsible if it will put massive new pressure on our electric grid at a time when it is more susceptible to extreme weather than ever before. These are the types of questions Dave Sovereign and other American Coalition for Ethanol leaders posed during the association’s 34th annual conference in August, which we cover in “No Better Time than Now,” on page 24. It was not our intention this month to continue covering the biofuels/EV battle for the future of low-carbon transportation energy, but the topic keeps manifesting in our pages. Our cover story, “Matching for More,” on page 12, is actually a story about ethanol blending practices, but it is set against the backdrop of climate change, auto manufacturing and, yes, our ability to compete long-term with EVs. The story’s central character is Dean Drake, a former GM policy analyst who believes vehicles running on high-octane, low aromatic mid-level ethanol blends—like E30—can and should have a shared future with EVs. Producing all the ethanol needed for this envisioned future where higher ethanol blends are ubiquitous—picture 20 or 25 billion gallons per year of ethanol being produced—will demand a lot from our industry. Fortunately, production technology continues to get better over time. For example, in “Instant Intel,” on page 18, we talk to two providers of inline spectroscopy. While this technology is not a replacement for HPLC, it gives producers an inside look at fermentations, and actionable, real-time information for better results—which is what everyone wants. Enjoy the read.

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March 14-16, 2022

The Prime F. Osborn III Convention Center, Jacksonville, FL (866) 746-8385 | BiomassConference.com Entering its 15th year, the International Biomass Conference & Expo is expected to bring together more than 900 attendees, 125 exhibitors and 100 speakers from more than 40 countries. It is the largest gathering of biomass professionals and academics in the world. The conference provides relevant content and unparalleled networking opportunities in a dynamic business-to-business environment. In addition to abundant networking opportunities, the largest biomass conference in the world is renowned for its outstanding programming— powered by Biomass Magazine—that maintains a strong focus on commercial-scale biomass production, new technology, and nearterm research and development. Join us at the International Biomass Conference & Expo as we enter this new and exciting era in biomass energy.

June 13, 2022

Capturing and storing carbon dioxide in underground wells has the potential to become the most consequential technological deployment in the history of the broader biofuels industry. Deploying effective carbon capture and storage at biofuels plants will cement ethanol and biodiesel as the lowest carbon liquid fuels commercially available in the marketplace. The Carbon Capture & Storage Summit will offer attendees a comprehensive look at the economics of carbon capture and storage, the infrastructure required to make it possible and the financial and marketplace impacts to participating producers.

EDITORIAL President & Editor Tom Bryan | tbryan@bbiinternational.com Online News Editor Erin Voegele | evoegele@bbiinternational.com

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EDITORIAL BOARD

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Ringneck Energy Walter Wendland Little Sioux Corn Processors Steve Roe Commonwealth Agri-Energy Mick Henderson Aemetis Advanced Fuels Eric McAfee Western Plains Energy Derek Peine Front Range Energy Dan Sanders Jr.

From its inception, the mission of this event has remained constant: The FEW delivers timely presentations with a strong focus on commercialscale ethanol production—from quality control and yield maximization to regulatory compliance and fiscal management. The FEW is the ethanol industry’s premier forum for unveiling new technologies and research findings. The program is primarily focused on optimizing grain ethanol operations while also covering cellulosic and advanced ethanol technologies.

2022 Biodiesel & Renewable Diesel Summit

June 13-15, 2022

Minneapolis Convention Center, Minneapolis, MN (866) 746-8385 | BiodieselSummit.com The Biodiesel & Renewable Diesel Summit is a forum designed for biodiesel and renewable diesel producers to learn about cutting-edge process technologies, new techniques and equipment to optimize existing production, and efficiencies to save money while increasing throughput and fuel quality. Produced by Biodiesel Magazine, this world-class event features premium content from technology providers, equipment vendors, consultants, engineers and producers to advance discussion and foster an environment of collaboration and networking through engaging presentations, fruitful discussion and compelling exhibitions with one purpose, to further the biomass-based diesel sector beyond its current limitations.

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ETHANOLPRODUCER.COM | 7

View From the Hill

Choosing America’s Farm Fields Over OPEC Oil Fields

Geoff Cooper

President and CEO Renewable Fuels Association 202.289.3835

gcooper@ethanolrfa.org

Anyone who has been around the ethanol business for very long knows that one the founding pillars of our industry was the dire need for a more secure energy supply. It all started with the oil embargoes of the 1970s. President Carter, in a major televised speech on the energy crisis in 1979, vowed that “this nation will never use more foreign oil than we did in 1977—never,” and ethanol was part of the solution he presented. Likewise, when President George W. Bush signed the Renewable Fuel Standard into law just over a quarter century later, he spoke of the role renewable fuels would play in this area. “Every time we use a home-grown fuel … we're going to be helping our farmers, and at the same time, be less dependent on foreign sources of energy.” It was therefore understandably difficult to recently learn that President Biden was calling on the OPEC+ nations to increase oil production as a way of combatting higher fuel prices at the pump. In a letter to the president two days after this announcement, the Renewable Fuels Association made clear our position—a position that many of the president’s predecessors would agree with: The key to cleaner and more affordable energy for American consumers lies not in the oil fields of Saudi Arabia and Russia, but in the farm fields of our nation's heartland. We do agree with President Biden that higher gasoline prices threaten to derail our nation’s economic recovery from the Covid-19 pandemic, and we support the administration’s call for an investigation into the true causes of recent higher gas prices. However, rather than hoping Iraq, Iran, Venezuela and other OPEC+ countries will provide the cure to escalating gas prices in the United States, we urge the president to pursue a real and immediate solution to higher pump prices—increased production and use of low-carbon renewable fuels like ethanol. Using more domestically produced ethanol would not only result in lower fuel prices for consumers, but it would also support this administration’s goals related to clean energy, climate change, and jobs. While some oil refiners continue to falsely claim the RFS somehow increases the cost of gasoline, the facts are clear. Expanded use of ethanol under the RFS has lowered gasoline prices by an average of 22 cents per gallon in recent years, saving the typical American household $250 annually. In recent weeks, gasoline containing just 10 percent ethanol (E10) has typically sold for 30-40 cents per gallon less than gasoline with no ethanol, on average. And by increasing our liquid fuel supply, it helps dampen gasoline price shocks that result from sudden oil market disruptions. With the right policy and regulatory actions, renewable fuels can do even more to keep pump prices in check, reduce petroleum dependence, and reduce carbon emissions. We encourage the Biden administration to take three steps: Quickly finalize robust RFS volume requirements for 2021 and 2022, take action to ensure consumers have year-round access to gasoline containing 15% ethanol (E15), and work with Congress to ensure upcoming legislation includes the incentives necessary to support increased FFV production and expanded infrastructure for higher ethanol blends like E15 and E85. U.S. ethanol producers stand ready to work with the Biden administration and Congress to deliver immediate and effective solutions to the challenges posed by high pump prices and our long history of over-reliance on petroleum. Rather than calling on the cartels of the Middle East to solve our problems at the pump, our leaders in Washington should be calling on the farmers of the Midwest.

8 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

Global Scene

As Nations Seek Carbon Neutrality, Demonstrating Ethanol’s Role Is Vital Brian Healy

Director of Global Ethanol Market Development U.S. Grains Council 202.789.0789

bhealy@grains.org

As policymakers in Japan, South Korea and Taiwan consider new emission reduction initiatives to achieve carbon neutrality by 2050, the U.S. Grains Council is working to demonstrate the pathway for decarbonization through increased ethanol blending into local fuel supplies. Each country is focused on reducing economy-wide emissions and the transport sector remains high on the list in terms of achievable emissions reductions. Japan’s strategic energy plan is being revised this summer and policies are in development to achieve the country’s carbon neutrality goals by 2050. Direct blending of ethanol presents an immediate opportunity for the country to further reduce transport emissions to achieve these policy outcomes. Today, Japan does not currently blend ethanol directly; it relies on pre-blended ethanol in the form of ethyl tertiary-butyl ether (ETBE) that reduces 712,000 tons of carbon dioxide emissions per year. With an average blend rate of just 1.9 percent, direct blending of at least 10 percent would drastically reduce carbon emissions for the transport sector. Currently, the total potential U.S. market share in Japan for ethanol is up to 66 percent of the estimated demand of 217 million gallons of ethanol used to make ETBE, equal to 142 million gallons per year. Investment to reduce carbon intensity of U.S. ethanol paid off in that market where U.S. product previously had no market share for the first decade of a policy that began in 2009. Even as the greenhouse gas (GHG) reduction requirement became more stringent under that policy’s revision in 2018, U.S. ethanol gained access due to carbon intensity improvements made by the U.S. industry during that time. Much like Japan, South Korea announced a goal last fall of achieving carbon neutrality by 2050, and the Korean public and private sectors have prepared scenarios and implementation measures for carbon reduction, including creating its Carbon Neutrality Committee that in the future will help set carbon neutrality policies. The council’s Korea office has been providing stakeholders information on ethanol’s contributions to these goals and helping to create an environment for expanding ethanol use by demonstrating to the government the importance of introducing a fuel ethanol renewable fuel standard. Council staff has spoken at events hosted by the Korea Biofuel Forum and the Transportation Sector Working Group of the Carbon Neutrality Committee, that focuses on the importance of a local policy in achieving 2050 carbon neutrality in South Korea. The Council will co-host the Climate Crisis and Biofuel Symposium in September. Taiwan is the most recent entrant in the region to announce similar targets to achieve net zero emissions. Like Korea, Taiwan does not blend ethanol into fuel. In the past, Taiwan has looked to pilot programs to blend ethanol in the market, but uptake was minimal, and the programs were discontinued. The enormity of the opportunity is immediate to demonstrate the role that ethanol has in supporting these policies as the U.S. ethanol industry value chain invests further to access these markets in the long term.

ETHANOLPRODUCER.COM | 9

BUSINESS BRIEFS PEOPLE, PARTNERSHIPS & PROJECTS

ACE re-elects seven board members to three-year terms The American Coalition for Ethanol announced the re-election of several board members during its annual business meeting in August. Seven incumbents were re-elected to ACE’s 21-member board of directors for three-year terms, including Bill Dartt, Cardinal Ethanol; John Christianson, Christianson PLLP; Ron Alverson, Dakota Ethanol; Kenton Johnson, Granite Falls Energy; Brian Vasa, Nebraska Public Power District; Anthony Mock, North Dakota Corn Growers Association; and Doug Punke, Renewable Products Marketing Group.

“ACE is grateful for the leadership and guidance of the dedicated active volunteers who make up our board of directors and represent the grassroots diversity of our entire membership,” said Brian Jennings, ACE CEO. “Each year brings new challenges and opportunities, and we’re appreciative we can turn to these leaders to help chart a path forward under a new administration and market conditions. ACE members can rest assured they’re well-represented by the resolve, expertise and experience the board members bring to the table.”

USGC recognizes industry partners for decade of service In August, the U.S. Grains Council recognized three industry professionals for supporting the organization for ten or more years. The USGC lauded Sean Broderick, Brian Arnold and Greg Krissek for helping the trade group build demand for ethanol coproducts around the world. Sean Broderick of CHS Inc., who markets DDGS for U.S. ethanol producers, is a member of the USGC’s Board of Delegates and has led its Value-Added Advisory Team (A-Team) while traveling internationally with the USGC.

Brian Arnold of The DeLong Co. Inc., who has worked with the council since the late 2000s, has served on the USGC’s Board of Delegates and as an A-Team lead. Greg Krissek of Kansas Corn, has been working with USGC since the 1990s, first with the Kansas Department of Agriculture and later in his roles with the corn commission, which offers robust checkoff support to the USGC.

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Green Plains breaks ground on fourth high protein installation Green Plains Inc. has announced that its wholly-owned subsidiary Green Plains Mount Vernon LLC has broken ground on the construction of a Fluid Quip Technologies’ MSC system. Mount Vernon is the fourth Green Plains location to install MSC. “We are continuing the transformative rollout of our plan to deploy Ultra-High Protein production across our entire platform,” said Todd Becker, president and CEO of Green Plains. “Each groundbreaking further demonstrates the continued execution of

our multi-year transformation to the biorefinery platform of the future, creating sustainable ingredients that matter, to help meet growing global protein demand.” Installation of the system is expected to take nine to 12 months. It will have the capacity to produce approximately 54,000 tons of Ultra-High Protein feed annually, bringing the coampany’s overall capacity to more than 250,000 tons. Among other benefits, the MSC system will increase the plant’s distillers corn oil production capacity by 50%.

Study confirms feasibility of CCS at two Aemetis plant sites A recent study concluded that more than 2 million metric tons (MT) per year of carbon dioxide could viably be injected at or near Aemetis’ two biofuel plant locations in California. The carbon capture and sequestration (CCS) geologic formation review and drilling study was completed by a subsidiary of the ethanol producer, Aemetis Carbon Capture, and was conducted by global energy services company Baker Hughes. The study estimated that 1 million MT per year

of CO2 could be sequestered in saline formations located deep underground at or near Aemetis’ ethanol plant in Keyes, California; and up to 1.4 million MT per year could be injectable at or near the company’s Riverbank location. Each MT of CO2 should yield $200 of value through the California Low Carbon Fuel Standard, and $50 per MT of IRS 45Q tax credit value. Legislation is pending in Congress to increase the tax credit to $80 per MT.

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Blends

MATCHING FOR MORE

Liquid fuels have a long, shared future with electric vehicles if ethanol blending methods, engine technology and policy can align. By Melissa Anderson

The warning Dean Drake and others heard at a General Motors global warming summit in 1989 was both clear and alarming: the levels of carbon dioxide in Earth’s atmosphere are rising—fossil fuel emissions are to blame—and it will soon cause a potentially dangerous planetary temperature increase.

That and other early notices went mostly unheeded for two decades as novel global warming predictions of the ’80s and ’90s evolved into today’s scientifically indisputable climate crisis. The developed world has benefited from fossil fuels for over a century, and it is now scrambling to make up for it. Along with the proliferation of renewable energy—bioenergy, solar and wind—the age of electric vehicles (EVs) appears imminent—their widespread adoption is now a matter of time, public acceptance and momentum. Most predict EVs will mostly 12 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

replace the internal combustion engine (ICE) within three or four decades. However, with the Biden administration calling for EVs to make up 50% of all new vehicle sales Drake in the U.S. by 2030, an earlier transition seems plausible. Drake, however, says we should step back and consider our options. He offers an alternative future where ICE vehicles persist much longer, and more abundantly than predicted, with higher-ethanol blends matched with octane-optimized engines offering as much, or more, carbon reduction as EVs. His plan isn’t simple or easy; it requires an unprecedented degree of alignment among the biofuels, petroleum and automotive industries that, to date, has been elusive. And Drake has seen windows of opportunity like this close quickly before.

Early Opportunities Lost

Drake, a former GM public policy analyst and founder of the Michigan-based consulting firm Defour Group LLC, says that, in addition to high-level, inter-industry cooperation, proactive policy development is a must. “I was part of a company that believed the best way for the auto companies to survive and prosper was not to just blindly fight regulations but develop regulations that helped the company adapt to the future,” he says, explaining that his work in the ’80s and ’90s with GM placed him at the forefront of policy and regulations includ-

MORE AND LESS: Dean Drake believes match blending ethanol to gasoline designed for E20 or E30 would produce a low-carbon fuel with substantially lowered aromatics. The mid-level blends sold today at blender pumps utilize splash blending.

ing cap-and-trade and concepts that would eventually be incorporated into the Renewable Fuel Standard. Drake helped organize GM’s global warming summit 32 years ago, and he believes the world would be in a better position today if action would have been taken then. “We could have put together a package that, by now, would have taken climate change out of the picture, he says, explaining that legislation based on work done by GM and the Environmental Defense Fund in the early ’90s under the first Bush administration could have reversed the buildup of carbon dioxide in the atmosphere we

are seeing today. As early climate change policy stalled, opportunities for successful climate change response diminished. In late 1992, GM underwent a management upheaval that changed the course of the company and the direction of the U.S. automaker involvement in climate change mitigation. For the next seven years, Drake worked in the shadows, continuing his pursuit of ecofriendly car policies. A signal that his work was never going to reach fruition came in 1999 when GM introduced one of the least fuel-efficient vehicle in its history, the Hummer. A short time later, Drake retired from GM.

Next Stage, New Vision

Never losing interest in clean automotive solutions, Drake reemerged from retirement in 2007 intent on combating climate change. He founded Defour Group with some retired GM coworkers and climate summit collaborators. Together they worked with ethanol interests studying the economics and environmental benefits of high octane, low carbon mid-level ethanol blend fuels. Now, with his focus on biofuels and climate change front and center, he sees EVs emerging as the next big evolution in automotive transportation, and he gets it. ETHANOLPRODUCER.COM | 13

Blends “The electric vehicle just has a lot of inherent advantages,” he says. “It has no tailpipe emissions and people keep forgetting the importance of local toxic pollutants. One of the things you’re doing is putting pollution out in a single smokestack away from the cities instead of in front of someone’s windows.” And perhaps the biggest advantage EVs have over their liquid fuel rivals, he says, is that more energy—nearly 80 percent—reaches the wheels, versus the most efficient liquid fuel cars getting only 40 percent of potential energy to the wheels. But EVs aren’t perfect. The transition will require trillions of dollars of new infrastructure spending, and sources of electricity are varied, ranging from fossil fuels to eco-centered wind and solar, which is intermittent. Electric vehicles are only practical for light-duty applications—long-haul EV trucking is still not viable—and only half of the vehicles in the world are currently light-duty, urban-based cars and trucks. EV range is improving but still limited at 60 to

300 miles between charges, and batteries are heavy and dubious from an environmental and human rights perspective. Furthermore, it is predicted that more than 50% of all cars and trucks on the road will still be ICE vehicles in 2050, meaning practical solutions to reducing the carbon intensity of liquid transportation fuels today, and over the next 30 years, are needed. Drake believes ethanol is the answer. “Biofuels are really the greatest alternative for the rest of the fleet that cannot be electrified, and that’s probably half the fleet or more,” he says. “Ethanol is the best contender.”

Blending Models

While ethanol and gasoline are reluctant but ubiquitous companions today, a more evenly balanced integration of the two fuels—not just utilizing ethanol as a blend stock, but treating it as an harmonizing octane mate—would have immense benefits for both industries, especially with optimized blending.

SHARED SPACE: NuVu Fuels in Ionia, Michigan, which has for years offered higher ethanol blends, now has two EV charging stations on site.

Drake believes mid-level ethanol blends like E30 are a perfect fit if the fuels and automotive industries come together and treat the engines and ethanol blends like an integrated system to optimize vehicle efficiency

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and lower emissions. Higher compression engines would benefit the most from these higher blends, he says, explaining that current automakers could quickly recalibrate existing engine setups to benefit from higher ethanol blends in a matter of a few years. He says that while adding more ethanol to regular gasoline (splash blending) will reduce the resulting fuels’ carbon intensity, match blending the fuel (adding ethanol to a gasoline specifically blended for use with higher ethanol blends) at the “sweet spot” of 20 to 30 percent ethanol, could produce a low-carbon fuel that also lowers local toxic emissions by reducing aromatics. New vehicles optimized to run on this fuel could have the lifetime environmental impact of electric vehicles. And vehicles on the road today could also use the higher ethanol blends. Speaking at the 2021 International Fuel Ethanol Workshop & Expo in Des Moines, Iowa, in July, Drake explained that ethanol

Next Generation Fuels Act of 2021 Introduced in August In late August, Rep. Cheri Bustos, D-Ill., introduced the Next Generation Fuels Act of 2021, a bill that, in part, aims to establish a new high-octane, low-carbon fuel standard. Bustos introduced similar legislation in 2020. The legislation would require automakers to manufacture vehicles for fuels with a 95 RON or higher by 2026; and a 98 RON or higher by 2031. It would require gasoline retailers to meet corresponding requirements with compatible dispensing equipment by 2026 and 2031, respectively. The Next Generation Fuels Act would also require automobile manufacturers to

design and warranty their vehicles for use with higher blends—25% by 2026 and 30% by 2031. Under the legislation, the octane used in the fuel must reduce greenhouse gas emissions by a minimum of 40 percent when compared to a 2021 baseline. And U.S. Department of Energy’s GREET model would be used to determine lifecycle emissions of the fuels. Notably, the bill includes provisions that would set a limit on aromatics in gasoline, and ensure that all ethanol blends receive the same Reid vapor pressure (RVP) treatment as E10.

Blends increases RON (research octane number) octane in gasoline more effectively that the aromatics refiners routinely use to achieve desired results. Based on modeling done by the Defour Group, he says only E20 and E30 could meet a 95 RON octane standard when additional ethanol is added to regular blend stock. While splash blended E30 can achieve decreased aromatic levels by as much as 29%, Drake says match blended E30 optimized for low aromatic content can achieve a 70% decrease. He says establishing octane and aromatic standards for fuel now is the key to allowing ethanol to fulfill its true potential and, ultimately, enable liquid fuels to achieve low-carbon parity with EVs.

Possible Effects

Steve Vander Griend, fuel and engine technology manager with Urban Air Initiative, attended Drake’s presentation in Des Moines and spoke with him afterwards. While Vander Griend thinks the easiest and most readily available solution is to splash blend ethanol into current gasoline, he appreciates Drake’s overall vision. “Dean’s approach to aromatic reduction is high level by taking the octane blending value of aromatics compared to the octane blending value of ethanol,” says

16 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

WELL MATCHED: Based on modeling done by the Defour Group, splash blended E30 can achieve decreased aromatic levels by as much as 29%, while match blended E30 optimized for low aromatic content can achieve a 70% decrease.

Author: Melissa Anderson Contact: editor@bbiinternational.com

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Vander Griend, explaining that Drake’s concept is relevant to a soon-to-be-released study that shows how ethanol has already significantly reduced aromatics in the U.S. gasoline supply by moving to an E10 market. Vander Griend agrees with Drake that mid-level blends should strive for low-carbon parity with EVs, and ethanol’s ability to reduce aromatics in the fuel supply is key. “We often project the carbon reduction of an optimized vehicle on E30 but don’t talk about how current vehicles are benefitting from ethanol displacing aromatics and reducing vehicle emissions in urban areas today,” he says. “EPA models don’t credit ethanol for this reduction, further complicating the ability to truly compare the carbon intensity of EVs and ethanol.” Reflecting on Drake’s presentation and his own concerns about EPA modeling, Vander Griend says, “I believe we can show how a clean, high-octane fuel can reduce as much carbon per year as a high rate of adoption for EV’s over the next 25 to 30 years. I do think that, besides getting a good regulatory pathway implemented, we need to have a means of correcting EPA’s models and maybe have EPA use a little common sense. There are plenty of pro-EV folks at EPA, but some of the past rulemakings by EPA clearly show petroleum gets the benefits while ethanol is devalued.” Drake says, for now, one of the most effective ways for consumers and the ethanol industry to counter the influence of Big Oil and flawed EPA rulemaking is to support retailers with blender pumps offering mid-level ethanol blends today, like NuVu Fuels in Ionia, Michigan, which also has two EV charging stations on site. “We can already see what the future might look like,” he says. “It could be a lot like that neighborhood station back home in Ionia, with higher ethanol blends and EV charging all in one place.”

Rapid. Ready. Reliable.

Process

INSTANT INTEL Ethanol Producer Magazine talks with two providers of inline spectroscopy about the actionable insight of seeing inside fermentations in real time. By Tom Bryan

Until recently, the only way to understand what was happening inside a given fermentation was to analyze samples— offline, in the lab—after the process was done or approaching completion. While still necessary and effective, post-fermentation HPLC does not necessarily give ethanol producers the actionable data they need to make adjustments in real time. Today, that’s changing, as high-tech spectrometry instruments are being installed at ethanol plants inline— tied into the process—giving producers a continuous picture of conditions inside fermenters and allowing them to spot and correct problems as they occur. Ethanol Producer Magazine spoke with Steen SkjoldJørgensen, vice president of Biofuels Business at Specshell ApS—maker of automated, inline spectrometry systems for ethanol production called Zymon—and Jonathon Speed, product and applications manager at Keit Spectrometers—maker of the IRmadillo FTIR spectrometer. Here’s what each had to say.

18 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

TOUGH TECH: Keit’s IRmadillo spectrometer has no moving parts, making it robust and reliable. The instrument can be bolted onto the ethanol process—typically on recirculation lines—with no need for protection, flow cells or fiber optic probes.

EPM: Steen, how is process monitoring with mid-infrared spectroscopy a true modern marvel in terms of how it gives producers eyes on fermentation while it is happening, giving them actionable, real-time information? Skjold-Jørgensen: Online monitoring of mashing and fermentation processes is an old dream, pursued by many, that has been elusive until now. So far, mapping of what was going on in a fermentation was done by tedious sampling procedures in combination with offline laboratory analyses, resulting in delayed information subject to human errors. Hence, much value has been missed due to lack of intervention in clearly sluggish or infected batches, and the insights around changes in processes and inputs were slow to materialize. EPM: Jonathon, Keit has had success in applying its static optics FTIR spectrometry technology to ethanol production. Explain what a static optics FTIR spectrometer is, and how it can benefit today’s ethanol producers? Speed: FTIR spectrometers use infrared light to record a spectrum of the liquid they’re inserted into.

Skjold-Jørgensen

Speed

LIVE LOOK: Specshell’s automated inline spectrometer technology, Zymon, gives ethanol producers live insight into the fermentation process—without manual sampling—by combining spectroscopic detection with attenuated total reflectance.

The spectrum is a record of all the chemicals that are dissolved in the liquid, and can be used to calculate the concentrations of them— the same information that’s given by an HPLC instrument but in real time and with no need to take a sample offline. Our instrument—the IRmadillo—has no moving parts at all, making it incredibly robust and reliable. The real benefit is the ability to see what’s happening inside the fermenter at all times, with no need to take a sample and no wait between taking samples and getting results. EPM: Steen, your company’s automated inline technology, Zymon, gives ethanol producers live insight into the fermentation process without manual sampling. In what other ways is this platform an improvement over previous and existing technologies? Skjold-Jørgensen: Specshell set out to develop an online instrument that could report the liquid composition of fermentations—information that is very similar to what you get today from laboratory-based, offline HPLC. We combined this spectroscopic detection principle with so called attenuated total reflectance—a sample interface configuration that is ideal for providing signals only from the liquid part of a slurry. We get our passing sample stream “filtered” for its coarse insoluble constituents. By substituting today’s manual and slow procedures, the plant gains obvious advantages in terms of data quality, speed of information and, in the end,

better processes and higher yields. There is no more waiting for insights with how the batch develops, and you gain the opportunity to intervene and plan before it is too late. EPM: Jonathon, how can Keit’s technology be leveraged by producers at a higher level to become a true “analyzer,” able to spot various process states and enable plant managers to make informed operational decisions? Speed: The spectrometer needs to be calibrated to a customer’s process—because they’re all slightly different—and in that phase we can find out the states the customer cares about and factor them in. For example, “stressed yeast” could be raised when glycerol rises quickly, and “inactive enzyme” states could be raised when the rate of change of sugar profile slows down. We can also report the absolute concentrations so the operators can spot when things look good and when concentrations are low, allowing them to make decisions on the spot. EPM: Steen, how is mid-infrared technology different than, and largely superior to, near-infrared technology? Skjold-Jørgensen: We chose mid-infrared (MIR) spectroscopy, that provides spectra with a very good resolution. If infrared spectroscopy sounds familiar to you it may be because its cousin, near-infrared (NIR) spectroscopy, has been repeatedly attempted for this job—with little success. The reason being that the spectra from ETHANOLPRODUCER.COM | 19

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Process ZYMON NIR vs MIR NIR NEAR-INFRARED TECHNOLOGY

▪ Easier to implement inline ▪ Limited information

▪ Unable to differentiate very similar molecules

▪ Superior to NIR in accuracy ▪ Dissolved species only

Fundamental vibrations

Absorbance

MIR MID-INFRARED TECHNOLOGY

Absorbance

NIR are much more blurred than what you get with MIR, and NIR is inaccurate as soon as you move a little bit outside the compositions covered by the calibration. MIR is a very robust technology because the wavelengths applied lead to signals about the primary bends, stretches and vibrations of specific chemical bonds. So, your spectrum gets some very distinct peaks. Specshell went ahead and generated a very extensive and deeply characterized set of calibration data—and with the model we built on these data have been able to serve a number of customers without the need for plant-specific calibration. And without periodic recalibrations.

Overtones TYPICAL IN-LINE NIR PROBES

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EPM: The IRmadillo is clearly a robust MIR ADVANTAGES: According to Specshell, mid-infrared (MIR) spectroscopy provides spectra with superb resolution, while spectra generated from near-infrared (NIR) spectroscopy are comparatively device, Jonathon, but explain what more blurred. MIR is also quite robust because the wavelengths applied produce signals that indicate the makes it a tough instrument, and how it primary bends, stretches and vibrations of specific chemical bonds. is a major improvement from standard spectroscopy. with a clever arrangement of static mirrors. line, meaning we can measure every drop of Speed: Traditional FTIR spectros- This means we can bolt the spectrometer fermentation as it is pumped around the copy needs a moving mirror inside the spec- right onto the process itself with no need fermenter—getting very representative meatrometer, which needs to be protected from for protection, flow cells or fragile fiber op- surements and spotting problems early. vibration (i.e. pumps, machinery, etc.). We’ve tic probes. That means we normally mount removed the moving mirror and replaced it the spectrometer ETHANOL PRODUCER_HALF PG AD_CERTIFIED TECHNICIANS_03-24-2021.pdf 1 3/25/2021 10:11:42 AM directly on the recirculation

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EPM: Steen, tell us more about some of the other tools Zymon offers, like LiveView software, available alarms, etc.? Skjold-Jørgensen: Zymon comes with its own user interface plotting the development in concentrations, enzyme activity, as well as yeast activity. In addition, it comes with an alert to the user for high levels of organic acids—an indication of infections or maybe issues with recycled water. Additionally, the data and alarms of Zymon may be easily integrated into an ethanol plant’s current control system. EPM: Jonathon, tell us about some of the beneficial findings Keit has uncovered from early commissionings of the IRmadillo, particularly insight about the process of calibration? Speed: The obvious one is we’ve spotted problems early: in one case a bacterial contamination and in another an issue with the enzyme. With the first we saw a huge spike in lactic acid over the first three hours or so, and this made the customer

dose with antibiotics to resolve the issue. The other was seeing a slowdown in rate of DP2 and DP1 production—which showed the enzyme wasn’t performing as expected. We’ve also had one customer use the spectrometer to gradually improve their process and make small tweaks—resulting in an uplift of total ethanol concentration from 15 to 15.1%, which has a huge implication on overall profit. EPM: Ultimately, Steen, maximized ethanol production is the goal. Describe how Zymon has the potential to help corn ethanol producers achieve better fermentations, dosing, efficiency and data? Skjold-Jørgensen: Through our extensive testing of the instrument at ethanol plants we have demonstrated a number of value creations. They range from savings in operator and laboratory time, support to process optimizations and recipe changes, all the way to early detection and intervention in case of infections or sluggishly fermenting batches. Ending up with

an unfinished batch is costly and may lead to problems beyond just this particular batch. With our initial clients, this has led to proven savings equating to several hundred thousand dollars per year. EPM: What’s next for your team, Jonathon? Share a few of the latest developments on the horizon for this exciting new segment of technology from Keit. Speed: We’re looking at how to reduce the time to calibrate, and are making some exciting developments in doing so. We’re also looking at other applications in distillation and corn oil processing. If the process is a liquid, slurry or suspension, then we can measure it—and that’s very exciting! Author: Tom Bryan Contact: editor@bbiinternational.com

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Event

ACCOLADE APPRECIATED: Upon accepting the honor, 2021 FEW Award of Excellence winner Kurt Rosentrater told conference attendees: "It truly is a humbling feeling. You go to work, you try to help the industry, but to be recognized for your work … It's a fantastic feeling.” PHOTO: BBI INTERNATIONAL

NECESSARY QUESTIONS: American Coalition for Ethanol President Dave Sovereign, addressing ACE conference attendees, challenged common assumptions about electric vehicles. PHOTOS: ACE/ZIMMCOMM

NO BETTER TIME

THAN NOW In August, the American Coalition for Ethanol’s annual conference convened in person for the first time since the onset of the pandemic. By Anna Simet

24 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

While “accelerate” was the theme of the American Coalition for Ethanol’s 34th annual conference—market growth being vital—the myriad policy, investment and operational issues explored at the event orbited largely around the industry’s overarching lowcarbon ambitions. And with the rise of elec-

tric vehicles (EVs) seeming imminent, ACE leaders tackled the central question of why policymakers and consumers remain fixated on emerging climate change solutions when ethanol and other biofuels are here today and widely available. That and related concerns were thoroughly and thoughtfully dissected during the opening general session, which

ON POINT: The 2021 ACE annual conference included dozens of speakers including Christianson PLLP Managing Partner John Christianson (top left); ACE/Dakota Ethanol Director Ron Alverson (top right); and U.S. Rep. Angie Craig (bottom right). Bottom left, the 2021 ACE conference was well attended and included many top ethanol plant executives. PHOTO: ACE/ZIMMCOMM

began with remarks by Dave Sovereign, ACE president. Despite the big push toward EVs and their seemingly pristine image, lawmakers and consumers generally have a murky understanding of the many challenges that accompany their widespread adoption, said Sovereign, who pointed out the irony in using EVs that run on power generated from fossil fuels. “People see the clean, green car and are excited,” he said. “But what’s behind the curtain? They don’t see that the electricity is being generated from coal. And how are the batteries going to be disposed of ? The public doesn’t know this, and some choose not to know.” Sovereign continued, “We also have to

wonder about all the applications—are they practical? Pickups pulling campers, boats, livestock trailers … is it really practical in every application, and to totally eliminate the internal combustion engine?” During an extreme heatwave this summer, Californians were asked to avoid charging EVs to protect the grid. Sovereign suggested this problem indicates the electrical grid needs a tremendous amount of investment and upgrades to withstand the kind of load that is expected with widespread EV adoption, work that will take years to complete. One of the industry’s priorities should be to educate the public that clean-burning fuel like ethanol is also an alternative, Sovereign said. He conclud-

ed his remarks by emphasizing that even though the industry is very active in promoting itself, considering the big push for EVs, there is not a more critical time to actively participate in low-carbon and greenhouse gas conversations. “When lawmakers and policymakers come around, we need to be active and get in front of them,” he said. “Get engaged, and participate.”

Overcoming Obstacles

Following Sovereign, Brian Jennings, ACE CEO, steered the conversation to longstanding and new industry hurdles, and the organization’s continued work to help members overcome them. “Have we encountered some roadblocks? Nearly 100 small refinery ETHANOLPRODUCER.COM | 25

Event

ETHANOL'S ROLE: Brian Jennings, ACE CEO, encouraged conference attendees to "go on the offense" and convince elected leaders that increasing the use of ethanol today will make the nation's goal of net zero emissions by 2050 more attainable. PHOTO: ACE/ZIMMCOMM

exemptions (SREs), a global pandemic, backto-back courtroom losses and irrational exuberance for EVs—if those qualify, then yes, we have.” As for SREs, it may seem as though the Supreme Court is keeping the flood gates open for them, Jennings said. He was referring to the June 25 reversal of the Tenth U.S. Circuit Court of Appeal’s ruling that the U.S. EPA can extend SREs to small refineries whose earlier temporary exemptions

had lapsed. “[But] They simply ruled that refineries can seek waivers at any time— that’s it. The justices did not make it easier for refiners to get waivers, and they did not say the U.S. EPA must rubber stamp every exemption request they get. In fact, so long as the EPA adheres to other limits set by the Tenth Circuit—limits that make those exemptions harder to obtain—the days of runaway SREs should be over. Biden’s EPA must judiciously act, using the precedent

applied by the Tenth Circuit Court on the 60-plus refinery waivers that are currently pending.” Moving onto the topic of E15, Jennings said that in early July, the D.C. Circuit Court invalidated the EPA’s 2019 rule to allow year-round E15 sales. “Obviously, losing the conventional gasoline marketplace from June to September could significantly undermine ethanol demand,” he said. “That’s why there is a real sense of urgency to pursue all legislative, legal and regulatory options at our disposal to ensure we keep E15 use year-round.” Jennings highlighted the bipartisan E15 legislation sponsored by Minnesota Rep. Angie Craig—who was at the event and later took the stage—and said there is hopeful optimism that she or other supporters in Congress will find a way to attach it to the infrastructure appropriations bill, the omnibus spending bill or any other legislation between now and next summer. Appeals have already been filed, he said, and ACE expects E15 to continue to be on the market. “Just last week, ACE sent a letter to President Biden indicating the quickest way to reduce greenhouse gasses is to ensure uninterrupted market access for E15 and set maximum volumes under the RFS,” Jennings said. “Let’s face it, the past two administrations have sided with refiners to undermine the RFS as law, and that has

Answering Compatibility Questions Ron Lamberty, senior vice president of ACE, highlighted the success of ACE’s Flex Check online tool, flexfuelforward.com, launched in September 2020. Focused on making it easy and convenient for fuel retailers to determine if their equipment is E15 compatible, the tool was built off National Renewable Energy Lab studies and ACE’s research with other companies. By entering the manufacturer or model number of tanks, piping and other equipment, retailers can identify compatible parts and equipment, and ensure the equipment they are told needs replacing actually needs to be. “We knew the number of compatible E15 sites was a huge number,” Lamberty said. “In fact, almost all underground storage tanks and lines installed since 1994 are compatible with 100% ethanol … We know widespread E15 use can only happen with massive conversion of stations, not just putting in new stuff.” Lamberty said out of approximately 150,000 U.S. gas stations, approximately 120,000 could sell E15 with little or no expense. “We wanted to make sure they knew it,” he said, adding that over 31,000 users have accessed Flex Check since it was introduced. PHOTO: ACE/ZIMMCOMM

26 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

undercut and limited the use of low-carbon biofuels. As they ponder what to do about the 2021 and 2022 RVOs (renewable volume obligations), the Biden Administration has a choice to make: Follow the law or help refiners escape. It really is that simple.” If the Biden administration is not willing to ensure the RFS calls for 15 billion gallons of low-carbon ethanol that is already being produced and able to replace petroleum at the pump, Jennings continued, legitimate questions will and should be asked about the merits of nonbinding goals for less-deployable technologies. “And yes—I’m talking about EVs.” Referencing a recent Intergovernmental Panel on Climate Change report, Jennings said scientific consensus is that time is running out to take meaningful action to dramatically reduce fossil fuel use and avoid the worst effects of climate change. Though some believe Biden and Congress’s laser focus on reaching net zero emissions by 2050 could mean the end of internal combustion engines and liquid fuels, Jennings said ACE is confident that ethanol is the best low-carbon alternative to petroleum that provides meaningful GHG reductions. “In other words, we refuse to concede the climate conversation to EVs,” he said. “That is why we have been highlighting how smart farming practices, efficiencies at the ethanol plants and the capture and sequestration of biogenic CO2 from facilities can help ethanol on this unique trajectory, to not only reach net zero emissions, but net negative emissions.” Jennings said ACE has also helped mobilize diverse coalitions comprised of environmental groups and EV advocates to propose new, technology-neutral, clean fuel policy at state and federal levels to ensure a growing market for ethanol, even as overall petroleum use shrinks or declines. “To those who are uncomfortable with this lowcarbon strategy and prefer to hunker down instead of protecting the fuel market from EVs, I have a question: Why place it into the hands of refiners? If we have an opportunity to expand ethanol use by decarbonizing liquid fuels, why would we spend time and resources trying to protect the

status quo, which limits our market to just 10%? I am concerned there are plenty of politicians and groups fantasizing that this is their moment to get rid of internal combustion engines, and yes, the use of liquid fuels, but here is the thing about fantasies— they aren’t real.” Jennings concluded his remarks by encouraging the industry to go on the offense and strategize to get elected leaders to realize that increasing the use of ethanol today will immediately benefit the climate and make

achieving the goal of net zero emissions by 2050 much more attainable. “We can start making progress right now with low-carbon ethanol—that is a message ACE intends to deliver over and over again,” he added. “While we’re at it, we intend to hold elected leaders accountable. Do they really want to reduce greenhouse gasses? Or do they just want to talk about it?” Author: Anna Simet Contact: editor@bbiinternational.com

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Investigating the Effectiveness of Antibiotic Combinations Utilized in Fuel Ethanol By Jennifer Starner, Ph.D.

Bacterial infections during fuel ethanol fermentations can negatively impact the fermentation process and lower ethanol yields. Lactic acid-producing bacteria (LAB), such as Lactobacillus, Lactococcus, Weissella and Pediococcus, are a common source of contamination due to their ability to grow in the harsh conditions, low pH, high temperatures, and high concentrations of ethanol present during fermentation. LAB are problematic as they not only compete with the yeast for nutrients and ferment-

able sugars, but also produce lactic and acetic acids that influence yeast metabolism. Ultimately, untreated bacterial infections cost plants time and money. Antibiotics, such as the β-lactam antibiotic penicillin G and the streptogramin antibiotic virginiamycin, are commonly used during fermentations to control bacterial growth and support robust ethanol yields. In response to a competitive antibiotic market and increasing antibiotic resistance, antibiotic combinations, particularly combi-

nations of penicillin G and virginiamycin, have recently been employed. However, there is little evidence supporting the use of a penicillin G/virginiamycin combination treatment during fuel ethanol fermentations. When drugs such as antibiotics are applied concurrently, drug interactions must be considered. Drug interactions can be classified as additive, synergistic, or antagonistic (Figure 1). An additive interaction is when two drugs do not interact with each other and the response to the com-

CONTRIBUTION: The claims and statements made in this article belong exclusively to the author(s) and do not necessarily reflect the views of Ethanol Producer Magazine or its advertisers. All questions pertaining to this article should be directed to the author(s).

28 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

Bacterial Control

bination is the sum of the individual drug responses. Drugs are synergistic when use of the two drugs together creates a greater response than either drug individually. In direct contrast, drugs are antagonistic when the combination leads to a lesser or less successful response compared to the individual components. Synergistic drug pairs are rare occurring in only 4-10% of drug pairs tested, and if the drugs target different metabolic pathways, the chance of antagonism increases (Cokol, et al., 2011). Penicillin and virginiamycin target very different metabolic pathways within the bacteria cell. Penicillin G inhibits cell wall synthesis, while virginiamycin inhibits protein synthesis by targeting the 50S ribosomal subunit. There is significant research examining how penicillin interacts with other antibiotics. Penicillin has a mixed response profile; it is synergistic with some classes of antibiotics such as aminoglycosides and antagonistic with others, particularly antagonistic with protein synthesis inhibitors that target the 50S ribosomal subunit, such as virginiamycin (Yeh, Tschumi, & Kishony, 2006) (Johansen, Jensen, Dessau, Lundgren, & Frimodt-Moller, 2000). To explore the relationship between penicillin and virginiamycin when used as a combination treatment during ethanol fermentation, we compared the efficacy of each individual antibiotic and various combinations of the two against both lab bacterial strains and isolates collected from operating ethanol plants. Pediococcus pentosaceus, a common bacteria found in ethanol fermentations, was grown in the presence of either no antibiotic, penicillin G or virginiamycin alone, or 1:1, 2:1, or 3:1 ratios of penicillin to virginiamycin. Isobolograms, a common graphical tool used to analyze drug combination results, were used to determine whether the drug combinations were synergistic (more effective), additive (neutral), or antagonistic (less effective) (Tallarida, 2012). Isobolograms look at the concentration of the antibiotic required to achieve a desired response, such as a 25% reduction in growth

FIGURE 1: Graphical representation of possible interactions between drug A and drug B: additive (blue), antagonistic (red), and synergistic (green). Figure adapted from (Yeh, Tschumi, & Kishony, 2006). SOURCE: KURITA AMERICA (ADAPTED FROM YEH TSCHUMI & KISHONY, 2006)

FIGURE 2: Investigating drug synergy and antagonism using isoboles. a) Example of an isobole where concentration of drug A and drug B give an equal response. Any point on the line is an example of additive or neutral drug interactions. Any point below the line is synergistic and any point above the line is antagonistic. b) Isobole of Pediococcus growth response to penicillin G (PenG) and virginiamycin (VM). All points on the graph represent the concentration of the specified antibiotic that achieves 25% reduction in growth. All antibiotic combinations tested (1:1 (red), 2:1 (green), and 3:1 (purple) penicillin to virginiamycin) showed antagonistic interactions. SOURCE: KURITA AMERICA

when compared to no antibiotic treatment. If the drug combination is synergistic, the concentration of the antibiotics required to achieve that response will be lower than the individual antibiotic concentrations. If the drug combination is antagonistic, a greater concentration will be required to achieve that response (Figure 2a). Pediococcus pentosaceus results clearly showed that the penicillin/virginiamycin combinations, regardless of the ratio used, were antagonistic; and on an equal dose comparison, the individual antibiotics were more effective at controlling bacterial growth (Figure 2b). In addition to testing a lab strain, we also tested fourteen isolates from nine different operating ethanol plants over the

past couple years. As with the lab bacterial strain, isolates were grown in the presence of either no antibiotic, each individual antibiotic, or various combinations. For analysis of the results, we chose to focus on 40%, 25%, and 10% growth reduction responses as the average antibiotic concentration required fell within the typical range of antibiotic doses used in the field, 1.8, 1, and 0.5 ppm respectively (Figure 3). While there were a few examples of synergy seen with the penicillin/virginiamycin combinations, the results overall showed a significant trend toward antagonism. This becomes especially true at lower antibiotic concentrations. When looking at the results that correspond to a 0.5 ETHANOLPRODUCER.COM | 29

9 8 7 6 5 4 3 2 1 0

1.8 ppm Number of Samples

Number of Samples

Bacterial Control

Synergistic

Additive

Antagonistic 14

Number of Samples

8 7 6 5 4 3 2 1 0

1 ppm

Synergistic

Additive

Antagonistic

0.5 ppm

10 8 6 4 2 0 Synergistic

Additive

Antagonistic

FIGURE 3: Responses to antibiotic combinations by isolates from operating ethanol plants. Plant isolates respond primarily antagonistically especially at lower antibiotic concentrations. The average antibiotic concentration required to achieve the specified growth reduction is shown in red. SOURCE: KURITA AMERICA

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ppm average antibiotic dose, twelve of the fourteen isolates reacted antagonistically with the combination products. Our results show that greater doses of the combination products would be required to achieve the same antibacterial activity of either penicillin or virginiamycin alone. Antibiotic combinations are less effective at controlling bacterial growth compared to the individual antibiotics. Development of antibiotic resistance is a major concern for the continued use in fuel ethanol production. With so few antibiotics approved for use, development of multi-drug resistant bacterial strains would be extremely detrimental. Combination products are applying two of the available antibiotics at the same time increasing the risk of multi-drug resistance (Bischoff, Skinner-Nemec, & Leathers, 2007). In fact, research has shown that synergistic drug combinations increase the rate of resistance compared to the individual drugs by selecting for multi-drug resistant cells (Pena-Miller, et al., 2013) (Bollenbach, 2015).

However, alternating or cycling different antibiotics slows resistance development (Kim, Lieberman, & Kishony, 2014). To further investigate how the antibiotic application method influences development of resistance, Pediococcus pentosaceus was once again grown in the presence of either penicillin, virginiamycin, a 1:1 penicillin to virginiamycin combination, or an alternating schedule of penicillin followed by virginiamycin. Pediococcus was grown in a series of wells with a gradient of antibiotic. Each day, cells from the highest concentration of antibiotic that still saw growth were used to inoculate a fresh set of media supplemented with an increased gradient of antibiotics (Figure 4). After a single day of growth, all antibiotic treatment methods tested showed growth at ≤ 0.7 ppm antibiotic. After twelve days, both penicillin and virginiamycin exposed cells showed significant gain of resistance, showing growth at 7.5 ppm and 15 ppm respectively. The 1:1 penicillin/virginiamycin blend exposed cells developed re-

— PenG

— VM —1:1

[Antibiotic] (ppm)

— PenG/VM

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FIGURE 4: Comparison of the development of antibiotic resistance in Pediococcus when dosed with penicillin G (blue), virginiamycin (red), a 1:1 combination of penicillin and virginiamycin (green), and alternating penicillin for a day followed by virginiamycin for a day (purple). SOURCE: KURITA AMERICA

sistance to 3.8 ppm antibiotic. Alternating penicillin and virginiamycin was the most successful at limiting resistance development; these cells developed resistance to only 1.3 ppm antibiotic. Only the alternating method kept antibiotic resistance at or below typical antibiotic doses used in fuel ethanol fermentation. Overall, our results show that penicillin G and virginiamycin when applied simultaneously act overwhelmingly antagonistically against both lab bacterial strains and field isolates. Antibiotic combination products are more expensive, generally less effective, and increase the likelihood of multi-drug resistance. In addition to thorough CIP, use of a single antibiotic with periodic switching to an alternative antibiotic with a different mode of action provides the most effective bacterial control while limiting development of multidrug resistance. References Bischoff, K. M., Skinner-Nemec, K. A., & Leathers, T. D. (2007). Antimicrobial susceptibility of Lactobacillus species isolated

from commercial ethanol plants. Journal of Industrial Microbiology and Biotechnology, 739-744. Bollenbach, T. (2015). Antimicrobial interactions: Mechanisms and implications for drug discovery and resistance evolution. Current Opinion in Microbiology, 1-9. Cokol, M., Chua, H. N., Tasan, M., Mutlu, B., Weinstein, Z. B., Suzuki , Y., . . . Roth, F. P. (2011). Systematic exploration of synergistic drug pairs. Molecular Systems Biology, 544. Johansen, H. K., Jensen, T. G., Dessau, R. B., Lundgren, B., & Frimodt-Moller, N. (2000). Antagonism between penicillin and erythromycin against Streptococcus pneumoniae in vitro and in vivo. Journal of Antimicrobial Chemotherapy, 973-980. Kim, S., Lieberman, T. D., & Kishony, R. (2014). Alternating antibiotic treatments constrain evolutionary paths to multidrug resistance. PNAS, 14494-14499. Pena-Miller, R., Laehnemann, D., jansen, G., FuentesHernandez, A., Rosenstiel, P., Schulenburg, H., & Beardmore, R. (2013). When the most potent combination of antibiotics selects for the greatest bacterial load: The smile-frown transition. PLOS Biology, e1001540. Tallarida, R. J. (2012). Revisiting the isobole and related quantitative methods for assessing drug synergism. Perspectives in Pharmacology, 2-8. Yeh, P., Tschumi, A. I., & Kishony, R. (2006). Functional classification of drugs by properties of their pairwise interactions. Nature Genetics, 489-494.

Author: Jennifer Starner, Ph.D. Research Scientist Kurita America 763-497-1226 j.starner@kurita-water.com

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Understanding CIP Additive Packages for Ethanol Production

PHOTO: STOCK

By Lance Renfrow The history of proper clean-in-place (CIP) cleaning predates modern fuel ethanol production, dating back to the late 1960s. In its early days, CIP was primarily used in the food and beverage industry, which for years used strong acids and alkali products for cleaning. Caustic soda was, and often still is, the product of choice because of its excellent organic dissolving and saponification powers. Over the years, compounders formulated a wide variety of cleaning compounds, with the result being commercially available concentrated cleaners. Today, many people are unaware of how the additives are used, which is relevant to understanding how they function. The base of many cleaning solutions is caustic soda. Typically, the concentration of a CIP cleaner is 90% caustic soda that is 50% “active” sodium hydroxide. The remaining

10% is often a mixture of other chemical components. The current U.S. market for liquid caustic soda is approximately 11 million short dry tons, with a world market of approximately 43 million short dry tons. The market is generally sold on a dry ton basis and is generally billed on the active NaOH content. Most formulators, distributors, or manufacturers, when blending, will sell product on an “as is” pound basis or by the gallon. Some plants will use high-purity (membrane-grade) material because the chloride content of the lower grades of caustic soda has a long-term detrimental effect on stainless steel. Accurate blending of caustic soda is also important as the density and content of caustic soda changes at a non-linear relationship.

Formulating CIP Solutions

Clear Solutions USA and some other companies blend what is called an “additive package” into caustic soda to create more effective and efficient CIP solutions. These additive packages often consist of a chelant, a scale inhibitor, a dispersant and a surfactant. Some ingredients can be multifunctional. The formulation should vary from plant to plant because the effectiveness of this package depends on operating conditions of temperature, water hardness, pH range and, lastly, the final percentage of the working solution or the “set point.” The operating temperature should be known because certain chemical components are affected by the temperature and may not clean as well in high or low temperatures. The water hardness is also important because dif-

32 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

Cleaning

HOW IT'S MADE: Membrane-grade caustic soda production diagram. SOURCE: CLEAR SOLUTIONS USA

ferent amounts of chelating agents and scale inhibitors should be added depending on how high the water hardness is. The seasonal variances of the water hardness should also be noted, and the maximum value should be considered in formulating to maximize cleaning efficiency. The pH range determines the type of chelation package. The final set point should also be known because it determines the final concentration of caustic soda and the additive package. Once the operating conditions are known, the proper additive package can be determined.

Additive Package Components

Chelating Agent: The word chelant is from the Latin word chela meaning “claw.”

Chelants are materials that work in aqueous solutions to tie up metal ions so they are no longer effective. The term “chelating agent” refers to a molecule that contains two or more complexing sites or claws capable of coordinating around a metal ion. In technical terms, chelation is a kind of sequestration process whereby the chelating agent forms a nonionic ring structure with a di polyvalent cation by ionic valence bonding. Chelation is important because the chelating agents tie up the metal ions in hard water and inhibit their ability to interact with the other cleaning agents. The concentration of chelating agents needed is directly related to the water hardness. The harder the water, the higher the concentration required. When formulating an additive package, it is important to note the water hardness as well as the fluctuation of the water hardness in the plant.

WHAT'S INCLUDED: While the four components of a CIP additive package are constant, the concentration of each additive can vary from plant to plant, and seasonally. SOURCE: CLEAR SOLUTIONS USA

Cleaning

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CONDITIONS DEPENDENT: The effectiveness of a CIP additive package depends on several operating conditions: temperature, water hardness, pH range and the final percentage of the working solution, or “set point.” SOURCE: CLEAR SOLUTIONS USA

Scale Inhibitor: Scale is defined as deposit adhering to a surface. The scale inhibitor virtually modifies and attacks the crystal growth by changing the structure and prevents the scale from forming. In ethanol plants, scale can be formed with the presence of calcium, magnesium, iron, and other trace minerals. The most commonly formed scale is calcium carbonate, followed by calcium oxalate (beerstone). Dispersants: Dispersants attack the undesired species by using a high negative charge. This works much like two magnets with like charges (the magnets repel one another). The charge of the dispersants causes the contaminants to be more suspended within the solution, which allows for easier washing. Surfactant: The real breakthrough in CIP formulations was the addition of surfactants. Surfactants effectively lower the surface tension of a given solution. The decrease in surface tension allows for easier wetting of a surface as well as easier rinsing. This increase in wetting allows for less product use because the low surface tension allows for more spreading across a given surface as well as easy removal with a water rinse. Together, this also amounts to a decrease in cleaning time because the product is able to spread across the surface quickly as well as rinse easily. When first introduced, surfactants led to large amounts of foaming during the clean-

ing cycle. Over time, new low-foaming surfactants were developed and have eliminated the foam problem. The use of surfactants has been limited over the years due to caustic soda’s high concentration (50%). The high concentration of caustic soda limits the ability of surfactants to couple and causes the product to have difficulty going into solution. Clear Solutions has successfully trialed its CIP additive package at several ethanol plants in Indiana, Michigan, and Minnesota. These plants are currently using our formulations, which are patented and patent-pending. Producers using the package are realizing reduced caustic usage by 25 percent; elimination of calcium carbonate and calcium oxalate, reduced or eliminated hydroblasting of the evaporators; reduced amount of time needed to clean evaporators and other heavily soiled equipment; higher flow rates without additional steam, faster cleaning and reduced utilities (gas, electricity, water, and wastewater treatment) costs. The reduced time to clean has resulted in increased overall production and allowed for more time and resources for cleaning difficult equipment. Author: Lance Renfrow President & Founder Clear Solutions USA LLC 480-539-4276 lance@clearsolutionsusa.com

Spotlight BY TOM BRYAN

Next-Level Grain Grading for Ethanol’s Next Stage

Eurofins Grain Inspection supports industry with third-party grading and inspection services

Heinzman

While Eurofins is a global company with a network of 900 labs across 50 countries, the focus of its specialized Midwest grain segment—ready and waiting to help ethanol plants grade corn to more rigorous specifications—is the branch U.S. ethanol producers might soon rely on. Eurofins Grain Inspection, which offers robust inbound grain grading services for numerous large-scale processors including ethanol plants, can facilitate rail car inspection as well as submitted sample analysis— testing corn for moisture, foreign material, mycotoxins and more. While ethanol plants can and do grade corn effectively in house, an increasing number of them are working with third-party inspectors to enhance their grain inspection programs. “The need for submitted sample analysis is growing in the ethanol industry,” says Ben Heinzman, business unit manager for Eurofins Grain Inspection. “As more facilities switch to high-protein feed production,

36 | ETHANOL PRODUCER MAGAZINE | OCTOBER 2021

the quality of their inbound grain is becoming increasingly important—specifically as it relates to damage.” Producers working with Eurofins Grain Inspection will typically send the company corn samples that have already been graded for damage in house. “We can provide a cross-check—a verification of that initial grade,” Heinzman says. “With a scorecard system in place, the client will be able to see if they’re grading within spec, according to standard operating procedures (SOPs) we’ve set up together. If our grades don’t match up, we’ll work with them to figure out what’s going on, figure out what needs to be changed, and get things back in spec.” For many ethanol producers, adhering to rigorous grain inspection can be a major drain on personnel. “That’s especially true in this tight labor market, with hiring being difficult,” Heinzman says. “But when a plant works with us, our qualified grain inspectors go to work for them.”

Spotlight BY TOM BRYAN

Lab Products Tailored for Precision

Enertech and o2si are together supplying ‘dead-on accurate’ reference standards

Smith

Biggerstaff

When Jeff Smith's military career ended in 2007, he could not have foreseen the rewarding profession in ethanol he would embark on, much less that he would build a company known as one of the industry’s most trusted suppliers of HPLC lab supplies. “I was fortunate to have entered ethanol during the height of its buildout,” says Smith, CEO of Enertech Solutions. “And through that experience, I became aware of an opportunity to better serve the everyday needs of ethanol plant labs. There were plenty of suppliers focused on the big items, but almost none that cared about the smaller consumables critical to performance—from pipettes and tubes to HPLC columns, moisture pans and syringes.” Building Enertech’s reputation as a responsive, costconscious supplier, Smith continually expanded Enertech’s offerings, even custom manufacturing mobile phase products for its clients. The company’s years-long collaboration with reference standards maker o2si, for example, has resulted in the availability of tailored, industry-leading

standards (i.e., solutions used to calibrate lab equipment). In fact, Enertech and o2si, working together, are the only companies in the industry manufacturing and supplying certified reference materials under ISO 17025 and ISO 17034. “Customization is the bedrock of what we’re about,” Smith says, explaining that ethanol plants previously had to work with standards that were not precisely formulated for their needs. Dan Biggerstaff, Ph.D., of o2si says ethanol plants were largely confined to catalogue standards before his company began working with Enertech to bring the industry more tailored offerings. “There were a very small set of premade standards that all ethanol labs had to use, and they had to change the way they ran their labs to match those standards,” Biggerstaff explains. “Today, we are providing the standards they need, at the concentrations they need—which are dead-on accurate—to get the best data possible to optimize their process.”

ETHANOLPRODUCER.COM | 37

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