Ethanol HPLC: Making Standards More Specialized

With an impeccable production partner, deep roots in ethanol and a customer base looking for tailored HPLC products, Enertech Solutions is elevating reference materials through customization and robust accreditation.
By Tom Bryan | October 16, 2022

Enertech Solutions is best known as a responsive provider of ethanol plant lab supplies from everyday consumables like vials and filters to containerized liquids like buffer solution and sulfuric acid. But for half a decade, producers have also turned to the Ohio-based company for specialized high performance liquid chromatography (HPLC) products, including mobile phase bags and ethanol-specific reference materials, or “standards,” that can be tailored to each customer’s unique analytical needs.  

Jeffrey Smith, Enertech’s president, says the company’s growing volume of business in both areas is the result of building strong relationships with producers.

“We partnered with Dr. Dan Biggerstaff, of Charleston, South Carolina-based o2si—ISO accredited to 9001, 17025, and  17034—with the idea that there was a better way to provide calibration standards to the ethanol industry. This better way focused on supplying custom, made-to-order standards at prices and turnaround times comparable to off-the-shelf suppliers. Concentrating superior technical skills with world-class customer service has allowed the partnership with o2si to make that idea a reality and become a leader in custom ethanol calibration standards. This commitment to excellence has driven our growth into expanded markets, including organic and inorganic calibration standards, innovative laboratory products and specialty reagents and solutions.”

Called to Customization
The HPLC is the heart of every ethanol lab; it’s the eyes and ears of the entire process and gives daily critical information that directs the entirety of plant operations. Ethanol plants use HPLC to monitor environmental compliance, process conditions and the progression of ethanol fermentations—the conversion of sugars to ethanol, ethanol breakdown to acetic acid, yeast health and more. The process tracks analyte molecules as they separate and flow through an HPLC column; the analyte is characterized by comparative analysis to a manufactured reference standard. Reference materials have been used for decades, but until recently didn’t always offer the precise results ethanol producers wanted. The problem with established catalog standards, Smith says, is that a one-size-fits-all approach was too often not meeting the needs of an increasingly diversified ethanol industry producing not only fuel ethanol, but specialized alcohols and a wide range of high-value coproducts.

It is very difficult for an ethanol plant to carry out an optimization to get even 0.2% more alcohol out of a batch if the facility’s reference standards have the slightest variability. “But that’s what we make possible,” he says. “Those very tight optimizations call for reference materials that are absolutely dead-on accurate.”

To be clear, there is not a crisp line between a catalog standard and a custom-manufactured one, says Bezhig McMurtrie, a former ethanol plant lab manager who now works in sales and customer support at Enertech. “Actually, from the moment a producer accepts formulation, that new standard is officially their catalog item,” she says. “But, if over time that standard no longer fits their needs, it can be changed. So, think of it as a catalog standard that’s flexible.”

For those not familiar with the HPLC process, Biggerstaff explains that it’s not just a matter of designing singular reference standards for ethanol producers, but whole calibration sets that synchronize with a plant’s analytical objectives and fermentation profiles. “Early on, a standard calibration routine with, say, 13 components to it, would simply have higher and higher concentrations [of the same makeup], so everything kind of scaled the same in those calibration sets. That was standard operating procedure,” he says. “But actual fermentations have very high starch and sugar and very low ethanol when they start. Later, the ratios change with each level, so that they end up being high ethanol, low sugars. We’ve designed calibration sets to mimic the fermentation process so the actual responses and accuracies for those runs and calibration points are essentially dead on to what’s happening in the fermenter. That was not being offered to ethanol producers previously.”

McMurtrie concurs, saying that when she was working in ethanol production, and an early customer of Enertech’s reference standards, her lab followed the exact model described by Biggerstaff, dropping sugars from high to low and ethanol from low to high—across a five-level calibration set, achieving an ideal R2 of 1.0. “It was phenomenal for a fermentation set with that many components,” she says. “And there was nothing like it on the market.”

McMurtrie adds, “There should never be mystery peaks in reference standards, yet we see that with some of the products available to the industry. When they show up, they can interfere with the integration of intended analytes.”

McMurtrie also explains that most reference standards on the market are still made with the average fermentation profile in mind, but it’s hard to find an “average” plant these days. “Everyone in the ethanol industry knows each plant is very unique, in so many ways,” she says. “Custom standards allow producers to focus on specific components and ranges that are relevant to their own products and operation.”

She continues, “There was a time when the standards available to producers only went to, say, a 12 percent ethanol. The market outgrew that, but it took time for that manufacturing response to happen, for the market to catch up with rising performance standards in ethanol production.”

Furthermore, McMurtrie says, a decade of diversification in ethanol production has resulted in roughly 200 U.S. ethanol plants with uniquely diverging processes, products and testing methodologies, which makes customization vital. “There are a lot of frontiers to explore with analytics right now, and the way the industry is diversifying so rapidly, we can’t possibly sit back and expect a one-size-fits-all standard to meet the needs of anyone, let alone the whole industry,” she says. “We need to get out front with our customers pushing the limits of processing, and help them develop these processes optimally, so they are not flying blind.” McMurtrie adds that this includes not only HPLC standards but also standards for gas chromatography (GC) for denaturant, fusel oils and other impurities that are needed in the U.S. Pharmacopeia (USP) market, as well as ion chromatography (IC) standards.

Advantaged by Accreditations
The reference standards Enertech delivers to ethanol plants are not only tailored and custom formulated to the needs of today’s producers, but backed by very high levels of accreditation, pre-delivery analysis and manufacturing quality control.

Biggerstaff explains that accreditations associated with the production of reference materials are largely rooted in quality assurance but deliver the tangential benefit of legally defensible product analytics. “If any analytical number generated from a method finds its way into legal action for any reason, whether its regulatory, a trade dispute or whatever, being able to defend that reference material in court is absolutely vital for the producer that generates that data,” he says, detailing o2si’s reference material accreditations, specifically ISO 9001 (for overall quality management) and ISO 17025 (for quality control lab), which guarantees the supplier is using documented data quality, validated methods, validated instruments, proper training and numbers that are traceable back to National Institute of Standards and Technology (NIST) calibrated weights.

In addition, the company adheres to ISO 17034 for the actual manufacturing of the reference materials. “And what that says is that we’re making products in essentially the same manner and level of quality as NIST—which is the gold standard,” Biggerstaff says. “So, the whole process is highly documented. Everything is traceable. Everything is analyzed.”

Those accreditations set Enertech apart, Smith says. “We’re the only game in town with this level of accreditation behind our standards along with the gravitas of customization behind them,” he says. “They’re reference materials you can take to court, literally, if you need to. Producers want traceability—on the alcohol side and the feed side. Tracing back to NIST is important, but you need more than that. What are your accreditations and your auditing regimen? In all those areas, we’re ahead of the curve.” 

In addition to industry-leading accreditations, Enertech’s reference materials are manufactured by o2si with exacting levels of neat material characterization—including detailed breakdowns of purity and impurity levels in each component of a standard—along with uncertainty budgets, or error spreads, which are increasingly important to producers exporting ethanol or making USP alcohol or grain neutral spirits.

“If you want to sell your product into new or special markets, you’ve got to provide that,” McMurtrie says. “It’s especially true with higher-grade alcohol. There is zero room for error when it comes to alcohol for healthcare products or consumables; ISO accreditation lets you operate confidently knowing your data is going to be defensible. It’s the foundation of quality assurance.”

Smith and Biggerstaff agree that their ability to elevate, change and expand the existing catalog of ethanol plant HPLC reference materials has been a story of customization, producer engagement and rigorous manufacturing discipline.

“The amount of technique and knowledge and training that goes into making a reference material is incredibly complex, especially as it relates to reducing error to the smallest amount possible,” Biggerstaff says. “It’s very important that we get it right because people rely on us for their livelihoods, their health, their safety. Regulatory, policy and product quality decisions are based, in part, on the work we do. So, every single step we do is incredibly important, from the initial QC of the neat material, to the mixing, the bottling, the labeling, how we ship it—everything—it all has to be done right. After all, these reference materials have a major impact on not only ethanol production, but the world around us.”

Author: Tom Bryan
Contact: [email protected]