The new bio-based surfactant feedstock January 2022
By Rebecca Guenard
In This Section
- The new bio-based surfactant feedstock January 2022
- Lipid role in the immune system November/December 2021
- New essential dietary lipids? October 2021
- Gut Instincts September 2021
- Can computers make better plant-based foods? July/August 2021
- Poisson from a petri dish June 2021
- The latest additions to eco-friendly cleaning May 2021
- Preserving emulsions with plant-based antioxidants April 2021
- Developments in green surfactants for enhanced oil recovery March 2021
- Alternative base oils: a perspective March 2021
- The COVID-19 pandemic, one year later March 2021
- The green machine: commercializing microalgae products February 2021
- Bio-based (edible) oils: feedstock for lubricants of the future January 2021
- The latest on liposomes January 2021
- Fatty acids and athletic performance November/December 2020
- Where are lubricants headed November/December 2020
- New developments in vegetable oil materials science October 2020
- Agriculture at risk: preparing the oilseed industry for a warmer world September 2020
- Science highlights from a cancelled 2020 AM&E July/August 2020
- Managing your career in times of change June 2020
- Lipidomics comes of age May 2020
- Minimally processed oils April 2020
- The high-throughput frontier March 2020
- Nurturing innovation: how AOCS industries are fostering progress February 2020
- The trouble with studying omega-3s and the brain January 2020
- Understanding pulse anti-nutrients January 2020
- Digitizing manufacturing: how companies are using data to improve production November/December 2019
- Weaving together genetics, epigenetics, and the microbiome to optimize human nutrition October 2019
- Taking the cream out of ice cream September 2019
- Science highlights from St. Louis July/August 2019
- Biotechnology conquers consumer goods June 2019
- Cool characterization methods and where to find them May 2019
- Fermentation, the new protein supply chain April 2019
- Oleogels for drug delivery March 2019
- The complexity of clean-label cosmetics February 2019
- Rethinking plastic packaging January 2019
- Trends in synthetic and natural antioxidants for shelf life extension of meat and meat products November/December 2018
- The icing on the cake October 2018
- Enhancing oxidative stability and shelf life of frying oils with antioxidants September 2018
- Under arrest: investigating factors that govern partial coalescence July/August 2018
- Unconventional Oils June 2018
- Beauty from within May 2018
- Pulses rising April 2018
- Lessons learned from Hurricane Harvey March 2018
- Clean meat February 2018
- What makes your shortening suitable for fancy croissants, puff and Danish pastry? January 2018
- Strategic role of peanuts in sustainable global food security November/December 2017
- Science beyond borders: international student exchange October 2017
- Clean label: the next generation September 2017
- Science snapshots from Orlando July/August 2017
- Five new AOCS methods June 2017
- The whys and wherefores of life-cycle assessment May 2017
- China’s evolving edible oils industry April 2017
- The mysterious case of the arsenolipids March 2017
- Red palm oil February 2017
- The Highs and Lows of Cannabis Testing October 2016
- Chia: Superfood or superfad? January 2017
- Generational training divide November/December 2016
- Storage stability of roasted nuts and stabilization strategy using natural antioxidants September 2016
- Good vibrations: online and at-line monitoring of edible oils with vibrational spectroscopy July/August 2016
- Benchtop NMR spectroscopy for meat authentication June 2016
- Coconut oil boom May 2016
- Sink or swim: fish oil supplements and human health April 2016
- Pulsed electric field: groundbreaking technology for improving olive oil extraction March 2016
- Prescribing dietary fat: therapeutic uses of ketogenic diets February 2016
- Organogels of vegetable oil with plant wax January 2016
- The power of peptides November/December 2015
- Separation anxiety: membrane cleaning in the 21st century October 2015
- Using direct solid phase extraction to analyze persistent organic pollutants in oily food samples September 2015
- Big fat controversy: changing opinions about saturated fats June 2015
- Use of spent bleaching earth for economic and environmental benefit May 2015
- An introduction to cosmetic technology April 2015
- Food texture and nutrition: the changing roles of hydrocolloids and food fibers March 2015
- Scientists rank thousands of substances according to potential exposure level March 2015
- Clean smell does not always equal clean air February 2015
- Biotechnology: Using living systems to solve problems February 2015
- Flush to fuel January 2015
- 1970s fish oil study criticized January 2015
- Developing a high-performance, low-streak degreaser November/December 2014
- Detection, monitoring, and deleterious health effects of lipid oxidation November/December 2014
- Modified protein mimics taste and texture of fat October 2014
- Development of the first efficient membrane separations of cis fatty acids October 2014
- Regulatory updates on FSMA and combustible dust September 2014
- How enzymes are transforming manufacturing September 2014
- Two advances in biodiesel technology July/August 2014
- 2014 AOCS Annual Meeting & Expo July 2014
- Peanut genome sequenced June 2014
- A customized approach to frying oil June 2014
- Omics reveals subtle changes in carbon flux that lead to increased oil biosynthesis in oil palm May 2014
- Cannabis testing: a review of the current landscape May 2014
- Industrial hemp gaining traction April 2014
- Emulsions: making oil and water mix April 2014
- Lipid co-oxidation of proteins: One size does not fit all March 2014
- FSMA marches on March 2014
- Disruptive technology? Walmart’s “green” product line may signal a big change February 2014
- Pathways to novel chemicals February 2014
- Specialty lipids in pet nutrition January 2014
- EFSA releases preliminary report on occurrence of 3-MCPD in food January 2014
- Seven new biobased surfactant technologies November/December 2013
- Do oil color scales make you see red . . . or yellow? November/December 2013
- Shortage leads to green route to olefins October 2013
- Sesamol: a natural antioxidant for frying oil September 2013
- FSMA update September 2013
- Patent rights and biotech seeds July August 2013
- The other vitamin E July 2013
- Frac fever heats up June 2013
- Fat fight: Catch-22 for Western oleochemicals? June 2013
- Health and Nutrition News April 2013
- FDA asks for fees from industry to fund FSMA June 2013
- What does it take to start a biodiesel industry? April 2013
- What’s in a Claim? Would a Food Not Labeled “Natural” Taste as Sweet? March 2013
- Regulatory overview March 2013
- The preservative wars February 2013
- Plants producing DHA February 2013
- Swift response to paper on feeding GMO corn, glyphosate January 2013
- AOCS: supporting international standards January 2013
- TSCA and the regulation of renewable chemicals July August 2013
- trans Fatty acid content of foods in China January 2013
- A novel green catalytic process for biodiesel production from Jatropha November/December 2012
- The America Invents Act: Groundbreaking US patent law changes are here November/December 2012
- “Super Phos” esters: the key to higher-performance products November/December 2012
- Advances in field-portable mass spectrometers for on-site analytics October 2012
- EFSA sets upper intake level for LC-PUFA October 2012
- Malaysia: economic transformation advances oil palm industry September 2012
- High-oleic canola oils and their food applications September 2012
- Using enzymes to prepare biobased surfactants July/August 2012
- Oilseeds: at the center of food, water, and energy security July/August 2012
- Health & Nutrition News June 2012
- Hydrocolloids get personal June 2012
- The secrets of Belgian chocolate May 2012
- Plants “remember” drought, adapt May 2012
- The power of mass spectrometry in the detection of fraud April 2012
- Oil in biomass: a step-change for bioenergy production? April 2012
- The Future of LAB March 2012
- World supplies of rapeseed and canola likely to remain tight in the 2012/13 season March 2012
- Methods for differentiating recycled cooking oil needed in China February 2012
- Supercritical fluid-based extraction/processing: then and now February 2012
- Singapore: the place to be in 2012 February 2012
- The Food Safety Modernization Act and its relevance to the oilseed industry February 2012
- Oilseeds in Australia January 2012
- Hydrogen peroxide in home-care formulations November 2011
- A new generation of renewable fuels is on the horizon November 2011
- Omega-3 fatty acids: $13 billion global market October 2011
- Soy and breast cancer October 2011
- EU approves food labeling rules September 2011
- IOM panel recommends tripling vitamin D intake: Panel’s conservative approach receives criticism September 2011
- Self-assembly of lyotropic liquid crystals: from fundamentals to applications August 2011
- Sustainability watch July 2011
- Sustainability Watch July 2011
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- The trouble with crystal polymorphism June 2011
- Insect oils: Nutritional and industrial applications May 2011
- Reconstructing formulas April 2011
- US eggs now lower in cholesterol April 2011
- How to control eating behavior--in mice March 2011
- Maybe we don’t know beans March 2011
- Short- and long-term price forecasting for palm and lauric oils February 2011
- New 3-MCPD (glycidol ester) method February 2011
- Regulatory issues associated with the international oils & fats trade January 2011
- Point-counterpoint on UC Davis olive oil report January 2011
- Biomass--The next revolution in surfactants? December 2010
- One person’s response to a high omega-6 diet November 2010
- Crop residues as feedstock for renewable fuels November 2010
- Universal detectors for determination of lipids in biodiesel production October 2010
- New very long chain fatty acid seed oils produced through introduction of strategic genes into Brassica carinata October 2010
- Surfactants based on monounsaturated fatty acids for enhanced oil recovery September 2010
- Questioning the virginity of olive oils September 2010
- Dietary guidelines report released August 2010
- Keeping up with detergent chemistry August 2010
- News from the Expo floor July 2010
- Degumming revisited July 2010
- First high-GLA safflower oil on market June 2010
- AOCS 2.0 debuts June 2010
- Palm fatty acid distillate biodiesel: Next-generation palm biodiesel May 2010
- Palm oil pundit speaks May 2010
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- The ultra-low-linolenic soybean market April 2010
- Dealing with the media: A cautionary tale March 2010
- Hempseed oil in a nutshell March 2010
- Carbon management 101: A conversation with Eric Jackson February 2010
- Giants of the Past: Hermann Pardun (1908-2009) February 2010
- Q&A with Bill Christie February 2010
- Update on Jatropha January 2010
- Unique properties of carbon dioxide-expanded lipids January 2010
- The market situation and political framework in Germany for biodiesel and vegetable oil December 2009
- Industrial oil crops-when will they finally deliver on their promise ? December 2009
- Chemically enhanced oil recovery stages a comeback November 2009
- Field-portable mass spectrometers for onsite analytics: What's next? October 2009
- To make biofuels, or not to make biofuels:That is the question. September 2009
- Melamine analysis at the forefront September 2009
- Global oil yields: Have we got it seriously wrong? August 2009
- Omega-3 fatty acid profiling and dietary forensics August 2009
- Oilseeds of the future part 3 July 2009
- The rise and fall of surfactants lore July 2009
- Oilseeds of the future: Part 2 June 2009
- Codex Alimentarius Commission update June 2009
- Raw material sources for the long-chain omega-3 market:Trends and sustainability. Part 3. May 2009
- Oilseeds of the future: Part 1 May 2009
- Chloroesters in foods: An emerging issue April 2009
- Raw material sources for the long-chain omega-3 market: Trends and sustainability. Part 2. April 2009
- Synthetic HDL created March 2009
- Raw material sources for the long-chain omega-3 market:Trends and sustainability. Part 1. March 2009
- A convenient way to increase legume intake February 2009
- Vitamin E’s safety controversy January 2009
- Universal mechanism of aging uncovered? January 2009
- Conventional soybean oil is not common for making laundry surfactants since the long chain length of its fatty acids leads to molecules that lack the physical properties necessary for stain removal. Epoxides of conventional soybean oil can further lead to rapid side reactions causing undesirable by-products.
- Epoxidized high-oleic soybean oil (HOSO), however, offers the flexible chemistry necessary to adjust functional groups, bio-based content, and hydrophilic-lipophilic balance.
- Researchers claim they have developed 49 HOSO surfactant candidates, including cationic, anionic, nonionic, and amphoteric, with up to 100% biobased content that are stable over a range of pHs.
- New HOSO surfactants are poised to launch in a range of business areas.
Scaling and commercializing sustainable surfactants has been an arduous challenge manufacturers attempted to surmount starting in the early 2000s. Researchers continue to pursue a solution since the ubiquity of surfactants for both home and industrial use implores sustainable sourcing. For example, analysts predict continued growth in the global cleaning products market alone will reach $58.3 billion by 2024 (https://tinyurl.com/6jb5hjvy). Low-toxicity, natural alternatives to petroleum-based surfactants would guarantee the sustainable use of these compounds in household cleaning, as well as agriculture, bioremediation, and personal care applications, for decades to come.
Pursuit of naturally sourced surfactants has taken many routes. One way to get environmentally friendly products is to take advantage of the surfactants present in the roots, seeds or leaves of plants. Although a small number of compounds, like lecithin and saponins, have achieved some level of commercial success, most remain too expensive to process at a high enough yield to commercialize for a large market. Biosurfactants, excreted from a microorganism, do not require as much chemical processing, but do undergo extensive purification to isolate the desired compound from a stew of biochemical products. Rhamnolipid biosurfactants have creeped into more household and personal care items, but so far cost of production has limited their wide-spread use.
Bio-based surfactants, made by replacing petroleum-sourced hydrophobic carbon chains with fatty acids from vegetable oils or animal fats, have proved to be the most economical way to produce a more sustainable ingredient. Coconut and palm kernel oils, containing up to 60% lauric acid (12:0), are currently the major feedstocks for the surfactant industry. Battelle Memorial Institute, a non-profit, technology development company in Columbus, Ohio, filed a patent last year introducing a new feedstock to compete against them.
“Since soybeans can be grown more sustainably than current feedstocks, we were interested in figuring out a way to make surfactants from C18 instead of C12,” says Dan Garbark, lead materials scientist at Battelle (http://www.battelle.org/). Instead of lauric acid, he says they focused on oleic acid as the building block for their natural surfactants.
The development groups of two different ingredient companies have also recently announced their efforts to take advantage of the more plentiful feedstock. Are soybeans likely to become a prominent bio-based feedstock?
According to industry groups like the United States Soybean Export Council, soybean oil is one of the most economical and sustainable bio-based feedstocks. Almost 100% of US farmers participate in the Soy Sustainable Assurance Protocol (SSAP) following a set of guidelines to ensure responsible farming. The US Department of Agriculture conducts audits on participating farms as an independent third party. In addition, they are held to the standards of the European Feed Association. While adhering to current benchmarks for protecting environmental resources, SSAP members commit to continuously improve their sustainability performance.
The reputation of soybean oil and meal as a petroleum replacement has grown in the past decade. Chemical and materials manufacturers are achieving the high-performance requirements for applications like asphalt and tires from soybean feedstocks in markets where petroleum-based products have been a holdout. In particular, high-oleic soybeans gained the attention of researchers interested in the development and commercialization of sustainable versions of performance-demanding products since its fatty acids remain stable in extreme conditions.
High-oleic oils contain concentrations of between 60 and 90% oleic acid content, with a corresponding reduction in the amounts of linoleic and linolenic acids compared to conventional oils (Fig. 1). Varieties of high-oleic sunflower, safflower, and canola have been available for some time. By comparison, soybean is new to the high-oleic scene, but its unique chemistry makes it well-suited for surfactant development compared to other high-oleic crops.
Garbark says his group used an epoxidation ring-opening reaction to produce surfactants with different hydrophilic-lipophilic balances. This versatile industrial reaction involves forming ether groups by adding alcohols onto epoxides at the site of unsaturation. The chain length and functionality of the hydrophilic portion of the resulting surface-active molecule can be modified for specific performance needs.
The single unsaturated bond in oleic acid simplifies the ring-opening epoxide reaction. Multiple unsaturated bonds, as in linoleic and linolenic acid, can lead to cross-linking during the ring-opening reactions. These reactions decrease water miscibility and cause sporadic gelation of the surfactant when attempting to formulate for laundry applications. By contrast, functional groups can be added to the epoxidized oleic acid without interference from nearby epoxides leading to undesirable properties.
Finally, surfactants made from high-oleic soybean oil cost less to produce at commercial scale than other plant-based materials since epoxidizes can be formed at low temperatures using enzymes. Also, since there are fewer reaction products, minimal purification is needed to isolate the desired surfactant.
Formulating for detergents
Currently, only about one percent of conventional soybean oil is used for surfactant production. Garbark says a highly reactive hydroxyl can be used effectively to functionalize the fatty acids in epoxidized conventional soybean oil for surfactant synthesis. However, new high-oleic varieties of soybeans, predicted to increase production to 600 billion pounds in the next two years, will bring a welcome expansion to current bio-based options.
According to Garbark, the detergents market in the United States will require an estimated 14.3 billion pounds of surfactants in 2022. Currently, only a third of the surfactants in cleaning applications are made from bio-based sources. Therefore, his organization chose to first target this growing market when developing high-oleic soybean surfactants. He says his research group synthesized molecules with a range of functionalities using plant-sourced chemicals, and then evaluated their effectiveness on stain removal.
Of the 49 surfactants Battelle developed, they created more HOSO equivalents for nonionic surfactant than for anionic surfactants. However, they synthesized HOSO replacements for cationic, anionic, nonionic, and amphoteric surfactants, typically using 60% soybean oil by weight; although, they could go as high as 100% bio-based.
In developing their product range, Garbark says they started by making ethoxylates and propoxylates of hydroxy-acids, such as citric, lactic, and malic (Fig. 2). The alkoxylates of those acids create a more reactive hydroxyl group which could lead to future production benefits. In addition to these initial structures, they created dozens of other soy-based surfactants with functionalities corresponding to popular surfactants currently on the market. Then the researchers tested those surfactants.
Performance and price
In early testing, the soy-based structure formed by a reaction with citric acid resulted in a surfactant with improved stain removal when replacing the nonionic surfactant in a standard laundry formulation. The standard formulations contained sodium dodecylbenzene sulfonate, sodium lauryl sulfate, cocamidopropylbetaine, and other surfactants that are common in name brands. Successful stain removal compared to the standards encouraged the researchers to test against off-the-shelf detergents (Table 1).
“A mix of all soy surfactants, with a small amount of sodium xylene sulfonate to maintain solubility, surprisingly resulted in equivalent cleaning to off-the-shelf detergents,” said Garbark.
The formulation, composed of nearly 90% bio-based content, achieved soil removal for common stains even when scaled up to 30 gallons. In addition, other newly developed surfactants showed potential for applications in oil recovery and hard surface cleaning. However, he says his group has not yet considered personal care surfactants.
Garbark said his group evaluated the costs of producing the surfactant candidates that performed stain removal best. Taking into consideration both capital expenditures and operating expenses, they found that several of their soy-based products were cost equivalent to surfactants currently on the market.
HOSO in personal care
Rob Comber, vice president of research and development at Colonial Chemical, in South Pittsburg, Tennessee (https://colonialchem.com/), also says that for certain products high-oleic soybean surfactants can bring down cost. For several years, his specialty chemical company has been evaluating where the longer fatty acid chains in soybean oil could be advantageous as personal care ingredients.
“The shorter chain lengths you get from palm and coconut oils are traditionally more popular in a surfactant company because they provide more detergency and foaming,” Comber says. “But soy-based products provide different benefits, like thickening and shine, that are important in the personal care space.”
Comber says, for customers interested in developing sustainable, palm-free surfactants, his group at Colonial has expanded their soy-based product line to include HOSO surfactants. Among other compounds, they have a hair conditioning ingredient proven to lower combing forces and a deodorizer that enhances odor removal. He says his group also developed a high-oleic soybean oil equivalent to replace olive oil in product formulations. The HOSO surfactant significantly reduces the price to manufacture personal care products that contain olive oil.
“So far, the personal care side of the business has been more involved with finding uses for what we have developed,” Comber says. “With time, I think other business areas will find applications for some of these candidates.” He says the utility of soy should not be considered for personal care alone, it can be used for a broad range of industries.
Enhancing biosurfactant processing
In addition to the synthesis of new bio-based surfactants from HOSO, biotech manufacturer Jeneil, based in Saukville, Wisconsin, is evaluating HOSO’s potential as a substrate for rhamnolipid production (https://www.jeneilbiotech.com/). Researchers compared the fermentation of different oils to see how they affected rhamnolipid yields. They found that more of the biosurfactant formed in the presence of high-oleic oils than those containing a greater proportion of linoleic acid.
Tom Overbeck, research scientist at Jeneil, says the company hopes to optimize its established soybean oil fermentation processes using high-oleic varieties. If the switch successfully increases rhamnolipid yields, the cost of producing the biosurfactants would decrease, lowering a barrier for bringing more of these surfactants to the marketplace.
The GMO hurdle
While high-oleic soybean oil has great potential to revolutionize the plant-based surfactants industry, opposition to genetically modified (GM) organisms could limit its potential. In 2018, the Court of Justice of the European Union in Luxembourg ruled that gene-edited crops mimicked conventional genetically modified organisms enough that they should be regulated according to the same strict standards. While the law is meant to impose restrictions for developing GM crops for food, business developers generally avoid any GM application to sidestep regulatory procedures and negative consumer perceptions.
The most efficient way to produce high-oleic soybean oil is through genetic mutation. By altering the genes that produce the enzyme responsible for removing hydrogen atoms and creating double bonds (known as fatty acid desaturase), scientists restrict how much linoleic and linolenic acids a soybean plant produces. Food-grade high-oleic soybean oil is gaining popularity in the United States as the product proves its value through longer frying times in restaurants and greater stability of baked goods. As industrial uses also gain success, the acreage of gene-edited soybean in the United States is likely to increase (https://tinyurl.com/eawptxb7).
Growers will have to wait and see if EU companies adopt high-oleic soybean oil for industrial use. So far, they remain hesitant. Garbark noted that Battelle has developed a handful of surfactants using commodity soybean oil for customers interested in ingredients that have not come from gene-edited plants. Comber says his company has also developed products from conventional soy. Regardless of the soybean oil’s source, these plant-based surfactants have proven their potential for manufacturing new products.
“You would not normally think of getting a detergent or surfactant from a molecule with a C18 chain length,” Comber says. “Battelle found a clever way to get into laundry by doing that. In the next ten years, we are going to see soy-based products like this in a lot more business areas.”
To find out more about HOSO surfactants, view two recent presentations outlining their development. During the 2021 AOCS Annual Meeting, Dwight Rust, commercialization manager for the consulting group Omni Tech International, introduced the new technology. A few months later, the consulting group hosted a webinar in which Dan Garbark described the bio-based chemistry in detail and Rob Comber discussed some of the soy-based surfactants Colonial Chemical has developed for personal care ingredients. Both innovations rely on high-oleic soybean oil as a platform for developing natural surfactants (https://tinyurl.com/3y7b8x4j).
About the Author
Rebecca Guenard is the associate editor of Inform at AOCS. She can be contacted at firstname.lastname@example.org
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