If you have an ACS member number, please enter it here so we can link this account to your membership. (optional)

ACS values your privacy. By submitting your information, you are gaining access to C&EN and subscribing to our weekly newsletter. We use the information you provide to make your reading experience better, and we will never sell your data to third party members.



What’s The Best Way To Make Green Cleaning Products?

Ingredient suppliers see more than one road to environmentally friendly products

by Michael McCoy
January 18, 2016 | A version of this story appeared in Volume 94, Issue 3

Credit: Yang H. Ku/C&EN/Shutterstock
Synthetic and biobased ingredients both seek a place in sustainable cleaning products.
An image of natural and synthetic ingredients in a detergent bottle.
Credit: Yang H. Ku/C&EN/Shutterstock
Synthetic and biobased ingredients both seek a place in sustainable cleaning products.

Calls urging the world’s citizens to lead more environmentally sustainable lives rang out from the highest reaches in 2015.

In May, the Vatican published a papal encyclical that singled out climate change as a source of poverty and inequality and urged an “ecological conversion” of the faithful.

In September, the United Nations launched a comprehensive set of sustainable development goals. And in December, leaders from 185 nations meeting in Paris pledged to hold the rise in global temperatures to below 2 °C by controlling greenhouse gas emissions through use of renewable energy and low-carbon products.

Terry F. Yosie, head of the World Environment Center, a business-backed environmental policy group, calls 2015 “one of the most consequential years for environmental/sustainability policy in our lifetimes.”

Yet it doesn’t seem as if the call is being heeded in the cleaning product aisles of the local Walmart and grocery store. After rising from 2007 to 2010, sales of cleaning products marketed as green or environmentally friendly declined from 2010 to 2014, according to the market research firm Packaged Facts.

U.S. retail sales of green household cleaners and laundry products fell to $600 million in 2014, Packaged Facts says, accounting for a mere 3% of the total cleaning product market. Outside of a few green-goods specialists, such as Seventh Generation and Method Home, cleaning product makers aren’t emphasizing natural ingredients or other environmental attributes on their bottles and boxes.

Is there a disconnect between what the environment needs and what the cleaning product industry is offering?

Managers who work for consumer goods companies and their ingredient suppliers insist the answer is no. Improving the environmental compatibility of their offerings is paramount for their businesses, executives contend. If “all natural” isn’t on the labels of the biggest brands, they say, that’s because natural ingredients aren’t the only—and may not even be the best—way to making cleaning products gentler consumers of the planet’s resources.

To be sure, nature-derived ingredients—often called renewable or biobased—are core for some companies. Seventh Generation, for example, says its laundry detergents are certified by the U.S. Department of Agriculture to be 97% biobased. Only minor ingredients, such as sodium hydroxide and preservatives, come from synthetic sources.

And even Procter & Gamble, the 800-lb gorilla in the laundry product aisle with brands such as Tide, Gain, and Downy, stakes a claim on biobased ingredients. “We are striving to create technologies to substitute our top petroleum-derived raw materials with renewable raw materials and will integrate those into our supply chain as cost and scale permit,” the firm said in its most recent sustainability report, released last month.

The report highlights P&G’s efforts to qualify bioderived versions of the polymers it uses to package many of its home and personal care products. The company says its next sustainability report will provide an update on efforts to develop biobased solvents, surfactants, and detergent acrylates.

Yet for several years P&G had a more ambitious goal: to replace 25% of its petroleum-based raw materials with sustainably sourced renewable materials by 2020. The company removed the numerical targets with the publication of its 2014 report.

P&G has made progress, says Jack McAneny, the firm’s director for global sustainability, pointing to the sugar-derived polyethylene it uses to package hair products and the corn-stover-based ethanol it adds to detergents as a solvent. But he says P&G has been challenged to find cost-effective renewable ingredients at the scale it needs.

McAneny also cautions that a company cannot blindly replace petroleum-derived ingredients with renewables. “Just because something is renewable does not necessarily mean it is ‘better,’ ” he says. “We continue to rely on life-cycle analysis and sustainable sourcing principles to help ensure the changes we make as we pursue our vision represent meaningful improvements.”

Companies that supply fossil-fuel-based ingredients to cleaning product companies take McAneny’s point even further. They assert that the meaning of sustainability for the cleaning product industry is evolving and becoming broader. For them, natural or renewable is far from the only road to green.

“I have seen the definition of green really evolve over the past five to eight years,” says Denise Peter­sen, global sustainability manager for BASF’s care chemicals division. “The evolution has been from a myopic approach focused on renewables to a more holistic one where there’s an awareness that there’s a lot more to being green than just renewable content.”

Kate Geraghty, global sustainability leader for Dow Chemical’s consumer care business, agrees. “Sustainability is not just about focusing on ingredients,” she says. “To focus purely on comparing synthetic and natural ingredients, you are actually missing most of the picture.”

Both sustainability executives explain that making sustainable consumer goods is also about lowering energy consumption and materials use throughout the product life cycle. Petersen says BASF works with customers to break down a retail product’s value chain into discrete links to better identify where its environmental profile can be improved.

Renewability comes into play mainly in the first link of that chain: ingredient raw materials. But the subsequent links of ingredient manufacturing, transportation to the customer, customer formulation, transportation to the retailer, and consumer use are individually just as important—and more important when taken as a whole.

“We look at the entire life cycle of a product to increase sustainability at every single step,” Petersen says.

Credit: Huntsman
A Huntsman technologist examines a sample of algae produced in a bank of photobioreactors as part of research into biobased surfactants.
A picture of a Huntsman researcher working with biobased surfactants.
Credit: Huntsman
A Huntsman technologist examines a sample of algae produced in a bank of photobioreactors as part of research into biobased surfactants.

With an eye on formulation by its customers, for example, BASF offers Plantapon 611 L, a high-active-content blend of three surfactants used in hand dishwashing detergents and other cleaning products, notes Michael Capracotta, who leads application technologies for the firm’s home care business. BASF consumes less fuel transporting such concentrates to customers, he notes, and customers consume less energy mixing them into the final product.

A bonus, Capracotta adds, is that BASF can often formulate such blends without synthetic preservatives because they contain little or no water.

Ingredients that help customers develop highly concentrated retail products also contribute to sustainability by reducing packaging and transportation costs, suppliers say. Calvin Chiu, director of Huntsman Corp.’s home and personal care business, points to his firm’s line of methyl ester ethoxylates, surfactants created by reacting a soy-oil-derived methyl ester with ethylene oxide.

Although these plant-based surfactants are efficacious removers of fats and oils, their low viscosity can make finished products appear watered-down. Huntsman says some companies have turned that shortcoming into an asset by creating highly concentrated laundry detergents that are dispensed more like a liquid hand soap than a traditional detergent.

One such product is Method Home’s 8X concentrated detergent, which the firm markets as requiring one-third less energy and plastic to produce. Chiu, who also heads the sustainability committee of the American Cleaning Institute, an industry association, won’t say whether Method is a Huntsman customer, but the 8X detergent’s ingredient label indicates that it does contain methyl ester ethoxylates.

At the end of the value chain, laundry detergents that work effectively in cold water also offer environmental benefits. In marketing its Tide Coldwater, P&G emphasizes that consumers can cut their laundry energy use 50%—and help the environment—by washing in cold water.

McAneny, the sustainability director, says P&G’s goal is to increase the share of machine washes completed in cold water around the world to 70% by 2020. The firm estimates that 56% of all loads are done in cold water today, up from 38% in 2010. Consumers who wash with cold water in high-efficiency machines, he adds, save both energy and water.

Given that opportunities for reducing the cleaning product industry’s footprint exist all along the value chain, Dow’s Geraghty cautions against an undue focus on whether an ingredient is synthetic or not. Better, she says, to explore how, regardless of origin, it can improve an end product’s environmental profile.

She cites Dow’s Acusol series of acrylic dispersant polymers. They can help European automatic dishwasher detergent makers remove phosphates from their products by a 2017 deadline and assist all companies in creating dishwasher detergents that work at low temperatures and in low-water rinse cycles.

Similarly, Thierry Sclapari, vice president of the Novecare home and personal care unit at Solvay, says synthetic polymers in product lines such as his firm’s Repel-O-Tex improve the efficiency of surfactants and can help customers design laundry detergents that work well in cold water. “If you meet sustainability goals with purely synthetic materials, so be it,” Sclapari says.

Although they are convinced of the environmental soundness of their synthetic ingredients, chemical company executives know that “natural” resonates loudly with certain customers and consumers. And the appeal of natural origins is undoubtedly higher for products applied in the home than it is for ones used in, say, construction or auto manufacturing.

Thus, most suppliers to the cleaning product industry are busy developing biobased chemicals to complement their traditional synthetic offerings. They want to be on the approved lists of customers looking to make green claims or reach renewable-content goals.

At Dow, for example, the biobased offerings include Ecosurf brand plant-based surfactants and Diamosolv 323 plant-derived solvent for hard-surface cleaners. In 2015, the firm introduced the Supracare line of cellulosic polymers, which add fabric-softening and color-rejuvenation properties to laundry products.

Of course, chemical makers are aware that customers and consumers alike can be wary if they have been burned by green products that don’t clean. “Customers want performance, and they’re not going to buy something that doesn’t work just to be green,” says Steven Snead-Smith, director of Evonik Corp.’s household care business.

Evonik has a lead in this game because its core line of fabric-softener actives is derived from natural fats and oils. One customer recently wanted even more, relates Dana Nystrand, an Evonik marketing manager, so Evonik is obliging by changing the solvent used with the customer’s softener from synthetic propylene glycol to a biobased solvent.

Another biobased heavyweight is Croda, which calculates that about 70% of the raw materials it consumes are from renewable resources. In an effort to push that number even higher, the firm announced plans last year to build a $170 million plant in New Castle, Del., that will produce ethylene oxide, a common surfactant raw material, from biobased ethanol rather than ethylene.

Croda and Evonik are outliers, but many companies consume a higher percentage of renewable raw materials in their home care ingredient businesses than they do as a whole. At Solvay’s Novecare business, for instance, renewables represent about 8% of the raw materials consumed, versus 4% for Solvay overall, according to Sclapari.

Petersen says renewables represent “significantly” more of the raw materials her business uses than the 4.5% share for BASF overall. By dint of its size, she adds, BASF is the world’s largest supplier of renewable ingredients for home care.

Even if sales of cleaning products marketed as green are slipping, demand for biobased ingredients is healthy, executives say. Huntsman’s Chiu estimates that they have grown from 5 to 6% of the cleaning ingredient market in 2009 to about 8% today.

As the market grows, though, constraints emerge. Many biobased surfactants are based on tropical oils such as palm kernel and coconut, and manufacturers are painfully aware that these tropical oilseeds are often being grown and harvested at the expense of rain forests and their wild inhabitants.

“There is no way we can ignore the threat posed to orangutans and other indigenous species,” Solvay’s Sclapari says.

Solvay, Croda, BASF, and other companies are members of the Roundtable on Sustainable Palm Oil, an industry organization that seeks to end the clearing of virgin forests and fragile ecosystems to plant palm trees. At the same time, ingredient manufacturers are looking beyond tropical oils to other biobased raw materials for their products.

Last July, BASF and the microalgae oil firm Solazyme launched what they call the first commercial surfactant derived from algal oil. The product, Dehyton AO 45, is a version of a betaine that is more typically produced by reacting a coconut fatty acid with an amine. It’s intended for use in shampoos, liquid soaps, and hand dishwashing liquids.

Evonik has developed a line of sophorolipid surfactants that it produces by fermenting sugar and a nontropical vegetable oil such as rapeseed in large vessels operated by its animal feed business. Nystrand, the Evonik marketing manager, says sophorolipids offer mildness and tailored foaming properties for applications such as hand dishwashing and hard-surface cleaning.


Solvay is working with a plant breeding firm to modify rapeseed oil to produce fatty acids with carbon chain lengths suitable for surfactant production, Sclapari says. The oil yields mostly 18-carbon fatty acids, whereas 12- and 14-carbon acids are best suited for surfactant production.

Partnering with L’Oréal and nongovernmental organizations, Solvay also runs an initiative in India to promote sustainable production of guar, a legume that yields guar gum. The gum’s main applications are in hair care, ice cream, and oil drilling fluids, but Sclapari says Solvay’s derivatization capabilities are opening markets such as dishwasher detergents.

Cleaning product industry newcomers also see a market for novel biobased ingredients. Logos Technologies recently started marketing research quantities of rhamnolipid surfactants, which are produced, like sophorolipids, by fermenting vegetable oil. Dan Derr, who leads Logos’s new NatSurFact business, says companies have long been interested in rhamnolipids for their mildness, low ecotoxicity, and biodegradability but have been stymied by a lack of large-volume production.

And last fall, the Montana-based start-up Rivertop Renewables began producing commercial quantities of glucaric acid, a six-carbon sugar acid made by carbohydrate oxidation. Glucaric acid is the main ingredient in Rivertop’s Riose, a phosphate replacement for automatic dishwasher detergents.

Gerry Nuovo, Rivertop’s vice president of market development for consumer products, says Riose sequesters calcium as well as phosphates and synthetic agents do. It also helps prevent corrosion in dishwashers. The product is now being introduced in a regionally distributed detergent, he says.

As biobased chemistry proliferates, chemical companies and their customers need to come together to scientifically determine which new ingredients are actually “greener” than the ones they replace, urges Chad Holzer, global business director for Dow Home, Institutional & Personal Care. “In our opinion, it’s still a little bit cloudy just what is a sustainable biobased solution,” he says.

And Holzer’s colleague, Geraghty, suggests the industry raise its aspirations beyond incremental improvements to sustainability. She points to the European Commission’s recently launched Circular Economy Package, which aims to promote recycling and stimulate what the commission calls industrial symbiosis—turning one industry’s by-product into another industry’s raw material.

Geraghty envisions a future in which cleaning product ingredients that end up in the environment are not just benign but actually restorative. “That would be a holy grail, a very high bar,” she admits. But for any ingredient that reaches that bar, whether it is natural or synthetic would be almost beside the point.  


U.K. organizations join to develop synthetic palm oil

Credit: U of Bath.
Chuck inspects a fermentation vessel containing a strain of M. pulcherrima to make palm oil in his lab in Bath.

Chuck inspects a fermentation vessel containing a strain of M. pulcherrima to make palm oil in his lab in Bath.
Credit: U of Bath.

In their quest to develop biobased ingredients, suppliers to the cleaning product industry can find themselves looking outside their own labs.

Specialty chemical producer Croda has joined a U.K. consortium to develop a fermentation process for converting waste lignocellulose into surfactants and other products that are similar to those derived from palm oil. The other partners are England’s University of York, University of Bath, agricultural technologies firm AB Agri, and engineering firm C-Tech Innovation.

Palm oil, a mixture of triglycerides , is one of the world’s chief sources of raw material for making surfactants. At $480 to $600 per metric ton, it is also one of the cheapest. But palm oil comes at a steep cost to tropical rain forest, which is often cleared to make way for palm plantations. A synthetic palm oil process could slow this deforestation.

The U.K.-based research project is set to optimize and scale up a lab-based process developed by Chris Chuck, a research fellow with Bath University. His team uses engineered Metschnikowia pulcherrima yeast to convert straw into palm-oil-like triglycerides. The research partners’ goal is to generate a product cheap enough to compete with palm, Chuck says.

The project has $6.5 million in funding—about $5 million from U.K. science funding agencies and the rest from Croda and the participating universities. Croda, a major palm oil consumer, is intent on making its supply chain sustainable, says Chris Sayner, vice president of global accounts.

The partners kicked off their four-year collaboration in late 2015. One of the engineering problems the scientists will have to solve is managing the heat the yeast generates when it respires. “This will be a challenge at scale,” Chuck says.

To date the yeast has proven to be hardy, performing under nonsterile conditions. It can tolerate a wide temperature range and low pH as well as high concentrations of inhibitors, Chuck says.

In addition to being suited to the production of a palmlike oil, M. pulcherrima has metabolic pathways that could be augmented to generate other commercially interesting compounds including flavors and fragrances such as 2-phenylethanol, which smells of roses. “There is enormous variety among the strains,” Chuck says.

His team has successfully tested the palm process in a 30-L reactor operated by Croda. Within the next two years Chuck hopes to test the process in a 2,000-L reactor. Once the project has made good headway, a researcher from Bath will be located at Croda for two years to work with the firm’s 30,000-L pilot fermentation facility.

York University’s role in the project is to apply a microwave heating technology for depolymerizing cellulosic material into sugars and oligosaccharides that can be consumed by the yeast. Later, microwaves blow the yeast cells open so that the oils can be recovered. Currently there is no industrial-scale biomass microwave process.

Chuck estimates that the process his team already developed could make a palmoil-like material for about twice the cost of natural palm oil. “We have so many angles to work on we are very confident that at the end of the four years we can reduce these costs further,” he says.—Alex Scott


This article has been sent to the following recipient:

Chemistry matters. Join us to get the news you need.