Verdezyne, CB&I, Albemarle, Dow AgroSciences, Newlight Technologies land 2016 Presidential Green Chemistry Challenge Awards

In Washington, the EPA announced that Verdezyne, CB&I, Albemarle, Dow AgroSciences, Newlight Technologies and Princeton Professor Paul Chirik are winners of the 2016 Presidential Green Chemistry Awards.

Though less well-known than the Presidential Challenge on Fitness, Sports and Nutrition — think of it as basically the same thing, only for really tiny athletes. In this case, molecules, microbes and their metabolic and synthetic pathways by which they do important work but with a smaller carbon footprint.

An independent panel of technical experts convened by the American Chemical Society Green Chemistry Institute formally judged the 2016 submissions from among scores of nominated technologies and made recommendations to EPA for the 2016 winners.

During the 21 years of the program, EPA has received more than 1600 nominations and presented awards for 109 technologies. Winning technologies are responsible for annually reducing the use or generation of more than 826 million pounds of hazardous chemicals, saving 21 billion gallons of water, and eliminating 7.8 billion pounds of carbon dioxide equivalent releases into the air.

The Winners in Brief

– Verdezyne is being recognized for developing a yeast that produces a chemical used to make high performance nylon 6,12 for hairbrushes toothbrushes, adhesives, coatings, fragrances, and automotive and aviation oils. In addition to using a plant-based feedstock and having lower greenhouse gas emissions, this process is also safer because it does not use high temperatures or concentrated nitric acid. The product has qualified for the USDA Certified Biobased label.

– Newlight Technologies is being recognized for developing a plastic made from methane-based greenhouse gas. It is now used to make bags, cell phone cases, containers, furniture and other products, and has been adopted by Dell, Hewlett Packard, KI, Sprint, Virgin, the Body Shop and other companies. This plastic is net carbon negative. It is less expensive and has equal or greater performance than traditional petroleum-based plastic products. It is commercially successful, with contracts for almost 30 billion pounds of product and a 50 million pounds per year expansion plant that is already sold out.

– Dow AgroSciences is being recognized for developing and commercializing Instinct, an additive that reduces fertilizer nitrate leaching ground and surface waters. It also reduces atmospheric nitrous oxide emissions. Nutrient pollution is one of America’s most widespread, costly and challenging environmental problems.  Reducing nutrient run-off from agricultural operations is a high priority for EPA. Retaining applied nitrogen longer in the plants’ root zones is optimal for crop utilization and yield, and for reducing run-off. In 2014 alone, the Dow AgroSciences technology added about 50 million bushels of additional corn – equating to about $205,500,000 additional production revenue for U.S. corn growers – and reduced carbon dioxide emissions by about 664,000 metric tons.

–  Professor Paul Chirik of Princeton University is being recognized for discovering a new class of catalysts that are used to produce silicones, found in silicone rubber, tires, shampoos, furniture fibers and paper coatings without using hard-to-obtain platinum. This could reduce the mining of ore which reduces costs, greenhouse gas emissions and waste. This technology could cut energy usage by 85 billion BTUs/year, waste generation by 8.5 million kg/year and carbon generation by 21.7 million kg/year.

– CB&I and Albemarle are being recognized for developing and commercializing safer technology to produce alkylate, a clean gasoline component produced at about 30 billion gallons per year, 60% of which is produced in North America. CB&I, Albemarle, and Neste have replaced the traditional toxic and corrosive liquid acid catalysts with safer technology that has a lower environmental impact.

Reaction from EPA

“From academia to business, we congratulate those who bring innovative solutions that will help solve some of the most critical environmental problems,” said Jim Jones, EPA’s assistant administrator for chemical safety and pollution prevention. “These innovations reduce the use of energy, hazardous chemicals and water, while cutting manufacturing costs and sparking investments.  They even turn pollution into useful products. Ultimately, these manufacturing processes and products are safer for people’s health and the environment. We will continue to work with the 2016 winners as their technologies are adopted in the marketplace.”

The winners in detail

CB&I, Albemarle: AlkyClean Technology:  An Inherently Safer Technology for the Production of Gasoline Alkylate

Summary of Technology: 

Alkylate is a highly valued “clean fuels” blending component for motor gasoline. It consists of clean-combusting isoparaffins that have low vapor pressures and high octane values. Alkylate also does not contain toxic components such as aromatics, olefins, or sulfur compounds. Alkylate is the preferred gasoline blending component for compliance with relevant environmental regulations.

Alkylate is produced from the reaction of isobutane and light olefins (C3-C5). Alkylate production is currently about 30 billion gallons/year worldwide, of which 60% is located in North America. A challenge facing refineries today is that alkylate production requires the use of liquid acid catalyzed processes, typically hydrofluoric acid or sulfuric acid. Hydrofluoric acid, in particular, is extremely toxic and, upon release, forms clouds that can be lethal for up to five miles.

For more than 40 years, scientists have been trying to replace liquid acid technologies with a greener solid acid catalyst technology. Prior approaches failed because of poor product selectivity and/or excessively rapid catalyst deactivation, coupled with the lack of an acceptable catalyst regeneration procedure. In some cases, these catalysts used leachable corrosive components such as halogens, triflic acid, and boron trifluoride, which could migrate into product streams.

Albemarle and CB&I developed a catalyst-process combination technology, the AlkyClean® solid acid alkylation process, which coupled with CB&I’s novel reactor scheme, produces high quality alkylate without the use of liquid acid catalysts. Additionally, neither acid-soluble oils nor spent acids are produced, and there is no need for product post-treatment of any kind.

Albemarle’s AlkyStar catalyst was designed for use exclusively with the AlkyClean® alkylation process. It uses a type of zeolite catalyst that is well-proven in the industry. The strength and the number of acid sites on the catalyst have been optimized to enhance hydrogen transfer reactions over multiple alkylation reactions. The catalyst particle size and porosity were also optimized using a pilot plant and a demo unit that allowed the investigation of regeneration procedures as well.

The world’s first commercial-scale, solid catalyst alkylation unit was started up in August, 2015. The unit employs the AlkyClean® technology and has a capacity of 2,700 BPD alkylate production. The plant has met or exceeded all performance expectations and is producing an alkylate product of quality that is on par with existing technologies.

Dow AgroSciences: Instinct Technology – Making Nitrogen Fertilizers Work More Effectively for Farmers and the Planet

Summary of Technology: 

The demand for higher crop yields and agricultural productivity is ever increasing, and so are concerns for the negative impacts on the environment caused by agricultural activities. Human activities related to farming account for a significant percentage of nitrate in ground and surface waters as well as nitrous oxide emissions. An estimated 75 percent of all nitrous oxide emissions, for example, come from agricultural activities such as applied nitrogen fertilizers and manures.

Crop genetics and precision application methods have improved the efficiency of applied nitrogen fertilizers, but losses to the environment are still significant after soil bacteria quickly convert nitrogen from the applied urea or ammoniacal form to nitrate. In the nitrate form, nitrogen fertilizer is susceptible to losses through leaching or as emissions in the form of nitrous oxide. Furthermore, nitrate fertilizer that leaches out of a plant’s root zone is no longer available to provide nutrients to the crop.

Scientists at The Dow Chemical Company discovered a powerful nitrification inhibitor that can inhibit soil bacteria from rapidly converting nitrogen in the ammoniacal form to nitrate, thereby retaining more nitrogen in the more stable ammoniacal form. By keeping nitrogen in the root zone for a longer period during the season, Dow’s nitrogen stabilizers improve Nitrogen Use Efficiency and reduce nitrogen loss through leaching and nitrous oxide emissions. N-Serve® was the first commercial product introduced by Dow in 1974, but it is only suitable for use with anhydrous ammonia fertilizer applications due to the limitations of its physical-chemical properties.

In 2010, Dow AgroSciences launched a novel, aqueous microcapsule suspension product, Instinct®. This patented technology can be conveniently used with other commonly used nitrogen fertilizer sources, enabling adoption of the product for multiple crops in the U.S. and around the world. As an aqueous suspension of a microencapsulated active ingredient, Instinct®, also provides additional environmental benefit by significantly reducing the amount of petroleum-based solvents used per treated acre.

In less than five years, acres treated with stabilized nitrogen have grown more than five-fold. In 2014 alone, based on calculated adoption of Instinct® in the U.S., it is estimated that use of the technology reduced carbon dioxide equivalent emissions by about 664,000 metric tons and increased U.S. corn production by about 50 million bushels, equating to about $205,500,000 additional production revenue for U.S. corn growers.

Newlight Technologies: AirCarbon: Greenhouse Gas Transformed into High-Performance Thermoplastic

Summary of Technology: 

Methane is emitted by natural sources such as wetlands. It is also the second most prevalent greenhouse gas emitted in the U.S. from human activities, such as leakage from natural gas systems and the raising of livestock. Methane’s lifetime in the atmosphere is much shorter than carbon dioxide, but methane is more efficient at trapping radiation. Pound for pound, the comparative impact of methane on climate change is more than 25 times greater than carbon dioxide over a 100-year period.

Newlight Technologies developed and commercialized a carbon capture technology that combines methane with air to produce AirCarbon, a high-performance thermoplastic material that matches the performance of a wide range of petroleum-based plastics while out-competing on price. Newlight’s biocatalyst combines air and methane-based carbon to produce polymers at environmentally friendly, ambient conditions. Despite the conceptual simplicity, previous technologies utilizing carbon capture to manufacture plastics resulted in production costs that were significantly higher than petroleum-based manufacture of plastics.

To overcome this long-standing cost challenge, Newlight developed a biocatalyst that does not “turn itself off” based on the amount of polymer being produced. To do this, Newlight developed a process to disable the negative feedback receptors on polyhydroxyalkanoate polymerase, the central polymer production enzyme in the biocatalyst. As a result, the biocatalyst is able to continue to polymerize significantly beyond previous maximum limits and generate a yield of nine kilograms of polymer for every one kilogram of biocatalyst (9:1) – nine times more material compared to previous technologies. Newlight’s AirCarbon™ technology also reduces unit operations by a factor of three and capital cost by a factor of five, resulting in a net operating cost that enables AirCarbon™ to be cost and performance advantageous compared to petrochemical incumbents.

Within 24 months of scaling in 2013, AirCarbon was adopted by a range of leading companies including Dell, Hewlett-Packard, IKEA, KI, Sprint, The Body Shop, and Virgin to make packaging bags, containers, cell phone cases, furniture, and a range of other products. These products use a greenhouse gas in a carbon-negative process as a cost-effective replacement for petroleum-based plastics.

Verdezyne: Renewable Nylon Through Commercialization of BIOLON DDDA

Summary of Technology:

Verdezyne developed a yeast fermentation technology platform to provide manufacturers and consumers with renewable alternatives to existing petroleum-based chemical intermediates. This technology focuses on the production of dicarboxylic acid chemical intermediates such as adipic acid, sebacic acid and dodecanedioic acid (DDDA). The first of these to be commercialized will be BIOLON DDDA, which will be used primarily in the manufacture of nylon 6,12 for engineered plastics that require special properties such as high chemical, moisture, or abrasion resistance. Other uses for DDDA are in the manufacture of adhesives, coatings, corrosion inhibitors, lubricants, and fragrances.

The current global demand for DDDA is estimated to be 100 million pounds per year. All DDDA currently on the market is produced from fossil-based sources, with the largest volume manufactured via trimerization of butadiene, followed by hydrogenation and oxidation with nitric acid. Verdezyne’s process for production of BIOLON DDDA uses fatty acid feedstocks sourced from the co-products of vegetable oil refining as the starting raw material. In addition to providing a renewable alternative, this process offers a higher level of manufacturing safety since high temperature and pressure and concentrated nitric acid are no longer needed. Moreover, Verdezyne’s process also results in reduced greenhouse gas emissions.

Verdezyne’s production of BIOLON DDDA is an aerobic fermentation process integrated with downstream product isolation and crystallization. The fermentation converts the twelve carbon fatty acid, lauric acid, to DDDA through the activity of Verdezyne’s proprietary, genetically engineered Candida sp. yeast. The biochemical pathway involved is the three-step ω-oxidation pathway that sequentially oxidizes the terminal end of an alkane (or a fatty acid) to a carboxylic acid. Verdezyne scientists specifically engineered this yeast to enable rapid, high-yield production of DDDA while minimizing the accumulation of pathway intermediates that can be toxic to the organism and detrimental to final product purity.

Verdezyne’s proprietary method for producing renewable BIOLON DDDA has been successfully demonstrated on a larger scale, enabling the production of over 70,000 pounds thus far. The product has met all industry quality specifications and has also earned the USDA Certified Biobased product label. The company’s first commercial production facility is scheduled to open in 2017.

Professor Paul J. Chirik of Princeton University: Catalysis with Earth Abundant Transition Metals

Summary of Technology:

Metal-catalyzed chemical reactions have enabled many of the technological innovations of modern society with applications ranging from the synthesis of advanced materials to new medicines. For decades, catalyst technology has relied on some of the least abundant elements in the Earth’s crust – palladium, platinum, rhodium, and iridium. In addition to their high cost, price volatility, and toxicity, extraction of these elements has significant environmental consequences. Obtaining one ounce of a precious metal, for example, often requires mining approximately 10 tons of ore which creates a CO2 footprint that is estimated to be 6,000 times that of abundant metals such as iron.

Alkene hydrosilylation is an example of a metal-catalyzed chemical reaction that is used on an industrial scale in the manufacture of silicones from alkenes and silanes. Silicones are found in a range of consumer products including adhesives, household utensils, medical devices, health care products, and low rolling resistance tires. The platinum catalyst used in alkene hydrosilylation reactions is often not recovered, however, which results in a significant environmental footprint for this commercially important process.

Professor Chirik and his research group, in collaboration with Momentive Performance Materials, discovered a new class of hydrosilylation catalysts based on earth-abundant transition metals such as iron and cobalt that have superior performance to existing platinum catalysts. This base metal catalyst technology offers the opportunity to enable new chemical processes that provide the desired product exclusively, eliminate distillation steps, and avoid generation of byproducts and unnecessary waste. This technology is based upon “metal-ligand cooperativity,” a broad catalysis concept pioneered by the Chirik group, where electron changes occur concomitantly between the metal and the supporting ligand.

Hydrosilylations to produce various commercial silicone products have been conducted on multi-gram scales using this new technology. The discovery of these air-stable, readily-synthesized iron and cobalt catalysts with unprecedented activity and selectivity may ultimately transform the industrial approach to commercial silicone products.