In a new study, Northwestern University chemists have introduced a new plastic upcycling process that can drastically reduce - or perhaps even fully bypass - the laborious chore of pre-sorting mixed plastic waste.
The process harnesses a new, inexpensive nickel-based catalyst that selectively breaks down polyolefin plastics consisting of polyethylenes and polypropylenes - the single-use kind that dominates nearly two-thirds of global plastic consumption. This means industrial users could apply the catalyst to large volumes of unsorted polyolefin waste.
When the catalyst breaks down polyolefins, the low-value solid plastics transform into liquid oils and waxes, which can be upcycled into higher-value products, including lubricants, fuels and candles. Not only can it be used multiple times, but the new catalyst can also break down plastics contaminated with polyvinyl chloride (PVC), a toxic polymer that notoriously makes plastics "unrecyclable."
"One of the biggest hurdles in plastic recycling has always been the necessity of meticulously sorting plastic waste by type," said Northwestern's Tobin Marks, the study's senior author. "Our new catalyst could bypass this costly and labor-intensive step for common polyolefin plastics, making recycling more efficient, practical and economically viable than current strategies."
"When people think of plastic, they likely are thinking about polyolefins," said Northwestern's Yosi Kratish, a co-corresponding author on the paper. "Basically, almost everything in your refrigerator is polyolefin based - squeeze bottles for condiments and salad dressings, milk jugs, plastic wrap, trash bags, disposable utensils, juice cartons and much more. These plastics have a very short lifetime, so they are mostly single-use. If we don't have an efficient way to recycle them, then they end up in landfills and in the environment, where they linger for decades before degrading into harmful microplastics."
A world-renowned catalysis expert, Marks is the Vladimir N. Ipatieff Professor of Catalytic Chemistry at Northwestern's Weinberg College of Arts and Sciences and a professor of chemical and biological engineering at Northwestern's McCormick School of Engineering. He is also a faculty affiliate at the Paula M. Trienens Institute for Sustainability and Energy. Kratish is a research assistant professor in Marks' group, and an affiliated faculty member at the Trienens Institute. Qingheng Lai, a research associate in Marks' group, is the study's first author. Marks, Kratish and Lai co-led the study with Jeffrey Miller, a professor of chemical engineering at Purdue University; Michael Wasielewski, Clare Hamilton Hall Professor of Chemistry at Weinberg; and Takeshi Kobayashi a research scientist at Ames National Laboratory.
The main reason for this disappointing recycling rate is polyolefin's sturdy, stubborn composition. It contains small molecules linked together with carbon-carbon bonds, which are famously difficult to break.
"When we design catalysts, we target weak spots," Kratish said. "But polyolefins don't have any weak links. Every bond is incredibly strong and chemically unreactive."
Another option involves heating plastics to incredibly high temperatures, reaching 400 to 700 degrees Celsius. Although this process degrades polyolefin plastics into a useful mixture of gases and liquids, it's extremely energy intensive.
"Everything can be burned, of course," Kratish said. "If you apply enough energy, you can convert anything to carbon dioxide and water. But we wanted to find an elegant way to add the minimum amount of energy to derive the maximum value product."
"The polyolefin production scale is huge, but the global noble metal reserves are very limited," Lai said. "We cannot use the entire metal supply for chemistry. And, even if we did, there still would not be enough to address the plastic problem. That's why we're interested in Earth-abundant metals."
For its polyolefin recycling catalyst, the Northwestern team pinpointed cationic nickel, which is synthesized from an abundant, inexpensive and commercially available nickel compound. While other nickel nanoparticle-based catalysts have multiple reaction sites, the team designed a single-site molecular catalyst.
The single-site design enables the catalyst to act like a highly specialized scalpel - preferentially cutting carbon-carbon bonds - rather than a less controlled blunt instrument that indiscriminately breaks down the plastic's entire structure. As a result, the catalyst allows for the selective breakdown of branched polyolefins (such as isotactic polypropylene) when they are mixed with unbranched polyolefins - effectively separating them chemically.
"Compared to other nickel-based catalysts, our process uses a single-site catalyst that operates at a temperature 100 degrees lower and at half the hydrogen gas pressure," Kratish said. "We also use 10 times less catalyst loading, and our activity is 10 times greater. So, we are winning across all categories."
Amazingly, not only did Northwestern's catalyst withstand PVC contamination, PVC actually accelerated its activity. Even when the total weight of the waste mixture is made up of 25% PVC, the scientists found their catalyst still worked with improved performance. This unexpected result suggests the team's method might overcome one of the biggest hurdles in mixed plastic recycling - breaking down waste currently deemed "unrecyclable" due to PVC contamination. The catalyst also can be regenerated over multiple cycles through a simple treatment with inexpensive alkylaluminium.
"Adding PVC to a recycling mixture has always been forbidden," Kratish said. "But apparently, it makes our process even better. That is crazy. It's definitely not something anybody expected."
Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C-C bonds
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