the catalyst review · 2019. 12. 2. · the catalyst review 1 september 2019 industry perspectives...

The Catalyst Review September 2019 1

Technical & Commercial Progress in the Global Catalytic Process IndustriesTechnical & Commercial Progress in the Global Catalytic Process IndustriesTechnical & Commercial Progress in the Global Catalytic Process Industries

Industry Perspectives: Transient Kinetics: A New Opportunity for Data-driven Catalyst Development

September 2019 A Publication of The Catalyst Group Resources, Inc. Volume 32, Issue 9THE CATALYST REVIEW

Recovery of Critical Materials from Recycling of EV Batteries, Fuel Cells and Renewable Power

Systems - CRM Supply-Demand Challenges

The Catalyst Review September 20192

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CONTENTS

In This IssueIndustry PerspectivesTransient Kinetics: A New Opportunity for Data-driven Catalyst Development .....1

CommercialA First for Oil & Gas: Clariant Opens Cutting-Edge High Throughput Experimentation Lab in Houston, US ...................................................................... 2Commercial Debut for an Upgrading Process. ........................................................2LyondellBasell Announces Agreement for Expansion in China ...............................3

China's Zhejiang Satellite Wins Approval for $4B Petchem Plant to Use US Ethane ............................................................................................................... 3

Avantium Awarded €6 Million EU Grant to Accelerate its Technologies ................3

Petrochemical Companies Form 'Cracker of the Future' Consortium ....................4

India’s Top Refiner Plans $28B Investment by 2023 ...............................................4

TechnipFMC Intends to Create Two Industry-Leading, Independent, Publicly Traded Companies .................................................................................................. 4

ProcessSelenium Anchors Could Improve Durability of Platinum Fuel Cell Catalyst ..........5Cheap Water Treatment ......................................................................................... 5Special FeatureRecovery of Critical Materials from Recycling of EV Batteries, Fuel Cells and Renewable Power Systems - CRM Supply-Demand Challenges ..............................6ExperimentalEnhanced Lithium-Ion Conductivity of Polymer Electrolytes by Selective Introduction of Hydrogen into the Anion ............................................................... 14

Dynamic Frustrated Lewis Pairs on Ceria for Direct Nonoxidative Coupling of Methane ................................................................................................................. 14

Efficient Electrocatalytic CO2 Reduction Driven by Ionic Liquid Buffer-Like Solutions................................................. ................................................................ 15

Catalytic Performance of Layered Double Hydroxide (LDH) Derived Materials in Gas-Solid and Liquid-Solid Phase Reaction .........................................16

New Method Places Single, Specific Monomers in Polymer Chains .......................17

Movers and ShakersSteven Olivier, MS ................................................................................................... 18

THE CATALYST REVIEW (ISSN 0898-3089) September 2019, Volume 32, Number 9 Published by The Catalyst Group Resources, Inc., 750 Bethlehem Pike, Lower Gwynedd, PA 19002, USA+1-215-628-4447 Fax +1-215-628-2267 [email protected]

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CEOClyde F. Payn

PRESIDENT John J. Murphy

MANAGING EDITOR Mark V. Wiley

CONTRIBUTORS Rebecca Fushimi, PhDMichelle K. Lynch, PhD

Eugene F. McInerney, PhDSteven Olivier, PhD

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Jayant D. Divey, PhDGeorge Huber, PhDBrian Kneale, PhD

Warren S. Letzsch, MSMichelle Lynch, PhD

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continue on page 13

Transient Kinetics: A New Opportunity for Data-driven Catalyst DevelopmentInformatics, data science, data mining, artificial intelligence, machine learning: the frequency of hearing these words associated with fundamental catalyst development/discovery seems to be ever-increasing (Medford et al. 2018). We often use these words interchangeably to indicate an approach to derive new understanding based on models and statistical methods that extract information from data. Rather than simply identifying patterns or accelerating methods, these tools need to derive actionable intelligence for how a catalytic system works; and thus, how it can be made to work better. The type of data one has available (whether data on the chemical environment, catalyst material, or reaction kinetics) naturally dictates the type of tools that are best utilized and ultimately the type of information that can be extracted.

High-throughput methods that endeavored to tackle the vast parameter space across chemical environment and catalyst composition received a great deal of attention in the first decade of 2000. Statistically exploring the parameter space, however, quickly becomes intractable; a mixed metal oxide catalyst composed of five metal elements will yield more than 150 million possible combinations to test. Evolutionary or learning tools such as genetic algorithms are needed to guide the search. In one example, to understand more about the boundaries of achievable throughput, researchers from Bayer presented a screening workflow to parse through 10,000 heterogeneous catalysts per day (Duff et al. 2004). They found that an increase in throughput requires simplifying the reaction and testing procedure which unfortunately results in a limitation on the information content that can be derived from each experiment. While high-throughput methods may be useful for finding areas of promising activity, microkinetic information is needed to increase understanding for why these ‘hot spots’ exist and how to exploit them.

At the other end of the spectrum, in the microkinetic realm, there has recently been an increasing focus on the application of data analytics to guiding computational studies, most often employing density functional theory (DFT) calculations. These studies provide data regarding the energetics of molecular binding along with transition states for bond rupture/formation on different surfaces. The derived information is highly valuable for understanding the structure-activity link; however, DFT calculations are computationally intensive and high-throughput enumeration of different surface compositions/configurations likewise becomes prohibitive. Descriptor-based scaling relations have drastically reduced the number of calculations needed to predict catalyst activity and are increasingly employing machine-learning techniques. Statistical methods, compressed sensing and graph theory techniques have also been used to exploit existing data to enhance and accelerate predictions on untested materials, compositions and structures (see references in Medford et al. 2018). One alternative to a descriptor-based approach is the use of local atomic structures as the input to regression models to predict potential energy surfaces and accelerate the calculation of adsorption energies.

Both the macroscopic catalyst testing and microscopic computational approaches are accelerated by the tools of data analytics. While macroscopic reaction testing provides coarse kinetic screening on complex (near industrial) materials, computational studies can provide microkinetic detail on idealized systems. Somewhere between the two, transient kinetic experiments provide another approach to catalyst development that includes both detailed microkinetic information and real materials. The most common tools used to provide transient data in catalysis are temperature programmed desorption (TPD), steady-state isotopic transient kinetic analysis (SSITKA) and temporal analysis of products (TAP). Modulation excitation spectroscopy (MES) is a newer transient technique that provides both reaction and spectroscopic data, but further development is still needed for quantitative kinetic analysis (Srinivasan et al. 2019). Aside from TPD, the complexity of instrumentation design and the advanced mathematical models that are required to extract information from raw data makes transient techniques less-widely adopted. By and large, the data analysis methods in common use will simply reduce the transient information to a singular quantity: a desorption temperature maximum, a residence time or higher order integral quantities. While these dynamic experiments provide rich time-dependent kinetic data suitable for the exploitation of data-driven analytical methods, efforts are only beginning to emerge.

Figure 1: 3D kinetic space sampled during the pulsed oxidation of platinum

In the case of the TAP experiment, a recently developed analytical method enables conversion of the experimentally observed exit flux into a more meaningful time-dependence of the reaction rate, gas, and surface concentration (Yablonsky et al. 2007). It should be emphasized that in a steady-state experiment, the surface concentration is fixed by the gas concentration, but in a dynamic experiment the two are decoupled and comparative analysis of their trends can yield useful insight. For example, Figure 1 shows the 3D kinetic space of the reaction rate, gas, and surface concentration calculated from exit flux data in an incremental pulsed oxidation of platinum (Kunz et al. 2018). It would be extremely time-consuming to sample the same parameter space using conventional steady-state experiments. While steady-state parallel reactor screening explores the high-dimensions of process and composition space, transient techniques can provide high-throughput kinetic exploration. Herein lies an opportunity:


COMMERCIAL NEWS

A First for Oil & Gas: Clariant Opens Cutting-Edge High Throughput Experimentation Lab in Houston, US...

Clariant has opened its next High Throughput Experimentation (HTE) laboratory in Houston, Texas. The location is key as the new facility will be the first of its kind supporting the oil & gas industry, offering new and sophisticated solutions for customers. This lab is part of a global Clariant initiative to expand HTE capabilities to all Clariant business units, including direct support for oil services in North America, the Asia Pacific region, Latin America, Africa and the North Sea. HTE is an innovative approach and methodology where automated instrumentation, specialized software tools and alternative techniques are able to provide optimized formulations in a rapid timeframe. While it has been widely used in other industries for many years, Clariant is the first company to adopt this technology for the oil & gas industry as a standard tool. As a new addition to the existing lab located at Clariant Oil Services Headquarters, Clariant specialist chemists and innovation experts are now able to utilize miniaturization, parallelization, intelligent design and enhanced analytics – all proven to increase efficiency and productivity. The facility will help to meet current and outstanding needs in the oil & gas industry, with special emphasis on pour point depressants, hydrate inhibitors, asphaltene inhibitors, corrosion inhibitors and scale inhibitors. Source: Clariant, 9/6/2019.

Nakhodka Mineral Fertilizer Plant Selects Topsoe for World-Scale Methanol Plant...

Nakhodka Mineral Fertilizer Plant has chosen Haldor Topsoe technology for a 5,400 tons-per-day methanol plant near Vladivostok in the Eastern part of Russia. China Chengda Engineering Co., Ltd., has been chosen for engineering, procurement and construction (EPC). Topsoe will provide license, basic engineering, catalysts, and proprietary hardware for the methanol plant which will be based on Topsoe’s two-step reforming technology. Source: Haldor Topsoe, 9/6/2019.

Johnson Matthey's Latest ATR Technology License Underway...

Johnson Matthey (JM) announced that it has been awarded the methanol plant license for Methanex Corporation’s Geismar 3 plant, incorporating the world’s largest standalone autothermal reformer (ATR) in the methanol marketplace. In mid-July, the Methanex Board of Directors reached a final investment decision to construct a 1.8 million tonne methanol plant in Geismar, Louisiana (US) adjacent to its existing Geismar 1 and Geismar 2 facilities. Johnson Matthey was awarded the contract to supply the licence for the ATR methanol technology flowsheet, including associated basic engineering, proprietary equipment and catalyst supply. Construction on the $1.3–1.4 billion plant will begin later this year with operations targeted for the second half of 2022. When Geismar 3 operations commence, this will become the eighth Methanex plant in operation to use JM-licensed methanol technology and the second to use a JM ATR. JM’s world scale methanol generation technology has been licensed for more than four decades with over 90 plant licenses granted in that time. Source: Johnson Matthey, 9/10/2019.

Commercial Debut for an Upgrading Process...

After four years of project development and execution, the new PolyFuel unit at Petrobrazi petroleum refinery in Romania has been started-up and is fully functional since April 2019. Based on the PolyFuel technology licensed by Axens, the OMV Petrom’s project at the Petrobrazi refinery enables operators to increase the fluid catalytic cracking (FCC) products value by upgrading liquefied petroleum gas (LPG) and light cracked naphtha into high-quality fuels. “The PolyFuel unit of Petrobrazi refinery is the first of its kind, valorizing C4 and C5/C6 fractions into high-quality gasoline and middle distillates [diesel or Jet A1, or both], increasing the overall production of these products,” says Bruno Domergue, Axens Clean Fuels, Bio, Olefins and Gas business line director. In the PolyFuel process, light olefins are oligomerized catalytically in fixed-bed reactors operating in series. Conversion and selectivity are controlled by reactor temperature adjustment, while the heat of reaction is simply removed by feed-effluent heat exchange. The reactor section effluent is fractionated to produce a gasoline fraction with low olefins content and a middle distillates fraction. A spare reactor is provided to ensure a continuous operation of the process, thus avoiding unwanted FCC shutdowns. The management of the reactors is optimized to maximize catalyst run-length. The PolyFuel process uses the IP 811 catalyst that was first commercialized for Selectopol and Polynaphtha technologies. Source: Chemical Engineering, 9/1/2019.

Novel Process Developed to Recover High Value Products from Natural Gas...

Linde developed a novel process to recover high value products from natural gas, successfully combining leading technologies of BASF and Linde. The process simultaneously recovers valuable helium, liquid hydrocarbons, and purified carbon dioxide (CO2) in addition to conditioning natural gas for pipeline transportation by adjusting the water and heavy hydrocarbon dew point, as well as the CO2 concentration. The hybrid process eliminates the need for cryogenic conditions, giving access to a new highly profitable helium source. The process consists of two stages of Linde’s HISELECT® powered by Evonik membranes, an upstream BASF Durasorb™ hydrocarbon removal unit (HRU), an integrated BASF OASE® acid gas removal unit (AGRU) and an integrated Linde Helium PSA unit. The two HISELECT® membrane stages are simultaneously used for helium enrichment and adjustment of CO2 to pipeline specification. The Linde Helium PSA purifies the enriched helium up to 99.999% with highest yield. BASF’s OASE® AGRU is used to selectively remove the CO2 from an internal recycle without any helium or methane loss. BASF’s DurasorbTM HRU removes heavy hydrocarbons and water to meet pipeline dew point, produce liquid hydrocarbons as valuable byproduct and to ensure high membrane performance. Source: BASF, 9/9/2019.


COMMERCIAL NEWS

Air Products Advances Gasification Growth Strategy via New Syngas Project with Debang Group in Jiangsu Province, China...

Air Products announced a new JV with Debang Xinghua Technology Co., Ltd., a subsidiary of Jiangsu Debang Chemical Industrial Group Co., Ltd. (Debang Group), to build, own and operate a coal-to-syngas processing facility in Xuwei National Petrochemical Park, Lianyungang City, Jiangsu Province, China. Air Products will own 80% of the JV, and Debang Group will own 20%. The JV will own and operate the air separation unit (ASU), gasification and purification assets under a 20-year contract for a fixed monthly fee, supplying syngas to support Debang Group’s 350,000 tons-per-year chemicals facilities. The project is expected to be onstream in 2023. Source: Air Products, 9/9/2019.

PKN ORLEN Licenses Honeywell Technology to Boost Petrochemicals Production in Poland...

Honeywell announced that PKN ORLEN has licensed the UOP MaxEne™ process, which can increase production of ethylene and aromatics and improve the flexibility of gasoline production. The project, for the PKN ORLEN facility in Płock, Poland, currently is in the basic engineering stage. The MaxEne process separates full-range naphtha into a stream of normal paraffins which are ideal for steam crackers because they produce high yields of light olefins, and a second stream of isoparaffins, naphthenes and aromatics that are perfect for catalytic reforming units because they produce high yields of aromatics. Both products are the primary components of a wide variety of plastics. PKN ORLEN would be the first refining and petrochemicals company in Europe to use the Honeywell UOP MaxEne technology for molecule management of a naphtha stream to produce high-quality products including olefins, aromatics and gasoline. Source: Honeywell UOP, 9/9/2019.

LyondellBasell Announces Agreement for Expansion in China...

LyondellBasell announced it has signed a Memorandum of Understanding (MoU) to expand in China through a Joint Venture (JV) with the Liaoning Bora Enterprise Group (Bora). Under the MoU, Bora and LyondellBasell will form a 50/50 JV in Panjin, China. The JV will operate a 1.1 million ton ethylene cracker which will produce olefins and polyolefins (PO) used in all manner of construction and consumer products including, but not limited to, pipe, durable plastic containers and agricultural films. The polyolefin products produced at the complex will be marketed by LyondellBasell. When complete, the plant will employ LyondellBasell’s Hostalen ACP polyethylene (PE) technology and both Spheripol and Spherizone polypropylene (PP) technologies. Bora began construction of the state-of-the-art facility in 2019. Source: LyondellBasell, 9/5/2019.

Praj’s 2G Ethanol Technology for USA’s First Ever Bagasse-based Bio-Refinery...

‘Enfinity’, Praj’s proprietary and award-winning technology, will be deployed to produce ethanol and other co-products using sugarcane bagasse in what would be USA’s first bagasse-based bio-refinery. The bio-refinery is being jointly promoted by Florida based Omega Energy USA, a developer of renewable energy projects, while Louisiana based Lasuca Sugar, a producer of cane sugar, will supply bagasse feedstock. The promoters have issued a formal letter confirming their interest to engage Praj for developing the design and project program for a cellulosic ethanol bio-refinery in USA. The proposed project in the cane-sugar belt of the country will have the capacity to produce 10-15 million gallons per year (MGPY) of cellulosic ethanol. Source: Praj, 9/3/2019.

China's Zhejiang Satellite Wins Approval for $4B Petchem Plant to Use US Ethane...

A large Chinese chemical producer has won regulatory approval to start building a $4.2 billion petrochemical complex in east China to process ethane from the United States, a company official said. Zhejiang Satellite Petrochemical Co Ltd's plant will be the second China-based petrochemical facility aiming to cash in on cheap and abundant US ethane unlocked by the shale revolution in North America, analysts said. Zhejiang Satellite will start construction in September on a 1.25 million tonnes per year (tpy) ethylene plant in Lianyungang in Jiangsu province, Ding Liping, an investor relations officer, told Reuters. "This is the company's phase-one investment for a total of 2.5 million tonnes per year ethylene production facilities that will process fully U.S. ethane," said Ding, adding that construction was expected to take about a year. Source: Hydrocarbon Processing, 8/29/2019.

Avantium Awarded €6 Million EU Grant to Accelerate its Technologies...

Avantium N.V. announced that it has been awarded €6 million as part of a SPIRE grant to accelerate its Dawn and Mekong technologies in addition to utilizing its expertise in Catalysis. In its Renewable Chemistry business, the company is scaling up its new biorefinery process called Dawn and a novel catalytic process for plant-based MEG (monoethylene glycol) called Mekong. Avantium’s Dawn Technology™ converts non-food plant-based feedstock into industrial sugars and lignin. The Mekong technology converts these industrial sugars into plant-based MEG. Together, these processes enable the production of nature derived polyesters and supports the transition of the chemicals and materials industries to non-fossil resources. The integration of Dawn Technology™ with the production of plant-based MEG by the Mekong technology will be further improved by using the advanced high throughput R&D systems of Avantium Catalysis. Source: Avantium, 8/26/2019.


COMMERCIAL NEWS

Study on Collaboration for Promotion of Gasification Chemical Recycling of Plastic Waste...

JGC Corporation, Ebara Environmental Plant Co., Ltd., Ube Industries, Ltd., and Showa Denko K.K. announced that they started a study of collaboration for an Engineering, Procurement and Construction (EPC) business for plastic waste gasification facilities utilizing the Ebara Ube Process (EUP) following conclusion of a non-disclosure agreement on July 31, 2019. The EUP is a process that gasifies plastic waste using partial oxidation with oxygen and steam and produces synthesis gases that can be utilized in synthesis of ammonia, olefins, and other chemicals. The four companies aim to conclude an EUP licensing contract within the year, and then actively implement sales efforts for gasification facilities for plastic waste adopting EUP in Japan and other countries and conduct EPC activities. Source: JGC Corporation, 8/29/209.

Petrochemical Companies Form 'Cracker of the Future' Consortium...

Six petrochemical companies based in Belgium, Germany, and the Netherlands have announced a consortium to investigate how naphtha or gas steam crackers could be operated using renewable electricity instead of fossil fuels. The ‘Cracker of the Future’ consortium—which includes BASF, Borealis, BP, LyondellBasell, Sabic, and Total—aims to significantly reduce carbon emissions from production of base chemicals. The companies have agreed to invest in R&D and knowledge sharing as they assess the possibility of transitioning base chemical production to renewable electricity. Members of the consortium have started exploring and screening technical options. If a potential solution is identified, the parties will determine whether to pursue joint development projects, including R&D activities that could include a demonstrator for proof of concept in the case of base chemicals. Source: Chemical Week, 8/27/2019.

KBC Releases Industrial Energy Transition Manifesto...

KBC has released its Industrial Energy Transition Manifesto for the process industries. The Manifesto provides deep insight into current realities, scenario predictions and how major players are adopting a range of substantially different strategies to adapt. The Manifesto outlines the actions that are available to be taken now and indicators of the pace and scale of the transition. Source: KBC, 8/29/2019.

India’s Top Refiner Plans $28B Investment by 2023...

Indian Oil Corp (IOC), the country’s top refiner, plans to invest $27.98 billion in five-seven years to meet energy needs of diverse user groups, Chairman Sanjiv Singh told a shareholders meeting. IOC, through its 11 refineries, controls about a third of India’s 5 million-barrel-per-day (bpd) refining capacity. Singh said the investment was required to help IOC “evolve into a future ready corporation that provides comprehensive energy solutions to diverse user groups”. The company is investing over 200 billion rupees by 2023-24 to expand its petrochemicals capacity and another 100 billion rupees in eight years for expansion of city gas distribution projects in the country, he said. Source: Hydrocarbon Processing, 8/28/2019.

BP to Sell Alaska Business to Hilcorp...

BP announced that it has agreed to sell its entire business in Alaska to Hilcorp Alaska, based in Anchorage, Alaska. Under the terms of the agreement, Hilcorp will purchase all of BP's interests in the state for a total consideration of $5.6 billion. The sale will include BP's entire upstream and midstream business in the state, including BP Exploration (Alaska) Inc., that owns all of BP's upstream oil and gas interests in Alaska, and BP Pipelines (Alaska) Inc.'s interest in the Trans Alaska Pipeline System (TAPS). Under the terms of the agreement, Hilcorp will pay BP a total consideration of $5.6 billion, comprising $4.0 billion payable near-term and $1.6 billion through an earnout thereafter. The deal forms a significant part of BP's plan to divest $10 billion of assets over 2019 and 2020. Source: BP, 8/27/2019.

Clariant to Significantly Expand Production of Maleic Anhydride Catalysts in China...

Clariant announced it will significantly expand the capacity of its catalysts production facility in Panjin, Liaoning province, Northeast China. A double-digit CHF million investment will further optimize the existing facility and enable the creation of a new state-of-the-art production line for Clariant’s SynDane maleic anhydride (MA) catalyst. Global demand for MA is expected to jump from 1.75 million tons in 2018 to 2.07 million tons in 2022. Clariant’s SynDane catalysts are optimized for cost-efficient MA production via selective oxidation of n-butane in fixed-bed tubular reactors. Thanks to their innovative microstructure and chemical composition, they offer superior yield, selectivity and operating stability. This greatly reduces the formation of by-products (such as acrylic acid and acetic acid) as well as their downstream polymerization, thus minimizing downtime for equipment. Source: Clariant, 8/27/2019.

TechnipFMC Intends to Create Two Industry-Leading, Independent, Publicly Traded Companies...

TechnipFMC plc announced its Board of Directors has unanimously approved its plan to separate into two industry-leading, independent, publicly traded companies: RemainCo, a fully-integrated technology and services provider, continuing to drive energy development; and SpinCo, a leading engineering and construction (E&C) player, poised to capitalize on the global energy transition. The separation is expected to be completed in the first half of 2020, subject to customary conditions, consultations and regulatory approvals, at which time all outstanding shares of SpinCo will be distributed to existing TechnipFMC shareholders. Source: TechnipFMC, 8/26/2019.


PROCESS NEWS

Selenium Anchors Could Improve Durability of Platinum Fuel Cell Catalyst...

Platinum has long been used as a catalyst to enable the oxidation reduction reaction at the center of fuel cell technology. But the metal’s high cost is one factor that has hindered fuel cells from competing with cheaper ways of powering automobiles and homes. Now researchers at the Georgia Institute of Technology have developed a new platinum-based catalytic system that is far more durable than traditional commercial systems and has a potentially longer lifespan. The new system could, over the long term, reduce the cost of producing fuel cells.

The researchers described a possible new way to solve one of the key causes of degradation of platinum catalysts, sintering. To reduce such sintering, the researchers devised a method to anchor the platinum particles to their carbon support material using bits of the element selenium. The process starts by loading nanoscale spheres of selenium onto the surface of a commercial carbon support. The selenium is then melted under high temperatures so that it spreads and uniformly covers the surface of the carbon. Then, the selenium is reacted with a salt precursor to platinum to generate particles of platinum smaller than two nanometers in diameter and evenly distributed across the carbon surface. The covalent interaction between the selenium and platinum provides a strong link to stably anchor the platinum particles to the carbon.

Because of the increased specific surface area of the nanoscale platinum, the new catalytic system initially showed catalytic activity three and a half times higher than the pristine value of a state-of-the-art commercial platinum-carbon catalyst. Then, the research team tested the catalytic system using an accelerated durability test. Even after 20,000 cycles of electropotential sweeping, the new system still provided a catalytic activity more than three times that of the commercial system. They found that the selenium anchors were effective in keeping most of the platinum particles in place. Source: Georgia Tech, 9/5/2019.

Cheap Water Treatment...

A team led by Anna Śrębowata, professor at the IPC (Institute of Physical Chemistry, Polish Academy of Sciences) has improved a method of catalytic hydrotreatment, that is, transforming trichloroethane (TCE) into hydrocarbons that are environmentally less harmful. TCE used to be commonly used in, amongst others, organic syntheses, dry cleaning and for the industrial degreasing of metals during their processing. Due to its negative impact, its use has been officially banned since 2016. However, considering its stability, it may remain in both the water and soil for many years to come, explains MSc. Emil Kowalewski, a member of the team that developed the innovative method of removing this compound from water. "Today we deal with such compounds mainly by the process of sorption. However, in this way we're only transferring the threat from one place to another. An attractive solution seems to be catalytic hydrotreatment, i.e. transforming the TCE into less harmful hydrocarbons. However, in order to fully exploit the potential of this method, it was necessary to develop an efficient, stable and cheap catalyst," says Dr. Anna Śrębowata, professor at the IPC. "Previously, we carried out research with palladium catalysts. They were effective but expensive," notes Emil Kowalewski. The new nickel catalysts, developed at the IPC PAS, allow for a cheap and effective method of conducting the process of water treatment in flow mode, and at the same time they are easy to synthesize. "Using a catalyst in which nickel nanoparticles with a diameter of about 20 nm are deposited on the surface of activated carbon, we combine the sorption properties of carbon and the catalytic activity of nickel," explains Kowalewski. In their research, the scientists from the IPC PAS also showed that nickel nanoparticles deposited on activated carbon with a partially ordered structure show higher activity and stability than an analogous catalyst based on a support with amorphous structure. Source: Phys.org, 9/9/2019.


Recovery of Critical Materials from Recycling of EV Batteries, Fuel Cells and Renewable Power Systems — CRM Supply-Demand Challenges

By Michelle K. Lynch, PhD

Over the last decade, demand has risen to an unprecedented level for a set of key critical raw materials (CRM) mainly consisting of metals (precious metals, strategic transition metals and rare earths). CRM are strategic to a nation’s prosperity and security because they perform many vital functions in everyday life from electrical goods to medical equipment, industrial operations, energy generation, and transportation. The supply of many CRM is quite limited, and each group is specific to certain countries—i.e., rare earth elements (REE) in China and platinum group metals (PGM) in South Africa and Russia.

In 2017, the EU set out a list of 27 CRM which are important for the European economy. Subsequently, in 2018, the US Department of the Interior issued a notice of 35 mineral commodities (including the 17 REE listed as one group) considered vital to the country’s national security and economic prosperity (Dept. of the Interior 2018). Figure 1 highlights the key elements from the EC report, with geographic concentrations indicating the supply vulnerability (Moss et al. 2017).

Clearly there is cause for concern where over 80% and as high as 95% of CRM supply stems from one country or region, especially if those countries tend to be associated with political, social, and environmental tensions (which is now more widespread than in the past). Climactic factors are also predicted to take effect—including the increasing frequency of wet bulb temperature environments where ambient temperatures of 35°C/100% humidity or 40°C/75% humidity are considered the limits for human survival. Even when close to these conditions, the ability for humans to work outdoors becomes limited. Likewise, in those regions the supply of water and electricity may become restricted as droughts become more common, and more energy is expected to be needed for air conditioning on very hot days (>40⁰C). The need for secure supplies of metal originating outside of the worst affected climate areas will become paramount.

Much of the pressure from the demand side for CRM has come from rapidly rising sales of automotive vehicles which all require increasing amounts of CRM and electric vehicles (EV) which need specific battery metals and REE for permanent magnets. Renewable energy is an increasing demand sector with the installation of renewable power systems (wind and solar). The existing staple market of electronics continues to grow as does energy efficient lighting.

Catalysts are a key consumer of all classes of CRM. Pollution control catalysts for Internal Combustion Engine (ICE) vehicles have been the largest market for Platinum Group Metals (PGM) for around 15 years now, having overtaken jewellery for first place. While PGM demand from the autocatalyst market has contributed to tight supply-demand fundamentals and price spikes, it has always been serviceable. However, as the vehicle fleet is diversifying to include plug-in hybrid and battery electric vehicles (PHEV and BEV) and fuel cells (FCEV) with water electrolyzers needed to produce hydrogen, the picture is becoming more complex—potentially much more PGM will be needed, as well as a whole host of additional CRM.

Future PGM supply-demand is being monitored closely by analysts and questions asked around the possibility of limitations on technology deployment. For instance, even 10% proton exchange (or polymer electrolyte) membrane fuel cells (PEMFC) technology deployment in the light duty vehicle (LDV) fleet at a future predicted platinum loading of 10 grams/100 kWh would soak up some 43% of the forecasted 2025 gross platinum supply of 8 million troy ounces/248 million tons (Wieber 2019). In reality, PEMFC will be deployed across many sectors with lower unit volumes—e.g., heavy duty, shipping, rail, manual handling vehicles and, once reliability has been established and technology moves on, the loading for a passenger car could be brought down to parity with a diesel engine catalyst (e.g., 3-4 grams/vehicle).

Figure 1. Countries accounting for largest share of global CRM supply.

Source: Moss et al. 2017

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As of now there is a platinum surplus, and rising concern around what will happen after 2040, when demand for PGM catalysts for gasoline and diesel engines is forecast to have peaked. PGM suppliers are working to ensure the future of the industry by giving strong support to emerging automotive and related hydrogen technologies which rely on PGM, such as PEMFC and PEM electrolysers (PEMEL).

Table 1. Consumption of platinum in fuel cells for light duty vehicles (LDV) as a percentage of market supply in 2025.

Source: Wieber J.2019

South African miner AngloPlatinum has begun investing in technology approaches which could result in the use of platinum and palladium in EV batteries. It recently set up a joint venture with Platinum Group Metals Ltd (the operator of the Waterburg PGM deposit project) called “Lion Battery Technologies Inc.” (AngloAmerican 2019). Incorporation of PGM in EV batteries would secure the long-term future of PGM in automotive applications. This would be good news for the industry as demand for PGM in many of the more mature industrial markets has been contracting (Lynch 2017).

Table 2. Critical resource materials, corresponding demand pressures and uses in non-automotive catalyst applications.

Source: Enabled Future Limited

Rare earth elements (REE) are facing even bigger supply-demand issues as they are needed for several different high growth sectors and future demand based is not expected to meet supply; recycling methods are in their infancy and would take over a decade to establish. The EU CRM analysis places REE at the highest supply risk along with other elements such as antimony, bismuth, magnesium, and phosphorus. These elements are all commonly found in a range of catalysts, so catalyst manufacturers also need to be aware and manage the supply constraints they face as a result of the future demand trends. Fluid Catalytic Cracking (FCC), for instance, uses significant quantities of REE, particularly lanthanum and cerium. The most critical PGM, REE and other elements used in battery materials and their corresponding use in catalysis is shown in Table 2. Nickel has not been included here (even though the high-grade from is required in large quantities for battery cathode materials) because it is not anticipated that it will be difficult to source. Potential disruption in catalyst supply could be pronounced for REE catalysts — specifically neodymium, which is employed for high-cis-polybutadiene for rubber car tyres and lanthanum and cerium for Fluid Catalytic Cracking catalysts (FCC). Undoubtedly new REE assets need to be developed, this is discussed further in the Magnets section of this article.

The recycling sector is clearly set to become more complex. Investors and stakeholders are keen to understand where the best opportunities lie and how to enter the market. The remainder of this article looks at valuable recycling feeds across several sectors and where there is potential to develop new and expanded recycling capabilities. Comments on strategies for existing and potential new entrants to help navigate the complexities of investing in new recycling sectors are provided.

Lithium-Ion Battery RecyclingIn 2018, some 1.1 billion tons of LIB were sold into the global marketplace including for small rechargeable batteries and larger batteries for transportation and stationary power. In the same year, 180,000 tons of LIB scrap were generated of which 75%


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came from electronic items. By 2025, the amount of LIB sold will have more than quadrupled and the scrap amounts will have risen to 720,000 tons. LIB recycling rates are already higher than one might think – around 58%, but the collection infrastructure and recycling capacity needs to grow on a global basis as the EV car park spreads out from Asia to cover more world regions (CES 2019). There has been some landfilling of batteries outside of China where there are fewer established battery recycling operations and this is an unnecessary and unsustainable practice which battery producers and recyclers need to work to eliminate. This will also serve to create profits through recycling services while enhancing security of supply. The recycling rate will drop back to 55% by 2025, as a factor of the lag in recycling capacity needed for the increase in recycling feed entering the market (Melin 2019).

There are several different battery chemistries already deployed and over the next five years, a sharp increase in end-of-life (EOL) batteries (mainly non-automotive) based on Lithium-Iron-Phosphate (LFP) battery chemistry is expected and a concurrent contraction in the proportion of lithium-cobalt-oxide (LCO) units (Melin 2019). There is some desire at the producer end to move away from cobalt formulations. For instance, Samsung has announced that it is introducing graphene batteries into its mobile phones as early as 2020 because they charge in a fraction of the time (Villas-Boas 2019). These effects could cause a decrease in both lithium and cobalt inclusion in batteries for electronics, especially if other phone and laptop manufacturers follow suit.

This will be offset, however, by the increase in the amount of LIB scrap from the automotive sector, where passenger car batteries can weigh up to 500 kg each and LDV up to 1 ton. In these applications nickel-manganese-cobalt (NMC) is a popular choice and it is expected to grow in share from the 26% seen in 2016 to 41% by 2025 (Pilot 2017). Most NMC currently is “622” (60% Ni:20%Mn:20%Co). There is a desire to move to NMC 811 but this is being hampered by technical difficulties based on the very high nickel content and so a reasonable level of cobalt can be expected to stay in EV batteries for some time to come. The total volume of batteries deployed will also continue to rise. Bloomberg New Energy Finance (BNEF) made its most bullish prediction yet for 2040, with EV reaching 57% in passenger cars and buses (>80%) as well as 30% in medium commercial vehicles (MCV) and 20% in heavy commercial vehicles (HCV) (Green Car Congress 2019).

Many companies already have established recycling operations for EV batteries, mainly in Asia where 90% of LIB recycling takes place. China has a system for becoming an approved battery supplier which involves being placed on the Chinese recycler’s whitelist. Around ten companies have achieved this status. Table 3 lists the companies who are currently active in the battery recycling space.

Umicore Battery Recycling ProcessThe battery recyclers each have their own technology variants. Taking Umicore as an example, the company offers a combined pyrometallurgical and hydrometallurgical process which covers a range of battery types and sizes including LIB and nickel metal hydride (NiMH). Depending on the size of the battery, it may be fed directly into the furnace, or it may need partial dismantling. Batteries up to 20 kg as shown in Figure 3, do not generally need to be dismantled. Batteries from vehicles (HEV or BEV), are dismantled into three fractions: the pack material (cable, steel and plastics), the electronic circuit boards, and the battery modules themselves. The pack material is sent to local recyclers for treatment and the electronics are routed to Umicore’s electronics recycling stream at Hoboken. The battery modules go into the pyrometallurgical (smelting stage) which converts them into a further three fractions.

The smelting step at the 7,000 metric ton plant at Hoboken, Belgium employs Umicore’s Ultra-High Temperature (UHT) pyrometallurgical route first introduced in 2011. It utilizes a sub-merged air-fed plasma torch generating temperatures of >3000°C and injects plasma gas into the melt. Oxygen gas is separately fed into the melt via a short tube and this allows higher oxygen partial pressures to be reached when needed, for example, for aluminium-containing feeds. Gas pressures of 1 x 10-12 to 10-14 are employed

Table 3. Global Companies Active in Recycling Critical Materials from Lithium-Ion Batteries.

Source: Enabled Future Limited

Figure 2. Profile of LIB Recycling and Critical Material Recovery in 2018 and 2025.

Source: Enabled Future Limited, adapted from Circular Energy Storage (CES) data, 2018


the process is met by the battery electrolyte, plastic and metals, resulting in lower utility consumption. The flue gas is quite clean, with fluorine captured in the flue dust and any dioxins and VOCs treated prior to exhaust.

Fuel Cells & Electrolyser RecyclingCompared with battery recycling, fuel cell recycling is in its infancy. There is very little fuel cell scrap being generated, and mostly it is from production waste and not end-of-life (EOL) units. However, with the rate of fuel cell deployment this is set to change. Between 2012-2018, some 2.8 million MW of fuel cells had been deployed globally, with just over 800 MW of this being sold in 2018 alone. Of the total 2.8 million MW, PEMFC and Phosphoric Acid Fuel Cells (PAFC) which both contain platinum, made up 72%. Most MW have been deployed in Asia and North America (E4Tech 2018). The key growth application in MW terms is PEMFC in transportation with Toyota, Hyundai, and Daimler all having brought fuel cell vehicles to the market. Non-automotive PEMFC are also key opportunities. Hyundai’s business model toggles between transport and back-up generators for instance and the use of PEMFC in other sectors including, rail, marine, materials handling, Combined Heat and Power (CHP), and Unmanned Aerial Vehicles (UAV).

PAFC in stationary is the other major area of growth with Doosan expanding its deployment both in Korea and North America. Fuji is second in PAFC deployment. PAFC technology overtook that of SOFC in stationary units in MW terms in 2017 and therefore these units are very significant future opportunities for recyclers with relatively high PGM loadings and simpler logistics due to their concentration at single locations.

The overall market snapshot is shown in Figure 4. Water electrolysers are not included in these estimates but are growing rapidly for generation of hydrogen for transport, stationary, industrial and power-to-gas (PtG) applications. The trend is being driven by the need to decarbonise non-automotive power, heat and industrial hydrogen requirements. Green hydrogen, ammonia, and methanol are all expected to play a role in multi-sector decarbonisation and therefore recycling of electrolysers and recovery of PGM from waste units is an important future opportunity for recyclers, starting with production scrap volumes.

Compared with an autocatalyst, a fuel cell stack has many more materials including several different plastics as well as adhesives, silicones, and rubber compounds. At its heart is a Catalyst Coated Membrane (CCM), although a few products have catalyst- coated Gas Diffusion Layers (GDL). The CCM is a coated polymer (Nafion/ePTFE) from

and the bath temperature is in the region of 1,450-1,650 ⁰C. While there are very high temperatures generated in this process, it does not have a high external utility demand. This is because much of the energy is contained within the batteries themselves and is released during processing. Overall the heat demand is relatively low compared with conventional pyrometallurgical recovery. The heat generated by the plasma increases fluidity and mixing. It allows carbon from the battery pack to burn off as CO2 then it can completely reduce the cobalt to a metal along with copper and nickel, while lithium, manganese and REE stay in a slag fraction. The advantage of this process compared with other smelting methods is that the deep cobalt recovery leaves very small quantities in the slag (0.1 wt%) and almost complete separation from lithium (Heulens et al. 2019)

The REE are removed from the slag as a concentrate and are further refined in conjunction with Solvay. The metal-rich phase is granulated and further refined via a hydrometallurgical process, set up at Umicore’s Olen plant in Belgium, which recovers metals and returns them to the cathode material production circuit. Copper is sent to recovery; cobalt and nickel are separated by solvent extraction and nickel is processed into nickel hydroxide. The lithium is recovered from the slag fraction as LiMeO2 where Me is a transition metal (e.g., manganese). Some of the energy for

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Figure 3. Umicore Battery uht pyrometallurgical/hydrometallurgical recycling process.

Source: Enabled Future Limited (compiled from Umicore sources)

Figure 4. Cumulative megawatts of fuel cell deployment 2012-2018.

Source: Enabled Future Limited based on E4Tech Data


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Gore or other Perfluorinated Sulphonic Acid (PFSA) material. It is this part of the fuel cell stack that contains the PGM catalyst and gives rise to the essential performance of the system. Everything that surrounds it is designed for a smooth process and to manage humidity, temperature, gas concentration and gas flows.

The first fuel cell electric vehicle (FCEV) to make headlines was the Toyota Mirai. The technology in its fuel cell stack is the result of decades of development at Toyota and it currently works in tandem with a NiMH battery system such as that employed on the original Prius mild hybrids. Each stack contains 370 CCM — in total there are around 10 m2 of coated area in one car. The catalyst is manufactured by Cataler and is based on a Pt-Co alloy with “advanced catalyst structures” (Horiuchi 2017). Cobalt improves the Oxygen Reduction Reaction (ORR) and catalyst durability compared with Pt/C. The Mirai FC unit originally had 30 grams of platinum, but this is undergoing aggressive thrifting down to 12 grams, with a target to get below 6 g. As already seen in Table 1, this goal must be reached if FCEV deployment is to reach meaningful levels.

Fuel Cell stack recycling represents a few challenges. The CCM is made from a Nafion™ perfluorosulphonated membrane (PFSA) from Chemours. Thermal degradation products of PFSA include several fluorinated and other acidic species which would badly corrode equipment during incineration and require scrubbing. Chemours recommends only landfill EOL option or incineration of very small quantities along with other refuse. Fumes can cause “polymer fume fever” which is a temporary flu-like condition which comes on 24-48 hrs of exposure. Hydrogen fluoride (HF) is extremely harmful to human health and all exposure must be avoided. The fibrous nature of the membrane also makes it a little more difficult to process and assaying can take longer than for other PGM-bearing materials.

Various approaches have been developed to get around these issues. Patented approaches from BASF and Johnson Matthey have utilised solvent and surfactant-based processes which do not require incineration. Heraeus patented a method for lagging the smelting furnace to prevent HF emissions (Romero et al. 2015). Umicore states that its plants can handle fuel cell scrap recycling using a method involving grinding the membranes up to a powder, then adding a calcium salt as a passivator, such that during smelting, HF is bound up as calcium fluoride which can be sold as a by-product or disposed of safely (Caffarey 2019). This is a simple and effective approach and gives Umicore a stronghold in EV recycling alongside its battery processing capabilities. The only word of caution is that it might be surpassed by a circular economy approach which allows the platinum to be separated from the membrane and each to be recovered and reused. Johnson Matthey developed such a process with Axion in the UK. The process was published in a patent application but to date has not been operated commercially (Coleman 2018).

Permanent Magnets

As set out in Table 2, there is a valuable source of REE and other metals in renewable energy equipment including magnets for wind turbines (and electric vehicles) and photovoltaic coatings for solar panels. Magnets come in two key varieties: permanent magnets and electromagnets. As the names suggest, a permanent magnet is constantly in possession of a magnetic pull whereas an electromagnet requires an electric field to be applied before it will generate a magnetic force. A permanent magnet (hard magnet) can induce a temporary magnetic field in some materials such as steel and these are referred to as temporary (soft) magnets. Permanent magnets are used in a variety of audio-visual equipment, electric motors, smartphones, power generation and other industrial applications. The main types are neodymium-iron-born (NdFeB), samarium-cobalt (SmCo), and ferrite. SmCo magnets are well established and have been in production for over 40 years. They are often used in high temperature applications, such as food manufacturing. SmCo contain a portion of other REE and transition metals (Pr, Ce, Gd and Fe, Cu, and Zr). Ferrite magnets are the cheapest of the three categories and are used in basic applications such as fridge magnets and low performance loudspeakers. They are formulated with a broad range of other transition metals including cobalt, manganese, nickel and zinc.

NdFeB magnets are the strongest in existence and they are seeing exceptional growth in the automotive industry and wind power.

Figure 5. Reactor design: optimization model for the key process steps in commodity chemical production.

Source: Chemours, Nafion Safe Handling in Use, Technical Bulletin T-01

*Significant level but could not calculate because HF reacts with and absorbs on cell walls.

**Mixture of products


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The formula is actually Nd2Fe14B and the composition is 65-70 wt% Fe, 1% B and 30% Nd/Pr,


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Outlook

The overriding message for the production and recycling of CRM is a very positive one with all metals and minerals having a long-term future in end-use applications. Security of supply is essential for economic growth, decarbonization goals, and global stability and security. Having state-of-the-art recycling processes is a key pillar of this supply security and creates a win-win for all parts of the supply chain and the environment. Introduction of new automotive and energy technologies is a gamechanger, and much investment is required to ensure the implementation of robust recycling processes with sufficient capabilities to meet future demand. At present there is a dearth of processes for recycling of fuel cells, with only one company (Umicore) confident about its capabilities. There are many opportunities for more companies to develop circular approaches. A host of companies have already entered the battery recycling market and are well established in China. In time some consolidation, mergers and acquisitions (M&A) are likely. REE remain the problem child and world-class research and development by academic-industrial consortia needs to continue for viable processes to be implemented at scale, or this is one sector which could see technology substitution to avoid the risks of a very uncertain supply chain. In all cases there are opportunities for considerable revenues from CRM recycling if the right investment choices are made.

ReferencesAngloAmerican. (2019). “Anglo American Platinum and Platinum Group Metals Ltd. Launch New Venture to Develop Next Generation

Battery Technology.” Press Release, July 15.https://www.angloamericanplatinum.com/media/press-releases/2019/15-07-2019.aspx

Argus. (2019). “Canada’s Geomega to Recycle Rare Earth Magnets.” News, August 28. https://www.argusmedia.com/en/news/1966820-canadas-geomega-to-recycle-rare-earth-magnets

Caffarey M. (2019). “Introducing Umicore and Fuel Cells.” IPMI Workshop: Atlanta, GA, April.Chemours Company. (2016). “Nafion Ion Exchange Materials: Safety in Handling and Use.” Technical Bulletin T-01. https://www.

chemours.com/Nafion/en_US/assets/downloads/nafion-safety-handling-technical-information.pdfColeman RJ, Ralph TR, Haig S, Plechkova NV (inventors). (2018). “Process”; US Patent Application US20180108932A1. Assigned to

Johnson Matthey Fuel Cells Ltd.Daly T and Singh S. (2019). “China Rare Earth Prices Soar on Their Potential Role in Trade War.” Reuters. https://www.reuters.

com/article/us-usa-trade-china-rareearths/weapon-of-choice-china-rare-earth-prices-soar-on-their-potential-role-in-trade-war-idUSKCN1T70IB

Dept. of the Interior. (2018). “Final List of Critical Minerals 2018.” A Notice from Interior Department. https://www.federalregister.gov/documents/2018/05/18/2018-10667/final-list-of-critical-minerals-2018

EU Cordis, (2019). “Sustainable Recovery, Reprocessing and Reuse of Rare-Earth Magnets in a Circular Economy (SUSMAGPRO).” https://cordis.europa.eu/project/rcn/223261/factsheet/en?WT.mc_id=RSS-Feed&WT.rss_f=project&WT.rss_a=223261&WT.rss_ev=a

E4Tech. (2018). “The Fuel Cell Industry: Review 2018.” https://www.californiahydrogen.org/wp-content/uploads/2019/01/TheFuelCellIndustryReview2018.pdf

Green Car Congress (2019); “BloombergNEF: electrics to Take 57% of Global Passenger Car Sales, 81% of Municipal Bus Sales by 2040.” https://www.greencarcongress.com/2019/05/20190516-bnef.html

Géoméga. (2019). “Corporate Presentation.” July 2019Guyonnet D, Planchon M, Rollat A, et al., (2015). “Material Flow Analysis Applied to Rare Earth Elements in Europe.” JCleanProd, 107:

215–228.Harler C. (2018). “Rare Opportunity to Recycle Rare Earths.” Recycling Today. https://www.recyclingtoday.com/article/rare-earth-

metals-recycling/Heulens J, Van Horebeek D, Quix M (inventors). (2019); “Process for smelting lithium-ion batteries.” US Patent: US10326182B2 2019

Assigned to Umicore NV SA.Horiuchi Y, Terada T, Hori A, et al. (inventors). (2017). “Fuel Cell Electrode Catalyst and Method for Producing the Same.” US Patent

Application: US20170338495A1; Assignee: Cataler Corp, Toyota Motor Corp.Hsu, J.; “Don’t Panic About Rare Earth Elements.” Scientific American. https://www.scientificamerican.com/article/dont-panic-about-

rare-earth-elements/Kitco. “Strategic Metals.” https://www.kitco.com/strategic-metals/ Liu J and Chinnasamy C. (2012). “Rare Earth Magnet Recycling.” Rare Earth Elements Workshop, May 10. https://clu-in.org/

download/issues/mining/liu-presentation.pdf Lynch MK. (2017). “Future Uses of Platinum Group Metals.” The Catalyst Review, 30(8): 8-14.Melin HE. (2017). “The Lithium-Ion Battery End-of-Life Market – A Baseline Study.” http://www3.weforum.org/docs/GBA_EOL_

baseline_Circular_Energy_Storage.pdfMoss RL, Tzimas E, Willis P, et al. (2017). “Critical Metals in the Path Towards Decarbonisation of the EU Energy Sector”; JRC Scientific


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and Policy Reports. https://setis.ec.europa.eu/sites/default/files/reports/JRC-report-Critical-Metals-Energy-Sector.pdfPillot C. (2017). “Lithium Ion Battery Raw Material Supply & Demand 2016 and 2025.” Avicenne Energy. http://cii-resource.com/cet/

AABE-03-17/Presentations/BRMT/Pillot_Christophe.pdfREE4EU. (2019). “Rare Earth Recycling Project for Europe.” http://www.ree4eu.eu/Romero JM, Meyer H, Voss M (inventors). (2015); “Device and Method for the Thermal Treatment of Products Containing Fluorine

and Precious Metals.” European Patent EP2700726 B1. Assigned to Heraeus Deutschland GmbH and Co KG.Shaw S and Constantinides S. (2012). “Permanent Magnets: The Demand for Rare Earths.” Presented at the 8th International Rare

Earths Conference; 13–15 November (Hong Kong). Villas-Boas A. (2019). “Samsung May Release a Smartphone with New Battery Technology That Can Fully Charge Less Than 30

Minutes.” Business Insider. https://www.businessinsider.com/samsung-graphene-battery-tech-super-fast-charging-2019-8?r=US&IR=T

Wieber J. (2019). Personal communication.Worrell E and Reuter M. (2014). “Handbook of Recycling: State-of-the-art for Practitioners, Analysts, and Scientists.” Elsevier.Yang Y, Waltan A, Sheridan R, et al. (2017). “REE Recovery from End-of-Life NdFeB Permanent Magnet Scrap: A Critical Review.”

J.Sustain.Metall., 3(1): 122-149.

About the Author

Dr. Michelle Lynch is the Director and Owner of Enabled Future Limited (EFL). EFL offers consulting, information training and thought leadership reports on chemicals and materials technologies and markets. EFL’s strategic focus is on evolution of industries, technologies, supply and value chains in line with the growth in Advanced Manufacturing, Circular Economy and Industry 4.0. Dr Lynch has over 20 years’ experience in the chemical industry including five years in consulting and 15 years with manufacturers. Roles held include consulting, information science, patent analysis, market research and chemicals development within Johnson Matthey, Nexant and IHS Markit. She currently lives and runs her consulting business in London, UK.

Industry Perspectives (continued from page 1)derive greater understanding of the catalytic system from the dynamic features of reactant and product rates and concentrations evolving together in response to a perturbation. At present, there is significant whitespace to apply the many tools of data analytics (supervised, unsupervised and classification algorithms) to exploit this rich source of data. Taken together with the more established methods for detecting and predicting promising activity, as data-driven transient kinetic analysis tools emerge, these combined efforts hold great promise for creating greater understanding for how complex industrial materials function and how to make them function better.

References

1. Medford AJ, et al. (2018). ACS Catalysis 8(8), 7403-7429. doi:10.1021/acscatal.8b01708.2. Duff DG, et al. (2004). Macromolecular Rapid Communications 25, 169-177.3. Srinivasan PD, et al. (2019). Reaction Chemistry & Engineering 4, 862-883.4. Yablonsky GS, et al. (2007) Chemical Engineering Science 62, 6754-6767.5. Kunz MR, et al. (2018). Chemical Engineering Science 192, 46-60.

About the AuthorDr. Rebecca Fushimi is a research scientist at Idaho National Laboratory working in catalysis and materials characterization. Her research is focused on using transient kinetics and the study of dynamics in chemical systems to understand gas/solid interactions at a fundamental level. She is an expert in the TAP (Temporal Analysis of Products) technique, of which there are less than 20 systems globally. Using TAP and other dynamic techniques her research group investigates selective oxidation, dehydrogenation, reforming reactions and ammonia synthesis on supported metals and mixed metal oxide catalysts. A main theme of this effort is to use a top-down approach to complexity of chemical systems by characterizing ultra-sparse perturbations in

composition with intrinsic kinetic descriptors. This provides fundamental information of how new materials can be used more efficiently to control the individual steps of a chemical reaction.


Enhanced Lithium-Ion Conductivity of Polymer Electrolytes by Selective Introduction of Hydrogen into the Anion...

Conventional lithium-ion battery technology has reached the threshold of its theoretical energy density (ca. 300 Whkg-1), a value insufficient to meet the requirements of next-generation batteries (>400 Whkg-1). However, rechargeable Li metal (Li0) batteries (LMB) are emerging as promising alternatives; although, the formation of dendritic lithium and the low Coulombic efficiency during repeated plating/stripping cycles is detrimental to the safety and energy density aspects of these materials. Current interest centers on the use of solid polymer electrolytes (SPEs) in an all-solid-state assembly of lithium metal batteries (ASSLMB) due to ease of processing, cost-effectiveness, excellent flexibility, lightweight, and the absence of highly flammable carbonate solvents. Herein, the authors describe a new strategy for boosting the Li-ion conductivity of SPEs via the introduction of protons able to form hydrogen bonds into the anionic structure of the lithium salt (Figure 1a). Figure 1b shows that the dissociation of Li+ cations from sulfonimide anions becomes more difficult with the increasing number of H atoms in the anion. Meanwhile, the adverse effect that the introduction of H atoms has on the anodic stability of the sulfonimide anions is clearly evident in Figure 1c.

Figure 1. a) Chemical structure of the studied lithium sulfonimide salts. b) Calculated dissociation energy (∆Ed) and c) oxidation potential (Eox) vs. the anionic structure of the lithium salts.

Figure 2. a) Arrhenius plots of the ionic conductivity for the LiX/PEO electrolytes (X=TFSI, DFTFSI, MTFSI, and MSI). Note that the ionic conductivities of LiMSI/PEO are raised by a factor of 100. b) Total and Li-ion conductivity (left y axis) and calculated dissociation energy (right y axis) vs. type of lithium salt for the LiX/PEO electrolytes (X=TFSI, DFTFSI, MTFSI and MSI). TLi+ of the LiMSI/PEO electrolyte is assumed as 1.0.

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The authors went on to find that ionic conductivity decreases with increasing number of H atoms in the anions: LiTFSI/PEO > LiDFTFSI/PEO > LiMTFSI/PEO LiMSI/ PEO (PEO= polyethylene oxide (Figure 2) — ascribed to the increase of dissociation energy as pointed out by the DFT calculations and the lowered ion mobility, which is a result of the Lewis acid-base interactions between the anion and the PEO.

Partial substitution of F atoms in TFSI-with H atoms can effectively enhance the Li-ion conductivity at a low expense of the total ionic conductivity. DFT calculations combined with experimental results suggest that the anodic stability of such H-containing anions is lower than that of TFSI-, but they are still electrochemically stable enough, considering the different voltage window of each kind of ASSLMB. The results indicate that a tailored anionic structure with consideration of the nature of the polymer matrices and electrodes should certainly boost the properties of SPEs and improve the electrochemical performance of ASSLMBs in the future. Source: Zhang H, Oteo U, Zhu H, et al. (2019). Angew. Chem. Int. Ed., 58: 7829–7834.

Dynamic Frustrated Lewis Pairs on Ceria for Direct Nonoxidative Coupling of Methane...

Frustrated Lewis pairs (FLPs), sterically encumbered Lewis acid and Lewis base combinations, have found increasing applications in the field of homogeneous catalysis. However, the problematic and costly recycling of these materials hinders the large-scale application of soluble FLPs. For this reason, considerable attention has been directed at developing heterogeneous FLP catalysts, which can be classified into two categories: semisolid FLPs and all-solid FLPs. Herein, the authors describe the results of their investigation of the formation rules and dynamic behaviors of solid FLPs on CeO2(110) surfaces using combined static DFT and AIMD calculations (Figure 1). Building upon this base, they went on to study their stability and dynamic behaviors under reaction conditions, and then explored the methane activation and the C−C coupling behaviors of solid FLPs under nonoxidative conditions (Figure 2).

The main conclusions arising from this work are: (1) The formation of stable FLPs on CeO2(110) is dependent on the number of surface oxygen vacancies (Vos). The FLPs constructed by three or more oxygen vacancies are naturally stable in thermodynamics.


EXPERIMENTALEXPERIMENTAL

The FLPs containing fewer oxygen vacancies (VO monomer and dimer) are less stable under vacuum, but they can be dynamically formed at reaction conditions such as thermal fluctuation at high temperatures and reactant-adsorption. (2) The dissociative activation of methane can be readily achieved at solid FLPs with the activation energy being as low as 0.74 eV on FLP-2VO and 0.63 eV on FLP-3VO. The superb activity of FLPs for methane activation is attributed to the stronger interaction with methane via the local electric field of Lewis pairs and the increased electron transfer from FLP-base sites to the antibonding orbital of C−H bond of methane. (3) The nonoxidative coupling of methane into ethane and ethylene is revealed to be feasible at CeO2(110)-based FLPs. The critical C−C coupling of methyl groups at FLP sites has a reaction barrier of 1.1 eV, much lower than that of previously reported methyl group desorption and gas-phase C−C coupling. Although the formation of hydrogen to regenerate FLPs seems to be difficult, it can be overcome at high temperatures.

These results provide insights into the formation of solid FLPs on CeO2 surfaces and methane activation at FLP sites. More importantly, this study uncovers a possible strategy for nonoxidative coupling of methane into valuable hydrocarbons on FLPs-contained oxide catalyst and may provide guidance for experimental design of FLP catalysts. Source: Huang ZQ, Zhang T, Chang CR, et al. (2019). ACS Catal., 9: 5523−5536.

Figure 1. (a) Root-mean-square deviation of atom positions of CeO2(110)-3VO surface in AIMD simulations at 300 and 700 K. Time evolution of Cartesian coordinates (z) of selected O atoms (colored in magenta, blue, and cyan) neighboring to VOs on CeO2(110)-3VO at both (a) 300 K and (b) 700 K. The dashed line at z = 8.2 Å is the reference coordinate. The structures in the upper panels in (b) and (c) correspond to the states labeled as green dots in the corresponding time evolution curves. The green circles marked within the structures denote the positions of the intact VOs

Figure 2. Nonoxidative coupling of methane to ethane on CeO2(110) surfaces. (a) Potential energy diagram of the reactions at FLP-2VO sites (blue curve) and FLP-3VO sites (green curve). The zero energy reference corresponds for the sum of energies of CH4(g), and the corresponding clean CeO2(110) surfaces. (b,c) Geometric structures of transition states in dissociation of the second methane, formation of ethane and hydrogen.

Figure 1. Examples of ILs used as electrolytes for CO2 reduction.

Efficient Electrocatalytic CO2 Reduction Driven by Ionic Liquid Buffer-Like Solutions...

Rising levels of atmospheric CO2 are driving the development of new methods for its capture and utilization. One approach that has generated considerable attention involves electroreduction using reusable electricity. Metals such as Ag and Au can electrocatalyze the reduction of CO2 to CO in aqueous media, but relatively high reduction overpotentials and low selectivities are often observed. Moreover, CO2 electro-reduction in aqueous media is complicated by competitive co-electrogeneration of H2, which reduces the faradaic efficiency for CO production, The use of ionic liquids (Figure 1), on the other hand, results in a dramatic reduction of the CO2-reduction overpotential in aqueous electrolytes.

Herein, the authors show that the use of basic ILs capable of forming buffer-like solutions in aqueous media allows electro-chemical reduction of CO2 at remarkably low overpotentials with high selectivity and faradaic efficiency for CO production. Specifically, they demonstrated that mixtures of [BMMIm][OAc], DMSO, and water can dissolve up to 43 mol% CO2 (27 mol% through formation of bicarbonate and 16 mol% through solvated CO2) at atmospheric pressure. The resulting solution supports selective electroreduction of CO2 to CO at Au electrodes at potentials as low as —1.40 V vs. Ag/AgCl. At —1.80 V vs. Ag/AgCl, faradaic efficiencies for CO formation above 98% are observed. Addition of large amounts of water to the electrolyte favors the formation of free bicarbonate, which reduces the energy required for the electro-chemical reduction of CO2, but this is accompanied by the co-electrogeneration of H2, yielding syngas that can be used for the formation of liquid fuel through follow-on processing.


Catalytic Performance of Layered Double Hydroxide (LDH) Derived Materials in Gas-Solid and Liquid-Solid Phase Reactions...

Layered double hydroxides (LDHs) or hydrotalcite-like compounds are a class of ionic lamellar compounds, consisting of positively charged brucite-like layers, charge compensating anions, and water molecules within the interlayer spaces (Figure 1). After thermal treatment, LDHs lose their layered structure and turn into layered double oxides (LDOs) whose structure possesses three kinds of active sites: (1) weak Brønsted basic sites (OH- groups on the surface), (2) medium strength sites Lewis sites (both Mg2+_O2- and Al3+_ O2- acid-base pairs), and (3) strong Lewis basic sites (O2- anions). This fresult renders LDOs promising catalysts for a variety of acid-base reactions. Herein the authors present a comprehensive study of catalytic behavior of different kinds of LDHs. LDHs were prepared by a conventional co-precipitation method with different M2+ (Mg, Cu, Ni, Zn) and M3+ (Al, Fe, Co) cations. All synthesized LDHs were thoroughly characterized using X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy(FT-IR), and nitrogen adsorption-desorption analyses.

EXPERIMENTAL

Figure 2. Onset potential for electroreduction of CO2 at Au electrodes in 0.1 moldm-3 [BMMIm][OAc] in DMSO containing increasing concentrations of H2O.

Figure 1. Schematic structure of LDH and its change to layered double oxides (LDO) upon calcination.

Figure 2. Methanol conversion over LDO catalysts as well as selectivities towards the different products [%] obtained over (a) CuAlOx, (b) MgAlOx, (c) NiAlOx and (d) ZnAIOx

The authors go on to propose that the CO2 moiety is more stabilized in the buffer solution, resulting in a consequent decrease in the onset potential, as shown in Figure 2. The 1-n-butyl-2,3-dimethylimidazolium acetate [BMMIm][OAc]/DMSO/H2O solution plays multiple roles in the process, acting as CO2 sorbent and producing bicarbonate that provides the stabilization of the CO2. This work provides clear evidence of the role of bicarbonate for effective CO2 reduction. This approach, employing basic ILs in solution that can produce buffer-like solutions, opens a new window of opportunities for the ambient-pressure CO2 capture and transformation. Source: Goncalves WDG, Zanatta M, Simon NM, et al. (2019). ChemSusChem, DOI: 10.1002/cssc.201901076.

The catalytic performance of these materials was then evaluated in the methanol conversion into hydrocarbons (Figure 2). While CuAlOx demonstrated a high selectivity in DME, NiFeOx showed a 100% selectivity to CH4 at full conversion and high stability (superior to 30 h), suggesting that NiFeOx could be a potential candidate for the timely reversible CH4 to methanol reaction.

Subsequently, selective liquid-phase oxidation of benzyl alcohol was studied over different LDH samples. In general, Ni and Cu-containing samples exhibit high activity (>50% conversion) in comparison with ZnAl sample, which only led to reach 15% conversion. Ni-samples demonstrated higher activity than Cu-samples, regardless of the nature of the trivalent cation (Al3+/Fe3+), with NiAl-LDH remaining the most suitable sample for a selective benzaldehyde production at an appreciable 71% conversion. The observed catalytic performance followed the order: CuAl-LDH ≈ CuCo-LDH>CuFe-LDH. Finally, the fact that benzoic acid could not be detected after the reaction accounts for the high efficiency of these materials in benzaldehyde production and, therefore, for their versatility in different processes. Source: Huang L, Megías-Sayago C, Bingre R, et al. (2019). ChemCatChem, 11: 3279–3286.


EXPERIMENTAL

New Method Places Single, Specific Monomers in Polymer Chains...

Cyclopropene monomers (shown here in ring-opened form with various substituents R1-R4) can be precisely placed at various locations along a polymer. Each block in the polymer can consist of different types of monomers, represented by different colors and RA, RB, and RC.

A new method allows chemists to precisely place single monomers at any position within a polymer chain made of other types of monomers. With this single monomer, chemists can add various types of functionality such as chromophores to produce sensors or another polymer chain to create novel polymer architectures. Previous methods for adding single monomers have lacked precision, either adding multiple monomers or none where only one was desired. In the new method, Yan Xia and coworkers at Stanford University use cyclopropene ester derivatives with ring-opening metathesis polymerization to add individual cyclopropenes at multiple locations in a polymer otherwise made from norbornenes.Cyclopropene monomers (shown here in ring-opened form with various substituents R1-R4) can be precisely placed at various locations along a polymer. Each block in the polymer can consist of different types of monomers, represented by different colors and RA, RB, and RC. Source: Chemical & Engineering News (C&EN), 8/26/2019, p.9.

JUST ANNOUNCED!

“Power-To-X: Techno-economic, Commercial and Strategic Developments for Production of Energy Carrier Chemicals, Petrochemicals and Sustainable Fuels”

In its most recent multi-client study proposal, The Catalyst Group Resources (TCGR) will address the latest commercial and technological progress related to the use of Power-To-X (PtX) technology in the production of energy carrier chemicals (gaseous and liquid), petrochemicals and sustainable fuels. Much of this is encapsulated by the production of green hydrogen from water electrolysis and its downstream value chains. Whether you are a producer or consumer of hydrogen, syngas, methanol, natural gas, ammonia or Fischer-Tropsch hydrocarbons, or have access to excess renewable power, you will want to use this in-depth analysis to inform you of the latest in the state-of-the-art technologies as well as guide you for further investment opportunities. The study will provide an understanding of the market drivers, challenges and opportunities for PtX, a detailed technology review of the green hydrogen value chain (e.g., H2, SNG, methanol, ammonia, etc.), techno-economic case studies of the world’s current flagship PtX projects and the resulting competitive and strategic implications.

Source: Frontier Economics, 2018; “INTERNATIONAL ASPECTS OF A POWER-TO-X ROADMAP: A report prepared for the World Energy Council, Germany”; p. 15

Critical to the potential success of PtX is water-splitting. A delineation of the strengths and weaknesses of the various approaches will provide an indication of the role to be played via technology and techno-economic advancements with implications in: 1) Water Electrolysis; 2) Green Hydrogen; Blue Hydrogen; 3) Power-to-Gas; 4) Syngas; CO; and 5) Power-to-Liquids. With an outlook covering the next 10 years (2020-2030), TCGR will consider commercial and technological developments that will provide expert information for current business operation and future business planning. By focusing on emerging technologies, TCGR will detail how changes occurring now and expected in the future via the Power-to-X approach will impact the chemical energy carriers, green petrochemicals and sustainable fuels markets of tomorrow. This report will look at the way in which hydrogen and its downstream value chain are being disrupted by the increased deployment of Power-to-X and will elaborate on strategies being adopted in a wide range of current pilot and large demonstration projects.

This study is a “by the industry, for the industry” assessment and a “must have” for future success in Power-to-X (PtX) globally! This proposed study is scheduled for completion in Jan./Feb. 2020.

Additional information, including the complete study proposal, the preliminary Table of Contents and the Order Form, is available at: http://www.catalystgrp.com/multiclient_studies/power-to-x-techno-economic-commercial-and-strategic-developments-for-production-of-energy-carrier-chemicals-petrochemicals-and-sustainable-fuels/ or by contacting John J. Murphy at +1.215.628.4447 or [email protected]

The Catalyst Group Resources (TCGR), a member of The Catalyst Group, is dedicated to monitoring and analyzing technical and commercial developments in catalysis as they apply to the global refining, petrochemical, fine/specialty chemical, pharmaceutical, polymer/elastomer and environmental industries.


Steven Olivier has 25 years global technical, sales, and executive experience in the catalyst industry with Akzo Nobel and Albemarle Corporation, during which time he spent 10 years in Asia. He holds a master’s degree from the University of Leiden, majoring in solid-state chemistry, with publications on high-temperature superconductors on the basis of perovskite-like materials. After graduation, Steven joined ExxonMobil as process engineer at their Rotterdam refinery. Subsequently he joined AkzoNobel as a technical specialist in refinery catalysts. From there he progressed to sales, sales management, and general management. Steven has led businesses in FCC, hydroprocessing, and other refining and petrochemical catalysts, leading the development and commercialization of several innovative new catalysts. Steven can be reached at [email protected].

Steven Olivier, MSManaging Director of the Catalysis BU of Avantium

MOVERS & SHAKERS

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The Catalyst Review asked Mr. Olivier to discuss recent advances in the field of “high-throughput” catalyst design.

Since its inception some 20 years ago, the concepts, technologies, and methodologies of high-throughput catalyst testing have been thoroughly adopted throughout the catalyst industry. Although in essence, “high-throughput” entails multiple-parallel testing of catalysts, in practice it has had a much more profound impact on how research and development is conducted. Whereas in the past, not only the testing itself but also the science was very much a serial process, with high-throughput techniques whole multi-dimensional spaces of active components and their respective ratios can be explored simultaneously. As an illustration of that impact, during its 2019 AGM Shell stated that high-throughput R&D, such as developed and supplied by Avantium, has helped reduce time-to-market of new catalysts from seven to three years. That is an impressive improvement. But what is the next frontier of accelerating catalyst R&D?

Up to now, the overall approach has focused on speed, accuracy, and reliability of tests. For example, at Avantium, we pursue all three in our Flowrence technology platform by testing at the smallest relevant scale, applying micro-fluidics to ensure identical conditions in each reactor and bringing online all analyses of products.

We see two related waves of acceleration in catalysis R&D. Firstly, integrated workflows, whereby as much data as possible is generated online and integrated into linked databases, will significantly boost efficiency. Catalysis research is unique in the multitude and divergent analyses applied from active component and catalyst preparation through to ultimate product analyses. Even today, with advanced LIM systems, significant amounts of that data are generated by separate labs, and often not integrated. Generating that data together will make it much easier to discover new leads. For example, unsuspected impacts of carrier aging times on certain product yields can only be uncovered if that data is linked.

Such integration of data will enable the next wave of acceleration. High-throughput testing delivers large amounts of testing data — more than can be handled by readily available analysis and visualization methods. Currently, data from high-throughput tests are often passed from the chemists to the statistics and modeling experts to extract knowledge. That interface between experts is a significant barrier — it costs time and introduces lost-in-translation risks. Adding to this issue is a somewhat perverse consequence of the success of high-throughput testing: the expansion of testing capacity has allowed for poorly desig

the catalyst review · 2019. 12. 2. · the catalyst review 1 september 2019 industry perspectives...

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