technical & commercial progress in the global catalytic

The Catalyst Review October 2018 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: Planning Under Extreme Uncertainty: The Impact of Low Cost and Abundant US Shale Gas and Unconventional Oil Production

October 2018 A Publication of The Catalyst Group Resources, Inc. Volume 31, Issue 10THE CATALYST REVIEW

Developing a Consistent Process Model through

a Project's Life Cycle

The Catalyst Review October 20182

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CONTENTS

In This IssueIndustry PerspectivesPlanning Under Extreme Uncertainty: The Impact of Low Cost and Abundant US Shale Gas and Unconventional Oil Production ..................................................1

Commercial NewsAlberta Joins Petrochemicals Boom with $2B Methanol Project Proposal ............3Japan Refiner Idemitsu Finalizes Deal to Buy Out Showa Shell ..............................3AkzoNobel Specialty Chemicals is Now Nouryon ...................................................3ExxonMobil Eyes Multi-Billion Dollar Investment at Singapore Refinery ...............4

Saudi Aramco and Total Launch Engineering Studies to Build a Giant Petrochemical Complex in Jubail ............................................................................ 4

Sahara Petrochemicals and Sipchem Sign MOU to Merge .....................................4

Clariant Bets Big on Cellulosic Ethanol ................................................................... 5

INEOS Signs Technology and Catalyst Agreement for New World-scale PDH Unit in Europe ........................................................................................................ 5

Process NewsNew Technology Advances Lead Anellotech to Announce Commercial Plant Engineering Plans ................................................................................................... 6 Catalyst Drives Carbon-Coupling Chemistry without Making CO2. .........................6 The Impact of Formulation and 3D-printing on the Catalytic Properties of ZSM-5 Zeolite ......................................................................................................... 6MOFs Hook Up with Frustrated Lewis Pairs ........................................................... 6Special Feature Developing a Consistent Process Model through a Project's Life Cycle .................7ExperimentalUltrathin Chiral Metal–Organic-Framework Nanosheets for Efficient Enantioselective Separation ................................................................................... 14

Continuous Gas-Phase Condensation of Bioethanol to 1-Butanol over Bifunctional Pd/Mg and Pd/Mg–Carbon Catalysts .................................................15

The First C-Cl Activation in Ullmann C-O Coupling by MOFs ..................................15

Electrooxidative Allene Annulations by Mild Cobalt-Catalyzed C−H Activation .....16

Movers and Shakers Jean-Philip Lumb, PhD ............................................................................................ 18

THE CATALYST REVIEW (ISSN 0898-3089) October 2018 Volume 31, Number 10 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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CEO Clyde F. Payn

PRESIDENT John J. Murphy

MANAGING EDITOR Mark V. Wiley

CONTRIBUTORSJean-Philip Lumb, PhD

Eugene F. McInerney, PhDJoseph Porcelli, PhDCharles Sanderson

BOARD OF ADVISORSSalvatore Ali, PhD

Michele Aresta, PhDMiguel A. Banares, PhD

Vijay Bhise, EngScDCarlos A. Cabrera, MBA

Gabriele Centi, PhDMatthew A. ColquittAvelino Corma, PhD

Frits Dautzenberg, PhDBurtron Davis, PhD

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

Warren S. Letzsch, MSVishwas Pangarkar, PhDJoseph Porcelli, DEngSciGadi Rothenberg, PhD

LAYOUT & DESIGNMeedah Spence

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The Catalyst Review provides busy executives, researchers, and production managers with a timely update on catalysis and process advances in the petroleum, petrochemical, environmental, and specialty chemical industries.


INDUSTRY PERSPECTIVESThe views expressed are those of the individual author and may not reflect those of The Catalyst Review or TCGR

Continues on page 2

Planning Under Extreme Uncertainty: The Impact of Low Cost and Abundant US Shale Gas and Unconventional Oil Production

Introduction

As a consultant for almost two decades, following a 40 year career primarily in petrochemical process development from research to commercialization, I have followed the chemical business and technical literature. I have been particularly interested in the causes and effects of the business cycles and the cycles in energy and feed stock prices, and their implications on R&D planning. Most recently, I’ve become interested in and concerned about the large number of ethane-to-ethylene plants being built in the US, based on low priced ethane recovered from shale gas.

At the beginning of 2008, the world was experiencing a “bubble” in commodity prices, including crude oil prices, which peaked at about $140 per barrel midyear. (Please note: I have used WTI crude oil prices, which until the last few years tracked the international Brent prices very closely.) By the end of that year, crude oil had dropped to about $40 per barrel, accompanied by a collapse in the financial markets. Driven by low interest rates, in some cases even negative ones, the global economy gradually recovered, until by 2011 crude oil touched $100 per barrel again, and for the next four years it fluctuated in the range from $80 to $110. Then, in 2014, after peaking at about $105 per barrel, the price again collapsed, reaching about $50 per barrel by the end of the year, with no sign of a bottom having been reached.

The First Study

In those last months of 2014, I became interested in the problem of how the chemical industry could plan under such uncertain circumstances, particularly because the typical time lag from first experiments to commercialization of a new catalyst or process technology could be as long as ten years. As a first step, I undertook a study of the drivers (both negative and positive) of crude oil and natural gas prices. Using a scenario approach, I then developed predictions of where the bottom would be for crude oil, and what future prices might be expected for both crude oil and natural gas.

The drivers for future crude oil prices at that time appeared to be the rate of recovery of the Chinese economy, the crude oil supply (OPEC over producing) and the growth of nonconventional oil (tight oil and shale oil), the global gasoline demand (increase in developing countries), and the long-term response of gasoline consumption to gasoline prices (slow reduction when prices are increasing, and rapid increases when prices are decreasing).

As I began my current study, I reviewed the scenario graphs and added on the actual prices for crude oil and natural gas for the year ends starting in 2014. Interestingly, my lowest price forecast for both materials were close to actuality (please see Figures 1 and 2).

Figure 1: The 2018 Figure is for early September. Source: Author, 2018 Figure 2: The 2018 Figure is for early September. Source: Author, 2018

The Current Study

I started the current study in early 2017 and based my analysis on ethylene from 2016. I completed my analysis just as Hurricane Harvey hit Texas and Louisiana, and the severe flooding interrupted much of the production of crude oil and natural gas. Several other Atlantic hurricanes hit in the next months, with one impacting the Gulf oil and gas production to a lesser extent than Harvey, but with devastating damage in the Caribbean Sea, particularly to Puerto Rico and the US Virgin Islands.


As late as November 2017, it was still not clear how long it would take before supply and demand in the US would fully recover to pre-hurricane levels. As it turned out, there were some delays in both production and consumption of crude oil and natural gas, and delays in the startup of some of the new US crackers. The long-term net effects were not very different from what might have developed in the absence of the hurricanes.

Global ethylene production (equal to consumption) in 2016 was reported in an article in ICIS Chemical Business (Davis, 2017) as 145 million metric tonnes/year, and global operating rate for olefin plants was reported as 88%, giving an estimated global plant capacity of 165 million metric tonnes/year. 2016 consumption in North American was reported separately as about 36 million metric tonnes amounting to a market share of about 25% and a plant capacity (at 88% stream factor) of about 40 million metric tonnes/year. Capacity in the rest of the world (ROW) would therefore have been about 125 million metric tonnes/year in 2016.

China’s market share was estimated for 2016 at about 20%; however, the China information is complex, because they have invested substantially in methanol to olefin technology (some producing propylene and some producing a mix of propylene and ethylene) and some direct production of some ethylene derivatives, such as ethylene glycol from coal. Second, China has traditionally consumed much more ethylene, its derivatives and propylene than it produces, with new facilities not always keeping up with new demand.

The same ICIS article gave historical ethylene production data back to 2010, and the average demand growth rate from that year to the present was about 3.2%. Using this growth rate through 2022 would project a global ethylene demand rate of about 175 million metric tonnes/year in 2022.

A 2017 list (Waldheim, 2017) of ethylene plants in North America operating, under construction, and expected to be operating by 2022 (the so-called first and second waves) led to an estimated added capacity in 2022 of 17 million metric tonnes/year, for a total NA capacity of 57 million metric tonnes/year. Adding that figure to the ROW capacity in 2016 (assuming no plants built outside of North America) through 2022) gives a global capacity in 2022 of 57+125 = 182 million metric tonnes/year, for an operating rate of 175/182 or about 96%.

On the other hand, a more realistic assumption would be that at least five or six and likely more new world scale plants would be built (at least one in Europe, one in India, several in China and one or two others in the Middle East and Asia) which could add 10 million metric tonnes or more of capacity, resulting in an average global operating rate of 175/192 or about 91%. This latter scenario suggests that there is nothing to worry about. However, changing the forecast growth rate of global ethylene demand from 3.2% to 2.5%, for instance, would change the results greatly, to operating rates of 92 and 87%, respectively. Lower operating rates lead to lower margins, causing in the extreme pressure on less competitive producers to shut down.

Under the current prices for natural gas and crude oil, the North American crackers still have a marginal advantage over most of the world except for the Mid-East. However, a continued up-trend in crude oil prices would hurt the competitive advantages currently enjoyed. Drivers to crude oil price growth include increased imbalance in supply and demand (global growth in oil consumption, supply disruption, sanctions on Iran, and other unpredictable events). The potential drivers of increased natural gas prices are supply disruption (weather), increased export of LNG and perhaps ethane) and current and future limitations to the expansion of pipelines and export terminals in North America. It is important to track investments and occurrences along the supply chains of natural gas, crude oil and their derivatives, in order to be able to better anticipate the evolution of the supply and demand of the products involved.

About the Author

Dr. Joseph Porcelli’s professional career spans more than 40 years, with such firms as Scientific Design Company, Inc., ChemSystems, Inc., and Halcon SD Group, Inc. He has been intimately involved in every aspect of chemical process innovation, including: evaluation of process concepts, carrying out and supervising process, catalyst research and development, and leading efforts to commission new plants, processes, and catalysts. Much of his career has been spent as a chief executive in the international chemical arena, wherein he has gained knowledge and experience in all company operating functions. He has

negotiated the sale and purchase of packages of technologies and businesses and has conceived of and executed international technology alliances. In 2001, Dr. Porcelli established JVP International, Inc. as a vehicle to offer the international chemical industry his technical expertise and management experience.

References1) ICIS News – Spotlight on demand as new ethylene and PE capacities hit - 08 February 2017 – Nigel Davis. 2) ICIS News – Chemical Profile: US Ethylene – 07 December 2017 – Jesse Waldheim.

INDUSTRY PERSPECTIVESThe views expressed are those of the individual author and may not reflect those of The Catalyst Review or TCGR

continued from page 1


COMMERCIAL NEWS

Alberta Joins Petrochemicals Boom with $2B Methanol Project Proposal...

Nauticol Energy Ltd., established in 2016, announced plans for a methanol manufacturing facility in Grande Prairie, Alta. If the proposed $2-billion methanol plant is built, the project would be the second methanol plant in Alberta. The Calgary-based company is working through the regulatory process and plans to make an investment decision in 2019 on the facility that will convert 300 million cubic feet of gas per day into 3 million metric tonnes of methanol per year. “The (final investment decision) will take a number of things into consideration,” CEO Mark Tonner said, including the credits, market prices, tightness in the labor market and financing. Once off-take agreements for the methanol are signed, Nauticol would be able to find financiers to back the project “without issue”, Tonner said, adding that he expected to make another announcement on financial partners soon. Nauticol had also announced plans to develop a methanol and urea project in Becancour, Quebec earlier this year. Source: Financial Post, 10/9/2018.

BP and Aker BP form Strategic Technology Venture Alliance...

BP announced that it has signed a ventures cooperation agreement with Aker BP to explore possible areas of cooperation in the development and deployment of advanced technologies in their businesses. Through their planned strategic alliance, BP and Aker BP intend to explore potential venture capital investments targeting technology and innovation improvements, including developments in digital twins, advanced seismic techniques and processing, and subsea and robot technology. The alliance is also expected to include identifying and evaluating innovations which could improve the environmental performance of offshore oil and gas production. Source: BP, 10/3/2018.

Japan Refiner Idemitsu Finalizes Deal to Buy Out Showa Shell...

Japanese oil refiner Idemitsu Kosan finalized a deal to buy out Showa Shell Sekiyu through a share swap in a deal worth about $5.6 billion. The new firm will target annual savings of around 60 billion yen ($535 million) in 2021/22 from the integration, up by 10 billion yen from a previous projection, the two companies said. The combined firm would account for about 30 percent of Japan’s domestic gasoline sales, second only to JXTG Holdings, which controls about half the market. Idemitsu President Shunichi Kito, who will serve as president of the combined firm, ruled out combining the group’s seven refineries in Japan with total crude refining capacity of 1.088 million barrels per day (bpd) as all were competitive with room for exports. The new firm has a higher ratio of residue cracking capability at its refineries than rivals, he said. The group could raise the capacity of heavy oil processing units at Idemitsu’s 190,000-bpd Chiba refinery in response to the International Maritime Organization’s move to ban use of high sulfur fuel, he added. Source: Hydrocarbon Processing, 10/16/2018.

ExxonMobil Catalysts and Licensing LLC and BASF Corporation to Demonstrate the Next Generation of High Performance Selective Solvent to Decrease Sulfur Emissions...

ExxonMobil Catalysts and Licensing LLC and BASF Corporation are conducting a full-scale commercial demonstration of a new gas treating solvent at Imperial Oil’s Sarnia Refinery. The companies jointly developed the new amine-based solvent aimed at meeting stringent sulfur emissions standards with greater efficiency. The innovative technology improves the selective removal of hydrogen sulfide (H2S) and minimizes the co-absorption of carbon dioxide (CO2) from gas streams. The highly selective properties of the solvent allow refiners and gas processors to increase capacity and lower operating costs in existing equipment. For new treating facilities, the usage of the technology will reduce the size of the equipment and the initial capital investments. Pilot plant testing has demonstrated superior performance characteristics over methyldiethanolamine (MDEA) formulations and even improvements over ExxonMobil’s FLEXSORB™ SE/SE Plus solvents. Source: BASF, 10/15/2018.

AkzoNobel Specialty Chemicals is Now Nouryon...

The former AkzoNobel Specialty Chemicals is being relaunched as Nouryon. The move follows the recent acquisition of the business by The Carlyle Group and GIC and marks the company’s transition to becoming an independent, global specialty chemicals leader. Nouryon has a history that stretches back nearly 400 years and its new name and brand identity reflect that heritage. Noury & Van der Lande was one of the first companies to realize the important role chemistry could play in everyday life; today, Nouryon is a world leader in essential chemistries used to manufacture everyday products. Nouryon will be working closely with customers and other partners to innovate, make strategic investments, and develop essential, sustainable solutions that meet customer needs and fuel shared growth. Source: Nouryon, 10/9/2018.

INEOS Selects Clariant’s Catofin® Catalysts for Europe’s Largest Propane Dehydrogenation Plant...

Clariant has announced that it was awarded a long-term supply contract by INEOS to supply CATOFIN catalysts and Heat Generating Material (HGM) for a major propane dehydrogenation plant to be constructed in Europe. Scheduled for completion in 2023, the facility is designed to produce 750,000 metric tons of propylene annually, which will make it the largest propane dehydrogenation plant in Europe. Source: Clariant, 10/17/2018.


COMMERCIAL NEWS

ExxonMobil Eyes Multi-Billion Dollar Investment at Singapore Refinery...

ExxonMobil Corp is considering a multi-billion dollar investment at its Singapore refinery, the company’s largest, ahead of new global shipping fuel regulations starting in 2020, a senior executive said. “We are currently assessing a multi-billion project in our integrated manufacturing facility here in Singapore,” Matt Bergeron, vice president of Asia Pacific Fuels Business at ExxonMobil, said at a bunkering conference. “Should the project proceed, we plan to implement proprietary technologies that will convert lower value by-products into cleaner higher value products including 0.5 percent sulphur fuels that we believe will be the compliant option for the vast majority of the marine sector,” Bergeron said. Source: Reuters, 10/3/2018.

Petrochemicals Set to be the Largest Driver of World Oil Demand, Latest IEA Analysis Finds...

Petrochemicals are becoming the largest drivers of global oil demand according to a major study by the International Energy Agency (IEA). Petrochemicals are set to account for more than a third of the growth in world oil demand to 2030, and nearly half the growth to 2050, adding nearly 7 million barrels of oil a day by then. They are also poised to consume an additional 56 billion cubic meters (bcm) of natural gas by 2030, and 83 bcm by 2050. The Future of Petrochemicals is among the most comprehensive reviews of the global petrochemicals sector. “Our economies are heavily dependent on petrochemicals, but the sector receives far less attention than it deserves,” said Dr. Fatih Birol, the IEA’s Executive Director. “Petrochemicals are one of the key blind spots in the global energy debate, especially given the influence they will exert on future energy trends. In fact, our analysis shows they will have a greater influence on the future of oil demand than cars, trucks and aviation.” Source: International Energy Agency (IEA), 10/5/2018.

Saudi Aramco and Total Launch Engineering Studies to Build a Giant Petrochemical Complex in Jubail...

Amin H. Nasser, President and Chief Executive Officer of Saudi Aramco and Patrick Pouyanné, Chairman and Chief Executive Officer of Total, signed in Dhahran the joint development agreement for the front-end engineering and design (FEED) of a giant petrochemical complex in Jubail, on Saudi Arabia’s eastern coast. Announced in April 2018, the world-class complex will be located next to the SATORP state of the art refinery, operated by Saudi Aramco (62.5%) and Total (37.5%), in order to fully exploit operational synergies. It will comprise a mixed-feed cracker (50% ethane and refinery off-gases) – the first in the Arabian Gulf region to be integrated with a refinery – with a capacity of 1.5 million tons per year of ethylene and related high-added-value petrochemical units. The project represents an investment of approximately $5 billion dollars and is scheduled to start-up in the 2024. In a move to further develop downstream industries in the Kingdom, the project will also provide feedstock for other petrochemical and specialty chemical plants located in the Jubail industrial area and beyond, representing an additional $4 billion investment by third party investors, benefitting the Saudi economy. The overall complex will represent an investment of approximately $9 billion. Source: Saudi Aramco, 10/8/2018.

Total and Sonatrach Strengthen Their Cooperation in Natural Gas and Petrochemicals in Algeria...

Sonatrach and Total have signed a shareholder agreement to create a joint venture known as STEP (Sonatrach Total Entreprise Polymères). STEP will be responsible for carrying out a joint petrochemical project in Arzew, western Algeria. The project includes a propane dehydrogenation (PDH) unit and a polypropylene (PP) production unit with an output capacity of 550,000 tons per year. The two partners (Sonatrach 51%, Total 49%) are planning to start the front-end engineering and design (FEED) from November. “Today’s agreements mark a new milestone in the development of the strategic partnership between Sonatrach and Total to continue developing the country’s gas reserves by providing the best of our technological expertise,” said Patrick Pouyanné, Chairman and CEO of Total. Source: Total, 10/7/2018.

Sahara Petrochemicals and Sipchem Sign MOU to Merge...

Sahara Petrochemicals and Saudi International Petrochemical Co. (Sipchem) signed a nonbinding memorandum of understanding (MOU) paving the way for a potential merger of equals. The two companies abandoned merger talks in 2014 but resumed discussions to combine operations in March this year. The two companies have reached a preliminary agreement on valuation, and subject to completion of due diligence, they intend to implement a binding agreement to merge. The proposed transaction is expected to deliver multiple strategic benefits. They include strengthening of the product portfolio, diversifying feedstock supply, and building out presence along the value chain; increasing scale and resilience in the evolving petrochemicals sector, both in the kingdom and internationally; building on the competitive advantages and complimentary capabilities of Sahara and Sipchem to provide benefits commercially, operationally, and functionally; driving efficiency and productivity of the closely situated industrial asset portfolios of Sahara and Sipchem at Jubail; and creating a platform with improved financial resources, capital market access, and product and technological expertise to take advantage of local and international growth opportunities, both organic and inorganic, the companies say. Source: Chemical Week, 10/3/2018.


COMMERCIAL NEWS

Clariant Bets Big on Cellulosic Ethanol...

Clariant is commercializing its cellulosic ethanol technology, called Sunliquid. In the Sunliquid process, straw is shredded and steam treated to open its structure. It’s hit with enzymes that degrade the material into C5 and C6 sugars. In a fermentation step, a strain of yeast converts the sugars into ethanol. The firm recently broke ground on a cellulosic ethanol plant in Podari, Romania. The Swiss firm is investing nearly $120 million to build the plant—including European Union subsidies of almost $30 million but on top of almost $50 million the firm spent developing the technology. Scheduled to start up in 2020, the plant will convert some 250,000 metric tons per year of straw from farms up to 80 km away into about 50,000 metric tons of ethanol/yr, largely destined for the fuel market. Given the [current low-cost feedstock] environment, some companies might have shelved the project. But Clariant says it took the time needed to enhance the efficiency of the process, making executives confident that Sunliquid will be competitive. Clariant claims its technology is fundamentally different from the ones that have failed. Perhaps the biggest difference is on-site production of the enzymes that degrade the straw, says Markus Rarbach, head of biofuels and derivatives for Clariant. This cuts out substantial transportation and stabilization costs, Rarbach says. The Swiss firm will provide its licensees with a starter batch of an organism for making the enzyme, which then reproduces on-site. Clariant has been improving its process at a pilot facility in Straubing, Germany since 2012. The pilot plant mimics a commercial operation, down to the engineering design, and even has 24-hour production shifts to mirror activity at a commercial-scale plant, Rarbach says. This attention to detail is one of the reasons why the company is confident Sunliquid will be competitive at industrial scale, he adds. Clariant predicts that the Podari plant will produce ethanol at 60–70 cents per liter, a cost similar to that of sugar-based ethanol. Source: Chemical & Engineering News (C&EN), 10/1/2018, p.26.

INEOS Signs Technology and Catalyst Agreement for New World-scale PDH Unit in Europe...

INEOS has selected McDermott’s Lummus CATOFIN® Technology as the operating technology for its planned propane dehydrogenation (PDH) unit and a license agreement has now been signed. In parallel, an agreement has been signed with Clariant for the long-term supply of catalyst for the unit. The PDH unit will have a nameplate capacity of 750ktpa of polymer grade propylene (PGP) and is planned to be commissioned in 2023. Propylene from the asset will feed INEOS’ polypropylene (PP) units, as well as a number of other downstream propylene derivative businesses. Source: INEOS, 10/2/2018.

LyondellBasell Grants Spherizone, Lupotech and Hostalen ACP Licenses to Zhejiang Petroleum & Chemical Co., Ltd. ...

LyondellBasell announced that Zhejiang Petroleum & Chemical Co., Ltd (ZPCC) has selected LyondellBasell’s polypropylene (PP), high-density polyethylene (HDPE) and low-density polyethylene (LDPE) technologies for five new plants. The plants will be built at Zhoushan City in ZPCC’s petrochemical complex in Zhoushan City, P.R. China. The complex will include two 450 KTA polypropylene plants that will utilize LyondellBasell’s Spherizone PP process technology and two LDPE plants, 300 and 400 KTA respectively, which will utilize Lupotech T process technology. The complex will also include a 350 KTA HDPE plant which will utilize Hostalen ACP process technology. At a total capacity of almost 2 million tonnes, these new licenses constitute the largest volume of new capacity ever licensed by LyondellBasell in a single location. Source: LyondellBasell, 10/2/2018.

McDermott Awarded Olefins Technology Contract in Thailand...

McDermott International, Inc. announced that it has been awarded a sizeable technology contract for Map Ta Phut Olefins Co., Ltd.'s (MOC) petrochemical plant in Rayong Province, Thailand. MOC is a joint venture company of SCG Chemicals Company Limited, which is a wholly owned subsidiary of SCG, and the Dow Chemical Company. McDermott will provide the basic engineering and license of Lummus' olefins technology and will design and supply the proprietary SRT® III heater for the MOC Debottleneck Project, a parallel gas cracker will be added to increase plant capacity which will utilize Lummus' side cracker technology, including a low-pressure chilling train and enhanced binary refrigeration. Source: PRNewswire, 10/1/2018.

Chemical Firms Back Depolymerization...

Ineos Styrolution has formed a partnership with two Canadian firms, Pyrowave and ReVital Polymers, to depolymerize polystyrene (PS). Separately, Indorama will create a joint venture with another Canadian firm, Loop Industries, to commercialize technology that turns polyethylene terephthalate (PET) into the monomers dimethyl terephthalate (DMT) and ethylene glycol (EG). The Styrolution partnership will use technology Pyrowave developed to break down polymers using microwave radiation. The start-up plans to roll out the technology in on-site units that process 400 to 1,200 metric tons of plastic per year. It already operates one such machine in Montreal. This isn’t Styrolution’s first such partnership. In April, the firm said it might deploy depolymerization technology from Agilyx at one of its plants. Agilyx operates a facility in Tigard, OR., that makes styrene via pyrolysis. Indorama and Loop, meanwhile, plan to build a plant based on Loop’s depolymerization process by early 2020. Loop won’t say much about the plant other than that it will be in the eastern U.S. Loop also has agreements with L’Oréal, Evian, and Gatorade. Source: Chemical & Engineering News (C&EN), 10/1/2018, p.6.


PROCESS NEWS

New Technology Advances Lead Anellotech to Announce Commercial Plant Engineering Plans...

Sustainable technology company Anellotech confirms significant progress in its Bio-TCat™ technology development program and has begun planning for scale-up design and engineering of a commercial plant with its process development and design partner IFPEN and commercialization, engineering, and licensing partner Axens. Commercially-viable process yields and catalyst performance has now been achieved at economic design conditions at Anellotech’s TCat-8® pilot unit in Silsbee, TX. TCat-8 has demonstrated consistently stable operation of major process steps and recycle loops, with highly-accurate analytic confirmation. These attractive results have been achieved with real world commercial feedstock, loblolly pine recently harvested from Georgia forests. Anellotech’s MinFree pretreatment process, operational at multi-ton scale, has been used to ensure low mineral content in the TCat-8 feedstock which is critical for catalyst performance.

TCat-8 has operated for over 2,000 hours with continuous catalyst circulation including a fluid bed reactor, catalyst stripper, catalyst regenerator, quench tower, and recycle compressor. The pilot plant is operating mass balance closures of 100% +/-2%, and regularly completes uninterrupted 24/7 runs. David Sudolsky, President & CEO of Anellotech, said, “Our TCat-8 unit consistently demonstrates stable, economic performance as we continue to further optimize process conditions. These advancements come from the dedicated and coordinated efforts of Anellotech, IFPEN and Johnson Matthey engineers and scientists. We are excited to begin commercial plant engineering activities with our partner Axens and open up engagement with potential partners for investments and locations for the first commercial plant.” Source: Anellotech, 10/16/2018.

Catalyst Drives Carbon-Coupling Chemistry without Making CO2....

A simple synthesis method converts iron oxide to a highly pure form of iron carbide, yielding a catalyst for industrial carbon-coupling reactions that produces exceptionally low quantities of CO2, according to a study. The finding may improve efficiency and may also reduce the energy consumption and cost of operating Fischer-Tropsch (FT) reactors. Iron catalysts are less expensive, but they convert up to 30% of the CO in syngas to unwanted CO2, which lowers process efficiency and is costly to separate. So a team led by Emiel J. M. Hensen of Eindhoven University of Technology examined conventional iron FT catalysts and found that in addition to containing iron carbide, the desirable component, they also contain metallic iron and iron oxides, the CO2-forming culprits. The team evaluated preparation methods and found they could make highly pure iron carbide from low-cost iron oxide by fully reducing the starting material in hydrogen and then treating it with nitrogen-diluted syngas. Under industrial conditions, the new catalysts generated as little as 5% CO2 and remained stable for more than 150 hours. Source: Chemical & Engineering News (C&EN), 10/15/2018, p.11.

The Impact of Formulation and 3D-printing on the Catalytic Properties of ZSM-5 Zeolite...

Structured catalysts can help to overcome the drawbacks of conventional packed bed catalysts and help to make more efficient use of the catalytic material in the reactor. One of the major disadvantages of coated structured catalysts is the limited catalyst loading per reactor volume. In this paper by Prof. Lefevere of the Flemish Institute for Technological Research (VITO) and the University Antwerp Laboratory of Adsorption and Catalysis, a robocasting 3D-printing technique was used to manufacture self-supporting macroporous ZSM-5 structures and so overcome the issue of low loading. Moreover, 3D-printing offers the possibility to optimize the architecture of the structured catalyst. In this work, methanol-to-olefins (MTO) was used as a test reaction to investigate the impact of 3D-printing on catalytic properties without changing the basic catalytic start material. Firstly, the influence of different binders and binder combinations in the self-supporting structured catalyst is discussed. Secondly, the architecture of the catalyst was varied by changing the diameter of the fibers of the structure, the porosity of the structure and the shape of the channels in the direction of the flow. The results show a significant impact of both the binders and the architecture on the catalytic properties of ZSM-5 for the methanol-to-olefins reaction. Source: Chemical Engineering Journal, Volume 349, 10/1/2018, p. 260-268.

MOFs Hook Up with Frustrated Lewis Pairs...

The use of Frustrated Lewis pairs (FLPs) has been limited by their lack of recyclability and their sensitivity to air and moisture. Now, researchers led by Shengqian Ma at the University of South Florida have developed stable FLPs. Anchored inside a metal-organic framework (MOF), they efficiently catalyze hydrogenation and imine reduction reactions. With simple filtration, the catalyst can be recycled in the latter reaction at least seven times without loss of activity. To construct the MOF-FLP pair, the team docked an amine Lewis base at the MOF’s open metal sites and then attached a boron Lewis acid (shown). The team then compared the heterogeneous MOF-FLP’s ability to catalyze reactions with that of a homogeneous catalyst. While the researchers observed comparable yields for the hydrogenation reaction, Ma says the MOF-FLP showed “interesting” steric and size selectivity in the imine reduction. The MOF-FLP matched the homogeneous catalyst’s high yield unless the substrate contained a buried imine, suggesting that the MOF environment restricts access to certain substrates. Substrates beyond a certain size were not reduced, likely because they can’t squeeze through the MOF’s pores, the authors say. Future MOF designs could easily introduce chirality or superhydrophobicity to expand the FLP catalysts’ reaction scope and durability, Ma says. Source: Chemical & Engineering News (C&EN), 10/1/2018, p.5.


Developing a Consistent Process Model through a Project’s Life CycleBy Charles Sanderson

Modeling tools are deployed in both academic and industrial settings and applied to all phases of a process’s development. However, the scope of value created by modeling projects is often limited to a single phase of the project or even to a specific team working on that phase. Among the reasons for this limited application are the lack of connectivity between the modeler and the broader project team, and the lack of a vision for how to leverage the model. The aim of this article is to lay out a framework to capture knowledge at each step and synthesize that knowledge into an asset, while including examples from real-world experiences.

Project Team and Phases

As a process moves through its life cycle, many disciplines are involved, each bringing different skills and perspectives. Figure 1 illustrates how these perspectives may influence expectations. Frequently, different disciplines will favor different platforms to capture their learnings so that knowledge is dissipated as the project moves from team to team. For example, research chemists may develop reaction kinetics in a tool like MatLab but transfer only the target extent of reaction to the process design team. Process designers may develop a detailed mass and energy balance in a tool like AspenPlus, but the model is not picked up and maintained by the Operations team. The business development team may work in Excel and not take advantage of the interactions described by the engineering model. The Operations team may develop statistical models in tools like JMP but not link their insights back to fundamentals.

The focus changes as a function of maturity of the process design, and this can result in significant changes in the personnel leading and involved with the project. Figure 2 illustrates the different phases of a typical project and the teams involved in each phase. The sections below explore a methodology that can capture much of that experience in a consistent framework, making it available throughout a process’s life cycle, as simplified into the following five key steps:

1. Conceptualization, where new chemistry and physics are exploited and a process flowsheet is developed to take advantage of new unit operation(s).

2. Feasibility, where the conceptual design is challenged in the real world.

3. Process Engineering, where the process design is scaled up, equipment and operating plans are developed, and capital is allocated.

4. Build and Startup, where the capital is deployed, and an operating plant is commissioned.5. Operation, where the design exposed to real-world challenges like equipment wear, feedstock variations, changes in market

conditions, and unexpected human interactions.

Process Development Requirements

Depending on the maturity of the process, the duration of, and the iteration between, steps will vary significantly. Figure 3 illustrates some of the different activities that are involved in creating a new manufacturing plant, and illustrates how some steps may not be required for different projects:

New-to-world products, where the product is novel and a whole process must be developed. Early prototypes of the product need to be evaluated to compare them to incumbent materials. As applications are developed, preliminary quality specifications (e.g., the acceptable level of byproducts) will be set. Such projects will spend significant time in the conceptualization, feasibility, and engineering stages.

New-to-world processes, where, for example, a new catalyst that enables a new route to a product, requiring an existing process to be altered. As the modified process is developed, then new equipment may be required (e.g., pumps that can develop higher pressures or vessels that can withstand the new conditions). The project may iterate as learnings from, say, commercial feedback from possible markets requires changes in the chemistry to meet purity targets.

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Figure 1. Different expectations that different disciplines will have from a given model; in this case a catalytic reactor.

Source: Author, 2018

Figure 2. Illustration of the phases of a project’s development and the different disciplines involved in each stage. Intensity of color indicates level of involvement of different groups.



New technology in an existing process, where existing assets are exploited, but significant process changes are possible. For example, a new catalyst may be developed to oxidize a vent gas stream, allowing replacement of an expensive thermal oxidizer. Existing constraints, such as equipment performance, utility supply and site logistics need to be considered. Before operating at full scale, the new approach may be tested on a slip-stream. As with earlier phases, intellectual property may be developed and reduced to practice in the testing phase. Once a working demonstration has been developed, then effort will also be required to understand how to scale the equipment up to commercial capacities.

Building a new site with existing technology, where the equipment may be well understood but the design may be modified for local economics, scale, and raw materials. For an established technology, the project may start in the process engineering step, and will benefit from the already-developed process design and well-established capital estimates. The new build does offer the opportunity to incorporate learnings from the past operation of similar sites (e.g., relieving bottlenecks, incorporation of improved equipment).

Proposed Modeling Approach

Despite this difference in emphasis, a common framework and approach allows value to be created across these different projects. With the tools available today it is possible to address all these needs with a single, integrated toolset. Using a common platform facilitates knowledge transfer and minimizes transcription errors, increases the speed of a development cycle and provides all parties with a better picture of the process.

Different audiences will have different needs in terms of the appropriate level of detail. For example, the chemist may want to understand the kinetics within a reactor, while the business analyst will be satisfied with the overall yield. As such, the ideal model will allow for varying levels of detail to be incorporated into the system—equation-based tools such as Aspen Custom Modeler and gPROMS are particularly suited to this.

Conceptualization

The earliest stages of development for a new process typically involve researchers in a lab developing novel chemistry, biology or separation techniques, and business people identifying gaps in the existing markets and new applications for existing products. The goal of this phase is typically to find commercially interesting ideas for new molecules or mixtures, to create novel routes to existing chemicals, or to improve methods for separating materials.

To achieve this effectively, the team needs to develop two things: 1) A good understanding of the conditions required to achieve this novel step. This often involves physical testing in a lab, though potentially guided by computer tools such as computational fluid dynamics or hybrid approaches (e.g., high throughput screening); and 2) The economic impact of incorporating the novel step(s) into an integrated process that converts available feedstocks into marketable products.

Describing the Novel Step – Unit Operation Models

During this early phase, unit operation models will be developed, and will typically incorporate (at least) five elements:

1. A set of components which generally will be distinct molecules (e.g., ethylene) but also may be composites (e.g., mixtures like “hexane” or amalgams like “catalyst”). Depending on the type of model, the components may be differentiated on some other characteristic (e.g., size of particle).

2. A set of physical properties to describe the physics of those components—enthalpy, density, viscosity, vapor pressure, and so on. Depending on the scope of the model, these properties may describe multiple phases (e.g., liquid, solid) and may describe the interaction of mixtures (e.g., the azeotrope of water and ethanol). It may be useful to “turn off” properties and regions of operation that are not required—a “catalyst,” for example, may only be physically meaningful as a solid-phase component, so there is no value in developing gas-phase correlations for it.

3. Heat transfer into and out of the modeled space and, potentially, within the unit operation (e.g., a thermal gradient within a catalyst particle).

4. Mass transfer in and out of the space, and potentially within a unit operation (e.g., mixing of two liquids in a pipe).5. Reactions and conversion of one component to another (e.g., phase change in a crystallizer). At a minimum, reaction

stoichiometry is required, but models may include reaction kinetics.

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Figure 3. Activities involved in different types of process design



While standard unit operations (e.g., heat exchangers) may be relatively uniform across applications, more complex units (e.g., reactors) will often need to be customized for specific applications. These aspects of a unit operation model are illustrated in Figure 4 as applied to a specific heat exchanger and catalytic reactor. For the heat exchanger, no reactions occur, and the fluids are assumed to remain well mixed, so no information on reaction kinetics or mass transfer is included. Heat transfer is described in some detail, and physical properties sufficient to describe just the liquid phase enthalpy are included. In the catalyst model, on the other hand, significant reaction detail is required as is sufficient detail to describe heat and mass transfer. In this case, the reactants are assumed not to change phase, so only a single-phase enthalpy / density description is required for physical properties.

In the conceptualization phase, the more complex unit operations are often represented by data from batch or discontinuous operation, so it is beneficial to develop the model in a framework that can handle dynamic (time varying) as well as steady state operation. It is also sometimes necessary to develop models that include spatial variation (e.g., concentration gradients in a separation column), so an ability to solve partial differential equations is useful. Finally, there is often a need to match model predictions to experimental data, so an ability to perform data regression is attractive. AspenTech’s Aspen Custom Modeler and PSE’s gPROMS support all these aspects of model development, and both incorporate interfaces to physical properties databases.

Once the framework is created, the unit operation can be extended as knowledge grows. In a catalyst reaction chemistry example, one might supplement the original product-forming model with reactions forming byproducts or impurities, or one might embed the reaction kinetics into a larger model representing the catalyst packed into a reactor tube.

While developing data for the new process, one often gathers data near the expected region of operation, while experiments that fall outside this region (e.g., due to unforeseen events) are considered of limited value. A structured model, however, can often deduce much from these “failed” experiments. Figure 5 illustrates this. If a catalyst is projected to operate near an equilibrium, for example, there’s a tendency to gather data near that point. However, data from much earlier in the reaction will be far more useful in understanding the kinetics. Data gathered well after equilibrium has been reached elucidate the degradation of the products. Understanding these kinetics will in turn allow for a more powerful prediction of what will happen if the system moves to a different operating region (e.g., higher temperature, lower time). The model, therefore, can be used to help design experiments—identifying regions of experimentation that are likely to be fruitful for data regression. In the most complex cases, one may consider competing descriptions of the system (perhaps whether a reaction is following Monod or first order kinetics). Experiments can be designed using the model to maximize the difference between competing predictions.

Process Development – Incorporating the Novel Step into a Design

While much of the conceptualization phase of a project will be involved with developing and understanding the chemistry and physics of the new step(s), it is important to incorporate the commercial and engineering aspects of the system as early as possible. There is a natural tendency for a team to focus on improving the performance against easily measured metrics (e.g., membrane flux) and well-defined problems (e.g., byproduct minimization), and this can lead the team to over-invest in the novel step(s) without considering the overall process. In our examples, the membrane flux may already be high enough to meet the economic targets, but the low purity may require a secondary clean-up step; or the overall amount of byproducts formed in the reactor may be reduced, but the concentration of a particularly challenging impurity may be increased. Developing an integrated process model, and overlaying process economics, early in a research project, is therefore important.

The integrated process model (Figure 6) may describe upstream and downstream unit operations, close recycle loops, and incorporate a description of utility demands and waste streams. Closing the overall balances can identify unexpected limitations— an impurity building up in a recycle loop, for example, or a low pH waste water stream requiring mitigation before going to a common treatment facility. It can also lead to serendipitous findings like an easily recovered coproduct or a heat recovery opportunity.

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Figure 4. Map of the aspects of a Unit Operation model. Shading indicates amount of detail included.

Figure 5. Illustration of different possible fits to an original data set for a reaction product as a function of time, illustrating the benefits of data well away from the typical operating regime.



The integrated process model can therefore shift research focus and inform new process-wide metrics that address new challenges. Figure 7 illustrates an example of reactor optimization that may occur with a catalyst driving a reaction of the form A → B → C, where B is the product of interest. In the right-hand panel, one can see that initially as A is consumed then B is formed so the yield increases. Since the concentration of B is still quite low, the rate of formation of C is also low and the selectivity (mass B / mass A consumed) remains close to 100%. As conversion increases, the concentration of B increases until C is formed more quickly than B, at which point the yield starts to drop. As the concentration of B increases, so the selectivity starts to drop, and decreases rapidly as the concentration of B increases.If one were to consider the reactor in isolation, then one would target the point of highest yield —the peak on the right-hand graph’s orange, continuous line. This translates to the left-hand graph on the green curve and offers a decent yield. However, if one can identify a downstream separation step that effectively recovers unreacted A from the product mixture, then that material can be recycled for a second pass through the reactor, making more product. In this scenario, a higher overall yield can be achieved by stopping the reaction earlier, at a point of lower yield but

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Figure 6. Map of an integrated process model incorporating several unit operations.


Figure 7. Illustration of the impact of a recycle on the overall yield in a catalytic reaction system where a raw material forms the product of interest, which then degrades to an unwanted byproduct. Stopping the reaction early, while selectivity remains high, may allow one to separate the product from the raw material, recycling the latter for a second pass through the reactor at high selectivity.

higher selectivity, and recycling the raw material to achieve a significantly higher overall yield. The benefits of the higher yield (which will approach the selectivity for a recycle with perfect recovery) may be offset by increased reactor size or preheating, but this is nonetheless an interesting area for potential further investigation.

The integrated model can explore aspects of safety and environmental impact. For example, a solvent that works well at lab scale for dissolving a feedstock or cleaning the catalyst bed may be switched out for one that has lower toxicity or is more easily recovered. The potential for thermal runaway in a catalyst bed can be identified, and mitigation measures explored. The need for and cost of air emission handling (such as refrigerated condensation or thermal oxidizers) or waste water impurities may impact design selection.

Techno-Economic Analysis (TEA) – Overlaying the Economic Details

An integrated process model gives the team many of the key data required to develop a detailed capital and operating cost model. While such a model may only be approximate in the conceptualization phase, it can provide useful insights that can be refined in later phases of the project. The integrated model can also help to quantify other process metrics—Carbon Footprint, Life Cycle Analysis, Water Intensity, or Corporate Inventory of Target Compounds (e.g., VOCs). To address these optimizations, it makes sense to link the process model to the techno-economic analysis platform. Doing so effectively will often require detailed interaction with specialists from other fields (e.g., capital estimation or business development), so developing a handshaking tool between the process model and a more widely understood modeling environment (such as Excel), can prove useful. Ideally, this platform should be capable of being used independently from the process model but maintain its ability to be re-linked and updated as the project continues.

In the spreadsheet, data from the process model (e.g., consumption rate of raw materials) can be combined with cost data (e.g., price of fuel). This can give a detailed breakdown of the variable costs for the process, and thus the production cost (e.g., $/lb product) or the projected spend rate (e.g., MM€/year). One can also pass size data into capital estimating tools, thus generating capital cost estimates, which in turn can provide inputs to the operating cost estimate (e.g., plant maintenance, insurance, depreciation). Further, one can take these data, together with projections for product sales volume and rate of market development, to develop cash flow estimates and project economic indicators such as Net Present Value or Internal Rate of Return. This part of the modeling framework is illustrated in Figure 8.


Figure 8. Framework linking the process model with operating and capital cost estimation to provide a techno-economic model.


As with other considerations, the economic predictions can drive the core research for the process. One particularly powerful technique in this regard is Monte Carlo analysis, where the process and economic model is run many times, with key inputs being varied within given distributions. These may include process parameters (e.g., expected yield), economic parameters (e.g., market growth rate), and project parameters (e.g., time to complete piloting). The output of such an analysis is a distribution of the likely outcomes for the predictions and input factors that have the greatest impact on that distribution.

Competitive Analysis

Depending on the market for the new product, it may also be worth investigating alternative routes to the target product—how well do other catalysts perform the similar reactions? In the cases where a new route is developed for an existing product, this will be a side by side comparison of the before and after cases. The tight integration of the process and tecno-economic models allows rapid comparison of different process considerations—things like scale, feedstock composition and product specifications. It also helps guide process optimization decisions like the impact increasing catalyst loading but reducing reaction time, for example. For similar plants in different geographies, there may be significant differences in raw material/utility costs, which may drive one to make different design and operating regime choices.

For processes offering a new route to an existing molecule, it may be worth developing models of the existing processes in the marketplace. This may reveal a competitor’s ability to change process conditions or product mix to open a significant margin gap, thus changing the economic targets for the new approach. It may also be worth reviewing the patent and research literature to investigate other new routes that are under development and which may have a significantly different economic structure.

Process Feasibility

Once an economically interesting design concept is developed, it needs to be tested in the real world. This will typically take the form of a continuous benchtop system, a pilot plant, or a tolling facility. In order to make the most of such a facility, it is important to make sure that the appropriate data is gathered from the equipment and that that data is used to maximize the learnings from the piloting efforts. Again, a detailed process model, linked to a more general tool like Excel, can be a powerful tool to consolidate process and analytical data with already-existing knowledge of chemical and physical properties. Closed mass, energy and component balances may highlight important anomalies that would otherwise be missed.

At the benchtop, typically only a few steps will be integrated, and the focus of the work will be to understand process dynamics that are difficult to observe in batch systems (like impurity buildup in recycle loops), long-term operational changes (e.g., fouling of a membrane or catalyst), or phenomena difficult to isolate in simpler system (e.g., reactions during distillation). Coupling the data from such systems with a model allows the team to refine the fundamental understanding of those steps. For example, the reaction kinetic parameters that were developed in a batch system may be supplemented with equations to describe the coking of the catalyst. This in turn may drive the experimenters to identify approaches to mitigating the coking. Where recycles are closed (e.g., around a reactor, within a liquid-liquid extraction loop), impurities may concentrate to levels that allow analytical discrimination. Coupling the pilot data with the model allows one to infer the amounts of those impurities delivered with the feedstock or created in the reaction; and it allows one to regress the behavior of that impurity in the system (e.g., the vapor-liquid equilibrium).

If one is testing a new process step at an existing facility, then the process model may prove useful in planning the production campaign. Tolling equipment is rarely configured and sized in the ideal way for a new process, and the model can identify bottlenecks and other operational constraints associated with that existing equipment. Once the run is underway, the model can compare the actual results with the expected performance—for example, there may be a daily review meeting where the model framework can be used to consolidate the analytical and process data and compare the results with model predictions. This can prove useful in spotting equipment wear (e.g., a valve at an unexpected position), instrumentation drift (e.g., a weigh cell reading high), performance drift (e.g., sudden poisoning of a catalyst), or operator misunderstandings (e.g., not following an operating procedure).If a custom piloting or demonstration facility is required, then a small engineering project will be required. Since the purpose of the pilot plant will typically be to operate over a wider range of conditions than an operating facility, the model may be particularly useful in helping to adapt the design to support this flexibility. For example, additional instrumentation may be added to allow mass balances to be rigorously closed. It may also be helpful in identifying the best places within the system to perform materials testing—the section of a distillation column where an acidic component may concentrate, for example, or the part of the reactor likely to see the highest temperature. It will also enable longer term equipment testing, such as the gradual degradation of a catalyst’s activity or the attrition of particles in a fluidized bed.

Most of the applications discussed for feasibility have been for steady state (time invariant) process models, but a good modeling platform allows one to convert the process description into a dynamic representation of the process. This can be particularly useful for systems that incorporate batch steps (e.g., some reactions, periodic equipment like ion exchange columns, clean-in-place cycles), or which are likely to be run as a series of campaigns designed to test the process at multiple “steady state” operating conditions

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(particularly common during feasibility). A dynamic simulation allows design for upstream/downstream surge capacity and development of operating procedures and schedules. While it is possible to convert the whole process flowsheet into a dynamic simulation, it’s usually more expedient to use just part of the larger model (Figure 9); the resultant simulation will run faster and is quicker to configure.

During feasibility and piloting, significant quantities of material may be produced, often under a range of operating conditions and with a range of quality parameters. These “test batches” are often very useful to develop an understanding of the new product’s performance in potential applications. Feedback from these trials can provide vital information for future production and quality parameters, and a robust model can be helpful both in isolating the conditions that produce good quality product and in adjusting the design/operating conditions to achieve in-spec material. While it may involve some iteration, this approach can help avoid the need for “end of pipe” solutions. It may be possible to tweak reactor conditions, for example, to minimize an impurity level and avoid the need to add a polishing column. There may be a small drop in reactor yield, but the overall process economics may come out ahead.

Process Engineering

Once an economically attractive process has been identified, then the work of developing a detailed engineering package for the process accelerates. This will typically have multiple phases and, for a large project, may extend over many months or years. In addition to detailed engineering deliverables (e.g., process flow diagrams, equipment data sheets), a detailed business case must be developed (e.g., cost to manufacture, capital estimates, market projections). As the engineering design develops, the core team working on the project will also evolve—less input will come from researchers and pilot engineers. As with other big shifts, this is a point where knowledge may be lost, but where a solid modeling platform can maintain a connection to key learnings.

During feasibility and the early phases of process engineering, there may be several options in play in terms of the process design, operating conditions, and equipment selection. For example, Figure 10 shows a flowsheet with a catalytic reaction that requires a preheating step. The product has three cleanup steps that may be required in sequence or separately:

1. To pass the reactor product through a secondary reactor that oxidizes the unwanted byproduct.

2. To pass it through a distillation column to remove the byproduct

3. To pass the material through an adsorption column.

A combination of capital and operating cost estimation will help to determine where the economic optimum lies, but market development and product testing may lead to changes in product specifications while business development may impact geography and thus the raw material / utilities price and composition. In the early phases of the project engineering, a modeling platform should support switching from one design to another, allowing rapid re-evaluation of the opportunities presented within the framework of the TEA. As the design develops, the cost of making design changes increases significantly, so the more iterations that can be performed early in the design phase, the better.

One impactful area to consider during engineering is the potential reuse and internal recycling of energy and water—in the example of Figure 10, the designer may choose to invest capital in a pre-heating exchanger to recover heat from the reactor discharge, thus reducing operating costs. While there are well established tools (e.g., pinch analysis), to look at heat integration, investigation early in the process design allows additional opportunities to be identified. For example, it may be possible to operate a distillation column or evaporator at a slightly higher pressure and so recover the heat into the process; or it may be possible to reuse water from a filter wash to slurry up a preceding reactor feed.

With a model that supports dynamics, the process designers can review sizing for equipment around discontinuous steps—the surge tanks isolating a dead-end filter, for example. One can also consider issues like startup, shutdown, and surge conditions. It can also be

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Figure 9. Sections of the larger process model can be abstracted and used for dynamic simulation.


Figure 10. Simple conceptual flowsheet for a catalytic reactor and downstream cleanup system.


instructive to use dynamic models to investigate the performance of a process at conditions that may be experienced during market development—operating the process at turndown conditions, for example, or in campaign mode with periods of downtime.

At the more complex end, it can be valuable to leverage the model to create an Operator Training Simulation (OTS)—a dynamic representation of the process that allows users to learn from a virtual process. Such a tool can be very valuable for process engineers and operators to develop an understanding of the new process—especially powerful in new-to-the-world processes or in plants where an innovative step may have significantly changed process dynamics and responses.

Even with a steady state model, some valuable control insights can be developed. Abstractions from the detailed model may allow inferential measurements to be made (e.g., estimate the temperature inside a reactor). Correlations from the model may also be useful in equipment design, for example, density and viscosity estimates can be essential for design of mixing equipment and pumps. In more complex systems, the model can also be helpful in determining where best to put instruments—consider a distillation column designed to recover a volatile solvent from water, as in Figure 11. The goal is to minimize the concentration of solvent in the bottoms stream, but the bottoms temperature is relatively insensitive to the solvent level once it is below, say 99.9% —overshooting the target temperature by even a small amount (0.5°C) can greatly increase the reboiler load. Thus, a control scheme might be developed that tracks the temperature a few trays up the column, where the solvent concentration is expected to have a more significant impact on the boiling point of the mixture. With this understanding, one can develop a more responsive control scheme at the cost of a single, well-place thermocouple.

Physical property correlations, reaction kinetics and expected process conditions from the integrated process model can also provide important inputs into detailed equipment design tools that may include heat exchanger design, Computational Fluid Dynamics (CFD), and Finite Element Analysis (FEA). One might use CFD, for example, to understand the impact of geometry and impellor design on a tank then overlay reaction kinetics into that model to understand the performance of a stirred tank reactor. With the learnings from that CFD model, one can adjust the expected performance of the reactor in the process model and thus the overall process economics. As mentioned earlier, the model can support process safety and environmental considerations. It will provide estimates of gas-borne emissions (e.g., dust in a dryer exhaust), liquid discharges (e.g., consolidated waste water) and solid wastes (e.g., ash from a combustion system), and may help direct design choices. Dynamic simulation may also be useful in identifying exceptional circumstances—pH swings in discharge water during cleaning cycles, for example. From a safety perspective, the model can be a useful adjunct during process safety reviews, giving insights into the impact of unexpected conditions and even the dynamics of process failures.

Plant Operation

Once the plant starts to operate, equipment will wear, surfaces will foul, and catalysts will start to degrade. Coupling the model to plant data allows the operator to:

1. Compare current plant performance to the model predictions at those conditions, allowing the user to identify possible deviations. For example, the operator may be able to catch unexpected catalyst degradation.

Compare current plant performance to model predictions at “optimal” conditions, allowing the user to identify tweaks to process conditions that will improve performance.

2. Use the model to “look ahead” and see where the process is likely to go if no actions or if specific actions are taken.

As process economics change and different equipment becomes available, opportunities will arise to debottleneck production, to reduce energy consumption and to improve process yield. Using the model to help understand the impact of these changes, while at the same time keeping the resource in synch with the plant.

Call to Action

A structured approach can be applied to a wide range of chemical engineering projects ranging from new-to-the-world product development to improvement of well-established operations. This framework can draw together the experience of commercial, scientific and engineering team members, and provide a bridge to link the experience of the many different players in multi-year projects. The model itself provides a valuable piece of intellectual property that can be leveraged to direct research, justify investments and provide services to the process’s end users. All the aspects of the work described here have been executed on real projects with commercially available software. In my experience, it is rare that full advantage is taken of this opportunity.

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Figure 11. Illustration of using a model to identify a more sensitive control variable for a distillation column.



About the Special Feature Author

Charles Sanderson grew up in England and studied Chemical Engineering at Imperial College in London and the University of Sydney in Australia. After working for AspenTech’s consulting group, he joined Cargill in Minneapolis, where he built a modeling team focused on both new process development and optimization of established facilities. In 2012, Charles joined Renmatix, where he led their research efforts. Charles now runs a consulting group that offers services in technology review, process development and simulation. He can be contacted at [email protected].

EXPERIMENTAL

Ultrathin Chiral Metal–Organic-Framework Nanosheets for Efficient Enantioselective Separation...

Chiral MOFs (CMOFs) arising from coordination between metal ions and chiral organic ligands have drawn extensive attention in the field of chirality-related research and development. In addition, efforts to reduce CMOFs dimensions from 3D bulk crystals to 2D nanosheets is seen as a viable route to improve mass transport and enhanced interaction with guest substrates. Until now, there has been no effective strategy available for the preparation of 2D CMOF nanosheets. Herein, the authors, inspired by the classic 3-sheet structures assembled by chiral polypeptide chains, demonstrate the design of one-dimensional (1D) helical metal–organic chains. These, in turn, serve as basic building blocks, which due to inter-chain hydrogen-bonding interactions, result in the formation of 2D layers followed by spontaneous organization into 3D CMOFs via weak interlayer interactions.

In order to increase rigidity of the ligand and promote its coordination along longitude axis, a pyridyl group was conjugated with chiral amino acids l(d)-threonine to form N-(4-pyridylmethyl)-l(d)-threonine·HCl (l(d)-Py-Thr). Subsequently, the l(d)-Py-Thr was allowed to react with Zn-(CH3COO)2 in water to obtain [Zn(l(d)-Py-Thr)(H2O)(Cl)] (l(d)-Thr-Zn) CMOF crystals. Next, a bottom-up inverse microemulsion (dioctyl sulfosuccinate sodium (NaAOT)/isooctane) method was developed to synthesize the corresponding ultrathin CMOF 2D l(d)-Thr-Zn nanosheets only six layers thick (Figure 1).

Because of the much larger number of exposed chiral sites, as-obtained l(d)-Thr-Zn nanosheets exhibit a superior enantioselectivity in chiral separation of Cr(ox)3

-3 compared to their bulk counterparts. Moreover, the generality of preparation and application of ultrathin CMOFs is demonstrated with l(d)-Thr-Cd and l(d)-Ser-Cu nanosheets as well as in the separation of chiral metal clusters.

A nitrogen adsorption experiment was carried out to characterize the surface area of both bulk crystals and ultrathin nanosheets of l-Thr-Zn. Clearly, both samples display nonporous type II isotherms (Figure 2.c), in agreement with their inaccessible interior spaces. These data support the belief that the increased surface area of ultrathin CMOF nanosheets is the major factor contributing to improved enantioselectivity. Source: Gou J, Shang Y, Zhu Y, et al. (2018). Angew. Chem. Int. Ed., 57: 6873–6877.

Figure 1. a) TEM image, b) AFM image, and c) XRD pattern of!-Thr-Zn nano-sheets. The inset in (a) shows the Tyndall scattering of!-Thr-Zn nanosheets dispersed in methanol. d) CD and absorption spectra of !(d)-Thr-Zn nanosheets.

Figure 2. a) CD and absorption spectra of as-separated chiral Cr(ox)3 3@ complex. b) Enantioselectivity obtained by ultrathin nanosheets and bulk crystals. \The absolute configurations and corresponding ee value are estimated based on literature values.[12] c) N2 sorption isotherms and d) t-plot of ultrathin nanosheets and bulk crystals.


EXPERIMENTALEXPERIMENTAL

Continuous Gas-Phase Condensation of Bioethanol to 1-Butanol over Bifunctional Pd/Mg and Pd/Mg–Carbon Catalysts...

Figure 1. Reaction scheme proposed for the ethanol condensation reaction in the liquid phase.

Table 1. Textural and structural parameters of supports and catalysts.

The ongoing interest in the use of 1-butanol as an alternative to ethanol as a gasoline substitute has prompted efforts to develop more efficient manufacturing methods, Traditionally, 1-butanol has been produced via the oxo process, in which propylene is hydro-formylated with syngas over a homogeneous rhodium catalyst to yield butanal, which is then hydrogenated to butanol. However, this route is not sustainable owing to the rising price of crude oil and has led to the re-emergence of industrial acetone–butanol–ethanol (ABE) bacterial fermentation in many countries. Herein, the authors describe the synthesis of 1-butanol from ethanol by acetaldehyde condensation using a fixed-bed continuous gas-phase reactor. They employed bifunctional heterogeneous catalysts based on Pd NPs and magnesium oxide, which incorporated basic properties and were unsupported or supported on HSAG (Table 1). Pd/Mg catalysts supported on graphite were the most selective to 1-butanol, and thermal treatment in helium at 723 K played an important role in the selectivity of the catalysts for the Guerbet condensation reaction of ethanol.

The distribution of reaction products can be explained by the different reaction pathways shown in Figure 1. Acetaldehyde is the primary dehydrogenation (R1) product which can undergo subsequent condensation reactions: reaction with another two ethanol molecules to form 1,1-diethoxyethane (R2), or with another acetaldehyde molecule yielding 3-hydroxybutanal (R3), which is readily dehydrated to 2-butenal (R4). According to the literature, the first condensation is an acid-catalyzed acetylation reaction, and the second is a base-catalyzed aldol condensation. Subsequent hydrogenation of 2-butenal gives rise to the desired product 1-butanol (R5, R6).

Characterization of the active sites by microcalorimetric CO2 chemisorption (revealing basic sites provided by MgO) and TEM analysis (revealing dehydrogenating/hydro-genating properties related to Pd particle size) provided an explanation for the differences in catalytic performance. Improved catalytic performance in terms of selectivity towards 1-butanol and stability was shown by the Pd catalyst supported on the Mg–HSAG composite after thermal treatment in helium at 723 K. This was presumably due to the compromise between two parameters: adequate size of the Pd nanoparticles and the concentration of strongly basic sites. The results indicate that the optimal density of strongly basic sites is a key aspect in designing superior bifunctional heterogeneous catalyst systems for the condensation of ethanol to 1-butanol. Source: López-Olmos C, Morales MV, Guerrero-Ruiz A, et al. (2018). ChemSusChem, DOI: 10.1002/cssc.201801381.

The First C-Cl Activation in Ullmann C-O Coupling by MOFs...

Diaryl ethers are important building blocks used in the synthesis of numerous natural products and biologically active compounds and are usually prepared via the copper-catalyzed Ullmann C-O coupling of haloarenes with phenols. Efforts to bring about more moderate reaction conditions using other catalysts (Scheme 1) have been hampered by high costs, product contamination, and tedious work-up. Herein, the authors describe novel mixed-metal magnetic MOF catalysts namely; maghemite anchored NiCuBTC and maghemite anchored AgCuBTC, and their application in the coupling of phenols with chloro-, bromo- and iodoarenes without any need for using expensive ligands.

Nanoparticles of amino-functionalized maghemite were prepared as an interphase compound. In one case the MOF CuBTC was loaded on the prepared interphase compound. In another, equimolar amounts of Ni and Cu sources were used to produce mixed-metal NiCuBTC loaded on the magnetic interphase compound. Also, maghemite anchored mixed-metal AgCuBTC nanoparticles were prepared by a post-synthetic exchange (PSE) of Ag(I) source with the prepared maghemite anchored CuBTC. The prepared compounds were characterized by different techniques including XRD, FTIR, SEM, EDS, ICP-AES, TGA-DTA, N2 adsorption/desorption, and BET.


EXPERIMENTAL

The maghemite anchored AgCuBTC nanomaterial efficiently served as a heterogeneous and reusable catalyst for the Ullmann C-O coupling reaction of various kinds of phenols with iodo- and bromobenzenes. A broad range of substrates including arenes, ethers, nitroarenes, and bicyclic arenes were tolerated. More importantly, the catalyst showed excellent reactivity in the C-Cl activation of chlorobenzenes in the coupling with phenols without using any complicated, expensive ligand. Reusability of the catalyst led to a total TON about 16000 which was gained in C-Cl activation during six runs. Based on their findings, the authors propose the following mechanism (Scheme 2B) wherein the electron transfer process of Cu(I) to haloarene leading to the formation of aryl radical (the rate-determining step) is promoted by the synergistic effect of Ag. Deprotonation of acetylacetone ligand generates acetylacetonate (acac) which promotes the rate-determining step by chelating the Cu(I) and converting neutral Cu(I) catalyst to a cuprate ion. Source: Ramezani L, Yahyazadeh A, and Sheykhan M. (2108). ChemCatChem, DOI: 10.1002/cctc.201801111.

Electrooxidative Allene Annulations by Mild Cobalt-Catalyzed C−H Activation...

Although allenes are considered to be important intermediates in the field of organic synthesis, their use in preparative strategies has relied upon lengthy, classical transformations involving prefunctionalized substrates. Alternative approaches have focused on direct C−H activations with allenes involving the use of precious-transition-metal catalysts. Although some progress has been made in extending the range of catalysts to include more earth-abundant metals, factors such as cost, toxicity, and product non-selectivity continue to pose challenges. Herein, the authors describe an electooxidative strategy to overcome these issues and which is characterized by a) oxidative C−H/ N−H transformations for electrochemical allene annulations, (b) cost-effective, earth-abundant cobalt catalysis, (c) mild reaction conditions, and (d) a user-friendly undivided cell setup.

They began their studies by exploring different parameters for the envisioned C−H/N−H activation for the annulation of allene 2a (Table 1). Preliminary experiments revealed that an operationally simple undivided cell setup proved viable without major interference arising from cathodic electrodeposition. The authors then studied the robustness of the C−H activation approach and found that the cobalt catalyst performed with excellent levels of position control. Nor was C−H/N−H activation was limited to arenes since heterocycles and alkenes were likewise identified as amenable substrates.

Detailed mechanistic studies were conducted, including reactions with isotopically labeled compounds, kinetic investigations, and in-operando infrared spectroscopic studies. Further, computational studies were supportive of a non-rate-determining C−H cleavage and gave key insights into the regioselectivity of the allene annulation.

Scheme 1. Various Cu-catalyzed approaches in CCl activation. Scheme 2. (a) The proposed defects formed in the structure of maghemite anchored AgCuBTC in Ag(I) positions in approximately 10% of the whole material that having formula of Ag1.5Cu1.5(BTC)2·xH2O based on ICP. (b) Plausible mechanism of C–Cl activation on bimetallic catalytic centers.


EXPERIMENTAL

STUDY UNDERWAY!ADVANCES IN SYNGAS PRODUCTION

CATALYST AND PROCESS DEVELOPMENTS UPDATE – 2018

TCGR provided its last update on syngas production advances in 2014, with a two-volume set of multi-client studies entitled “Natural Gas Conversion vs. Syngas Routes: A Future of Convergence-2014”. The purpose of this 2018 update is to focus more narrowly on syngas production and benchmark the numerous advances in catalysts, reactor internals and life cycle advances.

TCGR’s new assessment has (as always) allowed “charter” subscribers to help shape this update’s Table of Contents (i.e., content about which technologies are to be included), thereby creating a multi-company sponsored effort in a process we call – "by the industry, for the industry!" To highlight some of the envisioned subject matter without any particular order, we list the following:

• NewdryreformingtechnologytobelicensedfromBASF/Linde • ZoneflowNDaengineeredpacking• Advances in Chemical Looping Reforming/CLR • Crystaphase engineered packing• Advances in AGHR (JM) and KRES (KBR) • Advances in CPO• New syngas reactor technology being introduced from Haldor Topsoe – SynCor – to eventually produce ammonia or methanol• Thepotentialuseofanewrotaryreactorinpilot,beingpursuedandsupportedbyDowChemical• Further developments with hydrogen transport membranes (HTM) using Pd membranes• Johnson Matthey’s (JM’s) introduction and expansion Catacel SSR, metal substrates

Althoughnotmentioned,onebenchmarkistheprogressintri-reforming.Hydrotalcites(doublelayeredhydroxides,LDH’s)arefoundtobeespeciallyinterestingnewmaterialsfulfillingbothredoxandbasicproperties,whileoperatingatrelativelylowtemperatures(around 600 0C).

As usual TCGR’s insight into pipeline technology and developments provides a tool that is not available from other sources, which are more focused on market supply/demand or benchmarking just the top three (3) licensed processes in manufacturing technologies.

Additionalinformation,includingthecompletestudyProposal,theexpanded/refinedTableofContentsandtheorderformisavailableathttp://www.catalystgrp.com/multiclient_studies/advances-syngas-production-catalyst-process-developments-update-2018/ or by contacting John. J. Murphy at +1.215.628.4447 or [email protected].

Based on their experimental and computational mechanistic studies, the authors propose the electrochemical C−H/N−H activation to commence by anodic cobalt oxidation, which sets the stage for an efficient BIES C−H scission by carboxylate assistance (Scheme 1). Then, migratory insertion of allene 2 and reductive elimination deliver the exo-methylene isoquinolone 4, which upon isomerization provides the desired product 3. The active cobalt catalyst is thereafter regenerated by the key anodic oxidation, producing H2 as the only byproduct. This approach thus prevents metal-based terminal oxidants toward atom- and step-efficient C−H activation. Source: Meyer TH, Oliveira JCA, Sau SC, et al. (2108). ACS Catal., 8: 9140−9147.

Table 1. Electrochemical C−H/N−H activation with allenes: optimizationa.

Scheme 1. Proposed catalytic cycle.


Jean-Philip Lumb, PhD Associate Professor of Chemistry, McGill University, Montreal, Quebec, Canada

Jean-Philip Lumb obtained his BA from Cornell University in 2002, before moving to the University of California, Berkeley to pursue a PhD with Professor Dirk Trauner. As a graduate student, he focused on the biomimetic synthesis of complex natural products that relied on the orchestration of multi-step cascade reactions triggered by oxidation. From 2008 to 2011 he was a postdoctoral fellow at Stanford University, working under the supervision of Professor Barry Trost. As a postdoctoral fellow, he developed an atom economic synthesis of pyrroles using palladium catalysis and an asymmetric coupling of alkynes using palladium and copper-hydride co-catalysis. Lumb’s training

encompasses the themes of bio-inspired synthesis, and transition metal catalysis, which forms the cornerstones of his independent research career. Since moving to the Department of Chemistry at McGill University in 2011, he has advanced a research program on aerobic catalysis, with the goal of developing more selective and efficient methods for the oxidation of organic and inorganic molecules. He can be reached at: [email protected] and his Group Website is: https://www.mcgill.ca/lumbgroup/.

MOVERS & SHAKERS

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The Catalyst Review asked Professor Lumb to discuss his vision for more sustainable synthesis by employing molecular oxygen.Most synthetic chemicals are the result of an intricate industrial metabolism that upgrades petroleum from un-functionalized hydrocarbons to molecules containing oxygen, nitrogen, sulfur and a range of additional heteroatoms. The careful placement of these heteroatoms is critical to a molecule’s function and dictates whether a petrochemical feedstock will become a plasticizer or a pharmaceutical.

Chemical transformations that change the un-functionalized carbon-hydrogen bonds of petrochemical feedstocks into carbon-heteroatom bonds are called oxidation reactions, and they are critically important to the chemical value chain. However, while the value of oxidized intermediates is clear, the chemical community has, historically, overlooked the fate of the reagent that accepts the hydrogen atoms from the substrate—the necessary half-reaction of any oxidation, creating an unavoidable waste stream by reduction. Since oxidation reactions are required for petrochemical upgrading, mitigating their generation of waste is a fundamentally important challenge.

In order to develop more efficient oxidation reactions, the Lumb Group has drawn inspiration from biochemical oxidations that couple substrate oxidation to the reduction of molecular oxygen (O2). O2 is a renewable and non-toxic reagent that enzymes use in countless biochemical transformations as a receptacle of dihydrogen (H2). It is unique amongst oxidants in that it creates an innocuous by-product as the result of its complete reduction, (H2O). Its reduction also creates a great deal of energy (115 kcal/mol), which can be advantageous in cases where the substrate is being transformed from a stable molecule into a reactive, high-energy intermediate.

In addition to its role in biosynthesis, O2 is a valuable reagent for industrial chemistry, where it is the only economically viable oxidant for many large volume processes. However, oxidations for the synthesis of fine chemicals, including pharmaceuticals and agrochemicals, employ O2 infrequently, reflecting the difficulties of controlling aerobic oxidations in complex molecular settings.

In an effort to extend the scope of aerobic oxidations, the Lumb Group has turned to metalloenzymes, which employ metal atoms in their active sites to mediate the reactivity of O2. In so doing, they draw energy from air, creating intricate molecular landscapes with absolute precision. This has led the Lumb Group to design several aerobic oxidations catalyzed by copper inspired by the enzyme tyrosinase. These include the oxidation of phenols to ortho-quinones, the oxidation of alcohols to ketones and aldehydes, and the oxidation of amines to nitriles or imines. In each case, the group found that simple conditions could replicate the intricate chemistry of the metalloenzyme while maintaining high levels of control under operationally straightforward conditions. As is the case with all aerobic oxidations, these transformations produce water as their sole stoichiometric byproduct, but further benefits include the use of an earth-abundant and inexpensive copper catalyst in conjunction with inexpensive and readily available ligands.

In addition to the oxidation of organic molecules, Lumb and his group have also sought a more efficient means of oxidizing metals. Here, the use of O2 is problematic, since the resulting metal oxides are relatively inert and high melting. However, by using an organic co-factor to mediate aerobic oxidation, the team devised a route to oxidize metals where O2 is the terminal oxidant, but it does not come into direct contact with the metal center. In addition to their use in organometallic synthesis, the group believes that it could provide a new approach for separating mixtures of metals, which is increasingly vital for recycling post-consumer electronics.

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