As part of its expanded seminar series this year, the Chem Show is hosting a session that highlights outstanding achievements in chemical engineering that have led to successful commercializations. The presenters are all finalists for the renowned Kirkpatrick Chemical Engineering Achievement Award presented by Chemical Engineering magazine, a longtime exhibitor at the Chem Show (for more on the award, click here). Six companies — CB&I and Albemarle, Chemerty, Dow, Microvi and Praxair — will make presentations about their outstanding commercial successes. The presentations will be in room 1A03 at 11:15 a.m. on Tuesday, November 1. All Chem Show attendees are welcome to attend and hear first-hand accounts of these breakthrough technologies. A short description of each technology is given below.
CB&I/Albemarle — AlkyClean alkylation technology
AlkyClean gasoline alkylation technology is an advanced solid-catalyst alkylation process for the production of motor fuel alkylate. With AlkyClean technology, light olefins from typical petroleum-refinery sources, such as fluid catalytic cracking units react with isoparaffins to produce alkylate. Of primary interest is the reaction of butylenes with isobutane to form high-octane trimethylpentane isomers.
The novelty and success of the AlkyClean technology is the complete elimination of liquid acids and their associated hazards and operational complexity. Solid catalyst is used in multiple fixed-bed reactors, operating in cyclical mode, to continuously produce high-quality alkylate, while those off-line are being regenerated. The chemical engineering challege was to create the ability to fully recover catalyst activity over multiple cycles. Breakthroughs made with the catalyst formulation and the regeneration process make this possible.
CB&I and Albemarle offer a catalyst/process combination that eliminates the drawbacks of liquid-acid handling. Furthermore, neither acid soluble oils, nor spent acids, are produced, and there is no need for product post-treatment of any kind. Without these waste streams and the need for post-treatment, corrosion is virtually eliminated in the downstream fractionation section. With the use of particulate catalyst, liquid acids such as sulfuric or hydroflouric, are no longer required.
The AlkyClean process was developed at Albemarle’s research center in Amsterdam and at a CB&I demonstration plant in Porvoo, Finland.
The first commercial AlkyClean unit successfully started up in August, 2015, in Zibo, China. This 2,700-bbl/d unit has now been operating safely and successfully for more than 1.5 years producing an alkylate product at a quality on par with existing technologies, and meeting or exceeding all process guarantees.
Chemetry: eShuttle technology
Chemetry’s eShuttle technology provides a breakthrough in the synthesis of chlorinated organics by eliminating chlorine generation from the traditional chlor-alkali process. The first commercial application of the technology is the chlorine-free synthesis of ethylene dichloride (EDC), an intermediate in the production of polyvinyl chloride (PVC). eShuttle replaces the chlor-alkali and direct chlorination processes with a single, integrated process that uses a circulating stream of aqueous copper chloride to transfer chloride ions from NaCl to ethylene. Specifically, the process leverages the redox states of copper to convert CuCl to CuCl2 at the anode of the electrochemical cell. The CuCl2 then reacts with ethylene to form EDC, regenerating the CuCl, which is returned to the cell. Like the processes it replaces, the eShuttle technology uses the same feedstocks, NaCl brine, water and ethylene, to produce the same products, EDC, caustic, and H2, but at much lower energy and operating cost and without chlorine gas generation. Licensed by TechnipFMC, eShuttle has been commercialized through demonstration scale at Chemetry’s facility in Moss Landing, California.
The novelty of the technology lies in the elimination of chlorine as a chemical intermediate. By replacing the standard chlor-alkali anode reaction, 2Cl– à Cl2 + 2e–, with the copper oxidation reaction, Cu+ à Cu2+ + e–, the theoretical anodic voltage is decreased by 0.6V. This voltage translates directly to electrical savings of 25% and significantly lower operating costs. Because the chlor-alkali process is such a heavy demand on electrical power (representing 1% of total U.S. energy grid consumption), the reduction in electricity consumption of a single EDC plant with eShuttle would result in a reduction in carbon emissions approximately equal to the replacement of 90,000 automobiles with electric powered vehicles. Moreover, the elimination of Cl2 as an intermediate reduces the safety risk and costs associated with chlorine compression, storage, and transportation.
The e-Shuttle process was transferred from laboratory to commercial demonstration scale at Chemetry’s facility in Moss Landing, CA (see below) with integrated operation beginning in 2014. After careful review from their engineering teams, Technip obtained rights to the commercial license in 2016.
Dow Canvera: Polyolefin Dispersion Technology
New process innovations enable Dow Canvera polyolefin dispersions to address the stringent performance requirements of the food and beverage metal-packaging industry. Innovative processing enables thermoplastic polyolefins to replace epoxy can coatings with minimal change to current coating equipment. Novel Dow technology enables the dispersion of polyethylene as an aqueous dispersion, which after being applied, forms a polyethylene film after heating. The safety and sustainability of the can coatings are much improved, addressing consumer, brand owner, and government concern about incumbent epoxy, acrylic, and polyester coating technologies, such as leaching of bisphenol-A (BPA), epoxy, monomers, crosslinkers, and oligomers. Canvera offers excellent food and flavor protection, adhesion, corrosion protection, and film flexibility. Canvera polyolefin dispersions utilize existing manufacturing infrastructure to facilitate a cost-effective alternative via a very thin, protective thermoplastic film on the inside of metal cans.
Metal beverage and food containers require an interior coating to protect not only the container, but also the contents, ensuring preservation, flavor quality, and consumer food safety. A novel, new process for making aqueous dispersions from bulk polyethylene now makes polyethylene coatings possible in metal containers for the first time. Dow’s proprietary Bluewave mechanical-dispersion process transforms polyolefins from large polymer pellets into aqueous dispersions suitable for use as liquid coatings.
The engineering challenge was to develop and implement technology enabling the delivery of high molecular weight, semi-crystalline polyolefins in a low viscosity liquid form.
Commercialized in December 2015, and ramped to full commercial production in 2016, Canvera dispersions are used to coat the inside of millions of metal containers in the U.S. and European marketplaces providing consumers with suitable alternatives to the incumbent epoxy-based system.
Dow Coatings Materials: Paraloid Edge Technology
Urethane coating resins have many desirable and a few undesirable attributes. Paraloid Edge urethane coatings are made using a completely new process that is isocyanate and formaldehyde free. Paraloid Edge resins and cross-linkers retain and add to the desirable, while eliminating some of the most undesirable attributes of urethane resins. It is a superior, not a compromised, product.
The final coating forms by reacting a polycarbamate and a di-aldehyde, forming a polyurethane without isocyanates.. Dow Coating Materials developed processes for cost-effective production of a two-part, reactive urethane coating system using polycarbamates and di-aldehydes, replacing the isocyanates and polyols used in conventional urethanes. Typical polycarbamate production uses highly toxic methyl carbamate. Dow developed processes based on urea, overcoming process challenges that hampered development of urea-based routes in the past.
Extensive modeling and experimental work resulted in a robust, commercial process. The di-aldehyde, cyclohexanedicarboxaldehyde (CHDA), is produced through hydroformylation of tetrahydrobenzaldehyde (THBA) with carbon monoxide and hydrogen in the presence of a rhodium catalyst. Two continuously stirred tank reactors (CSTRs) under pressure, in the absence of oxygen, achieve >99% conversion. A proprietary Non-Aqueous Phase Separation, an innovative process that was first commercially implemented in this technology, recovers the rhodium catalyst for reuse. This process was first commercialized in 2015 in the U.S.
Microvi: Denitrovi Biocatalytic Nitrate Removal
Nitrate is one of the foremost drinking water challenges today, contaminating groundwater around the world and posing threats to human health. For the past ten years, Microvi — a global industrial biotech company based in the San Francisco Bay Area — has been working to provide a new solution to overcome the challenges of nitrate contamination. This technology, called Denitrovi, is based on Microvi’s MicroNiche Engineering platform, where novel materials science is used to control how microorganisms behave and perform in industrial bioprocesses.
Using Denitrovi, nitrate-contaminated water enters a reactor and the nitrate is degraded by microorganisms housed in biocatalysts and converted into nitrogen gas, a harmless byproduct. The key chemical engineering feat achieved by the technology is that it generates no sludge. Moreover, it has a lower organic substrate (supplementary carbon) consumption requirement, and has achieved NSF/ANSI 61 certification and Australian Water Quality Certification. In 2013, the Denitrovi technology was implemented for two Aboriginal communities in Western Australia—and the same biocatalysts are currently being used today with no deterioration in performance over five years.
In January 2017, Microvi and Sunny Slope Water Company of Pasadena, Calif. launched a new, 200 million gallon per year facility that uses Denitrovi to remove nitrate from groundwater.
At Sunny Slope, the technology reduces nitrate from ~40 mg/L to <5 mg/L in a matter of minutes of contact time, while virtually the eliminating secondary waste stream that would otherwise be associated with a biological technology. Most importantly, the technology was found to be 50% of the cost of existing treatment technologies such as ion-exchange.
The new installation comes after Microvi achieved a milestone: In 2015, the California Division of Drinking Water gave conditional approval for Denitrovi as the first biological drinking water technology for nitrate to be applied at full-scale. The certification, considered a gold standard in the water treatment industry, was the result of months of rigorous testing overseen by the agency.
Praxair: Oxygen-fired Combustion Process with Thermochemical Regenerators
Oxy-fuel fired glass-melting furnaces reduce fuel consumption by 10–15% and reduce NOx emission by as much as 80% relative to conventional fuel-air fired furnaces with efficient regenerators for waste heat recovery. Further improvements were hitherto limited to waste heat recovery by using recuperators to heat oxygen and fuel to 400 to 500°C, providing additional fuel and oxygen savings of about 8%. Potential heat recovery by regenerators to preheat oxygen to ~1,250°C is projected to increase the fuel savings to 11% over the oxy-fuel baseline, but material selection for high temperature oxygen preheating and high CAPEX prevented commercial development of oxygen heating regenerators.
The Optimelt thermochemical regenerator (TCR) process is the first commercial oxy-fuel fired glass melting process utilizing endothermic chemical reactions for waste heat recovery. During the heating cycle, waste heat from the glass furnace flue gas (1,550°C) is collected and stored in a regenerator. During the endothermic reforming cycle, this stored heat is used to heat and reform a mixture of natural gas and recycled flue gas to produce syngas at 1,200°C. No catalysts are required for the reforming reactions due to the high regenerator temperature. By using two regenerators, they can alternate between heating and reforming cycles so that one is always storing heat while the other is supplying preheated syngas to the furnace.
The demonstration of the Optimelt TCR process started in a 50 m.t./d container glass furnace at Pavisa in Mexico in late 2014 and the system was adopted for commercial operation in mid 2015. Fuel and oxygen savings of 15 to 18% and low NOx emissions were demonstrated. For a larger scale commercial furnace, expected fuel savings are about 20% compared to oxy-fuel and about 30% compared to air-regenerator furnaces. A larger commercial system will be installed for a tableware furnace at Libbey Glass in Holland in late 2017.
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