Electrosynthesis

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Redox Flow Batteries

Why Grid Scale Energy Storage

by Che-Nan (Josh ) Sun 

An Electrical grid equipped with energy storage system allows companies to manage and deploy the electrical energy in a much more efficient and flexible way. Key features such as peak shaving, frequency regulation and time shifting can be realized via such systems to enhance power quality and reliability. Moreover, a grid-scale energy storage system is able to serve as a buffer between the electric grid and an ever increasing demand for renewable energy generation such as solar and wind. These systems  smooth out the climate-dependent intermittency and allow the harvested energy to be distributed as needed. It has long been a global desire to increase renewable energy penetration in order to reduce the electricity sector’s carbon footprint as well as the fossil fuel consumption.

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Selected Patents & Publications

Electrosynthesis Company, Inc. maintains the strictest level of confidentiality in all of its R&D efforts. For this reason, we do not publish a list of the R&D clients that we have collaborated with. However, on occasion we are encouraged to publish work funded by others. The following selected publications will give an indication of areas in which Electrosynthesis Company and its employees have contributed to the advancement of electrochemical technology.

 
Electrochemical Technology; Cells, Electrode Materials etc.The status of electrochemical technology is extensively reviewed each year in the Journal of the Electrochemical Society. Dr. Ram Gopal compiled this report for 1993 and 1994:

  • Gibbons, D. W.; Gopal, R.; “Report of the Electrolytic Industries for the year 1993” In J. Electrochem. Soc. 1994, 414 (10), 2918-2933.
  • Fritts, S.; Gopal, R.; “Report of the Electrolytic Industries for the year 1994” In J. Electrochem. Soc.1993, 140 (11), 3337-3363.

There are very few books available that discuss the scale-up of electrochemical technology. Electrosynthesis – From Laboratory to Pilot to Production has proven to be a very popular compilation of successfully implemented technology.

  • Bockris, J. O’M.; Fletcher, S.; Gale, R. J.; Khan, S. U. M.; Kolb, D. M.; Mazur, D. J.; Uosaki, K.; Weinberg, N. L.; “Electrochemistry (1992-1995)” In Royal Society of Chemistry Annual Reports, 1996, 92 (C), 23-73.
  • Genders, J. D.; Pletcher, D.; Electrosynthesis-From Laboratory to Pilot to Production; Electrosynthesis: East Amherst, NY, 1990.

Research into electrode materials is always a “hot topic” in electrochemistry. Electrosynthesis Company has been the recipient of multiple awards from the National Science Foundation and Department of Defense to do research in this area.

  • Chandler, G. K.; Genders, J. D.; Pletcher, D.; “Electrodes Based on Noble Metals” In Platinum Metals Review, 1997, 41(2), 54-63.
  • Mazur, D. J.; Weinberg, N. L.; Bolster, M.; “Modified Carbons and Electrochemical Cells Containing the Same”; U. S. Patent 4 835 074, 1989.

 
Electroorganic SynthesisElectrosynthetic methods are well known in their application to synthesis of pharmaceuticals and various organic intermediates. Among the books that have made a significant contribution to advancing this field are the Weissberger series edited by Norman Weinberg.

  • Electroorganic Synthesis: Festschrift In Honor of Manuel Baizer; Little, R. D.; Weinberg, N. L., Eds.; Marcel Dekker: New York, 1991.
  • Mazur, D. J.; Weinberg, N. L.; “Industrial Electroorganic Synthesis in the United States and Canada”;Kagaku to Kogyo: Japan, 1990, (43), 2002-2005.
  • Technique of Electroorganic Synthesis: Scale-Up, Part III; Tilak, E.V.; Weinberg, N.L., Eds.; Techniques of Chemistry Volume V; John Wiley & Sons: New York, 1982.
  • Technique of Electroorganic Synthesis Part II ; Weinberg, N.L., Ed.; Techniques of Chemistry Volume V; John Wiley & Sons: New York, 1975.
  • Technique of Electroorganic Synthesis Part 1; Weinberg, N.L., Ed.; Techniques of Chemistry Volume V; John Wiley & Sons: New York, 1974.

Electrosynthesis has become a valuable tool in the pharmaceutical industry. Electrosynthesis Company has collaborated with several companies in this area. Among those that have published some of our findings are Schering-Plough, Pfizer and Eli Lilly.

  • Bernasconi, E.; Genders, D; Lee, J.; Longoni, D.; Martin, C. R.; Menon, V.; Roletto, J.; Sogli, L.; Walker, D.; Zappi, G.; Zelenay, P.; Zhang, H.; “Ceftibuten: Development of a Commercial Process Based on Cephalosporin C. Part II. Process for the Manufacture of 3-Exomethylene-7(R)-glutaroylaminocepham-4-carboxylic Acid 1(S)-Oxide,” Organic Process Research and Development,2002, 6, 158-168.
  • Chai, D.; Genders, D; Weinberg, N.; Zappi, G.; Bernasconi, E.; Lee, J.; Roletto, J.; Sogli, L.; Walker, D.; Martin, C. R.; Menon, V.; Zelenay, P.; Zhang, H.; “Ceftibuten: Development of a Commercial Process Based on Cephalosporin C. Part IV. Pilot-Plant Scale Electrochemical Reduction of 3-Acetoxymethyl-7(R)-glutaroylaminoceph-3-em-4-carboxylic Acid 1(S)-Oxide” Organic Process Research and Development, 2002, 6, 178-183.
  • Bernasconi, E.; Chai, D.; Genders, J. D.; Lee, J.; Martin, C. R.; Menon, V.; Roletto, J.; Sogli, L; Walker, D.; Weinberg, N. L.; Zappi, G. D.; Zelenay, P.; Zhang, H.; “Pilot Plant Scale-Up of a Pharmaceutical Intermediate” In the 12th International Forum on Electrolysis in the Chemical Industry; Electrosynthesis: Lancaster, NY, 1998.
  • Genders, J. D.; Pletcher, D.; “Electrosynthesis – ; A Tool for the Pharmaceutical Industry Today?” InChemistry and Industry, September 1996, 682-686.
  • Dunn, P.; Kendall, P. M.; Mazur, D. J.; Murtiashaw, C. W.; Pexxullo, S. L.; Zung, J. B.; “Electrochemical Deacetoxylation: Synthesis of 11-Ketotigogenin” In J. Org. Chem. 1996, 61, 405.
  • Kendall, P. M.; Mazur, D. J.; Schmidt, C. R.;“Electrosynthesis of Ketal-protected Glyceraldehyde” In the 7th Internationational Forum on Electrolysis in the Chemical Industry; Electrosynthesis: Lancaster, NY, 1993.

Electrosynthesis Company, Inc. has also been developing novel electrosynthetic methods for producing fine chemicals. A good example is a method for electrochemically producing the free base of Cysteine. In this approach the starting material cystine is dissolved in ammonium hydroxide to form a conductive ammonium salt. At the end of the electrolysis the ammonium hydroxide is simply evaporated to leave the pure product.

  • Genders, J. D.; Weinberg, N. L.; Zawodzinski, C.; “The Direct Electrosynthesis of L. Cysteine Free Base”  in Electroorganic Synthesis: Festschrift In Honor of Manuel Baizer; Little, R. D.; Weinberg, N. L., Eds.; Marcel Dekker: New York, 1991.

 
Inorganic ElectrosynthesisThe chlor-alkali industry is one of the world’s largest chemical process, the economics of which rely on the balance for the demand of caustic soda and chlorine. Since these are not always the same, Electrosynthesis Company and others have investigated processes for the production of caustic soda without the co-production of chlorine (see Watts New, “Electrochemical Salt Splitting“). One such process was developed under funding from the National Science Foundation and in collaboration with Chemetics International.

  • Genders, J. D.; Pletcher, D.; Spiegel, E.; Weinberg, N. L.; “Electrochemical Methods for the Purification of Alkali Metal Hydroxides Without the Co-Production of Chlorine”; U. S. Patent 5 246 551, 1993.

Hydrogen Iodide is a valuable product used in the manufacture of a number of high purity iodine compounds. Electrosynthesis Company, in collaboration with Benham Electrosynthesis, has developed an electrochemical method that produces HI of a higher purity.

  • Genders, J. D.; Hartsough, D. M.; Weinberg, N. L.; “Methods of Producing Hydrogen Iodide Electrochemically”; U. S. Patent 5 520 793, 1996.

Electrosynthesis Company has worked with Chemical Products Corporation to develop an electrochemical process for the production of high purity alkaline earth metal hydroxides.

  • Maudlin, L. B.; Adams, C.; Randolph, D. R.; Mazur, D. J.; Genders J. D.; Chai, D. M.; “Process for the Production of Alkaline Earth Hydroxide”, U. S. Patent 6 375 825, 2002.

 
Membrane Research Ion permeable membranes are an essential part of many electrochemical cells. Moreover, they are used extensively for electrochemical separation processes such as electrodialysis and salt splitting. Electrosynthesis Company has been working with several groups including the National Science Foundation and National Institute of Standards and Technology through an ATP NIST award with Eastman Chemical and Genencor International.

  • Genders, J. D.; Gopal, R.; Hartsough, D. M.; Kendall, P. M.; Long, W. J.; Mazur, D. J.; Zappi, G. D.;“Electrodialysis Methods for Recovery and Purification of Gluconic Acid Derivitives”, U. S. Patent 6 187 570 B1, 2001.
  • Genders, J. D.; Hartsough, D. M.; “Electrochemical Method for Recovery of Ascorbic Acid”; U. S. Patent 6 004 445, 1999.
  • Davis, T.; Genders, J. D.; Pletcher, D.; A First Course in Ion Permeable Membranes ; Electrochemical Consultancy: England, 1997.
  • Genders, J. D.; Thompson, J.; “Process for Producing Sodium Hydroxide and Ammonium Sulfate from Sodium Sulfate”; U. S. Patent 5 098 532, 1992.
  • Genders, J. D.; George, E. L.; Pletcher, D.; “A Study of the Transport of Formaldehyde and Ethlene Glycol Through Ion Permeable Membranes in Electrolytic Cells” In J. Electrochem. Soc. 1996, 143 (1), 175-178.

 
Environmental ElectrochemistryIt is well known that electrochemistry offers a unique approach to both cleaner processing and remediation or recycle of waste streams.

  • Electrochemistry For a Cleaner Environment; Genders, J. D.; Weinberg, N. L., Eds.; Electrosynthesis: East Amherst, New York, 1992.

The destruction of nitrates in a variety of waste streams can be achieved electrochemically. One area where we have been particularly active is in the destruction of nitrate in radioactive waste streams present at many of the DOE facilities. Electrosynthesis Company has been the recipient of several contracts from Westinghouse Savannah River Company for the destruction of such streams.

  • Lilga, M. A.; Orth, R. J.; Sukamto, J. P. H.; Rassat, S. D.; Genders, J. D.; “Cesium Separation Using Electrically Switched Ion Exchange” In Separation and Purification Technology 2001, 24, 451-466.
  • Genders, J. D.; Chai, D.; Hobbs, D. T.; “Durability Testing for the Recovery of Sodium Hydroxide from Alkaline Waste Solutions” In J. Appl. Electrochem. 2000, 30 (1) 13-19.
  • Genders, J. D.; Hartsough, D.; Hobbs, D. T.; “Electrochemical Reduction of Nitrates and Nitrites in Alkaline Nuclear Waste Solutions” In J. Appl. Electrochem. 1996, 26 (1), 1-9.
  • Hartsough, D. M.; Hobbs, D. T.; Genders, J. D.; “Electrochemical Treatment of Radioactive Wastes at the Savannah River Site” In the 4th International Fourm on Electrolysis in the Chemical Industry; Electrosynthesis: Lancaster, NY, 1990.

The destruction of organics in wastewater continues to be an area of interest to many companies. Electrosynthesis Company has been involved in the development of cell technologies in this field.

The electrochemical destruction of organic acids by converting them into combustible fuels is an attractive approach to the treatment of a waste stream. This approach was developed at Electrosynthesis Company in collaboration with DuPont Specialty Chemicals.

  • Genders, J. D.; Harstough, D.; Super, J.; “Electrochemical Destruction of Organic Acids”; The Electrochemical Society Extended Abstracts, 1994. Vol. 94-1, Abstract 761.

Electrosynthesis Company also successfully accomplished the electrochemical destruction of PCBs while working with Sandpiper.

  • Aurnou, E. A.; Liolios, E. A.; Kendall, P. M.; Mazur , D. J.; Weinberg, N. L.; “High Surface Area Electrode for PCB Destruction”; The Electrochemical Society Extended Abstracts, 1987. Vol. 87-2, Abstract 1857.
  • Mazur, D. J.; Weinberg, N. L.; “Methods for Electrochemical Reduction of Halogenated Organic Compounds”; U. S. Patent 4 702 804, 1987.

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Electrochemical Salt Splitting

by David Genders

Salt splitting is a relatively new technology dependent on the availability of modern membranes. Its development has usually been driven by one of two major factors, both environmentally based. The first is the desire to produce caustic soda without the co-production of chlorine, and the second is the increased cost of disposing of heavily laden salt solutions.

Caustic is in Demand

Caustic soda is produced in the USA at a rate of 14 million tons per year, almost entirely by the electrolysis of brine. In this process chlorine is produced at the anode and caustic soda at the cathode in stoichiometric quantities. There is a growing awareness of the need for new processes for the manufacture of high purity sodium hydroxide that do not lead to co-production of chlorine. This requirement exists because the chlorine and sodium hydroxide markets are rarely in balance.

Despite the high demand for chlorine in the last two years, it is still expected that environmental pressures on chlorine will lead to an increased demand for caustic over the coming decade. Predictions are for a long-term trend in which the demand for sodium hydroxide will outstrip that for chlorine.

Several present markets for chlorine are expected to experience significant downturns due to environmental pressures or concerns about health hazards; these include pulp and paper bleaching, fluorocarbons, water treatment and chlorinated hydrocarbons. At the same time, the demand for sodium hydroxide is predicted to continue to grow.

Another trend is towards modular plants that allow the manufacture of chemicals on various scales including generation on a relatively small scale at the site of use.

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Prudent Energy & Electrosynthesis Sign Technology Development Agreements

Prudent Energy Inc.  is pleased to announce it has entered into technology development agreements with Electrosynthesis Company Inc. (“ESC”).  ESC previously acted as a technology development partner with VRB Power Systems Inc. ESC is a privately held, independent research and development company specializing in the development of electrochemical technologies for energy storage systems,  electrodialysis, separations, and synthesis of inorganic and organic chemicals and recycling of waste streams. ESC offers internationally recognized expertise in electrochemistry and R&D services, engineering, and the sale of electrochemical systems to provide practical solutions for clients worldwide.

About Electrosynthesis

Offering expertise in electrochemical technology, Electrosynthesis Company, Inc. began as an R&D and consulting firm in 1977. In 1992, we moved into our current custom‐built laboratory facility where we have been providing electrochemical expertise to solve problems for clients worldwide. To date, our highly skilled staff has completed more than 200 different R&D projects for clients giving us a unique experience base.

About Prudent Energy Inc. (Prudent Energy)

With offices in Vancouver Canada and in Beijing, China, Prudent Energy is an energy storage technology developer, manufacturer and systems integrator, specializing in the patented VRB Energy Storage System (VRB‐ESS™). With a global market focus, Prudent Energy provides high‐quality environmentally safe, energy storage systems and solutions (VRB‐ESS) to improve power quality and reliability, enable large‐scale penetration of renewable energy generation, and improve the efficiency of energy distribution.

Website: www.PDEnergy.com

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Electrogenerated Hydrogen Peroxide – From History to New Opportunities

by Derek Pletcher

Hydrogen peroxide is probably a unique chemical, ideally suited to the present age where environmental considerations are always to the fore.

Why unique?

Firstly, it is capable of very diverse chemistry. Hydrogen peroxide may act as either an oxidizing agent or a reducing agent. As an oxidizing agent, its application ranges from highly selective oxidation chemistries applicable to the manufacture of many organic com-pounds, through the bleaching of pulp, to the total oxidation of large organic compounds to carbon dioxide. Its reactivity as an oxidizing agent is determined largely by the ratio of the concentrations of H2O2 to substrate and the reaction conditions, particularly the choice of catalyst and factors such as UV irradiation.

Secondly, it is a strong oxidizing agent that may be formed by cathodic reduction under mild and varied conditions, opening up the possibility of producing the same product at both anode and cathode. Thirdly, the feedstock for electrogenerated hydrogen peroxide may be air (an unusually cheap and available feedstock!) while its reactions lead only to oxygen and/or water.

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