This table contains information on each unique technology nominated for the Presidential Green Chemistry Challenge from 1996 through 2012. Although EPA has received 1,492 nominations during this period, only 755 unique technologies are represented here because sponsors may nominate a technology more than once.
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Of this traditional solvent blend, approximately 60 percent is Aromatic 100 (which includes ethyl benzene), 15 percent is xylene, 5 percent is Aromatic 150 (which includes naphthalene), and 5 percent is diethylene glycol monobutyl ether. In addition, the traditional blend contains 5 percent methyl ethyl ketone, which was previously classified as a hazardous air pollutant (HAP), but is no longer considered a HAP. BASF developed a coating composition using a solvent blend without HAPs, which required the company to replace 90 percent of the solvents in the blend it had been using.
The new coating eliminates solvents that are known or suspected to cause serious health effects (such as cancer, reproductive effects, or birth defects) or adverse environmental effects. It replaces a product line formulated with five HAPs that accounted for 8–10 percent of the product as delivered. It eliminates xylene, diethylene glycol ethers, and several other materials. The new BASF coating meets the U.S. EPA’s standard for being non-HAP as defined in the Miscellaneous Metal Parts and Products Surface Coating NESHAP. The new product has improved application efficiency and quality; it is cost-competitive, with a modest premium of only about $1 per gallon. At market projections, this product will reduce emissions of HAPs by about 500,000 pounds annually. BASF initiated commercial sales of its product in 2006 and is phasing out its previous technology.
This green technology provides a gallium alloy containing indium, zinc, and copper that conducts electricity, freezes below 0°C, exhibits high surface tension, and possesses a very high boiling point and very low vapor pressure. In addition, non-mercury switches and sensors can replace mercury switches and sensors without modifying existing technology. Mercury also is used in temperature sensors, pressure activated switches, pumps and filters, slip rings, liquid mirror telescopes, fluid unions, dental amalgam, and in medical devices such as sphygmomanometers and bougies. The non-mercury material also can serve as a substitute for elemental mercury in a many of these applications.
Both the oil separation and filtration apparati are housed within a recently developed parts washer unit, such that the aqueous cleaner/degreaser is recycled in-situ, eliminating the removal or transportation and special treatment of spent cleaner material off site. Testing results have shown that: (1) the resulting oil skimmed from the cleaner can, under current hazardous waste definitions, be managed as a 'spent oil" and combined with spent engine oil for beneficial reuse as a secondary fuel, and (2) the filter can be managed under current methods used to recycle other used combustion engine oil filters. Circuit Research Corporation believes there are in excess of 7,000 parts washers in Minnesota generating approximately 1.5 million gallons of spent Stoddard Solvent annually. Circuit Research Corporation"s alternative technology could significantly reduce the generation of this waste.
The amplification process can generate up to a 105 increase in phage and reduce incubation times to 1–5 hours down from 24–48 hours for traditional microbiological culture assays. The MicroPhage and CSM KeyPathTM
test is conducted with modern chemical detection methods on a milliliter scale. The test resembles a typical immunoassay whereby a blood culture containing a suspected pathogen is added to two reaction tubes: one containing phage and a nutrient media; and the second containing phage, media, and methicillin. The test samples are mixed with the tube contents and incubated, followed by analysis on a dual-track lateral flow immunoassay strip.
A positive result on the first track shows the presence of S. aureus. A positive result on the second track shows that the S. aureus is also methicillin-resistant. The manufacturing and use of the KeyPathTM kit address several of the 12 principles of green chemistry. This phage amplification platform is the first and only rapid in vitro diagnostic test approved by the U.S. Food and Drug Administration (FDA) to identify bacteria directly and determine their antibiotic resistance or susceptibility. During 2011, the FDA gave 501(k) approval for the sale of these human diagnostic devices and sales began in the United States.
Their technology consists of an aqueous solution of hydrogen peroxide, a phosphorus-based acid, phosphonate, and an anionic surfactant. This new technology yields safer cleaners by formulating them at a more neutral pH. Hydrogen peroxide provides a good bleach alternative that sanitizes more gently than chlorinated alkaline sanitizers. Overall, this technology cleans and sanitizes effectively using less toxic chemicals than current alternatives; it is also safer with respect to human health and the environment.
This technology has a great economic impact by performing the cleaning and sanitization at lower temperatures; it saves energy by as much as 43 percent, reduces plant downtime by as much as 18 percent, decreases water use by as much as 33 percent, decreases wastewater generation, and improves the long-term stability of the UF membrane. During pilot plant studies, JohnsonDiversey’s peroxygen products demonstrated superior performance versus the current competitive products. Compared to the typical system, JohnsonDiversey has demonstrated average savings of $700,000 per dairy plant per year. As of the end of 2004, JohnsonDiversey had tested and verified its new technology in a pilot plant membrane module for two years.
However, solid-acid catalysts deactivate rapidly due to coke retention in the pores. In gas-phase media, the heavy coke precursors (such as olefinic oligomers) are poorly soluble. In liquid-phase reaction media, the transport of coke precursors out of the catalyst pores is severely restricted resulting in their readsorption and transformation to consolidated coke. The work of Dr. Bala Subramaniam at the University of Kansas employs supercritical reaction media, which offer a unique combination of liquid-like density and gaslike transport properties for the effective removal of the coke precursors.
Employing carbon dioxide (Pc = 71.8 bar; Tc = 31.1 °C) as an environmentally benign solvent, 1-butene/isobutene alkylation was performed at supercritical conditions resulting in virtually steady alkylate (trimethylpentanes and dimethylhexanes) production in a fixed-bed reactor on solid acid catalysts (HY zeolite, sulfated zirconia and Nafion) for several days. The carbon dioxide-based supercritical process thus offers an environmentally safer alternative to conventional alkylation by eliminating a major technological barrier impeding the application of solid acid catalysts in alkylation practice.
Treating cooling towers with Smart Release® technology has many advantages over traditional liquid water treatments. Unlike traditional treatments, Smart Release® technology does not require toxic additives. Smart Release® treatments contain 95 percent active ingredients compared to 10–20 percent active ingredients in liquid treatments. The technology uses no pumps and so requires no electricity. Reduced packaging and shipping weight lowers its carbon footprint by 74 percent compared to that of conventional liquids. This technology may also help facilities gain up to eight LEED (Leadership in Energy and Environmental Design) credit points. Benefits to humans include safe handling because the coating prevents contact with active ingredients.
Because the concentration of active ingredients is so high, 100 pounds of Smart Release® chemicals equate to 600 pounds of standard liquid chemicals. The simplicity and reliability of Smart Release® technology means that less service time is required. Smart Release® technology has been endorsed by two of the leading water treatment companies in the United States and a leading global supplier of cooling towers, fluid coolers, and evaporative condensers. During 2010, Dober created an enhanced corrosion and scale-inhibitor tablet that contains no phosphate. Due to increased regulations limiting phosphate products, Dober expects this product to have large sales in the future.
By extending this approach to secondary refrigerants, the Sahinidis team has identified over 3,000 potential secondary refrigerants. These secondary refrigeration fluids have an estimated potential of reducing supermarket refrigerant leaks by 90%. This project has yielded a large number of chemical structures that are entirely novel: some of them appear in databases but were never used as refrigerants while others do not even appear in databases of chemicals. Furthermore, the nominated methodology is applicable to the design of a very broad spectrum of compounds, including pharmaceuticals and industrial solvents. Because it produces the entire set of possible compounds that satisfy physical property requirements, this methodology enables the use of environmental criteria to design novel compounds that are environmentally benign.
In the CEBC process, a highly reactive oxidation catalyst, methyltrioxorhenium (MTO), transfers an oxygen atom from hydrogen peroxide (H2O2) to ethylene with total selectivity, high conversion, no substrate or solvent burning (to cause CO2 emissions), and no explosion hazard. Despite requiring an H2O2 oxidant and rhenium-based catalyst that cost more than the LeFort system’s O2 oxidant and silver catalyst, the CEBC process can potentially compete economically if it has reliable in-service lifetimes of 2–3 months. Experiments indicate that the CEBC system should be capable of this critical in-service lifetime. Mechanistic studies with isotopic tracers identified only one detectable mechanism for catalyst destruction and conditions necessary to avoid it.
CEBC will soon attempt long-term, continuous process operations. The CEBC process has relatively high productivity (40–50 percent versus LeFort 10–15 percent) because it exploits the critical properties of ethylene to greatly increase its solubility. For similar production capacities, the carbon footprint of the CEBC process is net 23 percent lower than the LeFort process; thus, the additional carbon emissions from manufacturing H2O2 are considerably less than the emissions eliminated by not burning substrate or product. The CEBC process is the first economically competitive alternative to the LeFort process. The new EO process excels in conversion, selectivity, safety aand sustainability, and the two processes appear to be comparable in manufacturing costs and productivity. A U.S. patent for this process was allowed in 2011.
ADVAFLEXTM is an entirely new concept in PVC stabilizer technology that offers numerous advantages over conventional stabilizers. First and foremost, these are two-com-ponent systems containing new organosulfur chemistry and low levels of metal activators, such as zinc. The performance advantages include excellent thermal performance, competitive costs, good secondary performance attributes, compatibility with coadditives chemistries, and simplicity of PVC formation. The environmental and health benefits include: very low metal content (as low as 0.4%); low odor and volatility; and the absence of barium, cadmium, lead, phosphorous, alkylphenol, and other aromatic chemicals that are used in conventional technology.
ADVAFLEXTM has undergone a thorough toxicity screening that demonstrates that the product is essentially nontoxic and not mutagenic, carcinogenic, or environmentally hazardous. The metal activators in ADVAFLEXTM formulations are generally required at catalytic levels, and the preferred metal, zinc, is a required element of the human diet. ADVAFLEXTM technology is a commercially attractive alternative that improves on all aspects of the conventional technology, especially with respect to human and environmental safety.
While urea has many advantages over other nitrogen sources and has already captured a greatly increasing market share, a major drawback to the use of urea is its tendency to lose a substantial portion of the nitrogen values by ammonia volatilization. These losses can easily exceed 30% of the available nitrogen in urea under certain climatic and soil conditions. AGROTAIN® is a formulation containing N-(n-butyl) thiophosphoric triamide (NBPT) the precursor to the active ingredient, N-(n-butyl) phosphoric triamide (BNPO, the oxygen analog of NBPT). BNPO is far too unstable to be an article of commerce. NBPT serves as an effective precursor to BNPO, a urease enzyme inhibitor that inhibits the hydrolysis of urea by inhibiting the activity of the urease enzyme that catalyzes its hydrolysis.
This activity is the result of an interaction between the urease enzyme and the urease inhibitor. There is no interaction with soil microbes that generate the urease enzyme. Moreover, the recommended NBPT treatment rate is only 0.4 lb/acre, and NBPT is relatively unstable and presents no problems with long-term buildup in the soil. The use of NBPT with urea is also ideally suited for no-till agriculture applications. No-till agriculture is an environmentally friendly approach that involves little or no disturbance of the topsoil, resulting in less soil erosion and less energy intensive operation. Urea, however, has not been well suited for use with surface-applied no-till applications until the advent of NBPT because of the possibility of substantial ammonia volatilization losses.
Commercial coatings systems based on aldimine-isocyanate chemistry have been developed and are finding widespread acceptance as a solution to VOC restrictions. Current applications exist in the automotive refinish business where aldimines are used to make coatings containing only 20 to 25 percent volatile solvents, replacing products that have 40 to 50 percent volatile solvents by weight. Since the introduction of this technology in 1995, old technology resin systems requiring more than 100,000 kilograms of additional organic solvent have been displaced.
This volume will triple in 1996 and approach one million kilograms in 1997. More importantly, the volume of organic solvents displaced as other market areas adopt this technology is expected to increase dramatically. Additional benefits of this technology include: allowing low VOC coatings to be developed, resulting in large solvent savings for a given application without transferring environmental liability to production or use; it is already in significant commercial use, and will become a high volume product line by the end of the century, resulting in nontrivial source reduction of organic solvent emissions; it is compatible with existing and future coatings systems; it does not require significant capital investment to employ; and it increases productivity.
APG® surfactants are highly efficient cleaners and have led to a significant reduction in overall chemical consumption in cleaner formulations and ultimately the amount of chemicals released to the environment. APG® surfactants also permit the formulation of concentrated cleaners that require less consumer product packaging and consequently reduce packaging waste. APG® surfactants are considerably less toxic and safer to humans and the environment than other major surfactants. APG® surfactants permit the formulation of less irritating and safer consumer products and significantly reduce the possible environmental impact associated with an accidental spill. Henkel Corporation"s 50 million pound per year APG® surfactant plant has been operating in Cincinnati, Ohio, since 1992. A second plant was started up in Dusseldorf, Germany, in 1995, by Henkel Corporations"s parent company, Henkel KGaA.
Sulfuric acid technologies are extremely corrosive. Worldwide, they generate 10–20 billion pounds per year of spent acid, which must be transported and regenerated. For more than 40 years, academic and industrial researchers have searched for an economic, benign, solid acid catalyst technology to replace these liquid acid technologies. The AlkyClean® process is an economically attractive and environmentally safe alternative that is now commercially available. AlkyClean® replaces the liquid acids with a novel, true solid acid zeolite catalyst in an innovative process.
The zeolite-based formulation contains no halogens, has acid sites of optimum strength for alkylation, and exhibits the necessary activity, stability, and capacity for catalyst regeneration required for a successful process. Albemarle Catalysts of Houston, TX produced the zeolite catalyst, and ABB Lummus Global of Bloomfield, NJ designed and prepared a demonstration plant. This 10-barrel-per-day plant in Finland has been producing high-quality alkylate for more than 2 years using a refinery slipstream. During this time, the technology has been optimized for commercialization. Product quality is on par with existing technologies. The new process does not produce wastewater or sludge, and does not require any acid neutralization facilities or post-treatment of any kind.
They can be used in toners and printers, as additives for lubricants, and in the tire industry. Industrial collaborators, Superior Graphite and ConocoPhillips, have heat-treated CSs at higher temperatures; this improves their electrochemical performance as anodes for lithium-ion batteries. With a ferrocene catalyst, the process yields CNTs that Argonne has successfully tested as anodes for energy storage devices and additives for lubrication. This process is the cheapest, most straightforward way to fabricate CNTs in mass quantities.
It also avoids the air and water pollution caused by landfilling or incinerating WPBs. The process uses less energy to manufacture these materials than existing methods; it also replaces a petrochemical feedstock with WPBs. By diverting plastic bags from landfills or toxic incineration factories, this process reduces air and water pollution, ultimately reducing the hazards to public health and environment. Argonne has designed and built a prototype reactor with 80 cubic centimeter capacity and optimized the reaction conditions. Argonne is working with Grupo Simplex and G2 NanoTechnologies, LLC to commercialize this technology.
Eliminating the traditional protecting group to produce these drug substances reduces the combined environmental footprint by an average of 44%, as measured by the weight of materials used to produce one kilogram of product (E-factor). These combined improvements reduce the use of (1) solvents by an average of 27%, (2) water by 58%, and (3) raw materials by 78%. At peak production volumes for both drugs, estimated in the tens to hundreds of metric tons per year, these reductions could provide expected savings of 2.5 to 25.5 million pounds of raw materials per year. Further, manufacturers must often incinerate pharmaceutical aqueous waste streams to destroy the biological activity associated with their trace components, necessitating additional fuel consumption. Water reductions from the new syntheses alone should result in secondary fuel savings of 1.5 to 14.5 million cubic feet per year.
The new synthesis for duloxetine was demonstrated on a pilot plant scale in 2002; Eli Lilly is now developing its pilot plant process into an improved commercial process. The new synthesis for atomoxetine is currently being used at an Eli Lilly production facility.
In many cases, data quality objectives can be easily met using EDXRF spectrometry instead of ICP or AAS. The main environmental benefit of using EDXRF spectrometry is the significant decrease in the generation of laboratory waste in comparison to traditional methods. The primary reasons for this reduction in waste generation are that samples do not require dissolution in concentrated acids and calibration standards are not dissolved in acidic solutions and diluted to large volumes. Samples and standards are simply mixed with a nonhazardous substrate such as carbon or alumina prior to analysis or calibration. Also, the frequency of preparing and running standards is much less than traditional techniques because of the inherent stability of EDXRF systems. It is an environmentally friendly technique because it virtually eliminates the generation of hazardous lab waste.
In addition, a major byproduct of this brickmaking industry is a high level of air pollution—both particulates and toxic chemicals—that results from inefficient thermal design of the kilns and the use of cheap but readily available fuels. This industry is the third leading cause of air pollution in the El Paso-Juárez area. Redesign of the kilns to allow efficient energy recovery and to eliminate waste from over- and under-firing makes the use of nonpolluting fuels (e.g., natural gas) economically attractive.
The design challenge is to use inexpensive, readily available materials and equipment to avoid significant capital outlay. Laboratory investigations and process modeling were performed at the Los Alamos National Laboratory, and field tests are being performed at ECOTEC in Ciudad Juárez, Mexico, in cooperation with FEMAP, a private foundation in Mexico, and with the El Paso Natural Gas Company. The direct benefits of these improvements in the brickmaking process are reduced air pollution, safer operating conditions, and better bricks. In addition, process modeling indicates that fuel consumption can be reduced by approximately 55 percent and cost analyses project that this will result in an increase in profit of about 35 percent for the brickmakers.
Aqua Form wets out, mat/veil cloth, burlap, canvas, non-wovens, KevlarTM, SpectrafiberTM, woven roving, Dynel, graphite, carbons, polyester, and numerous E-glass Fiberglas cloths. Aqua Form accepts pigments, dyes, and fillers for viscous gels, Gesso’s, putties, and modeling pastes. It is suitable for interior/exterior applications, cleans up with tap water, and is used in small confined areas for vapor/odor free repairs, restoration, stiffening, lining, and structural reinforcement. Aqua Form is a user friendly planet kind "0" VOC consolidating binder for strong impact resistant composites. Aqua Form is for chemically sensitive individuals. Aqua Form can be painted/overcoated with solvent or water based lacquers, coatings, varnishes, epoxy finishes for wet/damp environments such as foliage, props, rain forest, swamp, scenic settings.
The hydrogen is compressed and stored, and can be delivered to a fuel cell-powered vehicle. The Home Energy Station changes the refueling paradigm from central facilities to clean, on-site fuel generation. By using catalytic and electrochemical processes, the Home Energy Station reduces atmospheric emissions and produces energy at higher efficiencies than traditional central generating stations. The Home Energy Station produces clean, reliable energy on-site, representing a significant milestone along the path to a hydrogen economy.
The Deoxo-Fluor reagent is effective in the conversion of alcohols to alkyl fluorides, ketones/aldehydes to gem-difluorides, and carboxylic acids to CF3 compounds with, in some cases, superior performance as compared to DAST. Within the past 2 years, Air Products and Chemicals, Inc. has successfully brought the Deoxo-Fluor reagent product from discover to commercial production. Major pharmaceutical companies in the U.S.A., Europe and Japan are currently using the reagent for the synthesis of pharmaceutical products in their development pipeline.
The solvents can be used as neat reaction or separation media, or they can be diluted in an inert environment such as in higher alkanes. Polymeric or oligomeric solvents have been synthesized using macromonomers incorporating the desired solvent functionality. These polymeric solvents are easily recovered using mechanical separations such as ultrafiltration rather than energy-intensive distillation processes. This new concept for the design and synthesis of solvents offers the potential for significant source reductions in air and water pollution and can be considered to be widely applicable to fine chemical and pharmaceutical synthesis, separations, and cleaning operations. It is expected to reduce the complexity of downstream processing options considerably and lead to energy efficient reaction/separation sequences.
Using fluoroether-functional affinity ligands, for example, Professor Beckman has shown that one can extract proteins from aqueous solution into CO2 with retention of activity following recovery by depressurization. Analogous chelating agents have been used to extract metals into CO2 as well. While initial work has targeted primarily extractions, the described CO2 soluble ligands can also be used to solubilize catalysts in CO2 (enzymes and metals are examples) for use in carrying out reactions either in CO2 or in CO2 water biphasic mixtures.
The work of Dr. Dharmaraj Raghavan at Howard University has led to the development of a technology that mixes rubber particles from scrap tires into portland cement resulting in a lighter material with improved performance of mortar and probably concrete. The worldwide production of cement exceeds 1 billion tons annually, with the possibility of it nearly doubling in the next 14 years. Cement based materials are inexpensive, easy to produce, and possess valuable engineering properties such as high durability and compressive strength. One of the major shortcomings of cement based material is the vulnerability of concrete to catastrophic failure and to plastic shrinkage cracking. An encouraging finding was that plastic shrinkage cracking can be reduced significantly and the vulnerability of concrete to catastrophic failure can be greatly diminished by the addition of sufficient fibrous rubber.
Chemical tests of the rubber retrieved from rubberized concrete showed no evidence of rubber undergoing any degradation and consequently no threat of released chemicals from the leached rubber into the environment. Possible uses of the rubberized concrete would be in subbases for highway pavements, highway medians, sound barriers, and other transportation structures. Currently the United States spends $250 billion annually on infrastructure projects. Even if rubberized concrete replaced only a small fraction of the conventional infrastructural material, the ramifications to the civil and composite industries will be substantial. The technology to reuse rubber tires into cement system yields value-added infrastructural material, while eliminating the imminent threat of health hazard and explosion potential because of the flammable nature of rubber tires.
TTA reacts with chlorine, producing a chlorinated species that is not protective to copper. When corrosion protection is lost, TTA feed rates are usually increased in an attempt to overcome the reaction with chlorine and maintain a high enough residual to protect the copper surface. Very high TTA dosages are frequently applied to improve performance, often with limited success. BetzDearborn has developed a new Halogen-Resistant Azole (HRA) that does not react with chlorine and protects copper when chlorine is present. The substitution of this new material for TTA provides substantial environmental benefits. These were demonstrated in a field test at a nuclear power plant that was utilizing chlorine for MB control. HRA was compared to TTA with respect to copper corrosion rates and discharge toxicities. Upon examination of the discharge, it was clear that copper-containing compounds, formed as a result of copper corrosion, were the most significant causes of toxicity to aquatic species. The use of HRA resulted in a five-fold decrease in the amount of copper released to the environment, compared to TTA.
Since HRA does not react with oxidizing biocides, considerably less chlorine or bromine is required for prevention of MB activity. A reduction in chlorine usage of 10 to 20% was observed at the above nuclear power plant, and reductions of 35 to 40% have been observed at other industrial sites. Lower chlorine usage means lower amounts of chlorine- or bromine-containing compounds ultimately being released in discharge waters. In addition, substantially lower concentrations of HRA are required for copper alloy protection compared to TTA.
At the nuclear power plant trial, the five-fold reduction in the copper discharged was obtained with 2.0 ppm HRA compared to 3.0 ppm TTA. Furthermore, a mass balance showed that only 9% of the TTA was recovered (compared to 90% of the HRA). The TTA loss was due to the reaction with chlorine and the formation of a chlorinated azole. Thus, the use of HRA resulted in a net reduction in the amounts and types of azole and halogenated azole compounds that were released into the environment. Finally, direct measurement of LC50 acute toxicities for fathead minnows, done on site in the plant effluent at the nuclear facility, showed a reduction in toxicity when TTA was replaced by HRA.
The many attributes of phase change ink make it a viable contender for a leading position in the printing industry to replace less environmentally friendly alternatives. Phase change ink, also known as hot melt or solid ink, addresses many of the limitations of the ink and printing processes associated with the well-defined, centuries old printing methods, (e.g., offset, flexography, gravure, letterpress). To demonstrate the enormity of the opportunity, chemical development of phase change inks has favorably addressed source reduction, pollution prevention, emission standards, ground-water contamination, airborne particulates, waste abatement, worker and consumer exposure, hazardous chemical reduction and nonreusable consumables. The traditional printing techniques that often have significant worker and environmental liabilities can now be replaced with modern technology sensitive to, and having an understanding of, complex "green chemistry" issues.
Tektronix is commercializing a four-color set of process shade, phase change inks (Spitfire Ink) for use in color printers also manufactured by Tektronix. The chemical design of Spitfire Inks started with consumer and manufacturing operator safety, environmental concerns and the expected application performance. A retro-synthetic analysis accounting for these primary "must haves" translated to the synthesis of new resins that were water insoluble, required no volatile organic solvents (VOCs) to manufacture or use, allowed for safe manufacturing, complied in "spirit and intent" with environmental regulations and provided a flexible technology to a growing and expanding industry. These goals were satisfied by foresighted design aimed at safer chemicals ultimately embodied in Tektronix’ Spitfire Ink.
Bergman has demonstrated that the employment of C-H activation reactions within synthetic sequences provides important progress toward this goal. Within the last two decades, the Bergman group has pioneered the direct activation of C-H bonds in organic molecules that are found in locations remote from other functional groups. Due to this pioneering work these C-H activation reactions are now being used successfully in the synthesis of various chemicals and pharmaceutical products. Ultimately this should have a profound impact on various fields and sectors of chemical manufacturing and production. Bergman’s studies of the mechanism of C-H activation have also provided a substantial amount of fundamental information about this important process, such as the factors that promote highly activation of different types of C-H bonds in hydrocarbons.
The original SAMMS® synthesis required toluene and other flammable organic solvents. The resulting waste stream contained water, methanol, toluene, and traces of mercaptan. It required disposal as hazardous waste. Steward Advanced Materials dramatically improved the SAMMS® synthesis with nonflammable, nontoxic supercritical carbon dioxide (SC CO2). With this patented, commercially viable, green chemical process, SAMMS® manufacturing is faster and more efficient; it also yields a higher-quality product. The only byproducts are carbon dioxide (CO2) and the alcohol resulting from the hydrolysis of the alkoxysilane. Th e CO2 and alcohol are readily separated, allowing the CO2 to be captured and recycled. The pure alcohol can be recycled as a feedstock, rather than becoming waste as in the original synthesis.
The SAMMS® materials emerge from the reactor clean, dry, and ready for use. Th e benefits of the green manufacturing process for SAMMS® materials coupled with the superior adsorption characteristics of SAMMS® materials currently deployed in the chemical industry result in substantially reduced releases of toxic metals to the environment. Commercial uses of thiol-SAMMS® include removal of: (1) multiple toxic heavy metals from contaminated mining impoundments, (2) heavy metal catalysts from pharmaceutical reaction mixtures, and (3) mercury from contaminated ground water and industrial process water with a discharge limit of 1.3 parts per trillion.
Three of the most important aspects of starch structure and chemistry that are in step with requirements for a green chemistry feedstock are its solubility in water, the richness of functional groups, and its optical purity. The same is true of lactose, a material that is underutilized and available in thousands of metric tons per year from cheese making. These three promising features represent the three most difficult technical challenges in attempts to use starch and lactose as raw materials. They are practically insoluble in other environmentally friendly solvents such as alcohols and esters thus limiting the range of relevant chemistries. The high density of functional groups (polyhydroxylation) has made it (until now) nearly impossible to do anything useful with these on a grand scale in a selective fashion. The optical purity is embodied in functionalities that make conserving it a challenge.
Over the past three years, Synthon Corporation has been working to overcome these technical barriers by developing, demonstrating, and commercializing a new chemistry that will fundamentally revise the position of these two important and critical raw materials on the list of renewable resources for manufacture of chemical commodities. In the process, these materials are oxidized in dilute aqueous sodium hydroxide under controlled conditions with peroxide anion to form (S)-3,4-dihydroxybutyric acid and 2-hydroxyacetic acid (glycolic acid) with very high conversion. (S)-3,4-dihydroxybutyric acid can be converted to the lactone by acidification and concentration.
Glycolic acid and the lactone can be utilized in the production of a variety of fine chemicals for particular use in the pharmaceutical, agrichemical, and polymer industries. Glycolic acid, for example, is used in the manufacture of specialty polyesters and in the preparation of paints. It is normally made by the environmentally unfriendly method of chlorinating acetic acid and hydrolyzing the chloro derivative with sodium hydroxide. The Synthon product brochure now lists over 30 such products available from gram to ton quantities. The process has allowed Synthon to take a substantial lead in the area of high-valued chiral intermediates through the green chemistry approach where the pool of natural raw resources is tapped.
LubriGreen has overcome the inherent disadvantages of vegetable oils and preserved their favorable properties by derivatizing fatty acids from triglycerides into estolides, which are oligomers of fatty acids. Patented oleic estolide esters are central to LubriGreen’s technology. Their synthesis proceeds by an acid-catalyzed SN1 addition of the carboxyl of one fatty acid to the site of unsaturation on another to form an estolide. (The catalyst is a recoverable, reusable organic superacid.) The free acid estolides are then esterified with a branched alcohol. The novel structure of oleic estolides gives them excellent lubricity, high viscosity indexes, and good cold-temperature properties. Like triglycerides, oleic estolides are beneficial in environmentally sensitive settings because they are biodegradable and nontoxic. Because the estolides are fully saturated and their secondary esters create a steric barrier to hydrolysis, they have good oxidative and hydrolytic stability.
Estolides are viable for the most severe lubricant and industrial applications, including PCMOs, hydraulic fluids, greases, gear oils, metal working fluids, and dielectric fluids. Estolides have the potential to displace a significant portion of the lubricant market, reducing emissions and the release of hazardous chemicals into the environment. Test results show that oleic estolide esters may also have advantages in performance and fuel efficiency over petroleum-based PCMOs. LubriGreen is currently working with the world’s largest formulators, lubricant distributors, and others to commercialize its products during 2013.
From 1986 to 1992, LMTAS produced mainly F-16 fighter aircraft at a rate of 220 to 350 aircraft per year. Throughout the 6 years, LMTAS used a general purpose wipe solvent containing 85 percent CFC-113 by weight throughout the manufacturing process. The use of the CFC-113 solvent blend resulted in the emission of approximately 255 tons per year of CFC-113 and 45 tons per year of volatile organic compounds (VOC) The implementation of DS-104 at LMTAS has reduced wipe solvent VOC emissions to 7 tons per year in 1993, 3 tons per year in 1994, and 2 tons per year in 1995, with no CFC emissions. After the LMTAS implementation, other companies and military operations throughout the United States have implemented this technology.
Additionally, this technology has been implemented in several countries, such as Australia, Canada, Greece, Israel, Mexico, the Netherlands, South Korea, Taiwan, and Turkey. Several other European countries will implement this technology in 1997. These cleaners were developed primarily for aerospace; however, they have found cleaning applications in many industries such as: automotive, bubble gum removal in movie theaters and universities, various ink removal industries, postal operations, electronics, building maintenance, steel industry, and nondestructive testing methods. EPA has recognized this technology in the Aerospace National Emission Standard Hazardous Air Pollutants and the proposed Aerospace Control Technology Guideline.
Catalysts are central to modern chemical manufacturing as well as to life. A good catalyst accelerates the rate of a desired reaction compared to unwanted, waste generating, side reactions. Enzymes are wonderfully selective and specific catalysts. Enzymes, however, evolved to work in living systems, and enzymes that work well in a chemical process plant have not been broadly available to chemists and chemical engineers. RBI has developed a new technology specifically to meet that unmet need. By turning state-of-the-art biotechnology to the problem of making useful enzymes for chemists, RBI has enabled a step change in the availability of useful protein-based catalysts for the chemical process industry.
RBI has developed and applied a powerful, new biodiversity search technology to scan natural sources for new enzymes. Once the best enzyme that nature has to offer for a particular application is identified, RBI applies additional high throughput technology to optimize the enzyme to make it more useful in a chemical plant. This new technology already has produced more than 150 new, robust biological catalysts for the chemical process industry and will generate more than 3,000 by 1997.
This pretreatment runs at up to 70 percent biomass with less than 10 percent ammonia by weight. Second, genetically engineered cellulase and hemicellulase enzymes from Hypocrea jecorina (a filamentous fungus) produce high yields and titers of fermentable 6-carbon and 5-carbon sugars. Third, the optimized metabolic pathways of a recombinant ethanologen (Zymomonas mobilis) produce ethanol efficiently by simultaneously metabolizing both the 6-carbon and 5-carbon sugars. Integrating and optimizing these three components enables a very efficient process, a green footprint, and lower costs, including less capital investment than other known cellulosic ethanol processes. If corncob feedstocks cost $50 per dry ton, the ethanol from DuPont’s process could cost less than $2 per gallon. Removing the yield, titer, and cost barriers to commercializing cellulosic ethanol is a significant step toward large-scale production of cleaner, more sustainable liquid transportation fuels.
Comprehensive well-to-wheel lifecycle assessments (WTW LCA) show that DuPont’s process could potentially reduce greenhouse gas (GHG) emissions by over 100 percent compared to gasoline, which is substantially larger than GHG reductions from other grain-based ethanol processes. A flexible-feedstock, 250,000 gallon-per-year demonstration facility in Vonore, TN is currently yielding over 70 gallons per U.S. ton of biomass and ethanol titers in excess of 70 grams per liter. In 2014, the first commercial-size facility to convert corn stover to over 25 million gallons of ethanol annually is expected to start up in Nevada, IA.
By elucidating the mechanisms that underlie the low activity of native enzymes in dehydrated environments, we have developed methods to dramatically activate a wide variety of commercially relevant enzymes in organic solvents. In particular, by engineering the microenvironment of the biocatalyst through lyophilization in the presence of simple salts, we have opened the door for the application of enzymes in many new processes. New enzymatic processes will offer all the benefits of biocatalysis including high activity and specificity, reduced byproduct formation, and environmentally-friendly processing, and thus will provide a green alternative to less efficient synthetic schemes. This technical achievement is particularly relevant for green processing in the chemical, food, and pharmaceutical industries.
It also eliminates the use of a stoichiometric amount of base if applicable substrates contain no acidic protons. Their novel technology has the additional benefit of rapid reaction times, ease of operation, and use of readily available catalysts and ionic liquids. These features should make this newly developed chemistry of great benefit to humans and the environment. The United States Patent and Trademark Office has granted four patents to Novartis for these novel inventions. In addition, leading peer-reviewed journals have accepted six publications. By the end of 2004, these papers had been cited thirty times by other scientists, confirming the utility and value of these inventions.
The new water-based microsphere materials that 3M uses in its Post-it® Super Sticky Notes yield the desired performance, generate fewer air emissions, have a reduced environmental risk profile, and are less expensive to manufacture than the original, proposed, solvent-based formulations. The formulations are trade secrets, but they are based on acrylate polymers. They do not contain any fluorochemicals, alkylphenol ethoxylates, poly(vinyl chloride), phthalates, or heavy metals intentionally added or present as impurities above de minimus levels. The new formulations reduce annual VOC emissions by 33,400 pounds (with pollution controls) or 2,170,000 pounds (before pollution controls) and Toxic Release Inventory (TRI) emissions by 20,500 pounds (controlled) or 1,024,000 pounds (before control) compared with the projected emissions of the proposed, solventbased process.
The water-based system eliminates the need for a thermal oxidizer to control VOC emissions, reducing 3M’s emissions of CO2 from fuel combustion. It also increases worker safety and reduces the possibility of fire, chemical release, or explosion. The waterbased system also generates significant cost savings. 3M’s Post-it® Super Sticky Notes are an excellent example of the benefits of green chemistry and the importance of integrating 3M’s core values into decision-making. Following its success with Post-it® Super Sticky Notes, 3M added water-based formulations to Post-it® Sticky Picture Paper for printing digital pictures and to other specialty applications in 2005.
Orono Spectral Solutions (OSS) developed a solid-phase, infrared-amenable extractor technology that both eliminates solvents from oil and grease analysis and provides more economical, accurate analyses. OSS’s extractor unit is small, robust, and disposable (or partially recyclable), and it contains no toxic substances. The extractor unit includes a TeflonTM
-based polymeric membrane to capture and concentrate oil and grease from water, a metal-membrane support, and a polypropylene housing designed for pressurized water samples.
The membrane does not absorb IR light in the spectral regions of interest; after drying, the device can be put into an IR spectrophotometer to determine the amount of oil and grease. This patent-pending technology has successfully completed ASTM (American Society for Testing and Materials International) multi-laboratory validation and received ASTM method number D7575. EPA is currently considering replacing method 1664 with this one. This replacement would save one million liters of hexane annually and produce estimated benefits to the U.S. economy of $50–$60 million. OSS is actively commercializing this technology worldwide.
With new catalysts and process-flow schemes, UOP can produce both diesel and jet fuels from many biofeedstocks including jatropha, camelina, algal oil, animal fats, and used cooking oil. Their products are compatible with the existing refinery infrastructure, technology, and distribution network. Even more important, UOP’s bioproducts can be blended directly into current fuels without modifying the jet or diesel engines or the delivery infrastructure.
Although the processes to make diesel and jet fuels are similar, the detailed flow schemes and catalysts are different because the two fuels have different specifications. A lifecycle analysis (LCA) estimates greenhouse gas (GHG) savings at 84 percent for Green Jet FuelTM and 89 percent for Green DieselTM. In developing the UOP/Eni EcofiningTM process for Green DieselTM, UOP and Eni SpA took these inventions from concept to full process design. They have now licensed their process to four refiners. Several organizations are partnering with UOP to bring renewable jet fuels to market. UOP and Eni have filed 30 U.S. patent applications for their EcofiningTM technologies.
It must be emphasized here that the enzymatic conversion of the toxic aromatic materials takes place in the very first step of the synthetic pathway and that all subsequent synthetic intermediates are harmless. The residual mass from the enzymatic processes is judged suitable for disposal to municipal sewers, thus further reducing the amount of actual waste. The key philosophy of our projects rests on the managed processing of aromatic waste to value added substances. A new definition of efficiency, "Effective Mass Yield," is provided as the percentage of the weight of desired product in the weight of all non benign mass requiring treatment or disposal that is used in the manufacturing process.
This simple process has several advantages and produces the desired enantiomer without expensive and environmentally unacceptable chiral catalysts or templates. It also replaces the environmentally undesirable solvents dichloromethane and acetonitrile. The second process, multicolumn chromatography (MCC), improves on route B3, retaining all of its advantages. The MCC process also re-epimerizes and recycles the undesired enantiomer, delivering an overall process with significant environmental benefits.
Detailed analysis demonstrates that the MCC-based process meets all commercial and quality criteria; in addition, it reduces the use of valuable resources and greatly decreases the process liquid waste streams. The traditional synthesis required 260 kg of input material and 194 kg of solvent per kg of product. The mass intensity of the MCC process is approximately 20 kg of input material per kg of product, an incredibly low number for a pharmaceutical product. The MCC process uses only 19 kg of solvent per kg of product, with potential for further recovery. GlaxoSmithKline performed a pilot study on medium-to-large scale in-house MCC equipment during 2003. At peak production, GlaxoSmithKline calculates that the MCC process could reduce the overall waste load by 5,000 metric tons per year.
First, dilute aqueous lubricants typically require large amounts of water on the conveyor line. The area near the conveyor line becomes very wet and the excess water must then be disposed of or recycled.
Second, some aqueous lubricants can promote microbial growth.
Third, diluting the concentrated lubricant before use can produce variable concentrations of dilute solution and thus, variable performance. Finally, variations in water quality can alter the performance of the dilute lubrication solution. For example, alkaline water can lead to environmental stress cracks in poly(ethylene terephthalate) (PET) bottles. The DryExx Conveyor Lubricant Program lubricates conveyor chains without added water. The DryExx Program consists of the DryExx chemical formulation and a dispensing concept.
The DryExx formulation contains a mixture of water-miscible silicone material and a water-miscible lubricant. It contains no hazardous ingredients in quantities requiring reporting. The product is targeted for food and beverage bottlers who package products in PET containers using conveyors with plastic or polyacetyl chains. Currently, Ecolab estimates this program is saving U.S. bottling facilities 240 million gallons of water annually and is preventing an additional 1 million gallons of conventional lubricant concentrate from entering the effluent stream.
PCE is a suspected carcinogen, petroleum-based solvents are flammable and smog producing, and CFC-113 is an ozone depletor and targeted to be phased out by the end of 1995. Health risks due to exposure to cleaning solvents and the high costs of implementing and complying with safety and environmental restrictions and regulations, have made dry cleaning a much more difficult business in which to achieve profitability. Solvents are suspected of contaminating ground water, air, and food products (i.e., in nearby markets). For these reasons, there is an ongoing search for alternative, safe, and environmentally friendly cleaning technologies, substitute solvents, and methods to control exposure to dry cleaning chemicals.
DryWashTM reuses carbon dioxide, a naturally occurring byproduct of combustion that is a readily available, inexpensive, and unlimited natural resource. It is also chemically stable, noncorrosive, nonflammable, nonozone depleting, and nonsmog producing. Performance has been demonstrated to major dry cleaning equipment manufacturers worldwide and to the EPA. Actual garments, along with International Fabricare Institute (IFI) standardized cleaning test fabrics, were used for the demonstrations. The performance of the DryWashTM cleaning process was quantified favorably against commercial perchloroethylene cleaning by Los Alamos National Laboratory, using IFI standards.
Following proof-of-principal testing, H and H engineers deduced that a combination of ammonium chloride, urea, and water would act to provide the necessary endothermic reaction. The product is fully non-toxic, non-caustic, non-hazardous, and heavily packaged for rough handling. DUAL-ICE® demonstrates a high cooling potential, maintains a shelf life of at least one year, and is air- and ground-shippable. Furthermore, the postendothermic reaction chemical byproduct is such that, after the initial use as an instant cold compress, DUAL-ICE® is fully reusable as a refreezable cold pack that remains flexible and conforms to an injured appendage or area.
This material is landfilled. The patented DuPont Petretec(SM) polyester regeneration technology provides an environmental and economical alternative to landfills and offers many advantages over recycling. Petretec(SM), DuPont"s proprietary form of methanolysis, makes polyester evergreen. The process provides a safer and more economical way to reuse materials, especially those with much higher contaminant levels than other recycling methods. It takes PET fibers, films, and resins currently going to landfills, unzips the PET molecule, and breaks it down into its raw materials, dimethyl terephthalate (DMT) and ethylene glycol (EG). The Petretec(SM) process allows these raw materials to retain their original properties so they can be reused over and over again in any first-quality application. The process accepts polyester with a broader variety of contaminants and at higher levels than any other process.
Petretec(SM) reduces dependence on oil-derived feedstocks and diverts polyester from the solid-waste stream into useful new products. In the Petretec(SM) technology, scrap PET reacts with methanol vapor at elevated temperature greater 260 °C) to produce a vapor stream of DMT, EG, and excess methanol. A glycol azeotroping agent, methyl p-toluate (MPT) is added and the components are separated. Purification is accomplished by extensive fractional vacuum distillation. The products are then shipped back to PET fiber, film, and resin producers. Each kilogram of PET made from the Petretec(SM) process using RDMT and glycol, reduces the demand for about one-half kilogram of the traditional hydrocarbon raw materials. DuPont invested $12 million to convert part of its Cape Fear facility, near Wilmington, North Carolina, to a methanolysis plant. the new plant can handle more than 100 million pounds of scrap PET and capacity is easily expandable. By actually unzipping the molecules, we can begin the cycle of using these materials in an endless series of new applications.
The development of durable AMPS® polymers at Lubrizol solves this problem. These polymers suppress mist formation at the source by stabilizing MWF against breaking up into small droplets that get suspended in the plant environment as mist. The reduction in mist minimizes worker exposure to MWF chemicals and other pollutants present in the mist, creating a safer worker environment. Because they are shear stable, the AMPS® polymers provide long-lasting mist reduction. The application and performance of the AMPS® polymers were evaluated during field trials at small machine shops and large Ford manufacturing plants. In a small machine shop field test, a one-time addition of 1,000 ppm AMPS® polymer resulted in a stable 60% mist reduction. During large-scale plant trials at Ford Motor Company, a one-time addition of 1,000 ppm AMPS® polymer resulted in stable 40 to 60% mist reduction over two months in the plant environment. The worker response to reduced mist levels during these trials was extremely positive.
It was felt that after the polymer addition, there was a distinct improvement in plant air quality, general improvement in working conditions, and less slippery floors from oil mist deposits. AMPS® polymers provide a low-cost method of suppressing mist generation and controlling exposure because they provide long-lasting mist suppression at low (ppm) concentrations. These polymers are less labor-intensive to implement in the field because they disperse easily in the MWF and do not require frequent addition. They are manufactured as aqueous solutions and do not contain any volatile organic compounds. Extensive sensory, inhalation, and dermal toxicity tests have shown that AMPS® polymers exhibit a profile of minimal toxicity under conditions of use. Waste water treatment evaluations have shown that they do not affect the waste treatability of aqueous MWFs.
Faced with a shrinking supply of petroleum wax and a rise in restrictions on wood-burning fireplaces by air quality districts (particularly in the Western states), the company has focused on developing manufactured firelogs using materials that are both cleaner burning and recycled or renewable. In 2004, Duraflame introduced a new all-natural firelog made from recycled biomass products such as wood sawdust, ground nut shells, recycled cardboard, and plant waxes (to replace petroleum wax) as a combustible binder.
Standard petroleum wax–sawdust firelogs produce approximately only one third of key air pollutants associated with residential wood combustion compared to an equivalent natural wood fire. In contrast, Duraflame’s new all-natural firelogs produce approximately one quarter of the emissions of an equivalent natural wood fire. The Duraflame® All-Natural Firelog is now available in supermarkets across the United States and Canada.
The conventional brands had significantly higher levels of 1,4-dioxane. The highest were Tide® with 55 ppm, Ivory Snow® with 31 ppm, and Tide® Free with 29 ppm. OCA has confirmed in their latest report for 2010 that ECOS® Laundry detergent by Earth Friendly Products was free of 1,4-dioxane. Since June 2008, Earth Friendly Products has successfully scaled up its formulas to produce natural products that do not contain any harmful chemicals, including 1,4-dioxane. The company uses a blend of coconut oil with anionic fatty acid chains that make excellent surfactants due to their dual hydrophilic and lipophilic properties. There is no sodium chloride salt added or used in any step of manufacturing or production of the company’s laundry products. Each product is made with sustainable, plant-based ingredients that are studied to ensure minimal environmental impact before and after production. This ensures that all of the company’s products are not only biodegradable, but also free of phosphate, caustic, formaldehyde, petrochemicals, chlorine, synthetic perfume, and ammonia.
With little or no modification of existing manufacturing processes, ecomate® foaming systems provide foam with insulating and structural characteristics equivalent to those of conventional polyurethane foams. Foam Supplies, Inc. developed ecomate® as a green replacement for both HCFCs and the high-GWP hydrofluorocarbons (HFCs), which have GWPs of 725 to 1,810. Each pound of ecomate® replaces about two pounds of alternative blowing agents. Using ecomate® as a blowing agent in polyurethane foams has eliminated almost one million metric tons per year (mt-CO2e) of high-GWP compounds such as HFC-134a and HFC-245fa. Using one million pounds of ecomate® would eliminate the equivalent of 1.4 billion–3.4 billion pounds of CO2 emissions or 0.6 million–1.5 million mt-CO2e. Ecomate® blowing agent costs substantially less than HFCs, and there are usually no significant capital expenses associated with implementing the ecomate® technology.
Ecomate® foaming systems allow manufacturers to help the environment without increasing their costs. Ecomate® has been demonstrated in pour-in-place, boardstock, and spray insulation systems as well as in boat flotation foam. Ecomate® currently has a variety of applications in several countries; its availability has allowed EPA to accelerate the phase out of HCFCs in the United States.
ECONEA® 028 degrades rapidly in seawater by hydrolysis, and in sediment by anaerobic and aerobic metabolism (half-lives of 3 hours, < 1 hour, and < 1 day, respectively). Environmental modeling indicates that ECONEA® 028 can remedy an existing environmental problem in San Diego Bay (SDB), where copper levels exceed clean water standards. Elimination of copper from U.S.Navy antifouling paints, by combining ECONEA® 028 for hard fouling with an existing antifoulant for soft fouling, potentially can reduce copper loading in SDB by over 7,000 Kg per year from hull leachate. The combined copper burden in aquatic ecosystems of four military ports can be reduced by over 25,000 Kg annually using this technology, with potentially over 98,000 kg copper annually by conversion of the entire military fleet.
These outcomes are achieved in two steps by a new multi-functional oxidant and catalyst system. This system is a thermally equilibrating, and thus inherently stable, aqueous ensemble of polyoxometalate (POM) salts. The ensemble is designed to include key species necessary for anaerobic (and hence, highly-selective) oxidative depolymerization and solubilization of lignin (step 1), for catalytic O2-mineralization of lignin (step 2), and for maintaining the pH near neutral at all times. In related work, 100% oxygen-atom-efficient catalysts for chemoselective O2-oxidations have been developed.
The novel design of IonSelTM stacks allows the cells to operate at high efficiency, consume 40 percent less energy, and generate high-purity products. The process rearranges ions in solution and is particularly suited to recycling salts generated in other applications including those from the pulp and paper industries and from the environmental control systems in coal-fired power plants. NSR’s process yields high-purity, food-grade products without mercury (a health hazard to children) or oxidizing species like chlorate and hypochlorite. The lower energy consumption per unit of KOH made by NSR’s process allows smaller plants to produce equivalent amounts of HCl and KOH profitably. Smaller plants cost less, can be built close to end-users, and reduce transportation hazards. NSR supplies food grade 7 percent HCl to Archer Daniels Midland by pipeline.
This efficient transfer eliminates the unnecessary transport and accidental release of fuming 35 percent HCl. NSR’s single plant eliminated the production of 2 million pounds of Cl2 during 2011; at full capacity, it would eliminate the production of 10 million pounds of Cl2 per year. NSR’s technology could potentially eliminate the production of billions of pounds of unnecessary Cl2 each year.
The metal residue, fission products, and transuranic elements from the spent fuel can be immobilized in highly stable waste forms for disposal in a geologic repository. Compared with conventional processing, electrometallurgical technology holds promise for significantly reduced costs, greatly decreased volumes of high-level radioactive waste, and negligible volumes of secondary or low-level wastes. This technology could facilitate the environmentally sound processing of most of the more than 2000 metric tons of spent fuel accumulated within the Department of Energy complex. This technology also has potential spin-off applications for industry, such as the treatment of enrichment tailings from nuclear plants and the disposal of nontoxic wastes (e.g., barium-contaminated slats) from industrial processes.
Earlier studies had shown that enzymes were an exciting, environmentally friendly alternative to the synthesis of many of these polymers. However, the mechanisms involved in these reactions only led to highly branched and often insoluble polymers that had very poor electrical conductivities and optical activity. While investigating new ways to overcome these limitations with the enzymatic approach, it was found that simple addition of a charged molecular species (polyelectrolyte or surfactant) to the reaction medium provides a type of biocompatible nanoreactor that not only optimizes enzymatic function and monomer coupling, but also provides water solubility of the final complex. The final polymers have enhanced electrical and optical properties and are processable, and the entire process is environmentally compatible. A number of templated polyanilines and polyphenols have been produced and characterized using this process. Enzymatic polymerization of anilinic and/or phenolic monomers is carried out in the presence of ionic templates to yield high-molecular-weight and water-soluble complexes of the polymer and the template used.
This approach is particularly attractive because it is completely benign and simple (one step) and uses very mild aqueous conditions. In addition, the process is general, as numerous ionic templates and derivatized monomers may be interchanged to build in desired functionalization. This process has the potential to revolutionize the use of electronic and photonic polymers because toxic catalysts or solvents are no longer required for the synthesis or processing of these polymers into useable forms. The technological applications for these enzymatically synthesized polymers are significant and diverse. Polyaniline is already well known as a promising material for electrochromic displays, electromagnetic interference (EMI) shielding, corrosion protection, electrostatic dissipation, and sensing. There is also great potential for these materials in photonic devices and batteries.
Polyphenols are currently being investigated in polymeric batteries that could be coupled to photovoltaic devices containing conducting polymers and light absorbing dyes to create environmentally friendly energy harvesting and storage devices. It was recently found that the mild and benign conditions of this biocatalytic approach even allow for the use of DNA as a template to form a conducting DNA/polyaniline complex. This material could have enormous opportunities in medical diagnostic devices, probes, and bioconductors. This technology offers both potential economic and environmental benefits to industry and society due to the commercial potential of the products made and the environmentally benign methods used to produce them.
Instead, it provides for oligomers that are dissolved in monomers of similar reactivity. This permits the formulation and application of the above listed products, which are then cured by the application of ultraviolet (UV) or electron beam (EB) energy that causes 100% copolymerization of the oligomers with the monomers forming high performance coatings, inks and adhesives. Since no solvents are used, the emissions are nearly zero. Converters to this technology are therefore free of VOC and HAP regulations even if their production increases substantially. Environmental and health benefits are great. This technology is currently in use in a wide variety of industries and is growing at a 10-12% annual rate.
Commercial Fluid Power is taking steps to reduce the use of industrial hard chrome or engineered chrome in the fluid power market. The company is developing and marketing Nitro-tuff tubes as safe, environmentally friendly replacements for chrome-plated tubes. Nitro-tuff tubes are ferritic nitro-carburized steel. During their manufacture, the surface of the steel is converted to a nonmetallic epsilon iron nitride (e-Fe3N) in an atmosphere of ammonia and carrier gas. Following nitriding, an oxidizing atmosphere is introduced to produce a thin, corrosion-resistant, black surface film of Fe3NO3-4. The iron nitride layer is the basis for the steel’s extraordinary wear and corrosion resistance.
Advances in mechanical properties, size, and finish control now allow Nitro-tuff tubes to substitute for chrome-plated tubes without losing quality or strength. These efforts are reducing the use of hexavalent chromium. Recent research, development, and testing have overcome earlier challenges and opened new markets for Nitro-tuff tubes and bars. In conjunction with NitroSteel and Nitrex, Commercial Fluid Power continues to strive to bring an eco-friendly, cost-effective solution to the fluid power market.
These accomplishments were achieved by converting to an aqueous-based photolithographic process in the PWB facility in 1989, an interim aqueous cleaning process in the ECAT facility in 1991 and 1992, and a final No-Clean process (eliminating the aqueous cleaning process) in the ECAT facility. Changing from a solvent-based photolithographic process to an aqueous-based process eliminated methyl chloroform (MCF) from PWB panel manufacturing (1988 usage of 181,000 pounds). The interim process changes to aqueous cleaning eliminated MCF from manufacturing processes in ECAT (1989 peak usage of 196,000 pounds) and were largely responsible for eliminating CFC-113 from all manufacturing processes at the IBM site. Although CFC-113 was eliminated from the site in 1991 and MCF was eliminated in 1992, ECAT’s ultimate goal was to convert all ECAT processes to No-Clean manufacturing processes.
Voluntarily, IBM began searching for alternatives to PFOS and perfluorooctanoate (PFOA). In 2006, IBM issued a Corporate Directive to eliminate PFOS and PFOA from all manufacturing processes by 2010. IBM worked with chemical suppliers to identify and qualify a non-PFOS replacement for the PFOS surfactant in buffered oxide etch (BOE) chemicals. In 2008, after a multiyear investigation and extensive qualifications, both IBM fabrication plants finished replacing the PFOS surfactant in all BOE chemicals with perfluorobutane sulfonate (PFBS), for which EPA has fewer environmental concerns. IBM also sought replacements for specific photoresists and antireflective coatings (ARCs) that contained PFOS or PFOA as a surfactant or photoacid generator (PAG).
In January 2010, after significant investment and qualification of replacement chemistries across many wet etch and photolithography processes, IBM completed its conversion to non-PFOS, non-PFOA lithographic chemicals. This change eliminates approximately 140 kilograms of PFOS and PFOA annually. Total annual PFOS consumption by the semiconductor industry worldwide is estimated at 8,000 kilograms. IBM believes it is the only company in the world to eliminate PFOS and PFOA compounds completely from semiconductor manufacturing. IBM has also developed PAGs free of perfluoroalkyl sulfonates (PFAS) for both dry and immersion 193-nm semiconductor photolithography processes, with equivalent performance in 45-nm and 32-nm semiconductor technology. IBM is pursuing technology transfer opportunities to commercialize its PFAS-free PAGs for a wider range of applications.
The Silaprene Adhesive was also a contributor to their HAP emissions, with a composition of 20% HAPs (Toluene, CAS# 108-88-3). The reason Uniseal began with the replacement / elimination of Silaprene Adhesive is because the Silaprene Adhesive is carried by trichloroethylene. A small-scale trial conducted by hand indicated that both types of foam can be laminated with the same primer. The primary ingredient in the 3M primer already in use is cyclohexane, and was already being used in this combination on one type of foam, so that became the replacement chemical. Efficiency and quality problems soon surfaced because the cyclohexane was not flashing off quickly enough. Next, the trial went to acetate, which also did not flash off quickly enough. Uniseal then decided to try using acetone, which is working rather well. The workability of the acetone is a benefit not only in that it is not a hazardous air pollutant, and not a regulated VOC, but it is also not an ozone precursor.
As proof of principle, Dr. Stewart’s group has created a yeast strain that catalyzes a broad array of enantioselective Baeyer-Villiger oxidations. While this reaction plays an important role in laboratory-scale syntheses, the severe environmental and safety problems associated with current reagents prohibit its large-scale use. Acinetobacter cyclohexanone monooxygenase was expressed in Saccharomyces cerevisiae and whole cells of the engineered yeast were used to oxidize several ketones in good yields and with high enantioselectivities. This process uses atmospheric O2 as the oxidant and produces water as the only byproduct. Cell biomass and spent culture medium can be discarded in sanitary sewers after heat inactivation.
EnvirezTM resins now contain more types and higher percentages (up to 40 percent) of renewable raw materials. Ashland has developed formulations for a wide variety of composite fabrication methods including infusion, pultrusion, casting, and gelcoats. These formulations expand the reach of EnvirezTM into an assortment of products and markets including green buildings and wind energy devices. They enable composite fabricators to use sustainable components. EnvirezTM technology leads to reduced dependence on petroleum, lower emissions, energy savings, and a smaller carbon footprint. In the last three years, EnvirezTM resins have incorporated over 12 million pounds of recycled PET.
Using a novel, biobased reactive intermediate, Ashland has developed EnvirezTM low styrene resins that lower the traditional styrene content by one-third and reduce both hazardous air pollutants (HAPs) and volatile organic compounds (VOCs). The EnvirezTM product line has experienced double-digit growth in the past several years. EnvirezTM low styrene resins have completed review under the Toxic Substances Control Act (TSCA) and are undergoing field trials at numerous composite fabricators.
Currently, the uses of carboxamides as delivery agents for the delivery of protein and macromolecular drugs in a wide range of settings are being sought and discovered. The amidation mediator, boric acid, has many promising and beneficial properties. The conventional methods reported in the literature for making carboxamides require the use of environmentally harmful reagents and generate hazardous wastes. This boric acid-mediated amidation employs only environmentally benign reagents and generates no by-products. This new alternative green synthetic pathway, using only a catalytic amount of boric acid, guarantees uncontaminated waste flow, thus assuring significantly reduced impacts on human health and the environment relative to the current state of art.
The metal indium, a relatively unexplored element, has recently been shown to offer intriguing advantages for promoting organic transformations in aqueous solution. The feasibility of performing organometallic/carbonyl condensations in water, for example, has been amply demonstrated for the metal indium. Indium is nontoxic, very resistant to air oxidation, and easily recovered by simple electrochemical means, thus permitting its reuse and guaranteeing uncontaminated waste flow. The power of the synthetic method, which often can exceed performance levels observed in purely organic solvents, includes no need for protecting groups, greatly enhanced ease of operation, and greatly reduced pollution risks.
Data have linked NPEs to endocrine disruption and mammalian reproductive concerns. Barricade International, with E.T. Sortwell conducting R&D, has developed a product to match the firefighting properties of the existing gel without its environmental and health concerns. The product is Barricade II, a dispersion of superabsorbent polymer in foodgrade vegetable oil (i.e., canola), sorbitan monooleate, and fumed silica. The superabsorbent polymer is typically a copolymer of acrylamide and acrylic acid derivatives such as salts.
Barricade II is more effective at fire prevention than its NPE–petroleum distillate competitor. In aerial applications, Barricade costs only about half as much as traditional retardants and is effective at about 1/18 the application rates. The U.S. Forest Service has placed Barricade II on its Qualified Products List. A U.S. patent has been allowed, and Barricade International has begun full-scale commercial production of this product. California’s Department of Forestry used Barricade II in aerial applications during the 2006 fire season with spectacular results.
These environmentally benign antibacterial agents (containing only magnesium and peroxide) are affixed as aqueous dispersions to textiles to impart antibacterial activity to natural, synthetic fibers and blends by pad-cure processes (10-17% active ingredients cured at 2-4 min. at 120-150?C). Modified textiles containing bound peroxide (0.1-1.7% by weight) are active against bacteria as low as 0.10% peroxide. Renewable fibers (cotton, others cellulosics) have the best affinity for the agents with cotton fabrics retaining their antibacterial activity up to 50 launderings. Marked improvements in fixation and durability of these agents to synthetic fibers have also been recently made by incorporating selected softeners in treating formulations.
The MLI chemistry has led to development of a wide array of products, many of which are now in or near commercial use. These products reduce the nation’s reliance on petroleum, assist the commercialization of biofuels, and reduce impacts on health and the environment relative to traditional glycol-based fluids. The MLI biomass-based fluids are infinitely soluble in water, are nontoxic, and act as corrosion inhibitors for ferrous metals. During 2005, MLI received a patent for D/A agents made from byproducts of biodiesel manufacture. Also in 2005, MLI released Caliber® FC-B antifreeze and Caliber® SBA-2 additive for chloride D/A products in collaboration with Archer Daniels Midland. Current sales of MLI D/A agents are 15 million gallons per year. Applications for these products include aircraft-related uses, airport runways, roadways, bridges, facilities, landscape, and consumer markets.
The technique takes full advantages of the solution enzymatic synthesis method but overcome its limitations by immobilizing the enzyme on a solid support as a catalyst. The stability of the enzyme is significantly increased through the immobilization process. Furthermore, the catalyst enzyme can be easily recovered and reused with the immobilizing technique. Since the solid support is used, it is ideal to fabricate an enzymatic reactor for polymer synthesis. Most importantly, the newly developed technology in this research makes the biological route for polymer synthesis become usable and practical in commercial production process. A patent application for this new technology was filed at USPTO in year 2001.
The synthesis of polyphosphazenes can occur by three routes: (1) traditional ring-opening synthesis; (2) living polymerization, which proceeds through formation of a silylphosphoranimine; and (3) the "DeJaeger" method. Each of these three types of synthesis has advantages and disadvantages. All of them, however, as now practiced by industry, require high-boiling halogenated solvents both for thermal control and dispersal. Our approach eliminates use of all halogenated hydrocarbon solvents and produces phosphoryl chloride, a byproduct chemical having commodity uses within the chemical industry.
Instead of performing several time consuming, solvent-based, chemical reactions in order to synthesize a series of candidate compounds for structure activity studies, this technique allows for the addition of simple, inexpensive, readily available 'complexing reagents.’ For this to be successful as pollution prevention, these assemblies must significantly reduce the number of synthetic reactions carried out. Often the formation of these assemblies involve no organic solvents. The supramolecular structures can be constructed via solid state grinding or aqueous dispersing techniques.
Professor Pirrung’s multicomponent reactions are 100 percent atom economical: they do not generate any byproducts. Because the reaction products are frequently insoluble in water, this technology also significantly facilitates product isolation and eliminates traditional energy- or material-intensive purification procedures such as chromatography or distillation. The only initial drawbacks of the technology were (1) the highly offensive odors of the isonitriles that are essential to the most powerful and commonly used multicomponent reactions and (2) their problematic preparation.
The second component is Professor Pirrung’s development of a much more environmentally friendly route to prepare isonitriles that also eliminates their stench. Traditional routes to isonitriles involve dehydration of formamides with phosgene. Phosgene is a highly toxic gas that was used as a chemical warfare agent; thus, there is strong resistance to using it in any chemical process. Other dehydrating agents used in its place are not as efficient. Professor Pirrung’s alternate route treats readily available oxazoles with a strong base to form isonitriles, eliminating formamide dehydration. The resulting isonitrile esters exhibit uncompromised chemical reactivity and do not have offensive odors. This safer route to isonitriles allows them to replace carbon monoxide in some reactions. Professor Pirrung’s technology should increase economy in the production of drug candidates, combinatorial libraries, and active pharmaceutical ingredients.
In 1990, Congress passed the Pollution Prevention Act, which introduced the concept of pollution prevention through proper waste disposal, waste treatment, source reduction and source prevention. In this regard, bismuth compounds are particularly attractive candidates for use as reagents in synthetic organic chemistry for several reasons: Bismuth is the least toxic of the heavy metals. The biochemistry, toxicology and environmental effects of bismuth compounds have been well documented. The majority of bismuth compounds are relatively non-toxic (e.g., the LD50 (g/kg) of BiOCl is 22 and that of Bi2O3 is 5 (compared with a LD50 of 3.75 for NaCl). Bismuth and several of its compounds are commercially available and are relatively inexpensive. This project is aimed at developing new applications of bismuth compounds in organic synthesis.
This technology improves the strength of paper and paperboard, reducing the use of chemicals to improve strength. Less energy is needed to give the required strength to paper products. The technology is already in use successfully in about 10–15 paper machines in North America, producing tissue papers, napkins, corrugated boxes, and other grades of paper. One paper mill that makes dinner napkins was able to use recycled fiber exclusively and save $1 million that it had been spending for virgin wood pulp each year.
Buzyme® products make it possible to recycle more paper, produce paper more efficiently, and manufacture higher quality paper. Enzymes produce several benefits: enzyme biotechnology comes from renewable resources, is safe to use, and is itself completely recyclable. Use of these enzymes reduces requirements for chemicals derived from petroleum feedstocks. These enzymes are nontoxic to human health and the environment. They are produced by fermentation from readily available renewable resources. Although this technology has been studied in laboratories for some years, Buckman has recently found the keys to make it successful on a full-scale industrial basis.
Because chlorine is reduced, the amount of AOX is similarly reduced by up to 95%. Since its commercial introduction in 2002, Equinox® has treated over 36 billion gallons of paper mill water, eliminating the use of an estimated 2.4 million pounds of chlorine and preventing the generation and release of over 128,000 pounds of AOX into the environment. Equinox® is now used in paper mills throughout the U.S. and Europe. Equinox® has other uses as well, but in the papermaking industry alone it has the potential to eliminate the formation of 3.3 million pounds per year of AOX pollutants. By reducing the amount of toxic AOX compounds released into the environment, Equinox® provides an environmentally safer alternative to the historically high use levels of chlorine biocides.
EthosTM secondary backing, made from PVB film reclaimed from windshields and other safety glass, can replace other structured carpet backings such as poly(vinyl chloride) (PVC), ethylene–vinyl acetate (EVA), polyurethane, polyolefin, and bitumen. Producing ethosTM backing from recycled material reduces the energy and environmental impacts associated with extracting, harvesting, and transporting virgin raw materials. Tandus evaluated PVB against 10 other polymer-based materials using stringent performance and environmental criteria. In these tests, PVB was superior to the other polymers in material availability, recyclability, reduction of virgin resources, avoidance of hazardous emissions (e.g., dioxin), and elimination of chemicals of concern such as chlorine, fly ash, and phthalate plasticizers. In addition, ethosTM backing has extremely low environmental lifecycle impacts compared to other products.
Tandus’s patented, closed-loop process can also recycle postconsumer carpet with ethosTM backing and other manufacturing waste into new floor coverings. Initially, Tandus successfully introduced a six-foot-wide ethosTM cushion backing, Powerbond, to meet the needs of Kaiser Permanente for high-performance, PVC-free, soft-surface flooring. In November 2009, the company introduced ethosTM modular. Its production has increased 18-fold in the last two years. Every square yard of ethosTM modular replaces approximately 5.25 pounds of PVC in carpet backing. To date, Tandus has recycled more than 10 million pounds of PVB into flooring products, keeping PVB from landfills, and potentially replacing 52 million pounds of PVC.
Recently, Professor Bennett found that ethyl L-lactate, an FDA-approved food additive, can replace the hazardous solvents commonly used to synthesize imines. Her method is extremely efficient under ambient conditions and requires less solvent than published methods. It has a median yield of over 92 percent and a median reaction time of less than 10 minutes. The resulting imines are usually pure enough without recrystallization, avoiding additional waste. Professor Bennett’s method "tunes" the polarity of ethyl L-lactate by adding water.
The starting materials remain dissolved, but the imine crystallizes out of solution as it forms. Although traditional methods often drive reactions forward by removing water, Professor Bennett’s method drives the reaction forward by removing the product through crystallization. To date, she and her undergraduate research students have synthesized nearly 200 imines using this method; her students in teaching labs have made more than half of these in a green chemistry project. In summary, the ethyl L-lactate method is faster, usually results in higher purity and yield, uses less energy, uses less solvent, generates less waste, and uses a more benign solvent than published methods. A patent application for this method was published in 2011. Professor Bennett is now studying these imines in biological and other applications. All are fluorescent and some are photochromic. Several show promise as fluorescent cell markers and antibacterial agents.
A broadly applicable reaction using ethylene to install highly versatile vinyl groups enantiomerically could thus have significant impact in organic synthesis. Professor RajanBabu and his group have developed highly catalytic (substrate–catalyst ratio up to 7,412:1) protocols for nearly quantitative (isolated yields can be over 99 percent) and highly selective (approximately 100 percent regioselectivity; enantiomeric ratios of over 99:1) co-dimerization of ethylene and various functionalized vinylarenes, 1,3-dienes, and strained alkenes. These reactions proceed under mild conditions (-52 °C to 25 °C; 1 atmosphere of ethylene) to produce intermediates such as 3-arylbutenes, which can be transformed to nonsteroidal anti-inflammatory drugs (NSAIDs) in two steps.
These reactions consume both starting materials, leaving no side products. Successes include highly enantioselective syntheses of common NSAIDs, such as ibuprofen, naproxen, flurbiprofen, and fenoprofen, from the corresponding styrenes and ethylene. Cyclic and acyclic 1,3-dienes also undergo efficient enantioselective addition of ethylene. Syntheses of several 1-vinylcycloalkenes and 1-substituted-1,3-butadienes achieve yields up to 99 percent. Professor RajanBabu has found expeditious routes to biologically relevant classes of compounds including bisabolanes, herbindoles, trikentrins, steroid D-ring 20S- or 20R-derivatives, (-)-desoxyeseroline, pseudopterosin A–F, G–J, and K–L aglycones, and helioporins. These syntheses require fewer steps than traditional methods and produce uncommon configurational isomers. In 2010 and 2011, Professor RajanBabu published five papers on this work.
As the pigment–polymer composites in paint dry to a film, the pre-composite polymers keep the individual TiO2 particles separated so they are evenly distributed. Performance benefits resulting from improved film formation and reduced photodegradation (due to reduced TiO2, which promotes photodegradation) are expected to improve exterior durability by 20 percent. Third-party validated lifecycle assessment (LCA) shows that TiO2 reductions facilitated by EVOQUETM Pre-Composite Polymer Technology in exterior house paint reduce the associated carbon footprint by 22.5 percent, water consumption by 30 percent, NOX and SOX emissions by 24 percent, potential water eutrophication (algal bloom) by 27 percent, potential chemical oxygen demand (COD) by 30 percent, and non-methane volatile compounds (NMVOC) by 35 percent.
These last two factors impede water quality and air quality, respectively. EVOQUETM Pre-Composite Polymer Technology is currently compatible with white and pastel acrylics, which account for approximately 165 million gallons of U.S. paint produced annually. Based on TiO2 removal alone, using EVOQUETM Pre-Composite Polymer Technology in half of this paint could reduce associated greenhouse gas (GHG) emissions by approximately 54,000 metric tons of carbon dioxide equivalents (CO2 eq.). The enhanced performance and durability expected from paints with EVOQUETM Pre-Composite Polymer Technology could increase this reduction to 123,000 metric tons of CO2 eq., which is comparable to the annual CO2 emissions generated from the gasoline used by approximately 14,000 cars.
With the advent of the Montreal Protocol eliminating production of ozone-depleting substances, the search for substitute materials for common items including air-conditioning and fire extinguisher fluids has to be intensive. Work at the U.S. Army Edgewood Research, Development, and Engineering Center was directed at finding filter leak test materials that were not destructive to earth’s stratospheric ozone layer and were capable of rapidly identifying filter assembly problems. Materials investigated included several hydrogenated fluorocarbons (HFCs) of differing volatility. HFCs do not contain chlorine or bromine, which have been implicated as potent stratospheric ozone destroyers. Two HFCs were identified as substitute filter leak test vapors: 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-4310mee) for in-service filters and 1,1,1,2-tetrafluoroethane (HFC-134a) for new filters. These materials have been adopted by the U.S. Army to test the integrity of filters used to provide respiratory protection against chemical warfare agents.
These actions form foam that solidifies into a char and shields the underlying material to stop the combustion cycle. FIREBLOCKTM resin is a commercially viable alternative to bromine-containing fire retardant UPRs used in a wide variety of composites. It is completely free of halogens, mutagens, carcinogens, and reproductive toxins. In addition to meeting the same standards on materials fire behavior as do traditional fire retardants, FIREBLOCKTM intumescent resin also has a lower density than standard unsaturated polyester resins. It is environmentally friendly, with a 13 percent reduction in carbon dioxide (CO2) emissions compared to standard fire retardants in the railway industry. A significant portion of today’s estimated 10 million pounds annual use of brominated UPRs could be converted into FIREBLOCKTM technology in the next five years in the United States.
The initial results on the functionalization (oxidation) of alkanes/alkenes, using in situ generated fluorous phase soluble RfMn2+-RfTACN and RfCO2+-RfTACN complexes (Rf = C8F17) as the precatalysts, in the presence of t-butyl hydroperoxide (t-BuOOH) and O2 gas as oxidants, demonstrated that alcohols, aldehydes, and ketones could be produced catalytically and that the oxidation products and fluorous phase soluble precatalysts were indeed in separate phases. The fact that fluorocarbon solvents are relatively non-toxic provides the FBC concept with an entry to the new "Green Chemistry" regime of being environmentally friendly, and therefore, attractive to a wide variety of industrial processes for the ultimate catalytic production of important organic chemicals worldwide.
The soy protein and plant polysaccharides are feedstocks for a natural resin system that binds the fibers together into biocomposites. e2e’s biocomposite material is 3–4 times stronger than today’s wooden particleboard and MDF. e2e can mold its biocomposites into three-dimensional parts (i.e., net-shape them into whole, structural components) that replace traditional 4 x 8-foot sheets. Net-shaping can create stronger components by molding them as one part rather than assembling them from pieces. The e2e biocomposites also retain screws better than wood composites. These features combine to create stronger furniture while reducing the total amount of material and weight. e2e’s biocomposites are inherently fire-resistant because they contain a modified soy protein instead of petrochemical resins.
They use only 19 percent of the embodied energy of today’s products because the manufacturing process requires less energy and regionally integrated manufacturing minimizes transportation costs. Products made from today’s wood composites have a $100 billion market. e2e is replacing those products with higher performing, safer, more efficient, and more cost-effective biocomposite-based products. These products complement its proprietary biocomposite core with green, cost-effective coatings. Following successful pilot production in 2011 and responding to strong demand for its commercial office furniture products, e2e recently announced a 100,000 square foot manufacturing expansion.
It can also include a natural gum, a flavoring agent, a dye, a de-foaming agent, maltodextrin, and an oil. When the mixture is exposed to UV light, it cures and cross-links, but does not coagulate. Used on food, the nominated coating will inhibit oxygen exposure and increase shelf life. GRAS coatings on food packages will also resist grease and can substitute for polyethylene or other petroleum-based coatings. Ecology Coatings’ GRAS coating can also be used as a photoinitiator with conventional UV-curable materials that are approved for direct contact with food. GRAS coating components in powdered form not only promote UV curing but can extend the coverage of pigments.
In this use, the nominated technology could replace silica fillers. Finally, the GRAS coating can be used as a matting agent, which cures into the finished film and enhances the UV-curing process. Combined with other biobased additives, the GRAS coating can produce a rough surface that resists water and grease migration. In 2010, Ecology Coatings filed a patent application for this technology.
It offers a solution to printers who want to increase productivity without compromising the health and safety of their employees. BRIGL is the only wash on the market that effectively cleans conventional, heat-set, ultraviolet, electronic-beam, and co-cure inks, so that printers can use only one wash for an entire pressroom instead of the usual four to nine solvents. More important, unlike other "green" blanket and roller washes, BRIGL is easily implemented into the print production environment. Since BRIGL’s introduction in October 2006, over 50 full-time users have switched to it, and the list keeps growing. Premier printers who took part in Amerikal’s trial phase of BRIGL reported prolonged roller life, reduced overall consumption, a reduction in pressroom odors, and essentially no hazardous waste streams from blanket and roller washes.
Printers also discovered that BRIGL could be used for manual and automatic wash-up procedures, reducing consumption by 50–70 percent compared with traditional washes and cutting overall costs. With over 1,200 customers, Amerikal has used its vision, innovation, and initiative to redefine the standard for pressroom chemistry. Amerikal is the first and only pressroom chemical manufacturer dedicated solely to developing products that offset petroleum use; preserve natural resources; eliminate hazardous waste streams; and reduce global warming, energy costs, and pollution.
Cellulosic biomass is, therefore, an attractive feedstock for the production of ethanol-fuel and numerous other industrial products by fermentation. Although ethanol has been produced by the fermentation of glucose-based feedstocks with Saccharomyces yeasts since the pre-industrial age, the conversion of cellulosic biomass to ethanol presented a major challenge. This is because cellulosic biomass contains two major sugars (glucose and xylose), and the Saccharomyces yeasts cannot ferment xylose to ethanol.
Dr. Ho has developed genetically engineered Saccharomyces yeasts that not only ferment xylose but can also effectively coferment glucose and xylose to ethanol. The genetically engineered yeasts produce at least 30% more ethanol from cellulosic biomass than the non-engineered parent yeasts. Dr. Ho’s group has also recently found that their stable, metabolically engineered yeasts can repeatedly coferment glucose and xylose (using pure sugars or sugars from cellulosic biomass hydrolysates) to ethanol with high efficiencies for numerous cycles requiring very little nutrients. The technology outlined can easily be expanded to make yeast for the production of other important industrial products, such as lactic acid and citric acid, using glucose and xylose derived from cellulosic biomass as the feedstock.
Adding nanoparticles to propylene glycol–water mixtures improves their heat transfer by 48 percent. ACTA also improves the heat transfer of Paratherm® LR (a food-grade, heat-transfer oil) by adding alumina nanoparticles at 2 percent by weight and a surfactant. The nanofluid Paratherm® LR is a better heat-transfer fluid than either ethylene or propylene glycol mixtures. Because ACTA’s nanofluids increase the heat transfer rate of the ground loop in a GHP, the ground loop can be smaller and the GHP can pump less fluid. This technology reduces both the initial and lifecycle costs. ACTA manufactures nanoparticles by a pyrogenic (flame) process. The resulting fumed nanoparticles have large surface-area-to-volume ratios that increase the heat-transfer rate and decrease the thermal response time. They are hydrophilic, with hydroxyl groups over approximately 40 percent of their surfaces. They are easily removed from nanofluids for recycling. ACTA’s technology offers circulating fluids for GHPs without the harmful effects of ethylene glycol. These greener nanofluids could also improve the fuel economy of automobiles because radiators could be smaller with less fluid to pump. ACTA applied for a U.S. patent for their technology in 2011.
The GLDA manufacturing process is also waste-free. As a chelate for calcium, GLDA is more than twice as effective as Baypure® (i.e., sodium iminodisuccinate, IDS), a previous Presidential Green Chemistry Challenge-winning technology. GLDA is also stronger than many other common, readily biodegradable counterparts. GLDA offers an impressive human and ecological safety profile that is comparable to IDS, but IDS and other green chelates are made almost exclusively from petroleum feedstocks. GLDA has a smaller environmental impact than EDTA, NTA, and STPP because it uses a renewable feedstock, biodegrades rapidly, and lacks phosphorous. These attributes make GLDA ideal for applications including household and industrial cleaners and detergents, gas sweetening, metal and oil industries, personal care products, polymer production, printing ink, textile processing, and pulp and paper processing. Since late 2009, AkzoNobel has expanded its Lima, Ohio, plant and commercialized GLDA as Dissolvine® GL.
It both improves gas mileage and reduces greenhouse gas (GHG) emissions; with petroleum diesel fuels, it reduces up to 35 percent of particulates. It is useful as a fuel system icing inhibitor (FSII) in military (JP-8) and commercial (Jet A) kerosene-type jet fuel. GTBE can replace PRIST®, the existing jet fuel FSII, which is severely detrimental to human health. CPS is focusing on improving the efficiency of the E10 and E15 blends of biofuels for the existing energy infrastructure. GTBE fuel additives are compatible with the U.S. energy infrastructure, providing tremendous advantages over alternatives that require new production facilities or new engines for vehicles. CPS recently completed manufacturing trials, and testing of GTBE showed extremely efficient, essentially emission-free combustion and an octane rating over 120. GTBE has been commercially available as CPS PowerShotTM since January 2011.
Arkema developed and implemented a beneficial process change that replaced the H2S in its manufacturing process with sodium hydrosulfide (NaSH). NaSH is safer for workers, is subject to fewer air, water, and waste regulations, is comparable to H2S in price, and is readily available in consistently high purity. Further, changing to NaSH involved little or no change in facility air or wastewater permits or disposal methods for spent materials. The substitution of NaSH solution for H2S gas in the TGA process allowed the Alabama plant to eliminate the cross-country transportation of millions of pounds of an extremely hazardous and toxic chemical, reduce the risk of accidental release of a toxic chemical, and lessen risk management activities at the plant. The major advantages of this substitution were improved worker safety and a reduced risk of environmental releases. At the same time, Arkema realized higher production yields of 1 million pounds per year. In 2004, Arkema finished switching over to NaSH and made engineering modifications to increase its production capacity.
For NCA production, Sigma-Aldrich eliminated NCA recrystallizations and reduced manufacturing runs by over 30 percent. They reduced phosgene and tetrahydrofuran by 30 percent and ethyl acetate and hexane by 50 percent, which reduced hazardous waste. Finally, they increased consistency in quality and yield. Sigma-Aldrich also applied green chemistry to manufacturing poly-l-glutamic acid, a major drug-delivery polymer, which requires hazardous operations with hydrogen bromide–acetic acid or hydrogenation as well as highly flammable solvents.
Replacing a benzyl protecting group with an ethyl group allowed them to replace hazardous chemicals with water-based chemicals, decrease cycle time by over half, decrease energy use and greenhouse gas emissions, and improve the scaleup potential 10-fold. Sigma-Aldrich achieved similar savings with new processes for polylysine polymers and polyamino acid copolymers.
For polylysine polymers, Sigma-Aldrich used only half the previous amount of hazardous chemicals (dioxane, hydrogen bromide–acetic acid, and acetone), but increased the yield from 10–30 percent to 43–53 percent. Sigma-Aldrich halved production runs, which is saving hundreds of gallons of hazardous chemicals, generating less waste, and saving energy. They also switched polyamino acid copolymer production to water-based systems that eliminate benzyl bromide, a hazardous lachrymator byproduct. Sigma-Aldrich believes its contributions will lead to efficient chemotherapeutic treatments for diseases such as cancer, multiple sclerosis (MS), and diabetes and pave the way for greener chemical industry practices.
The main raw materials for Green PolyurethaneTM are polyoxypropylene triols and epoxidized vegetable oils. NTI also uses primary aliphatic diamines prepared by biomimetic synthesis in its production of Green PolyurethaneTM. Green PolyurethaneTM is a potential replacement for current, isocyanate-based polyurethanes, especially those polyurethanes in foams and coatings that contain free isocyanates in aerosol form after polymerization. Green Polyurethane’sTM unique formulation combines the best mechanical properties of polyurethane with the chemical resistance properties of epoxy binders. Green PolyurethaneTM coatings contain no volatile organic compounds (VOCs).
They are solventless, 100 percent solids-based, 30–50 percent more resistant to chemical degradation, 10–30 percent more adhesive with some substrates, and 20 percent more wear-resistant. These coatings can also be applied on wet surfaces and will cure in cold conditions. Insulating foam made from Green PolyurethaneTM provides energy savings of more than 30 percent, has one of the highest R values per inch of all insulation materials, does not require a primer, and has greater adhesiveness. In 2010 EPA added Cycloate A, a key binder ingredient in Green PolyurethaneTM, to the Toxic Substances Control Act (TSCA) Inventory following Premanufacture Review. NTI submitted a Premanufacture Notice under TSCA for its proprietary hydroxyalkyl urethane modifier (HUM). Also in 2010, Nanotech Industries began commercializing its hybrid non-isocyanate polyurethane UV-resistant coating technology.
Both of these systems also identify which of 475 state, federal, and international regulatory lists include each chemical constituent of a product. Both systems can complete green analyses in 10-30 seconds. Any industry, facility, or location can utilize these systems, which have been available on the Internet since November 2003. GP-CAS and G-MACS can reap economic benefits throughout the product lifecycle. Chemical Compliance Systems can readily customize either system for special requirements and maintain confidentiality. Incorporation of these green analyses into complementary analytical systems is underway (e.g., their MSDS retrieval and manufacturing–import–export systems). No other capabilities of this type currently exist.
Two patented technologies are highlighted: a) applications in radiopharmacy to allow the use of cleaner neutron-irradiated isotopes rather than fission-produced isotopes, and b) applications in remediation where reduction of secondary waste streams or conventional technologies are anticipated. The separations approach followed in developing these technologies suggest a wider industrial application for VOC-free separations. Within a paradigm of pollution prevention and with industry participation, a tool-box approach to Green Separation Science & Technology can be developed based on the use of environmentally-benign polymers.
As a result, the properties of these materials can be tailored for given applications which include reverse osmosis and gas separation membranes; high temperature membrane reactors; size and shape selective photolysis membranes; low temperature deep-oxidation catalysts; room temperature photocatalysts; and energy storage devices such as thin film batteries, ultracapacitors, and fuel cells. The Green Technology for the 21st Century: Microporous Ceramics program is illustrated using three examples: an indoor air cleaner for the complete oxidation of volatile organic compounds; an inorganic photoreactor for the size and shape selective synthesis of desired compounds with a minimum of waste; and, finally, an inexpensive, thin film ultra-capacitor which exceeds the U.S. Department of Energy"s near-term goal for this type of energy storage device.
Waste generation is a serious environmental issue with the traditional processes used to make adipic acid: the oxidation processes produce large amounts of nitrous oxide and organic wastes that must be disposed of or destroyed. For example, with the current technology, the production of 5 billion pounds of adipic acid also results in the production of 2 billion pounds of nitrous oxide. Nitrous oxide is a known greenhouse gas with a global warming potential 300 times greater than carbon dioxide and is also a suspected ozone depleter. It has been estimated that release of nitrous oxide from adipic acid manufacture accounts for 10% of the annual releases of manmade nitrous oxide into the atmosphere worldwide.
As part of Solutia"s program to search worldwide for new technologies to reduce or eliminate waste from its operations, the company initiated a partnership with Boreskov Institute of Catalysis in Novosibirsk, Siberia, to develop an alternative method for manufacturing adipic acid. This new process recycles the nitrous oxide waste gas and uses it as a raw material in the production of phenol. This eliminates either the direct release of this greenhouse gas into the atmosphere or the use of expensive, energy intensive CO2 greenhouse gas producing abatement processes. At the same time, the yield of phenol from Solutia"s new technology is very high. Furthermore, since the cost of this alternative method of producing adipic acid is lower than the commercial method traditionally used by the chemical industry, the process is both environmentally and economically sustainable.
A pilot plant demonstrating the process on a continuous basis was started at Solutia"s Pensacola Technology Center in May 1996. The unit has operated successfully since startup and provided the data currently being used in design of the full scale commercial plant. The new plant will utilize all of Solutia"s nitrous oxide (250 million pounds per year) to produce more than 300 million pounds per year of phenol. This revolutionary process represents the first major breakthrough in the production of phenol in more than 50 years. The new efficient process saves energy and eliminates the emission of massive amounts of greenhouse gases, while greatly reducing the production of organic wastes.
Blue Marble’s unique polyculture fermentation uses no genetically modified organisms and resists environmental stress. This fermentation can process low-cost, nonsterile lignin, cellulose, and protein-based waste byproducts from food, forestry, and algae companies without chemical or thermal preprocessing. Using these feedstocks for fermentation prevents landfilling or burning them and abates approximately 15.28 tons of carbon dioxide equivalents (CO2 eq.) per ton of feedstock. Compared to microbial systems that use carbon- and energy-intensive virgin or preprocessed plant materials, Blue Marble’s system recycles waste biomass, capturing the carbon it contains. In 2010, the company scaled up production to a commercial facility in Missoula, MT.
This facility is currently undergoing food-grade and kosher certification. It will operate at 100 percent capacity in the first quarter of 2012. Each year, it will use 860 wet tons of feedstock to produce 414,900 kg of carboxylic acids, esters, thiols, and other organosulfur compounds. An on-site water recycling system will reuse 75 percent of the water required for fermentation, saving 574,000 gallons of water per month. Finally, all biogas from the fermentation system will run through an algae remediation system to reduce facility emissions by scrubbing CO2 and methane. Blue Marble is working with several major manufacturers in the flavoring, food, and personal care industries and with Sigma-Aldrich Fine Chemicals toward global distribution of seven compounds.
This strategy minimizes hazards by operating at a small reaction volume, performing metal activation only once for each campaign, and using 2-methyltetrahydrofuran (2-MeTHF) as a Grignard reagent and reaction solvent that may be derived from renewable resources. Grignard reactions using 2-MeTHF also result in products with enhanced chemo- and stereoselectivity. Relative to batch processing, the continuous approach allows rapid, steady-state control and overall reductions up to 43 percent in magnesium, 10 percent in Grignard reagent stoichiometry, and 30 percent in process mass intensity (PMI). The continuous approach reduces reaction impurities substantially. In addition, small-scale operation at end-of-reaction dilution allows all ambient processing conditions.
Lilly is using its CSTR Grignard approach to produce three pharmaceutical intermediates. One of these is the penultimate intermediate of LY2216684.HCl, a norepinephrine reuptake inhibitor that is under phase 3 clinical investigation for treatment of depression. Lilly uses a similar approach to synthesize an intermediate for LY500307, an investigational new drug candidate under clinical evaluation to treat benign prostatic hyperplasia. Lilly anticipates commercial production on 22 liter scales that will replace the 2,000 liter reactors used in batch processes.