Sustainability in the Chemical Industry Grand Challenges and Research Needs (2006) / Chapter Skim
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Appendix D. Workshop Summary
Appendix D. Workshop Summary
Pages 103-155
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D Workshop Summary EDUCATION In the first item on the agenda, participants debated the value of green chemistry on the curriculum of the future and spoke about the challenges of rooting sustainability in both the curriculum and textbooks. The need to educate faculty, industrial scientists, and the general public was also discussed.
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looked at some trends in green chemistry education. The ACS Green Chemistry Institute is a strong advocate for green chemistry education.
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As a result, they do not get covered in the main body of the course. However, Organic Chemistry is very encouraging; Solomon's most recent edition has five different green chemistry examples embedded in the text.
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Inertia is also another challenge. Today's educators have not been trained in green chemistry; it was not part of the curriculum when many of today's working chemists and chemical engineers were in undergraduate and graduate school.
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Educators should consider this even as they teach organic chemistry. Many textbooks do not include the by-products.
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St. Olaf College not only received $500,000 from the Keck Foundation to integrate green chemistry into their curriculum, but they also were awarded $98,000 from the Kresge Foundation for the design of an environmentally friendly science center.
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It is the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture, and application of chemical products. He added that many people think green chemistry is just about organic chemistry.
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He listed atom economy, less hazardous chemical synthesis, safer chemicals, design for energy efficiency, renewable feedstocks, catalysis, and finally, design for degradation. From the pharmaceutical industry perspective, this is the biggest challenge.
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"To me, that is an irreducible responsibility of green chemistry and it is one that so far, I think, has not been adequately addressed," Allenby pointed out. Allenby said green -- not environmental science, but green -- is a fairly normative kind of concept.
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DEMAND AND PRODUCT DESIGN Lauren Heine gave the participants some background on GreenBlue, and cradle-to-cradle design. She talked about some of the drivers and obstacles for green chemistry, product formulation, and gave some examples of projects that are designed to facilitate adoption of green chemistry.
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How well the strategies will work 10 or 20 years from now is not clear, as there may be more important strategies to take. Heine then named some of the obstacles to integrating green chemistry into product formulation.
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114 APPENDIX D ments that everybody needs to use the same MSDS format, and they only have to report what is hazardous anyway. Technical fact sheets can be very useful to formulators, because they give an idea as to whether or not it is useful to try this ingredient, based on performance properties.
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APPENDIX D 115 the Government Through Waste Prevention, Recycling, and Federal Acquisition.
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116 APPENDIX D Heine went on to talk about a small formulating company, Coastwide Laboratories, in Oregon that has used a green chemistry strategy in developing their products. They have established positive criteria for product efficacy and environmental health and safety by creating a product development standard that is publicly available on their web site.
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From page 117... ...
But even a 10 percent conversion factor would be great for the pharmaceutical industry, Cue said, which has a conversion factor of less than one percent. The industry has always argued that they produce more complex molecules, through more complex synthesis, with lower overall yields, so it is no surprise that it would be like that.
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By applying green chemistry principles companies could see a dramatic reduction in waste, by an order of 10-fold. Cue lauded Glaxo for doing a very nice job in life cycle analysis, which not many pharmaceutical companies do.
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For example, Foster-Miller is a company that manufactures a military robot to investigate potentially hazardous materials, and the same technology allows them to design lab automation for the pharmaceutical industry for a totally automated, analytical laboratory. One of the challenges is the science of scale.
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Equipment cleaning is a further important field, as a large amount of solvent or water waste is generated in cleaning chemical and manufacturing equipment. Right now, spray balls are kind of the gold standard, at least in the pharmaceutical industry.
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In general, LCA starts by looking at the intensity of energy use or mass use or pollutant emissions, such as the kilograms of CO2 per kilogram of product, or by looking at the economic side -- the dollar value of production per megajoule of fossil fuel use -- as an eco-efficiency. These values can be quantified in life cycle analysis.
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Another route based on patents published by BASF, using hydrogen peroxide as an oxidant instead of chlorine, was also used. A typical result from a life cycle analysis might show the megajoules of gross energy consumed per kilogram of product.
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This means the most appropriate impact assessment methodology for chemical processes should be found. Helling credited BASF, who has done a superb job advocating for eco-efficiency analysis.
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STRUCTURE-ACTIVITY TOOLS Robert Kavlock talked about computational toxicology, which uses the best of modern chemistry, information technology, and biology to do a better job at assessing risk. He talked about how the EPA views this research strategy and presented some of applications the EPA is using.
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Chemicals are then tested against them to see the similarity with estrogen or androgen receptor binding. Kavlock talked about the national center for computational toxicology.
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126 APPENDIX D Likely focus areas are information technology and prioritization. "How do we get into that list of 850 pesticidal inerts and tell the agency, these 63 are the ones you should worry about, and you should worry about 21 of them for birth defects and 32 of them for cancer effects, and be able to put some kind of a priori knowledge in the system?
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It is a more comprehensive approach of structure activity relationships, Kavlock explained. Kavlock then talked about some of computer databases that are useful for computational toxicology.
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The key drivers for renewable energy and energy efficiency are energy security, climate change, air emissions, and then electrical liability. Public acceptance of renewable energy is large, but public understanding of it isn't.
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The Department of Energy's program is now focused on this point. Biomass is the only renewable source that produces carbon-based fuels and chemicals.
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The lignin and other residuals can be subjected to a thermochemical process, and a variety of chemicals can be produced from there. Bull said industry in general does not associate the word biomass and its possibilities with their products.
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There are several ways to produce hydrogen, Bull said. But if it is derived from natural gas, coal, gasification, or other forms, then all the problems that conventional fossil fuels have are not avoided.
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Technology is important, the industry will need incentives, things like the production tax credit, Bull pointed out. He gave wind as an example.
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If they were to grow sweet sorghum at $40 a ton, they would double their income. If they were to grow energy cane at $40 a ton, they would triple their income.
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134 APPENDIX D drawbacks. For example, it raises the vapor pressure of gasoline.
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The process is geared toward ethanol at the moment, as that is where the tax credits are. The calcium acetate solution is run over several steps to produce ethanol.
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ROUTES AND COMMODITY CHEMICALS FROM RENEWABLE RESOURCES Douglas Cameron spoke about Cargill's work in the area of green chemistry and sustainability. He also talked about two carbohydratebased examples of the chemistry bio-refinery, lactic acid, and 3hydroxypropionic acid (3-HP)
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Cargill is now the biggest producer of lactic acid, and its process utilizes a wide range of renewable sugars, including glucose. Lactic acid produced by an anaerobic fermentation, which means it is not energy intensive since oxygenation is one of the most energy intensive parts of fermentation.
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"So, there are opportunities to figure out what to do with that," said Cameron. He also mentioned that Cargill has a very active research program in polyurethane polyols, and there are some compelling reasons to make polyols from vegetable oils.
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Eighty percent of all manufacturing energy, and 80 percent of all manufacturing wastes, are associated with the processing industries. Today, even though the chemical processing industries are considered to be energy intensive, energy cost has not actually been a dominant economic factor, not even in distillation processes.
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140 APPENDIX D ability, concentration, extraction cost, competition for the material, other alternatives, and how close the raw material is in chemical or physical structure and in oxidation state to the product. The oxidation state of material is a particularly important factor, especially for carbon.
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APPENDIX D 141 purification is oftentimes an issue. Sometimes a proportionation reaction will form the desired oxidation state.
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There are 6,000 gigatons of fossil fuels available, counting the biomass, peat in the ground, unrecoverable reserves, but not including the hydrates. At some price more and more -- but not necessarily all -- will be exploited, growing to three times the current demand of seven gigatons per year.
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APPENDIX D 143 Solar energy must be collected and stored. It could be stored in atmospheric pressure gradients as is done for wind.
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They are made by fermentation from renewable resources, and the excess biomass waste is used as a soil conditioner and fertilizer. Enzymes can improve product quality and save water, energy, chemicals, and waste while speeding up production processes and enabling new products.
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To demonstrate that the environmental burden of making the enzyme is outweighed by its sustainable applications, Novazyme performed a cradle-to-grave life cycle analysis. For the analysis, the company compares two systems: a combination enzymatic/chemical system and an enzymeonly system.
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All factors point to novel enzymes that can be genetically engineered to be tailor-made to specific industrial processes. Enzyme candidates can be integrated into an expression host, characterized biochemically, and tested on the conversion of pretreated corn stover to ethanol.
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MEMBRANE PROCESSES William Koros talked about membranes and separation processes and their energy saving potential. He showed that this technology has great potential with the help of some examples; nevertheless, it is nonetheless still underdeveloped.
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This technology is a very powerful energy saver. As calculated by Koros, capturing a cubic meter of water using this technology costs about 6.7 kilowatt hours per cubic meter (assuming 33 percent energy efficiency)
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A new unit costs about $50 million, but membranes could cut both energy costs and the capital costs, Koros said. The problem is whether such a membrane actually exists.
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150 APPENDIX D However, cost is still a problem. This process is about a thousand times more expensive per square meter of membrane than the polymer process.
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GREEN CHEMISTRY FOR CARBON MANAGEMENT Klaus Lackner talked about the challenge of using fossil fuels, a new fuel economy, and how to intelligently and safely dispose of CO2 produced by the world's population. The situation of fossil fuels is precarious.
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Current consumption of fossil fuels is about 600 gigatons per year, which is equal to the entire standing biomass. But it is not clear if fossil fuel use will increase by three or four times as much in the coming century.
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APPENDIX D 153 has to be built, and CO2 emissions between now and 2050 must be held constant. It also means the establishment of an energy economy at the current, or double the current, size that will not emit CO2 while simultaneously allowing the current CO2-emitting energy economy to exist.
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Therefore, a device to capture the CO2 produced per person would be a factor of several hundred times smaller than one to collect wind energy for that same person. With the ability to capture CO2 from the air comes the option of either making hydrogen from fossil fuels and collecting the CO2 at the hydrogen plant or running your cars on gasoline and capturing an amount of CO2 from the air that compensates for the emission.
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The world may then no longer need fossil fuels if this alternative energy carrier to hydrogen can be used in a vehicle. The future might hold a spectrum of pure carbon to pure hydrogen and, in that spectrum, there is a fuel of choice that can be oxidized.
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