Renewable Feedstocks: A Summary of the Biofuel Process PDF

CH3 Alternative Feedstock /Renewable Energy. Dr.Waseem Abu Oun RENEWABLE FEEDSTOCKS Image: Wikimedia Commons, Author: R. Möhler DAY 2 SESSION III www.greenchemistry-toolkit.org 4-DAY USE OF RENEWABLE FEEDSTOCKS A raw...

CH3 Alternative Feedstock /Renewable Energy. Dr.Waseem Abu Oun RENEWABLE FEEDSTOCKS Image: Wikimedia Commons, Author: R. Möhler DAY 2 SESSION III www.greenchemistry-toolkit.org 4-DAY USE OF RENEWABLE FEEDSTOCKS A raw material or feedstock should be renewable rather than depleting whenever technically and economically practical. Image: Wikipedia, Pongamia Pinnata Seeds  Topics To Be 1. Covered Energy and Feedstock Consumption 2. Petroleum 3. Renewable Feedstocks Biomass Feedstocks Carbohydrate Feedstocks Lipid Oils and Terpenes as Feedstocks Protein Feedstocks 4. Renewable Feedstocks as a Source of Energy 5. First, Second, and Third Generation Feedstocks 6. The Advantages and Drawbacks of Biofuel  RENEWABLE vs. DEPLETING FEEDSTOCKS Feedstock: A raw material to supply or fuel or industrial process. Renewable or Depleting is a question of time: A renewable resource is determined to be renewable if it can be replenished in a relevant amount of time. Image: Wikimedia Commons, Author: Fossil fuels are depleting because they cannot be Johnlacrosse replenished in a practical timeframe from vegetation. ENERGY CONSUMPTION: DATA AND PROJECTIONS Increasing world energy consumption since 1990. The graph includes a prediction for year 2035, where the projected energy consumption will reach 770 quadrillion British Thermal Unit [BTU]. Source: U.S. Energy Information Administration [U.S. EIA].  ENERGY FEEDSTOCK CONSUMPTIO N Oil, coal and natural gas remain the predominant sources of energy, but the use of renewables is still increasing. Source: Statistical Review of World Energy Increasing world energy consumption: 1970-2010. ENERGY FEEDSTOCK S SOURCES World energy consumption by source as reported in 2013. While the use of fossil fuels is still predominant, by 2013 there was an increase in the use of renewable sources of energy. Most renewable energy comes from biomass. Source: REN21 Renewables 2014 Global Status Report. WHAT ARE THE MOST COMMON FEEDSTOCKS TODAY? Image: Creative Commons WHAT IS PETROLEUM USED FOR? HOW IS PETROLEUM GENERATED AND USED? Biomaterials [Carbohydrates, Proteins, Lipids] Over llenni Highly Functionalized 1. Molecules High temperature, and pressure; mi a natural process of oil creation 2. Oil extraction and processing Petroleum Products [Hydrocarbons – highly reduced state] 3. Separation and oxidation, high energy input Functionalized Compounds [Olefins, Alkylchlorides] 4. Further functionalization, replacing reactive groups with functional groups of interest Highly Functionalized Molecules  Three major categories of reaction processes by which feedstocks are acted upon by reagents to yield products Petroleum hydrocarbon molecules are in a highly reduced chemical state and often must be oxidized to be used as a feedstock. The oxidation process consumes energy and often uses severe and hazardous reagents which are capable of oxidations of non reactive molecules. The majority of reactions for petroleum feedstocks are substitutions since reactive groups need to be replaced with the desired group. This process generates several byproducts, which oftentimes are considered a waste. HOW ARE PETROLEUM PRODUCTS MADE? 1. By using a fractionation column. 2. By oxidation (typically by a powerful oxidizing agent like chloride) and adding numerous additives. WHAT CAN BE MADE FROM ONE BARREL OF OIL? http://www.visualcapitalist.com/can-made-one-barrel-oil/ WHAT CHARACTERIZES AN IDEAL FEEDSTOCK? An ideal feedstock is renewable and poses no hazards to humans or the environment. An ideal feedstock can be converted to the desired product using only a few steps. The reaction gives a 100% yield and has 100% atom economy.  RENEWABLE FEEDSTOCKS Renewable feedstocks include the following materials: Biomass (algae, corn, switchgrass, poplar, willow, sorghum, and bamboo) Agricultural waste (ex. manure) CO2 WHAT CAN BE MADE FROM RENEWABLE FEEDSTOCKS? Defense and aerospace Automotive Household cleaners Adhesives Solvents Surfactants Coatings Polymers Fragrances Corrosion, inhibitors Fuels Dyes Electronics Agriculture Cosmetics Solder Pesticides Builders Housings Fungicides Chelating agents Displays Fertilizers Dyes Used in Academic Specialty Chemicals Pharmaceuticals Research Labs COMPANIES THAT MAKE BIO-BASED PRODUCTS Image: National Research Council. 2015. Industrialization of Biology: A Roadmap to Accelerate the Advanced Manufacturing of Chemicals. Washington, DC: The National Academies Press. https://doi.org/10.17226/19001.  BIOLOGICAL FEEDSTOCKS Organisms have provided a huge share of the materials used by humans throughout their existence. Biomass: Plant material generated by photosynthesis Biomass is the leading candidate to replace petroleum as a feedstock for the organic chemicals industry. Partially oxidized biomass material avoids expensive, and sometimes difficult oxidation steps in oxidizing petroleum Image: Wikimedia Commons, Author: Daniel Schwen BIOMASS PLATFORMS Biomass production in nature: 180 billion metric tons/year Only about 4% utilized by humans (food, ethanol, sweeteners) Carbohydrates Ligni Fats, proteins, terpenes, etc. n Building blocks for a diverse Nature’s richest source of Converted into polymers, chemical platform. aromatic carbon. Used in lubricants, and detergents. polymers, adhesives, production of phenolic chemicals. CARBOHYDRATE FEEDSTOCKS Carbohydrates can be used as feedstocks for chemical processes Carbohydrates are created in several forms: Sucrose sugar, C12H22O11, is squeezed from sugar cane as sap and is extracted from sugar beets and sugar cane with water. Starch, a polymer of glucose readily isolated from grains (such as corn) and from potatoes, and is readily broken down by adding water to produce glucose. Huge amounts of cellulose, which occur in the woody parts of plants, can be broken down to glucose with cellulase enzymes.  LIPID OILS AND TERPENES Lipid oils can be extracted from the Hydrocarbon terpenes can be tapped seeds of some plants. from rubber trees as a latex Volatile solvent n-hexane, C6H14 , is used suspension in tree sap. to extract the oils. Steam treatment and distillation are Solvents are distilled off from the extract used to extract terpenes from sources and recirculated through the process. such as pine or citrus tree biomass. Image: Wikimedia Commons, Marula - Sclerocarya birrea – Seeds, Author: Image: Wikimedia Commons, Rubber trees in Kerala, India, Author: Genet M.arunprasad  PROTEIN FEEDSTOCKS Grain seeds can be used as sources of protein. Grain seeds are generally used for food. They are potentially useful as chemical feedstocks for specialty applications. Transgenic plants can be used to make specialty proteins, such as medicinal agents. Image: Wikimedia Commons, Brown Flax Seeds, Author: Sanjay Acharya  HOW ARE BIOLOGICAL FEEDSTOCKS PROCESSED? ? Fermentation Microorganisms (aerobic, anaerobic) Enzymes Images: Creative commons  EXAMPLE: ENZYMATIC LIGNOCELLULOSE BREAKDOWN Lignocellulose is a complex polymer obtained from plant cell walls. It has many aromatic subunits. HO O O O OH OH OH O HO OH O HO O O O HO O OH O OH Lignin HO HO Plant Cell Wall O HO OH n O OH HO Hemicellulose OH O HO Plant Cell Wall O O O OH OH O HO O O O O HO O OH HO OH OH n O O Cellulose Plant Tissue O HO OH O OH HO O OH O O O O HO O O OH HO O MAIN INDUSTRIES FOR LIGNOCELLULO SE PAPER BIOETHANOL INDUSTRY INDUSTRY OH OH HO HO O OH O O OOH O O O O HO HO OH OH OH OH n n Cellulose Cellulose Plant Tissue Plant Tissue OH OH OH O HO O O O OH O HO OH HO HO OH n Hemicellulose Plant Cell Wall Lignin powder Bioethano l Burnt or Discarded LIGNIN: A SOURCE OF RENEWABLE ‘DROP-IN’ PLATFORM CHEMICALS O HO O O OH O HO HO O A Need of New HO Lignin Plant Cell Wall O O Technology: OH OH O O HO O Economical O O Sustainable O Selective HO OH Efficient phenol O O O The lignin structure includes aromatic HO OH O OH HO (ring) structures. O OH O O If it is broken down selectively, it can O O HO O O OH be a source of drop-in platform HO O chemicals such as phenol.  A DEPOLYMERIZATION STRATEGY FOR THE VALORIZATION OF LIGNIN With the addition of hydrogen and a selective catalyst, lignin can be broken down into phenols. Lignin Phenols EXAMPLE: PENICILLIN PRODUCTION USING FERMENTATION Penicillin antibiotics were among the first medications to be effective against many bacterial infections caused by staphylococci and streptococci. They are still widely used today, though many types of bacteria have developed resistance due to the extensive use. The secondary metabolite of a fungus - Penicillium chrysogenum - grows using a carbon source of glucose and lactose. Once the fungus reaches a stationary phase, it starts producing the antibiotic. REQUIREMENTS FOR A SUCCESSFUL FERMENTATION PROCESS Proper nutrients Sterile conditions Temperature regulation Oxygen level pH control The fermentation process is similar for other commodity products, such as antibiotics, insulin, ethanol, organic acids, vitamins and enzymes. THE TOP 10 CHEMICAL TARGETS (PLATFORM CHEMICALS FROM BIO- FEEDSTOCKS)  WHY USE RENEWABLE FEEDSTOCKS? Economic reasons: The inherent long-term tendency for petroleum price increases. A fluctuation of a few cents in the price of crude oil can result in massive price swings for downstream products. The constant decrease in cost of renewable resources. Scientific reasons: The constant improvement in quality of renewable feedstocks. Modern plant breeding. Genetic manipulation. Breakthroughs in catalysis (enzymes, etc.). Environmental reasons: Biological compatibility (to an extent). The use of waste streams (wood pulping, agriculture, etc.).  SOME POTENTIAL CHALLENGES OF USING RENEWABLE FEEDSTOCKS Feedstock cultivation Competition with food supply Land demand Nutritional needs Diseases Initial investment Harvesting method to maximise yields and minimise degradation of product Post harvest processing Product extraction and purification Product standardization Complexity Product storage, packing, and distribution New methodologies for alternative feedstocks WHAT ABOUT ENERGY FROM RENEWABLE RESOURCES?  ENVIRONMEN TAL CONSEQUEN CES At first glance, we might think that biofuels are inherently environmentally friendly, but is this true? That depends on how the biofuels are produced. Image: Flickr, Tribal Biofuel, Author: U.S. Department of Agriculture  ENVIRONMENTAL ISSUES Bioenergy can have positive impacts: Green house gas reduction (through fossil-fuel substitution). More agrobiodiversity, soil carbon increase, less erosion. But these impacts can also be negative: Green house gas from cultivation, soil carbon, life-cycle, direct and indirect land-use changes. Loss of biodiversity from land-use changes, water use, agrochemicals, erosion.  TYPES OF BIOFUEL First Generation Biofuels Grains are used to produce ethynol o Food versus fuel Second Generation Biofuels Using agricultural wastes lignocellulosics o Lignocellulosics for ethanol o Oils for biodiesel o Grasses These crops were not domesticated for use as biofuels Third Generation Biofuels (looking to the future) Algae FIRST GENERATION: THE CORN-BASED ETHANOL PRODUCTION PROCESS Grind up the feedstock so it can be easily and quickly processed. Sugar is dissolved out of the material. The sugar is fed to microbes that use it for food, producing ethanol and carbon dioxide in the process. Purify the ethanol to desired concentration. Images: Wikipedia Commons, Corncobs, Author: Sam Fentress; Wikimedia Commons, Biofuel Pumps, Author: Mario Roberto Duran Ortiz FOOD VERSES BIOFUEL: THE MATH To fill up an average 25 gallon SUV gas tank with ethanol requires the same amount of grain as it takes to feed 1 person for 1 year. Every person in the U.S. uses 500 gallons of gasoline per year. That means that each year, every person in the U.S. would use enough gasoline to feed 20 people for one year. There are 300 million people in the U.S. – if each person was using enough food to feed 20 people to run their cars, that alone would require enough grain to feed 6 billion people.  ETHANOL SUPPLY: THE EFFECT ON CORN SUPPLY AND ON GASOLINE SUPPLY  ETHANOL DEMAND AND CORN PRICES There is a large increase in demand for corn for ethanol production. Current production capacity is at over 5 billion gallons. This is projected to increase to over 9 billion gallons with plants currently under construction. Corn prices continue to fluctuate. Bushels of corn sold for over $8 (USD) each in July 2012. Graph: http://www.macrotrends.net/2532/corn-prices-historical-chart-data  TYPES OF BIOFUEL First Generation Biofuels Grains are used to produce ethynol o Food versus fuel Second Generation Biofuels Using agricultural wastes lignocellulosics o Lignocellulosics for ethanol o Oils for biodiesel o Grasses These crops were not domesticated for use as biofuels Third Generation Biofuels (looking to the future) Algae SECOND GENERATION BIOFUELS: CELLULOSIC FEEDSTOCK Switchgras Wheat Straw Hybrid Poplar Corn Stalks s Image, Wikimedia Commons, Author: David Hawgood SECOND GENERATION BIOFUELS To qualify as second generation, a feedstock must not be suitable for human consumption and meet the following criteria: Should grow on marginal (non-agricultural) land. Should not require large amounts of water or fertilizer. Certain food products can become second generation fuels when they are no longer useful for consumption: Waste vegetable oil (2nd generation feedstock). Virgin vegetable oil (1st generation feedstock). SWITCHGRASS AS A FEEDSTOCK Switchgrass still needs water Nutrients needed: and fertilizer to grow. corn versus switchgrass. Water Nitrogen fertilizer kg ha- 1 Corn Switchgrass yr-1 N 148 0 P 23 4 K 50 6 Data of Lee et al. and Muir et al, collated in Gressel, “Genetic Glass Ceilings, Hopkins, 2007 SECOND GENERATION BIOFUELS: OILS AND BIODIESEL Biodiesel refers to vegetable oil or animal fat-based diesel fuel consisting of long-chain esters. The main component of vegetable oil is triglycerides, which require transesterification prior to usage as a fuel. BIODIESEL  COMPARING THE ENVIRONMENTAL IMPACT Environmental Consequences Greenhouse Gas per Unit Energy Emissions per Unit Energy Soybean biodiesel needs less fertilizer Soybean biodiesel produces and pesticide than corn ethanol. significantly less green house gas. Data of Lee et al. and Muir et al, collated in Gressel“Genetic Glass Ceilings, Hopkins, 2007  ADVANTAGES OF BIODIESEL Reduces other pollutants. 35% reduction in unburned hydrocarbons through life cycle. Hydrocarbons are smog and ozone precursors. 8% reduction in sulfur oxides. The release of sulfur oxides can lead to acid rain. 3% reduction in methane. 32% reduction in particulate matter (PM10 68%). 83.6% reduction in particulate matter soot. 79% reduction in wastewater. 96% reduction in hazardous waste, but double the non-hazardous waste. Compared to conventional diesel processing, biodiesel requires additional processing and has a lower overall energy return. Energy return is one of the important parameters that enables engineers to evaluate the efficiency and viability of a process. Energy return describes the amount one can gain from the production verses the amount of energy input. Biodiesel lags far behind conventional diesel processing in this regard. STEPS REQUIRED TO PRODUCE BIOFUEL FROM SOYBEANS Retrieved: nancymeyersdesign.com  TYPES OF BIOFUEL First Generation Biofuels Grains are used to produce ethynol o Food versus fuel Second Generation Biofuels Using agricultural wastes lignocellulosics o Lignocellulosics for ethanol o Oils for biodiesel o Grasses These crops were not domesticated for use as biofuels Third Generation Biofuels (looking to the future) Algae THIRD GENERATION BIOFUELS: ALGAE FEEDSTOCK  WHAT IS ALGAE? Algae is a large and diverse group of simple, usually autotrophic, organisms that can have either unicellular or multicellular forms.  WHAT DOES ALGAE NEEDS TO GROW? Carbon dioxide Sunlight Water  IS ALGAE “GREEN GOLD”? Currently being developed. 30 times more oil per acre than current crops that are being used. No sulfur. Non-toxic Highly biodegradable, Not subject to a commodity risk like crude oil, corn, and soybeans are. ALGAE: THE PROS AND CONS Pros Cons Versatility in growth Energy intensive methods Not competitive against Versatility in uses foreign oil (yet) Speed of production Needs funding Potential for huge Technology not ready (yet) production levels CO2 reduction  HOW TO OVERCOME THE TECHNICAL ROADBLOCKS TO LOW-COST ADVANCED BIOFUEL PRODUCTION Make all of the components of biomass available for biofuel and co-product production: Use the appropriate parts of specific plants. Improve the efficiency of biomass to biofuel conversion: Do it faster, cheaper, and sustainably. Minimize the cost of biomass transportation. Move more for less. BIOFUELS AS AN ALTERNATIVE Biofuels are not THE answer to sustainable energy, but biofuels may be part of the answer. Biofuels may offer environmental and economic advantages over fossil fuels, but the magnitude of these advantages depends on how a biofuel crop is grown and converted into a usable fuel. TOPICS COVERED 1. Energy and Feedstock Consumption 2. Petroleum 3. Renewable Feedstocks Biomass Feedstocks Carbohydrate Feedstocks Lipid Oils and Terpenes as Feedstocks Protein Feedstocks 4. Renewable Feedstocks as a Source of Energy 5. First, Second, and Third Generation Feedstocks 6. The Advantages and Drawbacks of Biofuel  THANK YOU! QUESTIONS? This training material was developed in close collaboration with the Center for Green Chemistry and Green Engineering at Yale University. www.greenchemistry-toolkit.org