Grantee Research Project Results

Final Report: From Pollution to Possibility: A Sustainable and Interdisciplinary Solution to Biodiesel Production Wastewater

EPA Grant Number: SU835546
Title: From Pollution to Possibility: A Sustainable and Interdisciplinary Solution to Biodiesel Production Wastewater
Investigators: Crumrine, David , Lishawa, Shane C. , Waickman, Zach , Tuchman, Nancy C. , Abboud, Danielle , Dorger, Chad , Donald, Ryan , Herrera, Daniela , McGrath, Ainsley , Patel, Anup , Reese, Victoria , Shah, Mitali , Straitiff, Joe , White, Amber
Institution: Loyola University of Chicago
EPA Project Officer: Hahn, Intaek
Phase: II
Project Period: August 15, 2013 through August 14, 2016
Project Amount: $90,000
RFA: P3 Awards: A National Student Design Competition for Sustainability Focusing on People, Prosperity and the Planet - Phase 2 (2013) Recipients Lists
Research Category: Pollution Prevention/Sustainable Development , P3 Awards , P3 Challenge Area - Air Quality , P3 Challenge Area - Safe and Sustainable Water Resources , Sustainable and Healthy Communities

Objective:

Global climate change resulting from the anthropogenic combustion of fossil fuels, industrialized agriculture, and modified land-use practices, threatens the future of civilization by pushing conditions outside of a safe operating space for humanity (Rockström et al. 2009). Climate change is predicted to result in increased extreme weather events, regionally reduced fresh water availability, sea-level rise, increasing ocean temperatures, and ocean acidification (IPCC 2007). People will be particularly affected by an increased frequency of catastrophic weather events, destabilization of food supplies, and increased disease outbreaks (McMichael et al. 2003) leading to greater likelihood of conflict and violence with disproportionate impacts on the poor (Schwartz & Randall 2003). 

An increasing global water crisis is compounding the stresses that a changing climate is exerting on human and natural communities. Freshwater accounts for less than one percent of the planet’s water, the majority of which is unavailable for human and biological needs. The human population is estimated to reach over 9 billion people by 2050, exacerbating the stress of limited water availability. By 2025 nearly 2.5 billion people could be facing water scarcity in over 48 countries (Postel 2000, Sterling and Vintinner 2008). Every day, 2 million tons of sewage, human waste, and industrial effluents drain into usable water outlets (UN Water 2012). In developing countries, the main contributor to water pollution is the industrial sector; over 70% of industrial wastes are dumped into freshwater sources without primary treatment (UN Water 2012). In developed countries, sewage treatment is more advanced but incapable of removing many synthetic chemicals and non-target organic compounds that are increasingly found in waste water (Sterling and Vintinner 2008). 

As concerned citizens, educators, and members of a university committed to excellence in research, values-based leadership, service to humanity, social responsibility, and global awareness, we are compelled to address the global climate change and freshwater crises.

Summary/Accomplishments (Outputs/Outcomes):

The Loyola University Chicago, Searle Biodiesel Program

In 2007, a team of undergraduate students and faculty mentors seeking to take action against climate change, initiated the EPA P3 supported Loyola University Chicago Biodiesel Program (LUCBP) with the goal of reducing carbon emission and improving air quality. The use of biodiesel instead of petroleum diesel is one of the simplest actions to immediately decrease fossil fuel consumption. Biodiesel is an attractive alternative fuel because, it can be used in unmodified diesel engines; it can be produced safely and cheaply at very small scales; biodiesel combustion emits significantly less particulate matter, polycyclic aromatic hydrocarbons, carbon monoxide, sulfur dioxide and other forms of air pollution as compared to petroleum diesel fuel (EPA 2001) and; when farm production inputs are eliminated from biodiesel life-cycle analyses, Waste Vegetable Oil (WVO)-derived biodiesel reduces net greenhouse gas emissions by at least 85% as compared to petroleum diesel (data from Hill et al. 2006). The LUCBP has grown from a single class project into an institutionalized biodiesel production operation staffed by a full-time Lab Manager (a former biodiesel student) and several undergraduate interns. LUCBP continues to improve human well-being, promote economic development, and improve the environment by producing 2,500 gallons of WVO biodiesel per year, fueling the inter-campus shuttle fleet, improving air quality on campus and in our community, educating thousands of students and citizens, and generating revenue through fuel sales to support its operation. 

The production of WVO biodiesel requires the removal of solid contaminants from the oil before the metered addition of methanol and a catalyst (potassium hydroxide). The result is two aqueous layers with crude, contaminated glycerin separating from the biodiesel layer. The biodiesel is then stripped of any unreacted oils or excess chemicals with water and dehydrated with air bubbles. The LUCBP has consistently worked toward establishing a zero-waste process that utilizes all by-products for further biodiesel production or to create value-added products (i.e. soaps from the glycerin after an additional purification process). Although LUCBP has achieved a high-level of environmental and economic sustainability, the refinement process used to remove contaminants results in a contaminated waste product, biodiesel wash-water (BWW) contains a variety of pollutants including methanol, potassium hydroxide, and potassium salts of fatty acids (potassium soaps). Presently, LUCBP wash-water, and the wash-water of thousands of other small-scale biodiesel producers throughout the country, is minimally treated by neutralization with acid and poured down the drain. Therefore, waste-water management costs are treated as environmental externalities and shifted from producers to municipal wastewater treatment system, a practice which is unsustainable and unsatisfactory.

Proposed Projects

Phase 1 - Completed

Our Phase-I project focused on designing and constructing a biological wastewater treatment system to purify all contaminated wash-water in the LUCBP production process. The goals and objectives of our Phase-I project were to reduce the environmental impacts of biodiesel production to improve the health of people and the planet by: 1) designing, building, and conducting scientific research on a living system to purify biodiesel wash-water; 2) partnering with local biodiesel labs (e.g. High Schools and other Biodiesel Industry groups) to replicate and test the effectiveness of our living technologies; 3) providing Loyola University Chicago (LUC) students with invaluable scientific research and design experience testing the different components of a living machine, measuring chemistry throughout the treatment process, evaluating and enhancing the water treatment process, and designing the biological waste-water treatment system; 4) working with LUC’s Center for Math and Science Education to train ~100 Chicago Public School (CPS) teachers on water quality and sustainability modules, resulting in sustainability education reaching thousands of underprivileged, inner-city K-12 students; 5) creating a marketing and outreach campaign that includes: making a documentary film on the project, active marketing events on campus, presentations at LUC’s student research symposium, national scientific meetings, the annual Association for the Advancement of Sustainability in Higher Education conference and the P3 national mall presentation.

Phase 2 – Completed                                                                       

The goals of our project include: 1) Achieve the ultimate sustainability goal from our biodiesel production operations, zero-waste biodiesel production. We will evaluate our progress by continuing to monitor, measure, and record all energy and material inputs and outputs into our system. 2) Publish open-source, web-based plans for our ReAct Mobile Biodiesel Processor along with notes on a small-scale solar methanol recovery (SMR) unit for education, research, and for small-scale biodiesel producers. We will successfully achieve this goal when the plans are freely available online. 3) Leveraging our ReAct Mobile Biodiesel Processor as a teaching tool, create hands-on high school environmental curricula that demonstrates key environmental and physical science concepts. We will achieve this goal when the lessons have been incorporated in 5 Chicago high schools. 4) Complete research on hydroponic growth of Salicornia for salinity reduction and additional oil production. The success of this goal will be evaluated by determining the per/plant salinity reduction and oil production through well replicated scientific experimentation that involves growing Salicornia plants in several concentrations of waste water, evaluating pre- and post-experiment water and plant chemistry, plant biomass and growth, and oil seed production. 5) Develop a process and procedure for the reuse of methanol removed from biodiesel during production. This will be achieved when we have a final product, quality control procedures, and market testing completed. 6) Develop a process for the re-use of residual free-fatty-acids and contaminated biodiesel by conducting experimental acid catalyzed biodiesel production. We will evaluate the success of this goal by following established protocols for acid-catalyzation of FFAs and quantifying all inputs and outputs 7) Host a conference at LUC for the Collegiate Biodiesel Producers Network in March 2016. We will evaluate the success of this goal by quantifying the CBPN members who attend, conducting post-conference member evaluations. 

Continuing Research

The goals of this project going forward include: 1) Identify acid loving algae that can grow in our treated BWW and utilize the growth enhancing nutrients left behind by the biodiesel production and water treatment processes. 2) Complete a nutritional analysis of the most viable algae strains to select for balanced fat, carbohydrate, protein, and fiber content that is most appropriate for tilapia fish food. 3) Select other plants from the Loyola gardens to supplement and fill gaps in the nutritional value of the selected algae strain. 4) Conduct a study of tilapia growth rates and health fed on a diet of commercial food versus Loyola produced fish food made from algae. 5) Scale-up BW treatment system to both treat all Loyola BWW and provide fish food for the Loyola aquaponics systems.

Figure 1: Zero Waste Process Outline

Figure 2: Zero Waste Carbon Tracking

Figure 3: Carbon Capture and Solar Methanol Recovery Experimental Equipment                                            

Conclusions:

The development of a zero waste biodiesel production process hinges on the ability of the producer to minimize the creation of, and maximize the utilization of key byproducts. We have found the most challenging byproduct to fully utilize is the biodiesel wash water (BWW) resulting from the final polishing steps of the biodiesel production process. There is no inherent value in this by-product, so most processes will aim to minimize costs associated with its disposal. While our original concept of a biological treatment resulted in incomplete water treatment, we were able to identify the wash water by-products’ highest value use: nutrient solution. With a balanced treatment process that includes methanol recovery, fat removal, and pH balancing, the wash water by-product can serve as a nutrient solution for algal growth. This process in turn can return the water to a neutral pH and normal (tap water) nutrient profile, thus creating a closed water loop for biodiesel production.

Methanol Removal

On a small scale, BWW contains significant amounts of methanol (≤30%), soaps, and reaction products (biodiesel, free fatty acids, glycerin) trapped in a high pH environment. On larger production scale (industrial scale), the BWW profile remains the same save methanol which is recovered from the biodiesel prior to final polishing. Incorporating in-line distillation into a small scale process remains a challenge for small producers, but if the methanol is allowed to persist in the biodiesel when water is introduced for final fuel polishing then the methanol goes into solution with the water. This BWW is not treated in small-scale operations and is simply discharged to the local water treatment facility (or to the installed septic system). We recommend that methanol recovery be performed on biodiesel prior to polishing whenever possible. We have implemented this process in our own biodiesel production at Loyola University Chicago with great success. The resulting BWW is safer to handle (no methanol toxicity hazard), and recovered methanol has alternative uses. We have developed a windshield wiper fluid to utilize low purity, recovered methanol. This windshield wiper fluid uses 100% of our recovered methanol along with some additional water and blue dye. It has been tested in the lab and field tested in commercial shuttle bus service over a 3 month period. 

Salt Removal

The student researchers on this project spent a significant amount of time working on direct salt removal via a biologic medium. The salt removal utilized Salicornia virginica to sequester the potassium salts for later use. Through our growth trails we observed a significant reduction in potassium salts in our BWW, however further tests are needed to confirm the potassium has been removed from the system and is not accumulating in the soil. Dried, ground Salicornia was able to act as an ice melt for walkways, but did not perform well in comparison to commercial grain salt. The students on this research project had hoped that the added traction that the Salicornia biomass provided would make up for the slower ice melt rate. However, the level of grinding required to make the salts readily available for ice melting left the biomass too fine to provide measurable traction improvement. This treatment method was ultimately not pursued as the resulting biomass was not readily usable, and the total biomass required to scaleup the process was too large.

Fats Removal

With methanol removed from the BWW, we saw the next challenge was to lower the pH enough to allow reaction products (biodiesel, free fatty acids, and glycerin) to precipitate by breaking the potassium salt bonds. Current industry practice is to use highly concentrated sulfuric or hydrochloric acid for this task, however multiple small-scale commercial operators are voicing their concerns with the continued use of hazardous acids. We are now pursuing two different treatments options for the BWW: carbon gas captured from on-site equipment, and acids that can add to a positive water nutrient profile. Our first approach of neutralizing BWW with carbon captured from on-site equipment (namely boilers and generators running on 100% biodiesel) has shown promising results. We demonstrated, on a small-scale, that we are able to reduce acid use by 70% while reducing the Scope 1 (direct) emissions from our facility. This process simultaneously reduced the acid requirements, made nutrient positive acid treatment financially viable, and removed CO₂ from building emissions. We had hoped that with continued research we would be able to incorporate this process into our student-run biodiesel business by utilizing the emissions from our building’s boiler, but the infrastructure costs (especially retrofit of an existing facility) make scaling this approach infeasible. Our second approach of directly acidifying the BWW with nutrient positive acids proved to be viable, but more costly without the use of carbon emissions. Phosphoric acid was selected as our nutrient positive acid as the phosphorus left behind complimented the elevated levels of potassium already in the BWW from the biodiesel production process. We have shown we can achieve the precipitation of contaminants with phosphoric acid as is achieved with sulfuric acid in an industrial setting. This has the added benefit of adding important plant nutrients to the BWW. However, phosphoric acid can sell for as much as 8.5x the price of sulfuric acid, placing our treatment in direct conflict with current industry goals of minimizing costs associated with this treatment process. 

BWW Profile and Utilization

The final step in the process was be to complete a nutrient profile of the treated BWW. The nutrient profile showed that the treated BWW closely matched the ideal growth conditions for several acid loving algae strains, except for elevated levels of potassium and phosphorus. Both of these nutrients serve as growth drivers, and were not found at growth inhibiting levels. We are continuing with a series of experiments looking at our phosphoric acid treated BWW’s ability to serve as a growth medium for algae. A balanced process may deliver value, and cost savings, by growing lipid oils in the form of algae. Our current experiment is looking to identify acid loving algae that can grow in the acidified BWW and provide a balanced nutrient profile in their biomass so as to be useful as a fish food.

 

References:

• Intergovernmental Panel on Climate Change (IPCC). 2007. Climate change 2007, synthesis report: Contribution of working groups I, II and III to the fourth assessment report of the Intergovernmental Panel on Climate Change. Pachauri RK, and Reisinger A. (Eds.) IPCC, Geneva, Switzerland. pp 104.
• McMichael AJ. Campbell-Lendrum DH, Corvalan CF, Ebi KL, Githeko AK, Scheraga JD,
• Woodward A. 2003. Climate change and human health: risks and responses. World Health Organization/World Meteorological Organization/United Nations Environmental Programme, Geneva.
• Postel SL. 2000. Entering an era of water scarcity: The Challenges Ahead. Ecological Applications 10(4), 941-948.
• Rockström J, Steffen W, Noone K, Persson A, Chapin FS, Lambin EF, et al. 2009. A safe operating space for humanity. Nature. 461: 472-475.
• Schwartz P and Randall D. 2003. An abrupt climate change scenario and its implications for United States National Security. Prepared by Global Business Network, for the Department of Defense.
• Sterling, Eleanor, and Erin Vintinner. 2008. How much is left? An overview of the crisis. In Water Consciousness: How we all have to change to protect our most critical resource. Edited by Tara Lohan. (Independent Media Institute). 
• United Nations Water. 2012. UN Water Statistics - Water Resources. Accessed on March 18, 2013 at: www.unwater.org

Journal Articles:

No journal articles submitted with this report: View all 5 publications for this project

Supplemental Keywords:

Biodiesel, waste water, living system, carbon capture, education, alternative fuel, Chicago, emissions capture, waste reduction, halophyte, zero waste

Relevant Websites:

Biodiesel Program - LUC Exit

Progress and Final Reports:

Original Abstract

2014 Progress Report

2015

P3 Phase I:

From Pollution To Possibility: A Sustainable And Interdisciplinary Solution To Biodiesel Production Wastewater  | Final Report