© 2015, Algenesis Corporation

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Biofuels

The Beginning 

All petroleum fuels today are created from ancient algae, as a result, any material made from petroleum can ultimately be made from algae oil - as long as the appropriate chemistry is applied, including fuel. There are many advantages to using algae in this market. Algae is a non-food plant source, it doesn’t compete with putting food on the table to produce products from it. It is one of the most resilient organisms in the world, able to grow on non-arable land, in salt water and wastewater feeding off of the nitrogen and phosphates which would otherwise act as pollutants, and in high heat, like the deserts out in New Mexico where Sapphire Energy built their full-scale test facility for photosynthetic algae production and oil extraction. And there are upwards of 40,000 strains of algae that we know of, which means potentially thousands of different, viable oils to choose from.

 

 

Achievements in Biofuels and the reality of the market  

In 2008 the price of Oil peaked at over $130 USD a barrel. Companies like Sapphire Energy, founded by our own Stephen Mayfield, began to show up in an attempt to enter the market at a price range they could compete with. Algae was the perfect source for this new wave of renewable and sustainable biofuel. The Algae biofuel industry was crushed in late 2014 as the price of oil fell to its lowest point at just under $30 USD a barrel. This put biofuels well out of reach for the newly forming algae industry. With all of the newly built infrastructure, improvements in algae cultivation, production, and strain development, the stage was set for algae to become a major player in the petroleum industry, it just needed the right market.

 

 Urethanes 

The Rationale and Chemistry

In 2016 the global polyols market was valued at 21.60 billion USD and a projection has the market reaching 34.0 billion USD in 2022.  The 2015 global green and bio polyols market was valued at 2.63 Billion USD and is projected to reach 4.71 Billion USD by 2021.  North America is currently the largest consumer of green & bio polyols. The U.S. is the largest consumer of green & bio polyols in North America. Corn and Soybean are primarily used as feedstock to produce bio-based polyols in North America. The demand for green & bio polyols in this market is driven by end-user industries such as automotive, packaging and furniture. The automotive industry in North America is the largest consumer of green & bio polyols. Almost 70.0% of vehicles manufactured by Ford Motor Company in North America contained seat components that use green & bio polyols. (Global Trends & Forecasts 2018)

 

Biobased and Natural Oil Polyols, NOPs. Compared to conventional petroleum polyols, the production of natural oil polyols produce 36% less global warming emissions, use 61% less non-renewable energy for a total of 23% less energy demand. NOPs are renewable – plant lipids (TAGs) typically have multiple degrees of unsaturation, excellent for the generation of polyols. NOPs, by virtue of the ester linkages, are biodegradable. NOPs, in general, are considered renewable.  NOPs derived from algae have the added value of being sustainable as algae cultivation utilizes high cell density, efficient use of nutrients does not require arable land and compete with food production, does not require potable water and photosynthetic cultivation removes carbon dioxide from the atmosphere producing 1850 gal oil/acre/yr yielding lipids with high concentrations of unsaturated fatty acid chains.

 

The reactive double bonds that are prevalent in algae lipids can be chemically converted into polyols.  Algae can also express molecules such as succinic acid that can be converted into renewable, sustainable polyols.

 

Early Polyols

Trial And Error 

Early approaches – Our prior focus was in cultivation, harvesting, extraction, and production of biodiesel from algae.  With the price of petroleum remaining so low, we sought out a new higher value product that could be derived from algae, particularly the lipids we were already used to producing.  We have expertise and facilities as chemists with no real experience with polyurethanes.  We first sought to modify lipids from articles in the literature and convert these into foams using their starting point formulas.  As members of the university, we rarely let something like the lack of experience stand in our way. We will learn as we go.

 

Foams – The good and the bad.  Given our limited experience with polyurethanes, our initial trials were all over the map and we had issues, not just with the chemistry but also the methodology in the preparation of foams.  We encountered issues with shrinking, reactivity, and mixing.  We studied the foams we produced and using the literature got better.  A couple of the trials produced rigid foams that got very hard and did not shrink.  This is where the idea for surfboard foam got started.

 

Dialing in the formulation and process

Lab experimentation – After visits and consultation with Arctic Foam, we developed a simple device for producing the type of foam samples that utilized much smaller samples of our precious polyols.  Through multiple rounds of formulation we began to create foams in the lab that had many of the characteristics of the foams required for surfboards.  To help us during this period of development we utilized simple testing methods such as foam density and low-resolution microscopy to help guide our experimental decision making.  The one thing about the lab scale is that it rarely translates to the production scale. This was no exception.  It would take one person working all week to produce enough purified polyol to make a single surfboard.  Here luck was with us as our laboratory formulation was close enough that we made a reasonably successful surfboard on the third try.

 

What we quickly discovered was that we needed to better control the quality and functionality of the foam and we also need to manipulate the production process and fine tune the chemistry in order to create a formulation that would consistently produce high-quality surfboard foam.  Early foams started to exhibit problems with bubbles being generated during the glassing phase.  This was overcome on the production scale by through specific additions to help homogenize the mixing.  The interaction between the team and Arctic Foam and was key to developing a material and a process to meet the exacting standards of the industry.  We felt that is approach was the key to our success.  We could utilize our strength in chemistry and benefit from experts in manufacturing to help overcome our deficiencies and develop meaningful products.

 

Sharing Our Story

Student Participation: As members of a research university, we strongly believe in creating new knowledge through the research enterprise, and transferring knowledge to others through education and outreach. We have engaged in developing coursework and specialty seminars, as well as providing opportunities for students to immerse themselves in independent, project-based learning. By bringing undergraduate students into the research lab, we were also creating a value added educational experience that is not possible in classroom alone.

 

Outreach: We also want to share our love of science and discovery with the public. Both out of respect for being funded with taxpayer contributions, and to broaden the participation of young people to explore STEM careers by getting them excited about our science. Our members collaborate with high school students locally through the Castle Park High Biodiesel and Algal Studies Group, and with students across the country through the UC’s COSMOS program. Each year we also showcase our work in the San Diego Festival of Science and Engineering and the San Diego Makers Fair.


Media/Awards: Our efforts have received local and national accolades. In 2015, the Del Mar Boardroom Show awarded the Algenesis/Arctic Foam algae-surfboard “Best Sustainable Advancement”.  The following year in 2016, undergraduates Jack Lee and Stephen Lo, and graduate student Marissa Tessman won first place at the UC Carbon Slam poster session for their contributions to algae-based rigid foam research. Algenesis has also been featured in over 35 media outlets, including Nat Geo’s Smart Cities: San Diego.

 

Soft Foams WHat are the new challenges?

Difference between rigid and soft foams – One-way polyurethane foams can be categorized is their being rigid or soft foams.  As the two categories imply, these are solid gas mixtures that vary in density and structural strength and flexibility.  Rigid polyurethanes are primarily used by the insulation industry or surfboards, whereas soft foams are used mostly for cushioning (think furniture or car seats) and packaging.  

By manipulating the chemical composition of the polyols, we can create two types of phases: hard and soft.  These differ from each other based on flexibility and polarity.  The chemistry litany of “like dissolves like” applies here.  The harder, polar phases tend to align with each other and the more flexible nonpolar phases align together, creating structures within the foam.  By manipulating the phase separation and the organization of these structures, along with the cell size and density of the material, a wide range of finished product characteristics can be achieved.

 

No direct drop in formulations.  A “direct drop-in” is a material that can be inserted into a formulation to substitute for another component.  In the case of polyurethanes, the bio-based polyols are often different enough in their characteristics that they are not a direct drop in.  This is where Algenesis hopes to bridge a gap.  We propose to understand the impact of bio-based polyols on foam formulations and to devise new formulations that allow the use of the bio-based material to create a finished product of comparable or superior quality that is compatible with existing production parameters when possible.

 

Miscibility and Viscosity.  The miscibility, the ability to mix, and the viscosity, the resistance to flow, are two key physical properties of the formulation required to make high-quality foam compatible with typical polyurethane manufacturing processes.  The chemical basis of the polyols derived from petroleum and bio-based sources are different and prevent them from being a direct drop in and will require different additives to modify the miscibility and viscosity to produce the desired foams from bio-based sources.  This is the key expertise provided by Algenesis.

 

Data-Driven Metrics

What we lack in expertise in the area of petroleum polyurethane chemistry and manufacturing is not a complete liability for us at Algenesis.  There is not a wealth of prior knowledge about the use of the bio-based polyols.  We use the strength of our chemical knowledge along with a data driven approach to our experimentation to guide our development of the proper changes in formulation required to utilize bio-based polyols.  We started very simply with just measuring the bulk density and observing the cell structure under low resolution microscopy. This taught us a lot about the ratio of solids to gas and the structure and uniformity of the cells.  For rigid foams we also used a Shor hardness test to quantitatively measure the hardness of our rigid foams.

 

Moving up in sophistication, we used our outstanding facilities in Infrared spectroscopy and high resolution mass spectrometry to uniquely examine the chemical make-up of the polyol component.   These tools have allowed us to understand far better what is going on at the molecular level and guides our thought processes in formulation.

 

Our latest addition is the addition of force testing so that we can understand the relationship between the forces applied to a foam sample and the compression of the foam over a single or multiple compression cycles in either a static or dynamic mode.  These metrics not only allow us insight into are formulation process but also gather the data needed to deliver to the end user.  At Algenesis, we believe measurement is the key to understanding.

 

Flip Flops

We chose flip flop foam as our next project in commercial polyurethanes.  The flip-flop is a low-performance shoe which we, with no shoe experience thought would be a good entry point for us.  In addition, we also felt that flip-flops were from a marketing point of view, a product where there would be consumer interest despite an increase in the cost of the raw materials.  Our hope was that this cost increase would be offset by green consumers interested in carbon sequestration, and a renewable, sustainable casual shoe.  This we felt was certainly true in Southern California where the flip-flop is the unofficial shoe.

 

From an environmental point of view, after plastic bottles, polyurethane shoes, typically in the form of sandals and flip-flops, are among the most common forms of plastic pollution.  Our goal is to make a renewable, sustainable, biodegradable flip-flops that can not only serve as casual shoes for the SoCal lifestyle, but also be used to make the type of inexpensive footwear used worldwide that would reduce carbon dioxide in the atmosphere and not represent a long-term waste disposal problem.

 

The value to our students is that they are actively engaged in student-driven, project-based learning.  The Chancellor at UC San Diego started an 8-word campaign to describe UC San Diego. Student-centered, service-oriented, research focused public university. At Algenesis, we strive to make UC San Diego this type of institution by engaging our students in making the materials and products of the future derived from algae and other renewable, plant-based sources.

 

The Future

We have only begun to explore the biobased materials space. With respect to lipids, we will explore other PU applications such as coating, adhesives, sealants and elastomers, CASE. There are also other polymeric materials that can be derived from the base chemicals created through algal cultivation such as polyamides and polyesters. Another area we are currently looking at is nondiisocyante alternatives to making polyurethanes.  Diisocyante is toxic and is a health concern for the workers. We plan to build on the work that won Hybrid Coating Technologies the Green Chemistry award, developing nondiisocyante polyurethanes, NIPUs.  This not only makes the handling and manufacturing safer for all but it also addresses increasing the % renewability of the polyurethanes as we are developing these materials from non-petroleum sources to make the resulting polyurethane near 100% renewable.

 

We are only getting started and we tend to have no fear when it comes to using our imaginations to create the renewable, sustainable materials of tomorrow.