VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD Carbon capture and culture ph in microalgal cultures 24.1.216 Marilyn Wiebe Sebastian Teir, Kristian Spilling, Jonna Piiparinen
Carbon Capture and Storage R&D Program (CCSP) 18 industrial partners, 9 research partners, 1.1.211 31.1.216 Volume: 15 M, main part of the funding from Tekes Targets Technological readiness for pilots and demonstrations Strong scientific basis for development of CCS http://ccspfinalreport.fi 11/11/216 2
Why algae? CO 2 is captured, but not necessarily stored (relatively short term). CO 2 is released when the biomass is converted to fuel or digested as feed. CO 2 may be stored longer term in novel chemicals. Many microalgae have higher growth rates than plants this means they can also capture more CO 2 than the plants Note: not all algae grow faster than plants! Feeding CO 2 can increase the rate of algal growth i.e. CO 2 is limiting in the atmosphere Industrial CO 2 (flue gas) and industrial fermentations (e.g. bioethanol) can provide CO 2 for algal growth. There are many studies on the toxicity and use of flue gases. Need to consider how to transport and feed CO 2. * Approximate µ of a limited variety of strains, based on published values CO 2 feeding and light limitation are not taken into account. 11/11/216 3
CO 2 supply for production of algae 1) Direct injection of CO 2 (e.g. flue gas) CO 2 diffuses passively across algal cell membranes injection of gas provides mixing and removes oxygen only the CO 2 which dissolves into the liquid is available to the cells and much CO 2 is lost to the atmosphere injection of flue gas causes a reduction in culture ph 2) Indirect feeding of bicarbonate solutions CO 2 is captured as bicarbonate in separate absorbers / scrubbers (aqueous or chemical, e.g. utilising cultivation medium) bicarbonate (HCO 3- ) requires transporters to cross the cell membrane bicarbonate should be fed at ph values above 7. The ph of the culture system is important when considering how to supply the CO 2 to the algae 11/11/216 4
Algal growth and extreme ph Most algal cultivation is carried out at ph values between ~6.5 and 8 can species which grow outside this range be exploited to better understand the options for CO 2 provision? For ph ranges both below 6 and above 8, there are several species which grow at relatively high rates (>1 d -1 ). Physiologically, there is no inherent benefit (improved solubility) or disadvantage (energy costs) to feeding either bicarbonate (high ph) or soluble CO 2 (low ph). Specific growth rate (day -1 ) 2.5 2 1.5 1.5 Euglena gracilis Growth at low and high ph Euglena mutabilis Coccomyxa anubensi Thalassiosira oceanica Heterocapsa triquetra 2 3 4 5 6 7 8 9 1 11 ph Thalassiosira pseudonana Thalassiosira oceanica Thalassiosira pseudonana Thalassiosira oceanica 11/11/216 5
Algal growth and extreme ph Using known acidophilic and alkaliphilic algae we wanted to measure the effect of ph on carbon uptake. µ and CO 2 consumption were determined at near neutral and extreme ph values Strain ph expected µ (d -1 ) Temp. ( C) Euglena gracilis UTEX753 3 ~1.1 * 23 Euglena mutabilis UTCC451 3 ~.8 * 23 Coccomyxa anubensis UTCC58 3 ~.4 23 Thalassiosira pseudonana CMP1335 9 ~1.8 23 Phaeodactylum tricornatum SYKE > 9?** 23 Chlamydomonas sp. CCMP2294 9 ~.4 4 * Olaveson & Nalewajko 2, Vaquero et al. 214, Chen & Durbin 1994, ** unpublished (SYKE), Søgaard et al. 211 11/11/216 6
CO 2 uptake and extreme ph growth Each of the species was able to grow at essentially the same rate at the extreme ph (ph 3 or ph 9) as at ph 6-7.5. Exception: E. mutabilis grew very poorly at ph 7 Biomass production was higher at ph 9 than at ph 7, but measurement could include inorganic precipitates Although the alkaliphilic algae could grow as well as acidophilic algae, they stopped growing earlier and did not produce as much biomass (diatoms not ideal for these conditions). 1 2.5 Specific growth rate (day -1 ).8.6.4 Coccomyxa sp. E. gracilis E. mutabilis.2 Phaeodactylum tricornutum Thalassiosira pseudonana Chlamydomonas sp. 2 4 6 8 1 ph Biomass (g/l) 2 1.5 1 Coccomyxa sp. E. gracilis E. mutabilis.5 Phaeodactylum tricornutum Thalassiosira pseudonana Chlamydomonas sp. 2 4 6 8 1 ph Specific growth rates and biomass concentrations achieved for acidophilic (fed 1.8 to 2.3% CO 2 ) and alkaliphilic (fed.4% CO 2 ) algae grown in stirred photobioreactors with continuous light at 23 C or 4 C (Chlamydomonas sp. only). 11/11/216 7
CO 2 uptake and extreme ph growth & CO 2 consumption Alkaliphilic algae produced less biomass than the acidophilic algae. At ph 7, supplementation of air with CO 2 did not enhance growth of the diatoms and CO 2 uptake was difficult to measure since they generally consumed less than 5% of the input CO 2. CO 2 feeding (1.8%) at ph 9 resulted in excessive precipitate formation. CO 2 (%) 2.4 2.2 2 1.8 1.6 E. gracilis T. pseudonana CO2 feed 1.4 2 4 6 8 1 Time (h) CO 2 output from cultures of E. gracilis (red) and T. pseudonana (blue) grown at ph 7.2 with continuous light at 23 C and sparged with 2.3% CO 2 (grey line). ph 7,.4% CO 2 ph 7, 1.8% CO 2 ph 9,.4% CO 2 ph 9, 1.8% CO 2 Alkaliphilic algae were thus fed air (.4% CO 2 ) and did not require additional CO 2 at ph 7 or 9. 11/11/216 8
CO 2 uptake and extreme ph CO 2 consumption Measurement of CO 2 consumption and specific growth rate both support the conclusion that uptake of CO 2 at ph 3 or bicarbonate at ph 9 can be very efficient.. CO 2 consumption was similar at ph 3 and ph 6-7 (except for E. mutabilis which consumed most CO 2 at ph 6) Total CO 2 consumption was similar at ph 7 and ph 9 (except for Chlamydomonas sp., which consumed most CO 2 at ph 9) Maximum CO 2 uptake (% input) 8 7 6 5 4 3 2 1 Coccomyxa sp. E. gracilis E. mutabilis Phaeodactylum tricornutum Thalassiosira pseudonana Chlamydomonas sp. 2 4 6 8 1 ph Alkaliphilic algae consumed a higher percentage of the fed CO 2 partly because they were fed less CO 2. However, E. mutabilis and Coccomyxa sp. when grown on air consumed only 38% of the CO 2, whereas the diatoms consumed >6%. Total uptake of CO 2 was higher for acidophilic algae. CO 2 consumed per day (g day -1 ) 1.4 1.2 1.8.6.4.2 2 4 6 8 1 11/11/216 ph 9
CO 2 uptake and extreme ph bicarbonate feeding Bicarbonate feeding (without air sparging) increased the uptake of CO 2 at both ph 7 and ph 9. Only 1-6% CO 2 was lost to the atmosphere. More CO 2 consumed per day and per gram biomass. Precipitation of magnesium salts still a problem at high ph. 3.5 12 3. 1 2.5 2. 1.5 1. 8 6 4 Growth and CO 2 uptake parameters for E. gracilis (blue, ph 7.3) and P. tricornutum (green, ph 9) grown in photobioreactors fed with either CO 2 in the gas stream (solid bars) or with sodium bicarbonate (open bars)..5 2. CO2 uptake per g biomass (g/g) Max. CO2 uptake (%) 11/11/216 1
CO 2 uptake and extreme ph bicarbonate feeding Improved CO 2 utilisation comes at a cost specific growth rate and biomass production were both lower than in cultures fed with gas. Accumulation of dissolved oxygen limits growth. Sparging with air results in loss of CO 2 to the atmosphere 1.8 1.6 1.4 1.2 1..8.6.4.2. Specific growth rate (/day) E. gracilis 2.3% CO2 E. gracilis bicarbonate P. tricornutum air P. tricornutum bicarbonate Max. biomass (g/l) CO2 uptake per day (g/day) 3.5 3. 2.5 2. 1.5 1..5. CO2 uptake per g biomass (g/g) 12 1 8 6 4 2 Max. CO2 uptake (%) Growth and CO 2 uptake parameters for E. gracilis (blue, ph 7.3) and P. tricornutum (green, ph 9) grown in photobioreactors fed with either CO 2 in the gas stream (solid bars) or with sodium bicarbonate (open bars). 8 5 1 15 2 Time (h) 11/11/216 11 Dissolved oxygen (%) 26 24 22 2 18 16 14 12 1 po2 bicarbonate po2 sparged STIRR 5 4 3 2 1 Dissolved O 2 in an E. gracilis culture fed with sodium bicarbonate (or 2.3% CO 2, green). Agitation was increased to reduce DOT at 3 times in the bicarbonate culture. Agitation (rpm)
CO 2 uptake and extreme ph conclusions Algae which are tolerant to either high or low ph are able to grow and consume CO 2 equally well in the extreme condition as they do at near neutral ph. For these strains, CO 2 capture is not critically dependent on ph. Alkaliphilic algae may capture a higher percentage of fed CO 2 than acidophilic algae Acidophilic algae can capture a lot of CO 2, even if the percentage of captured CO 2 is lower than for alkaliphilic strains. Bicarbonate feeding can be used to increase the proportion of CO 2 consumed, even at ph 7 but removal of dissolved oxygen is also important. Coupling of alkali scrubbers with algal cultivation should be further developed so that loss of CO 2 to the atmosphere from systems currently using direct injection of CO 2 can be reduced. Production strains are chosen based on a variety of properties, but their ph tolerance should be considered when planning the mode of delivery of CO 2. 11/11/216 12
Thanks to all collaborators in the project! Scientific Sebastian Teir Dorothee Barth Kristian Spilling (SYKE) Jonna Piiparinen (SYKE) Mona Arnold Technical assistance Merja Aarnio Toni Paasikallio Financial contribution 11/11/216 13
Microalgal research at VTT contact persons Heiko Rischer, Plant Biotechnology heiko.rischer@vtt.fi Laura Ruohonen, Metabolic Engineering laura.ruohonen@vtt.fi Marilyn Wiebe, Bioprocess Technology marilyn.wiebe@vtt.fi Jaakko Pere, Renewable Materials Jaakko.Pere@vtt.fi Mona Arnold, Green Solutions for Water and Waste Mona.Arnold@vtt.fi 11/11/216 14
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