Patent Application
20140318000
The invention relates to the field of culturing algae and use of algae-derived products. The invention also relates to the reduction of CO2 emission and to a composition of a combined absorption liquids and algae growth medium useful for culturing algae.
Commercial and industrial algae cultivation has numerous uses, including production of food ingredients, food, fertilizer, bioplastics, dyes and colorants, chemical feedstock, pharmaceuticals, and algal fuel.
Water, carbon dioxide, minerals and light are all important factors in cultivation, and different algae have different requirements. The basic reaction in water is:
carbon dioxide+light energy+water=glucose+oxygen+water
The current method for culturing algae is to feed CO2 to an algae system by bubbling CO2 through a bioreactor. For an effective contacting of the CO2 with the liquid phase a considerable amount of energy is required.
There are two main bioreactor types that are being used to cultivate algae, these are open pond reactors and closed bioreactor, the latter are also referred to as photobioreactors. With respect to the photobioreactors, there are two main types and these are tubular reactors and flat panel reactors.
The two most important commercial production processes are using the alga Chlorella and the alga Spirulina for food supplements. In 2004, China alone produced around 40 000 tons of Spirulina, worth about 17 million United States dollars (USD).
The costs of nutrients, and especially the carbon nutrients which account for 10-25% of total operation costs, is a major component of the final production costs of Spirulina biomass.
For commercial production in open race-way ponds some CO2 is obtained from passively absorption. For most commercial production process other kinds of carbon sources (waste, bone meal, etc.) are used, instead of contacting with CO2.
One way of cutting down costs on carbon nutrients is to use carbon sources obtained from by-products of for instance coal-fired power plants or biodegradable waste. For instance, human and animal waste has been used. Although such by-products themselves are generally freely available, storage and transport of waste or other by-products, such as bone-meal, are costly.
Therefore, a continuous source of inorganic carbon, present nearby the algal culture farm is preferred. Such continuous source can, for instance, be provided by gas from a coal fired power plant or from a biogas plant. The CO2 production in a coal-fired 500 MW power plant is well over 2.5 million ton of CO2 per year.
A major advantage of using CO2 exhaust from a power plant in the culturing of algae is that less CO2 is emitted into the atmosphere. As CO2 is a so-called greenhouse gas contributing to global warming, use of CO2 from flue gas in algal culture decreases the amount of greenhouse gas emission and thus contributes to a reduction of global warming on the long term.
There are several review papers providing a good overview of the main aspects required for an efficient algae system for biofixation of CO2, including for instance the optimal type of photobioreactor (Ugwu et al., Bioresources Technology 2008, 99, 4021-4028), combining CO2 biomitigation and energy production (Wang et al., Applied Microbiology Biotechnology 2008, 79, 707-718), operational aspects of photobioreactors (Jacob-Lopes et al., Chemical Engineering Journal 2009, 153, 120-126), and the production of bio-fuels from microalgae (Brennan et al., Renewable and Sustainable Energy Review 2010, 14(2), 557-577).
The use of algae in bioconversion of CO2 from flue gas is known (e.g. Doucha et al., Journal of Applied Phycology 2005, 17(5), 403-412; Stewart et al., Energy Conversion and Management 2005, 46(3), 403-420; and De Morais et al., Energy Conversion and Management 2007, 48(7), 2169-2173). However, for direct injection of millions of tons of CO2 per year (which is about 40 000 litre of CO2 per second) into an algal pond, an open pond in the order of 5-10 km2 of area is required. Therefore, typically, the landmass needed for algal ponds, but also development of supporting systems, like CO2 injection systems (Benemann et al., Proceedings Second Annual Conference on Carbon Sequestration, May 5-8, 2003, Alexandria, Va., USA), restricts the use flue gas as a carbon source for algal culture. There is thus a need for other methods capable of using flue gas or biogas, but requiring much smaller areas of land or smaller bioreactors.
The invention provides a method for advantageously combining an aqueous absorption liquid for capturing CO2 with a growth medium normally used to cultivate algae in order to efficiently combine capturing of CO2, e.g. from flue gas, and bioconversion thereof by algae.
Absorption liquids capable of removing CO2 from flue gas are known and widely used. On a large scale, CO2 capture is performed with an absorption-stripping process using different types of solvents, including amines and amino acids. The regeneration of the solvent loaded with CO2 is done by heating the solvent, and this is the most energy consuming step for the full carbon capture and storage chain. Thermal regeneration of the solvents accounts for about 75% of the operational cost for the absorption-stripper process. It is estimated that sequestration of CO2 costs about 50 USD per ton, about three-quarters thereof are needed for thermal regeneration of the solvent, which amounts to approximately 100 million USD for a 500 MW power plant. It is estimated that the costs amount to about 10-25% of the total operational costs of a power plant. There is thus clearly a need for a more efficient way of regenerating of solvents.
By combining algae growth with CO2 capture it is to be expected that CO2 capture will become more efficient. There will be a clear reduction in the operational expenditure (OPEX), because the regeneration of the solvent normally done by heating the solvent well above 100° C. is now performed by the algae at ambient temperature. Furthermore, sulphur and nitrogen containing products, such as SOx and NORx which are considered environmental pollutants that are responsible, for instance, for acid rain, can be converted and beneficially used for algal production. The present invention thus provides a method that efficiently combines the reduction of CO2 emission with growth of algae.
Accordingly, in a first embodiment the invention provides a method of promoting growth of algae using an absorption liquid comprising carbon dioxide, the method including the steps of:
In a method of the invention, it is important that the CO2 can be “stored” in the absorbent liquid solution. The CO2 is chemically bound and will therefore not be released to the atmosphere as easily when compared to CO2 dissolved in water. Accordingly, it is preferred that the absorption of CO2 by the absorbent liquid leads to chemically bound CO2. It will thus be possible to have very high CO2 capture efficiency as compared to, for instance, when CO2 is bubbled through an aqueous growth medium. One advantage of the use of an absorbent liquid is that, e.g. when using an open pond, considerable loss of CO2 from the open pond is avoided. Second, a method of the invention enables regeneration of the absorbent liquid solution without using high amounts of energy, used in conventional methods of regeneration, described above. Preferably, the algal culture chemically converts the carbon dioxide from the absorbent liquid.
CO2 capture by an absorption process is one of the most common industrial technologies today and absorbent liquids for capturing carbon dioxide are well-known in the art. Alkanolamines are the most commonly used chemical absorbents for the removal of acidic gases today, but many other chemical absorbents are known to the person skilled in the art.
A method according to the invention can be operated both in continuous operation, and batch-wise operation.
In a preferred embodiment, a method according to the invention is provided, wherein
in step (1), a gaseous stream comprising carbon dioxide, preferably flue gas or biogas, is contacted with a liquid stream of absorbent liquid,
in step (3), the liquid stream is added continuously to the algal culture, and the method further comprises the step of:
When steps (1), (2) and (3) are performed simultaneously, the gaseous stream is added to an aqueous solution comprising the absorbent liquid and the algae. In such a method it is, for instance, possible to continuously add CO2 to a bioreactor comprising algal and absorbent liquid. The absorbent liquid prevents loss of CO2 as it efficiently captures the CO2 within the algal culture medium. Simultaneously, the algae convert the captured CO2, thereby regenerating the absorbent liquid. When, after a certain period of use, the algal concentration becomes too high, the algae can be harvested and the bioreactor with liquid and (new) algae be reused in the process. In a preferred embodiment, a method according to the invention is provided, wherein steps (1), (2) and (3) are performed simultaneously. Advantageously, this not only saves time, but also saves costs, because costly separate desorption can be avoided.
In another preferred embodiment, a method according to the invention is provided, wherein
in step (1), a fixed amount of carbon dioxide is first added to a batch reactor containing a fixed amount of an absorbent liquid, and
in step (2), the fixed amount of absorbent liquid is allowed to absorb the carbon dioxide for a fixed period of time before in step (3), said absorbent liquid is contacted with the algal culture.
In this configuration, the CO2 is first stored in an absorbent liquid before the solvent comprising the CO2 is added to an algal culture. One advantage is that, for instance, before adding the liquid to the algal culture, quality checks or purification steps can be performed on the liquid. Another advantage is that high concentrations of CO2 can be stored in relatively small volumes of liquid before the liquid is diluted in the algal culture medium.
In a more preferred embodiment, however, a method according to the invention is provided wherein
a fixed amount of carbon dioxide is added to a batch reactor containing a fixed amount of absorbent liquid, growth medium and algae, and the carbon dioxide is allowed for a fixed period of time to be absorbed by the absorbent liquid and to be converted by the algae, before harvesting said algae.
This configuration of batch-wise operation has the advantage that it is easy to reuse the aqueous absorbent liquid by first harvesting the algae from the batch reactor and just adding fresh algae and nutrients before adding a new fixed amount of CO2. In a preferred embodiment, a method according to the invention is provided wherein the regenerated absorbent liquid is reused in the method.
In a preferred embodiment, a method according to the invention is provided, wherein the CO2 captured in the absorbent liquid is from flue gas, preferably comprising between 4-25% CO2 and this amount of CO2 is balanced mainly by nitrogen (70-91%) and some impurities (<5%) at atmospheric conditions. In another preferred embodiment, a method according to the invention is provided wherein the CO2 captured in the absorbent liquid is from biogas, preferably comprising between 20-50% CO2, balanced by methane (45-75%) and some impurities (<5%), at a pressure of between 1 and 20 bar.
One way to operate a method according to the invention is to make use of algae that can tolerate a high pH, a good example is Spirulina Platensis. An absorbent liquid with high pH are able to absorb more CO2 than an absorbent liquid with neutral or even acidic pH. This is because, at alkaline pH, e.g. 8.0 and higher, the equilibrium between gaseous CO2, HCO3− and CO32− is shifted more to the right, enabling more CO2 to be taken up by the absorbent liquid at equal partial CO2 pressure. In all cases, the absorbent liquid can be fresh (no CO2 present), partially loaded with CO2, or saturated with CO2.
In a preferred embodiment, therefore, a method according to the invention is provided, wherein the absorbent liquid has a pH of 8.0 or more, preferably of 8.5 or more, more preferably of 9.0 or more, more preferably of 9.5 or more, most preferably of 10.0 or more.
In order for the algae to grow in an alkaline environment, which is beneficial for the absorption of CO2, the algae must of course be tolerant to such alkaline pH. In a preferred embodiment, therefore, a method according to the invention is provided, wherein said algae tolerate a pH of above 8.0, preferably above 8.5, more preferably above 9.0, more preferably above 9.5, most preferably above 10.0. The term “tolerant” is meant to indicate that the algae are at least not irreversibly damaged. Preferably, the algae do not deteriorate in said alkaline absorbent liquid. More preferably, the algae are able to thrive in an environment with a pH of above 8.0, preferably above 8.5, more preferably above 9.0, more preferably above 9.5, most preferably above 10.0. Preferred examples of algae which flourish in alkaline pH, i.e. a pH of above 8.0 or higher, are Spirulina platensis, Neochloris oleoabundans, Chlorella vulgaris, or Scenedesmus obliquus. The skilled person is aware of the effect of alkaline pH on other algae species and is able to choose a species that is suitable for use in a method according to the invention.
For some specific applications of the invention, other characteristics of algae may be very useful. For instance, algae tolerant to other constituents of flue gas, such as NOx and SOx, or of biogas, such as methane, may be very helpful in avoiding the need for pre-removal of these constituents. Also the capability to grow in temperatures well above 40° C. may be very useful, as for such algae, no strict temperature control of the absorbent liquid, which is generally heated up by the flue gas, is needed before adding the liquid to the algae.
For a good integration of the algae cultivation process and the absorption process on a large scale, different kind of activators for the absorption process can be used.
A carbonate solution, like sodium carbonate can be used to enhance the transfer of CO2 from the gas phase to the liquid phase (Hsueh et al., Chemosphere 2007, 66(5), 878-886). An amine, like monoethanolamine or an amino acid, like β-alanine can be used to enhance the reaction rate of CO2 binding in the amine or amino acid solution. Different activators that may be used in a method according to the invention are for instance listed in Table II.
For the chemical absorption of CO2 in a primary amine solution, like monoethanol amine (MEA, C2H7NO, 2-amino-ethanol) two reactions are relevant:
1) Carbamate formation from CO2 and MEA (HO—CH2—CH2—NH2): CO2+2HO—CH2—CH2—NH2→HO—CH2—CH2—NH—COO−+HO—CH2—CH2—NH3+
2) Bicarbonate formation for conditions with 6<pH<11: CO2+HO—CH2—CH2—NH2+H2→HCO3−+HO—CH2—CH2—NH3+
Amino acids may be used for CO2 capture. The term “amino acid” as used herein is meant to refer to all organic substances which contain one or more amine groups and one or more carboxylic acid groups and/or sulphonic acid groups. Hence, the term amino acid is meant to include, for instance, taurine which has a sulphonic acid group rather than a carboxylic acid group. The acid groups can be bound to one and the same atom of the organic substance (as is the case with the naturally occurring amino acids) or to different atoms. A preferred compound for capturing CO2 is taurine (C2H7NO3S, 2-aminoethanesulphonic acid), which surprisingly yields better results than amino acids containing one or more amine groups and one or more carboxylic groups.
Also, for amino acids two reactions are relevant for the binding of carbon dioxide:
1) Carbamate formation from CO2 and taurine (HO—SO2—CH2—CH2—NH2): CO2+2HO—SO2—CH2—CH2—NH2→HO—SO2—CH2—CH2—NH—COO−+HO—SO2—CH2—CH2—NH3+
2) Bicarbonate formation for conditions with 6<pH<11: CO2+HO—SO2—CH2—CH2—NH2+H2O→HCO3−+HO—SO2—CH2—CH2—NH3+
In general, it is important to enhance the solubility and the rate of uptake of CO2 in the solvents. If the solubility and/or the uptake rate (mass transfer and reaction rate) are too low, the absorption column must be enlarged in order to absorb most of the CO2 from the gaseous stream. A column which is too large is in general too expensive to be economically feasible.
By operating the algae cultivation at high pH, typically above pH 9, the absorption capacity, the amount of CO2 that can be solubilised, will increase. Not only the solubility of CO2 in an alkaline medium, like an absorbent liquid, is considerably higher than the solubility of CO2 in water, but also the reaction rate of CO2 binding to the liquid is considerably higher. For a chemical absorbent liquid, like an amine or an amino acid solution, the solubility of CO2 is 30 to 40 times higher than the solubility of CO2 in water. An important aspect is to separate the algae from the absorbent liquid to avoid settling of algae in the absorption column.
Besides the cost reduction related to the CO2 capture process, the combined system, that is absorbent liquids integrated with growth medium, can be beneficial for the algae cultivation process, because of a high CO2 content in the aqueous solution. The integrated system, consisting of the liquid and the growth medium, provides an abundant carbon source.
In one embodiment, therefore, the invention provides a composition comprising a mixture of an algal culture medium and an absorbent liquid. Typically, a standard algal culture medium is used and mixed 1:1 with an absorbent liquid. In a preferred embodiment, the composition comprises about one part standard algal culture medium mixed with one part absorbent liquid. In a preferred embodiment, the composition further comprises algae.
The terms “mixture” and “mixed” relate to the addition of the algal culture medium to the absorbent liquid or vice versa. It is also possible to mix individual ingredients of the standard growth medium and of the absorbent liquid instead of first preparing a growth medium or an absorbent liquid. The composition thus refers to the end product, obtainable by mixing an algal culture medium and an absorbent liquid, but also by other methods, and is not limited to a composition directly obtained by mixing both the medium and the liquid.
A composition which results in high growth rate, low doubling time, and the high (dry) algae density is, for instance, obtained with a standard growth medium for a specific algae species and the same amount of an absorbent liquid and half of the amount of algae. For a starting solution of 1 l aiming at an initial algae density of 0.2 g/l the following amounts can be used:
The different growth media used to cultivate algae are well documented (e.g. Mutanda et al., Bioresources Technology 2011, 102(1), 57-70; and Rodrigues et al., Bioresources Technology 2011, 102(11), 6587-6592). For Spirulina platensis different media are used, referred to as ‘Medium of Paoletti’ or Medium of Schlösser' (Rodrigues et al., Bioresources Technology 2011, 102(11), 6587-6592).
Another generally applied medium is the Acidic Bold Basal Medium. An overview of different recipes for cultivating algae is provided by Culture Collection of Algae and Protozoa, and list of about 100 different recipes is available online at www.ccap.ac.uk/media/pdfrecipes.htm.
The specific nutrients used for the growth media are give in Table II and Table III.
In a preferred embodiment, a composition according to the invention is provided wherein the composition comprises algal nutrients like nitrogen (N), phosphorus (P), and potassium (K), silica, iron, ethylenediaminetetraacetic acid (EDTA) and various micro-nutrients. Micro-nutrients include trace elements, trace metals, minerals, and vitamins. For sustainable growth of the micro-algae the N:P ratio should be in the range of 5-50, preferably in the range of 10-40, more preferably in the range of 15-35, more preferably in the range of 20-30, most preferably about 25.
With respect to the absorbent liquid the composition comprises an active component, such as amino acid or amine in a concentration of 0.1 to 4.0 M, preferably of 0.2 to 3.0 M, more preferably of 0.3 to 2.5 M, even more preferably of 0.5 to 2.0 M, and most preferably about 1.0 M. As active amino acid component taurine and β-alanine and as active amine component, monoethanolamine (MEA) and diethanolamine (DEA) can be mentioned. Other active components used for the absorption liquids are given in Table IV. In a preferred embodiment, the absorbent liquid comprises taurine, more preferably the absorbent liquid comprises taurine in a concentration in the range of 0.1-4 M.
There are only a few papers that deal with 1 used in combination with algal growth. All these papers deal with the use of solvents in the recovery, mainly by extraction, of valuable products from the algae (Lee et al., Bioresources Technology 2010, 101(1), S75-S77). Only two papers (Okumura et al., Archives of Environmental Contamination and Toxicology 2001, 41, 123-128; and Cho et al., Ecotoxicology and Environmental Safety 2008, 71(1), 166-171) describe the effect of solvents on the growth rate of algae. However, the papers only study the effect of traditional organic solvents, including methanol, ethanol, acetone, dimethyl formamide, dimethyl sulphoxide, and ionic liquids typically used in solvent extraction processes. None of the solvents studied can be used in a large scale absorption process to remove CO2 from flue gas, because of the limited affinity of these solvent for CO2.
The present invention for the first time identified solvents (viz. absorbent liquids) capable of both absorbing CO2 with high affinity and being compatible with use in algal culture.
Algae are categorised into microalgae and macroalgae. Although both algae may be used in the invention, it is preferred to use microalgae (also referred to as phytoplankton, microphytes, or planktonic algae). Macroalgae, commonly known as seaweed, may also be used, but due to their size and the specific requirements of the environment in which they need to grow, are less preferred.
It is preferred that monocultural algae are used. With mixed cultures, one species may become dominant over time and may change the properties of the algal culture.
The water in the algal pond or bioreactor must be in a temperature range that will support the specific algal species being grown. Especially if the pond or bioreactor is to be used throughout the year, it is important to be able to regulate the temperature of the water. In case of stripping CO2 from flue gas or the like, it is preferred to transfer (at least some of the) heat of the flue gas to the absorbent liquid, in order to warm up the pond or bioreactor to an acceptable temperature.
In order to convert CO2 into oxygen and glucose, algae need light. Direct sunlight is too strong for most algae, which need only about 1/10 of the amount of light they receive from direct sunlight. In a dense algal culture, light may only penetrate the top 3 to 4 inches (76-100 mm) of the water. When deeper ponds are used, the water should be agitated, such that the algae are circulated. This prevents both, over-exposure to sun-light and under-exposure, e.g. because algae on the bottom of the pond receive (almost) no light at all. Paddle wheels can stir the water and compressed air coming from the bottom lifts algae from the lower regions. Of course, the continuous stream of the absorbent liquid flowing into the pond or bioreactor can also be used to agitate the algae and is much preferred.
Another means of supplying light is to place the light in the system. Glow plates made from sheets of plastic or glass and placed within the tank offer precise control over light intensity.
As mentioned above, algae can be cultured in open-ponds (such as raceway-type ponds and lakes) and photobioreactors. Raceway-type ponds and lakes are open to the elements and may be contaminated by other microorganisms or chemicals, for instance from nearby plants. Moreover, open ponds are much less controllable with regard to temperature and lighting. Open ponds, however, are cheaper to construct, at the minimum requiring only a trench or pond. Large ponds have the largest production capacities relative to other systems of comparable cost.
One possibility of combining the best of both is, for instance, to enclose the open pond with a transparent or translucent barrier. This solves many of the problems associated with an open system. One important advantage of such enclosed open pond is that it, when heated, can be used throughout all seasons.
Algae and especially oleaginous algae, such as Neochloris oleoabundans, have drawn attention of researchers in the field of bio-fuel.
Many algae known in the art comprise bio-fuel precursors in the form of lipids or free fatty acids. Preferred species for use in a method according to the invention are Neochloris oleoabundans and Chlorella protothecoides.
In a preferred embodiment, therefore, a method according to the invention is provided, wherein said algae are oleaginous algae, preferably Neochloris oleoabundans or Chlorella protothecoides. Neochloris Oleoabundans is also capable to grow at high pH, which is advantageous for the reasons described above.
In a preferred embodiment, therefore, a method according to the invention is provided, wherein said algal culture comprises Neochloris oleabundans.
In another preferred embodiment, a method according to the invention is provided wherein said algal culture comprises Spirulina platensis, Chlorella vulgaris, or Scenedesmus obliquus
The bio-fuel precursors are then preferably extracted from the algae, after which bio-fuel can be produced by conventional methods.
In a preferred embodiment, a method according to the invention is provided, wherein the method further comprises the step of:
Methods for processing bio-fuel precursors obtained from algae are known in the art. Conversion of biomass into bio-fuel product typically encompasses two main routes (thermal and biochemical) (Okumura et al., Archives of Environmental Contamination and Toxicology 2001, 41, 123-128). Thermal conversion includes: gasification, liquefaction, pyrolysis, combustion, whereas biochemical conversion includes: digestion, fermentation, and transesterification.
The use of algae is, however, not necessarily restricted to the production of bio-fuel. Many uses are known in the art. The following examples of algal use should by no means be interpreted as restricting the invention in any way.
Another relevant alga for bio-fuel production is Botryococcus Brauni. This alga is available in different strains, which can be used to produce various long chain hydrocarbons, of the form CnH2n-10, typically lipids. The lipids have typically a chain length with n in the range of 30 to 40, and these hydrocarbons can be used in hydrocracking.
Several species of algae are raised for food. Purple layer (Porphyra), for instance is used in nori (Japan), gim (Korea), and layerbread (Wales).
Spirulina (Arthrospira) platensis is a blue-green microalga high in protein and other nutrients and is used as a food supplement. Spirulina can for instance be used as a source of phycocyanin. Chlorella, is also used as a nutritional supplement with possible effects on metabolic rate. Some allege that Chlorella can reduce mercury levels in humans (supposedly by chelation of the mercury to the cell wall of the organism).
Irish moss (Chondrus crispus), is a source of carrageenan, which can be used as a stiffening agent in instant puddings, sauces, and ice cream, or as a fining agent in beer.
Extracts and oils from algae can also be used as additives in various food products. Most plants produce Omega-3 and Omega-6 fatty acids, which have been shown to have positive health benefits.
Both microalgae and macroalgae can be used to make agar, which is an alternative to animal-derived gelatine.
Other possible uses of algae include the production of bioplastics, dyes, and pharmaceutical ingredients.
In a preferred embodiment, a method according to the invention of promoting growth of algae using an absorption liquid comprising carbon dioxide is provided, wherein the method further comprises the steps of:
In a more preferred embodiment, the method further comprises processing of said chemical species. For the processing of ‘biochemicals’ (dyes, pigments, nutritional species) a wide range of standard methods can be applied, including, mechanical destruction, freezing, membrane filtration, centrifugation, less standard methods are based on ultrasound and supercritical fluid extraction.
The invention is further explained in the following non-limiting examples.
To cultivate the various micro-algae growth media recipes given in the open literature have been used. A number of typical recipes for growth media are given in Table II and Table III.
For the absorbent liquids standard procedures were used to prepare the solvent solutions. For the absorbent liquids stock solutions with a molarity of 2 M were prepared. To test the growth, the molarities of the solutions were adjusted at the start of the experiments by adding a given amount of the aqueous growth medium.
The growth of the algae was tested with different solutions composed from different ratios (volume based) of growth media and absorbent liquid. This resulted in values for the molarity for the absorbent liquid, in the combined solution, of 0.1 M, 0.2 M, 0.3 M, 0.4 M, 0.5 M, 0.6 M, 0.7, M, 0.8 M, 0.9 M, and 1.0 M.
Initially, so-called toxicity tests were performed to determine to what value of the molarity of the absorbent liquids algae growth was possible. It is noted that these experiments were performed without adding CO2 to the solution.
Subsequently, a number of dedicated experiments were performed were a specific algae (and growth medium) was combined with a given absorbent liquid in the presence of CO2. The CO2 was added in two different ways.
In the first way, so-called batch operation, the algae, growth medium, and the absorbent liquid (with a given molarity) were prepared in a beaker (of about 1 l) or reactor (available with a volume of 10 l and 20 l) and the CO2 was bubbled through for at least 12 h to saturate the solution with a high flow rate (in the order of 200 ml/min).
In the second way, the same solution was used, composed of the micro-algae, growth medium, absorbent liquid, and the CO2 was bubbled through the solution in the beaker (or reactor) continuously at a given flow rate (in the order of 10 to 20 ml/min).
During the experiments the pH was measured on a daily basis.
At given times a small sample was taken from the beaker (or reactor) to analyse the micro-algae. The volume of the sample was determined, the sample was then dried in an oven, and subsequently the mass determined (by weighing) to obtain the dry algae density (g/l).
In
At the start of the experiment the aqueous solution with the nutrients, the micro-alga, and the taurine is first saturated with CO2 by bubbling CO2 through the solution for at least 12 h. The alga starts to grow after 3 to 4 days, reaching a constant level at a density of about 1.4 g/l (dry alga mass). At day 20 the solution (alga, nutrients, taurine) is loaded again with CO2. The CO2 is bubbled through the solution overnight for at least 12 h. After day 20, the alga starts to grow again to reach a final density of about 3.0 g/l (dry alga density).
For most of the time, the pH of solution is above 8.0, and only between day 20 and day 25 the pH drops to a value below 8.0, but after day 25 the pH starts to increases again to reach a final value for the pH of just above 9.0.
Extraction of different species, including β-carotene, chlorophyll, and phycocyanin, from Spirulina platensis.
An example of a relevant biochemical that can be extracted from Spirulina platensis is phycocyanin. Phycocyanin is being used for different applications in the pharmaceutical, food, and beverage industry. Phycocyanin is used in the food and beverage industry as a natural colouring agent.
A number of liquids have been combined with well-know recipes for growth media for different algae to see if is possible to grow micro-algae in the new solution combining growth media and an absorbent liquid. The composition of the solution was composed in such a way that the molarity of the absorbent liquid was in the range of 0.1 to 1.0 M.
In
Results have been obtained for different molarity. For the situation with 0.1 M taurine the dry algae density increased to about 2 g/l. For the situation of 0.2 M taurine an initial level of dry alga density of about 1.4 g/l was obtained, at day 20 the solution (alga, nutrients, absorption liquid) was loaded again with CO2, and eventually a dry alga density of just above 3.0 g/l was obtained.
This clearly indicated that the solvent can be reloaded with CO2 and that the solvent can be reused.
For various tests, Arthrospira (Spirulina) platensis was used. The Spirulina strain is kept in Schlösser's medium (Schlösser, Berichten der Deutchen Botanischen Gesellschaft 1982, 95, 181-276). Schlösser's medium contained per litre: 13.6 g of NaHCO3, 4.03 g of Na2CO3, 0.5 g of K2HPO4, 2.5 g of NaNO3, 1 g of K2SO4, 1 g of NaCl, 0.2 g of MgSO4.7H2O, 0.04 g of CaCl2.2H2O, 0.01 g of FeSO4.7H2O, and 0.08 g of EDTA (ethylenediaminetetraacetic). Some micronutrients are added as well.
The overall composition based on 1 l of total solution was obtained by combining: 400 ml of the growth medium, for example the Schlösser's medium, with 400 ml of an aqueous amino acids salts, with as ‘counter ion’ potassium hydroxide, solution, where the amount of amino acid was varied between 0.1 M and 1 M. Subsequently, 200 ml of algae solution was added.
There were several different test set-ups, glass reactors, to cultivate Spirulina. All set-ups consisted of stirring equipment, single or double walled beaker, fermentor, or aquaria, with external heating in case of the double walled aquaria and light sources. A flexible gas supply system, to add the CO2, was installed to the different set-ups.
With respect to the size of the glass reactors, reactors were available that can contain a solution with a volume of approximately 1 l, 6 l, 12 l, 20 l, and 35 l.
The temperature of the algal cultures was set to vary between 25° C. and 35° C.
In
Experiments were conducted in a sealed beaker, where flue gas was fed, and where the gaseous stream leaving the beaker was analysed with an online CO2 analyser. The composition of the ‘flue gas’ was 7.2% CO2 and 92.3% N2. In the case of water there was a clear CO2 concentration measured, after about 10 000 s, for both cases of water, the fraction was above 3.5%. This indicates that at least 50% of the CO2 fed to the beaker was leaving the beaker. In the case of the absorbent liquid no CO2 was measured, indicating that all CO2 remained absorbed in the liquid.
It is clear that the absorbent liquid can be used to store the CO2 over a considerable period of time.
In
Initially, there was some start-up effect of about two to three days for both cases, and after this period the density increased in the presence of the absorption liquid from 0.25 g/l to 1.7 g/l in about 5 days, while for the other situation the density increased from 0.25 g/l to about 1 g/l in 9 days.
There is also a clear effect in the finally density, after about 15 days, that is 2.1 g/l versus 1.4 g/l.
Spirulina
platensis
Neochloris
oleoabunduns
Chlorella
vulgaris
Scenedesmus
obliquus
For the Schlösser medium, EDTA was added as part of the micronutrient solution. Also, for the Schlösser medium, 6.0 ml of P-IV metal solution was prepared, with the following species in (g/l).
Subsequently, for the Schlösser medium, 1.0 ml of CHU micronutrient solution was prepared, with the following species in (g/l)
For the Paoletti medium, 1.0 ml of Fe-EDTA solution was prepared, with the following species in (g/l)
29.8 Na2EDTA
24.9 FeSO4.7H2O
Subsequently, also for the Paoletti medium, 1.0 ml of micronutrient solution was prepared, with the following species in (g/l)
To 1 l of distilled water 0.75 g of Na2EDTA was added and the minerals:
0.12 g Thiaminhydrochloride in 100 ml distilled water. Filter sterile.
0.1 g Cyanocobalamin in 100 ml distilled water, to 1 ml of this solution 99 ml distilled water was added. Filter sterile.
| Number | Date | Country | Kind |
|---|---|---|---|
| 11177293.5 | Aug 2011 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/NL2012/050558 | 8/10/2012 | WO | 00 | 6/30/2014 |
