US20110114556A1 - Soft Fail Algae Growth System and Method - Google Patents

Soft Fail Algae Growth System and Method Download PDF

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US20110114556A1
US20110114556A1 US12/943,922 US94392210A US2011114556A1 US 20110114556 A1 US20110114556 A1 US 20110114556A1 US 94392210 A US94392210 A US 94392210A US 2011114556 A1 US2011114556 A1 US 2011114556A1
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Prior art keywords
algae
tank
light
rod
led
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Matthew Edward Donham
Michael Edward VERES
Ari MA'AYAN
Nicholas Arthur RANCIS
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BIOVANTAGE INTERNATIONAL Inc
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BIOVANTAGE RESOURCES Inc
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Priority to US12/943,922 priority Critical patent/US20110114556A1/en
Assigned to BIOVANTAGE RESOURCES, INC. reassignment BIOVANTAGE RESOURCES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DONHAM, MATTHEW EDWARD, MA'AYAN, ARI, RANCIS, NICHOLAS ARTHUR, VERES, MICHAEL EDWARD
Publication of US20110114556A1 publication Critical patent/US20110114556A1/en
Priority to US14/094,287 priority patent/US8955249B2/en
Assigned to BIOVANTAGE INTERNATIONAL, INC. reassignment BIOVANTAGE INTERNATIONAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BIOVANTAGE RESOURCES, INC.
Priority to US14/622,337 priority patent/US20150156977A1/en
Abandoned legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G33/00Cultivation of seaweed or algae
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00Botany in general
    • A01G7/04Electric or magnetic or acoustic treatment of plants for promoting growth
    • A01G7/045Electric or magnetic or acoustic treatment of plants for promoting growth with electric lighting
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/24Devices or systems for heating, ventilating, regulating temperature, illuminating, or watering, in greenhouses, forcing-frames, or the like
    • A01G9/249Lighting means
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00Bioreactors or fermenters specially adapted for specific uses
    • C12M21/02Photobioreactors
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00Bioreactors or fermenters specially adapted for specific uses
    • C12M21/04Bioreactors or fermenters specially adapted for specific uses for producing gas, e.g. biogas
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M23/00Constructional details, e.g. recesses, hinges
    • C12M23/02Form or structure of the vessel
    • C12M23/18Open ponds; Greenhouse type or underground installations
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M23/00Constructional details, e.g. recesses, hinges
    • C12M23/58Reaction vessels connected in series or in parallel
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M27/00Means for mixing, agitating or circulating fluids in the vessel
    • C12M27/02Stirrer or mobile mixing elements
    • C12M27/06Stirrer or mobile mixing elements with horizontal or inclined stirrer shaft or axis
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M27/00Means for mixing, agitating or circulating fluids in the vessel
    • C12M27/18Flow directing inserts
    • C12M27/24Draft tube
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/06Nozzles; Sprayers; Spargers; Diffusers
    • C12M29/08Air lift
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M31/00Means for providing, directing, scattering or concentrating light
    • C12M31/08Means for providing, directing, scattering or concentrating light by conducting or reflecting elements located inside the reactor or in its structure
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V33/00Structural combinations of lighting devices with other articles, not otherwise provided for
    • F21V33/0064Health, life-saving or fire-fighting equipment
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0096Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the lights guides being of the hollow type
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21WINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
    • F21W2131/00Use or application of lighting devices or systems not provided for in codes F21W2102/00-F21W2121/00
    • F21W2131/40Lighting for industrial, commercial, recreational or military use
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21YINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00Light-generating elements of semiconductor light sources
    • F21Y2115/10Light-emitting diodes [LED]
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21YINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00Light-generating elements of semiconductor light sources
    • F21Y2115/30Semiconductor lasers
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0005Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type
    • G02B6/001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being of the fibre type the light being emitted along at least a portion of the lateral surface of the fibre
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/14Measures for saving energy, e.g. in green houses
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates generally to wastewater treatment systems and methods, and more particularly relates to wastewater treatment systems utilizing anaerobic and aerobic microorganisms for bioremediation.
  • Typical prior art wastewater treatment systems typically employ mechanical aeration and chemical treatment. These systems are expensive to build and to operate, not solely because of the high energy costs incurred in the aeration process, but also because of the manpower required to operate the expensive machinery employed in such systems.
  • Such mechanical/chemical treatment facilities even those that are considered “state of the art,” have a price tag in the millions and even up to hundreds of millions of dollars, making them so expensive that many communities, in the US and other parts of the developed world, have in the past been unable to afford such sewage treatment systems. As a result, the majority of the world's population lives with massive sewage pollution.
  • Bioremediation of wastewater has been proposed in the past.
  • Such bioremediation systems typically employ a combination of aerobic and anaerobic processes.
  • prior art systems have generally proposed the use of anaerobic bacteria for digestion of organic matter and the release of biogas, combined with phototrophic organisms that produce oxygen to accelerate the breakdown of organic matter by aerobic bacteria.
  • the aerobic bacteria produce carbon dioxide which is needed by the phototrophic organisms.
  • Anaerobic digestion kills most of the pathogenic bacteria found in raw sewage by depriving it of oxygen.
  • the anaerobic bacteria are able to digest most of the biologically activating solids.
  • Algae has long been proposed as a suitable phototrophic organism for use in such bioremediation of wastes.
  • One large project using such an approach is the St. Helena Wastewater Treatment plant in California, and other such plants have been put into service elsewhere in the world.
  • wash-out events e.g. from a rainstorm
  • wash-out events can severely dilute the algae culture density, such that the system is unacceptably slow to return to an effective culture density.
  • the present invention provides a system and method for efficient, cost-effective bioremediation of wastewater and other contaminated fluid streams.
  • the invention includes a photobioreactor (hereinafter sometimes “PBR” for simplicity) for growing high concentrations of algae.
  • PBR photobioreactor
  • the PBR comprises a tank having specially configured light pipes distributed therein to cause high density algae growth substantially throughout the tank. Fluid flow in the tank is maintained at a level low enough to prevent damage to the algae while at the same time allowing the fluid to circulate throughout the tank.
  • the nutrient system can comprise a plurality of separately selected components which are then assembled into a nutrient stream through a plurality of metering pumps, or, in some embodiments, can be derived from a portion of the effluent of an anaerobic digester.
  • the anaerobic digester forms a first stage of the overall bioremediation system.
  • the anaerobic digester stage aside from providing a stream rich in micro and macronutrients, also provides significant amounts of CO 2 to the PBR, which assists in the growth of algae in the PBR.
  • the anaerobic digester generates significant quantities of biogas, which can be utilized by a conventional biogas-powered generator to produce at least a portion of the electricity required to operate the bioremediation system of the present invention.
  • Carbon dioxide from the biogas can be used in the lagoon or pond to accelerate algae growth before, after, or instead of burning of the biogas.
  • the resultant heat energy can be used to warm the water in the lagoon, accelerating various of the desirable biological processes ongoing there.
  • Yet another aspect of the invention comprises a remediation lagoon or pond, typically although not necessarily using a raceway design, where the remediation pond is fed high-density algal inoculum from the photobioreactor system.
  • a portion, in many cases the majority, of the effluent from the anaerobic digester stage provides the incoming fluid stream to be remediated in the remediation pond.
  • the remediation pond can be a multi-phasic pond utilizing multiple biological capabilities enabling it to process the residual CO 2 , nitrogen and phosphorus remaining in the effluent from the anaerobic digester stage.
  • the multi-phasic ponds comprise a plurality of horizontal strata, for example: aerobic at the surface, aerobic/anaerobic, and anaerobic on the bottom.
  • the overall function is to remove residual nitrogen and phosphorus in the system through the use of phototrophic microorganisms, while simultaneously consuming CO 2 and creating O 2 to aid in the breakdown of residual effluent from anaerobic digestion.
  • These ponds can be sized individually for each implementation or user application.
  • FIG. 1 shows schematically an embodiment of a water remediation in accordance with one aspect of the invention.
  • FIGS. 2A and 2B show, respectively, a cross-sectional side view and an exploded view of an embodiment of a photobioreactor having a single draft tube in accordance with one aspect of the invention.
  • FIG. 2C shows an alternative embodiment of a photobioreactor having a plurality of draft tubes.
  • FIG. 2D shows another embodiment of a photobioreactor utilizing parallel plates with light rods in accordance with an aspect of the invention.
  • FIG. 2E shows an alternative embodiment of a photobioreactor utilizing parallel plates and external illumination.
  • FIG. 2F shows in flow diagram form the operation of the photobioreactor in accordance with an aspect of the invention.
  • FIG. 3A shows an embodiment of a light rod as used in an embodiment of the photobioreactor of FIGS. 2A and 2B .
  • FIG. 3B shows a first alternative embodiment of a light rod in accordance with the invention.
  • FIG. 3C shows a second alternative embodiment of a light rod in accordance with the invention.
  • FIG. 4A shows an embodiment of a nutrient system in accordance with an aspect of the invention.
  • FIG. 4B shows in flow diagram form the operation of an embodiment of the nutrient system in accordance with one aspect of the invention.
  • FIGS. 5A-5B show an embodiment of a multiphasic pond in accordance with an aspect of the invention.
  • FIG. 6 shows an embodiment of a bubbler in accordance with an aspect of the invention.
  • FIG. 7 shows in schematic form an alternative embodiment of a wastewater remediation system in accordance with an aspect of the invention.
  • FIGS. 8A-8B show in system and flow diagram forms a concentrator process in accordance with an aspect of the invention.
  • FIG. 9 illustrates in generalized flow diagram form an embodiment of a soft fail process in accordance with an aspect of the invention.
  • a bioremediation system in accordance with one aspect of the invention comprises a photobioreactor or PBR 10 , described in greater detail hereinafter, which receives a nutrient stream from a nutrient system 15 .
  • the PBR provides an optimized environment for the growth of highly concentrated algae.
  • the algae from the PBR 10 is supplied via a conduit 20 to a wastewater pond or lagoon 25 , which, in some but not necessarily all embodiments, is a multiphasic pond as discussed in connection with FIG. 5 .
  • the pond or lagoon 25 receives organic waste 30 , and, in many embodiments, can also receive atmospheric CO 2 as indicated at 35 .
  • the wastewater pond or lagoon 25 which can cover less than an acre to tens or hundreds of acres and could even be an open water area such as a lake or bay given sufficiently large algae supplies, comprises in some embodiments a relatively shallow pond having at least one remediation strata and, in the case of multiphasic ponds, a plurality of strata.
  • the algae from the PBR are provided to the lagoon in doses sufficient to inoculate the lagoon; that is, to provide enough algae to the lagoon that the natural conditions in the lagoon will permit the algae to thrive for a reasonable period of time, propagating naturally.
  • the algae typically, although not necessarily, operate symbiotically with bacteria with which they comingle in the lagoon.
  • bacterial action reduces BOD and TSS (Total Suspended Solids) and reduces nitrogen while producing CO 2 .
  • algae reduce BOD, TSS, and nitrogen to a lesser extent, and substantially reduce phosphorus, all while producing oxygen.
  • This symbiotic relationship in which the bacteria produce CO 2 consumed by the algae as the algae produce O 2 consumed by the bacteria, significantly accelerates the activity of both organisms. (In addition, some CO 2 and O 2 come in from the atmosphere.)
  • a final treatment 40 can be provided, in the form of an algae separation step and/or a maturation or clarification stage.
  • An algae separation step permits collection of the algae biomass for value-added applications (e.g. fertilizer).
  • a maturation pond, constructed wetland, or similar solution would promote settling of the algae and further reduction of nitrates and phosphates.
  • automated feedback indicated at 45 , can be provided which determines the water quality of the outflow and accordingly adjusts the level of inoculation to ensure that proper levels of water quality are achieved and maintained.
  • the water quality of the output of the pond 25 is used to provide feedback.
  • a draft tube 200 is centrally disposed within a housing or tank 205 .
  • the tank has a useful capacity of about 50 gallons with a diameter of approximately 22 inches, while the draft tube has a capacity of approximately 4.5 gallons and a diameter of approximately seven inches.
  • the relative volumes and diameters of the tank 200 and draft tube 205 can vary substantially, although in at least some embodiments a draft tube diameter of five to twenty-five percent of the tank diameter has been found useful.
  • the tank is sized to have a height/diameter ratio approximately 1.5:1, although this ratio is not limiting and the relative dimensions of the tank can vary significantly.
  • a plurality of light pipes 210 are also arranged within the housing 205 and around the outside of the tube 200 , The exact number of light pipes 210 both within the diffusion tube and arranged outside of the diffusion tube can vary depending upon the size of the tank and the particular implementation of the invention. In general, it is desirable to space the light pipes apart by approximately twice the absorption distance of the light emitted from the light pipes.
  • the light pipes are spaced approximately 10-15 centimeters apart, although the exact dimensions can vary depending on numerous factors, including the type of algae, the level of algae concentration desired for a particular PBR, and the wavelength and power of the LED's providing light to the light pipes.
  • the housing 205 contains growth media 215 , as described in greater detail in connection with FIG. 4 , together with algae selected to be appropriate for the particular remediation system.
  • Light of one or more preselected wavelengths, appropriate to facilitate growth of the selected algae, is supplied by one or more LED's 220 or similar light sources associated with each of the light pipes 210 . While LED's are the preferred light source for many embodiments, other light sources are acceptable for some embodiments, including lasers, diode lasers, diode pumped solid state lasers, diode pumped fiber lasers, high intensity discharge lamps and other lamps, infrared sources converted to wavelengths appropriate for the particular strains of algae, or even sunlight coupled to the light pipes using heliostats or similar devices.
  • the LED's 220 are disposed at the top thereof, typically above the top of the media, where light emitted from the LED's is transmitted down the light pipe through a coupling 225 .
  • multiple LED's can be used to emit light of different wavelengths along a single rod, a single LED can emit multiple wavelengths along a single rod, or some rods can have LED's emitting a first wavelength while other rods have LED's emitting other wavelengths.
  • various dyes can be used in the rods to convert light of one wavelength to another more appropriate for the strains of algae being grown in the tank.
  • Each of the light pipes can also include a homogenizer or mixer, as shown in FIG. 3A , to improve spatial uniformity in the light pipes, although the homogenizer is not required for all implementations.
  • Each of the LED's can have associated therewith a heat sink or heat exchanger 230 , to keep the LED's at an appropriate operating temperature. In at least some implementations, it is desirable to cool the LED's sufficiently that heat from the LED's does not adversely affect the growth of the algae within the tank.
  • one or more fans 235 can be positioned at an orifice in an air dome 240 , with a ventilation gap 245 disposed between the air dome 240 and a tank lid 250 to allow air to exit.
  • the purpose of the light pipes 210 is to transit light from the LED's as uniformly as possible throughout the tank, to encourage algae growth at all levels within the tank, while not transmitting the heat from the LED's into the tank and not impeding fluid flow within the tank.
  • the light rods are supported by a tank lid 250 , which has orifices 255 therethrough.
  • Each of the light pipes 210 slides through an orifice 255 so that the majority of the light pipe fits into the tank 205 .
  • the lid can also provide a connection point for one or more supports 260 for the draft tube 200 , so that the top of the draft tube is maintained somewhat below the surface of the liquid in the tank, and the open bottom of the draft tube is maintained above the bottom of the tank.
  • the algae are typically moved or stirred gently within the tank.
  • One technique for facilitating such slow movement is to blend CO 2 or other gas (depending on what algae is being cultured and for what purpose) with compressed air via a computer controlled valve 265 and blender 270 .
  • no compressed air is used.
  • the bubbled gas can be inert with respect to the growth medium and the culture being grown, or it can promote the growth of the culture such as by providing a nutrient, or it can otherwise regulate conditions in the tank such as by changing pH.
  • the combined stream is supplied to the bottom of the draft tube 200 via a flowmeter 275 and a diffuser 277 , where the diffuser operates to convert the gas stream into gas bubbles sized to be suitable for providing movement of the algae.
  • the bubbles of gas mixture entrain the growth media and move algae in the draft tube upward as indicated by the upward flow arrows.
  • typical bubble size is on the order of 1 mm, but can vary significantly, in a range of 0.2 mm to 3 mm, or more.
  • the algae and growth media flow over the top of the draft tube and move downward within the portion of the tank outside the draft tube, as indicated by the downward flow arrow.
  • a gas flow rate of 0.1-0.2 cubic feet per minute provides sufficient movement of the algae, although this flow rate is not intended to be limiting.
  • This movement promotes homogenaeity of the growth medium within the tank, prevents settling, and also facilitates the algae moving along the length of the light rods, so that the algae are relatively uniformly illuminated by the light emitted from the light rods throughout the volume of the tank 205 , thus yielding relatively uniform growth throughout the tank, rather than merely at the surface as found in prior art systems.
  • Additional growth medium can be supplied as necessary from a medium tank, as discussed in connection with FIG. 4 , via tube 280 A, while seed amounts of algae are supplied via tube 280 B or through an orifice in lid 250 .
  • the junction of the walls and bottom of the tank can be rounded to facilitate smooth movement of the algae and to prevent algae from clogging at what would otherwise be a sharp corner, although such rounding is not necessary in all embodiments.
  • the temperature of the growth media is controlled by means of a thermal control jacket 285 , the temperature of which can be regulated by thermal control unit 290 .
  • the thermal control jacket can, for example, be formed with tubes therethough for heating or cooling fluid flow, or can be comprised of polymer heating/cooling material.
  • pH, level, and temperature, indicated by sensors 295 A-C, are monitored by control system 295 D, typically a computer (not shown.)
  • a computer-controlled drain valve 297 permits the algae to be transferred to a lagoon or pond seen in FIG. 1 to facilitate the remediation process.
  • algae concentrations of less than 50 mg/L up to 5000 mg/L or more can be achieved, with concentrations from 50 mg/L to 1000 mg/L being easily obtainable.
  • FIGS. 2A-2B multiple draft tubes can be used and may be desirable in tanks having a larger diameter, as shown in FIG. 2C .
  • having a plurality of smaller diameter draft tubes distributed around a larger tank will provide better fluid flow, especially near the edge of the tank, than a single tube of equivalent flow in the middle of a tank.
  • a gas flow of approximately 0.1 to 0.2 cubic feet per minute per draft tube provides sufficient stirring and movement of the algae and growth medium within the tank, where the combined diameters of the draft tubes comprises approximately five to twenty-five percent of the total surface area of fluid within the tank.
  • FIG. 2C which is a cross-sectional view of a photobioreactor in which like numerals refer to like elements from FIG. 2A .
  • a plurality of draft tubes 200 are disposed within the tank 205 .
  • the design illustrated can accommodate a large range of draft tubes.
  • between one and four draft tubes are desirable for some embodiments where the tank is approximately 150 gallons, while an embodiment using a 300 gallon tank uses five draft tubes.
  • the foregoing numbers are exemplary only and are not limiting. In general the number and placement of the draft tubes is intended to facilitate appropriate upward and downward flow of the algae-laden medium as described before in connection with FIGS. 2A-2B , where the algae is permitted to grow throughout the volume of the tank, rather than just at the surface as in prior art designs.
  • FIG. 2D which shows in perspective view with a transparent front wall a still further alternative embodiment of the PBR shown in FIG. 2A
  • the shape of the tank need not be round, and in fact can be any shape that permits sufficient light to reach the volume of algae growing in the medium.
  • elements with like functionality are again shown with the same reference numerals used in FIG. 2A , and, for clarity, many elements with identical functionality to those discussed in connection with FIG. 2A are omitted.
  • the perimeter of the tank 205 shown in the embodiment of FIG. 2D is rectangular, with one or more baffles 2100 arrayed within the tank and extending from below the surface of the fluid to a distance above the bottom of the tank.
  • baffles thus create spaces having the same functionality as draft tubes 200 .
  • diffusers 2110 By placing diffusers 2110 with appropriate gas flow at the bottom of alternating baffled spaces, the desired upward and downward flows are created within alternating baffled spaces in the tank, as shown by the flow arrows.
  • a plurality of light pipes are disposed within the tank through a lid 2115 .
  • a linear array of light pipes 210 is shown in FIG. 2D , it will be apparent that the number and placement of the light pipes will vary with the dimensions of the tank 200 , and need not be linear.
  • the wall-to-wall baffles shown in FIG. 2D are not required in all embodiments, and instead can be replaced with draft tubes as shown in FIGS. 2A-2C .
  • the width of the tank can be varied as desired, with multiple draft tubes and multiple light pipes arrayed in accordance with the teachings given in connection with FIGS. 2A-2C .
  • light pipes can be placed in the corners of the tank, to prevent a fall-off in illumination at the corners, although such positioning could in some instances result in a less efficient use of the light from the corner light pipes. Adding a reflector behind the light pipe can reduce the loss.
  • the fluid flow in the corners is decreased and dead spots may occur.
  • FIG. 2E shows a still further alternative embodiment of a PBR in accordance with an aspect of the invention
  • the light pipes 210 can be replaced with externally positioned LED's or equivalent light sources 2105 .
  • a thermal jacket 2110 is still provided, with orifices therethrough to accommodate the placement of the LED's 2105 .
  • Heat sinks 2115 are provided in at least some arrangements, and a cover [not shown] can be provided to control the air flow through the heat sinks, effectively creating a plenum.
  • baffles or draft tubes are disposed within the tank to create the appropriate flow of the algae and growth medium. The remaining elements of FIG.
  • the width of the tank is preferably constrained to ensure good illumination throughout the volume of the algae and medium flowing within the tank, and thus the width of the tank is typically at most a few inches.
  • LED's 2105 are disposed on both sides of the tank.
  • Growth medium is supplied to the growing tank 2200 via tube 2205 from the medium preparation system ( FIG. 4 ), either manually or under computer control 2207 , as indicated by a level sensor 2210 .
  • Seed amounts of the selected species, one or more, of algae are added via tube 2215 , again either manually or under computer control, or through one of the orifices in the tank lid prior to inserting the associated light pipe.
  • Illumination 2220 is enabled from the control system, and the climate control sleeve 2225 , or thermal jacket, brings the growth medium in the tank to a temperature appropriate for growing the algae within the tank, as monitored by temperature sensor 2230 .
  • the control system blends gases such as CO2, air, nitrogen, or other gases, via solenoid valve 2235 and blender 2240 , and throttles the volume of gas supplied to the tank via flowmeter 2245 .
  • the volume of gas is controlled by the control system both for purposes of setting the pH, as monitored by pH sensor 2250 , and for the purpose of ensuring proper flow within the tank.
  • various other sensors are monitored by the control system, for example phosphate levels 2255 , nitrate levels 2260 , dissolved O 2 2265 , and turbidity 2270 .
  • a colorimeter and/or a chlorophyll fluorescence probe can be used.
  • a valve 2275 is opened and the algae-laden fluid is removed from the tank via outlet 2280 , either to be supplied to bioremediation lagoons or ponds, or otherwise used or disposed of.
  • a clear rod 300 sized of a length to permit the rod to reach substantially to the bottom of a tank of a photobioreactor, comprises a series of alternating frosted and unfrosted sections 305 and 310 .
  • the rod 300 is typically comprised of acrylic or other polymer, or any other suitable material which is optically clear at the wavelength of the light emitted by one or more LED's 315 and capable of having a surface texture created on portions thereof to create the frosted and unfrosted sections 305 and 310 .
  • the LED's can be of multiple wavelengths, with different wavelengths emitted from each rod, or all rods emitting multiple wavelengths, or all rods emitting the same wavelength. It is noted that, while the foregoing describes a single wavelength, those skilled in the art will recognize that, in this context, “wavelength” is more accurately a wavelength band, as LED's emit a spectral spread, where the center wavelength is described as the “wavelength” of the LED. Also, as noted previously, dyes can be used in or on the rods to convert light of a wavelength generated by the LED's to light of a different wavelength suited to the algae.
  • the LED's 315 are mounted in a mounting block 320 , which is thermally coupled to a heatsink 325 depending on the heat generated by the LED's 315 .
  • a homogenizer 330 can be disposed in the optical path between the output of the LED's 315 and the input 335 of the rod 300 .
  • the homogenizer 330 typically has a non-circular cross-section throughout most or all of its length and utilizes internal reflection, including total internal reflection depending upon the material used, to create spatial uniformity of the light at the output of the homogenizer.
  • the input face 335 of the homogenizer 330 is typically sized so that its input dimensions are substantially matched to the output of the LED's, thereby allowing the homogenizer to capture all or nearly all of the light output of the LED's.
  • the dimensions of the output face of the homogenizer are sized to substantially match the input of the rod 300 , so that the loss of light at the transition from the homogenizer to the rod is minimized. It is not necessary that the output of the homogenizer be congruent with either the output of the LED's or the input of the light rod. In the case of the output of the LED's, the input face of the homogenizer can be larger.
  • the output face of the homogenizer can, for example, be a square with its corners intersecting or contained within the circular face of the rod 300 , or can be any other shape reasonably contained within but substantially covering the input face of the rod 300 , although homogenizers with an odd number of sides offer improved performance in some instances.
  • the arrangement of frosted and unfrosted sections 305 and 310 control the location along its length and amount of light emitted from the rod.
  • Light entering the input to the rod is transmitted along the unfrosted sections by total internal reflection.
  • at each frosted section at least some of the light striking the sidewall of the rod is emitted, or coupled, from the rod.
  • the rod which may have any cross-section that permits total internal reflection, can have a uniform cross-section along its length, or can monotonically decrease in size.
  • the distal end 340 of the rod 300 can either be rounded and frosted to prevent light loss, or can be mirrored to cause the light to be retroreflected back up the rod, allowing transmission through the sidewall of the rod as described above. Because the end segment of the rod is a special case, where real coupling can be significantly less than theoretical coupling due to the exponential decay of the light, such mirroring or rounding and frosting can increase actual coupling to a reasonable approximation of theoretical coupling.
  • the length of the frosted section increases relative to the length of the adjacent unfrosted section for each successive portion of the rod.
  • the combination of an unfrosted section and the adjacent frosted section can be thought of as a single segment 345 , and the segment length remains the same along the length of the rod while the relative length of the frosted section within each segment increases for each successive segment.
  • the amount of light transmitted by each frosted section is proportional to its length, and so the relative lengths of the various frosted sections can be expressed mathematically.
  • ⁇ (z) can be a coupling coefficient that describes the strength of the fractional coupling of the light per unit length from the rod by the frosting as a function of z.
  • Q(z) be the light power coupled out of the rod per unit length at a particular distance z along the rod.
  • N 2: 1 1.0000 0.5000 0.5000 50.00% 2 0.5000 0.5000 0.0000 100.00%
  • N 5: 1 1.0000 0.2000 0.8000 20.00% 2 0.8000 0.2000 0.6000 25.00% 3 0.6000 0.2000 0.4000 33.33% 4 0.4000 0.2000 0.2000 50.00% 5 0.2000 0.2000 0.0000 100.00%
  • N 20 1 1.0000 0.0500 0.9500 5.00% 2 0.9500 0.0500 0.9000 5.26% 3 0.9000 0.0500 0.8500 5.56% 4
  • the distal end (the last segment) is a special case, where beveling, rounding or other shaping can be used to achieve nearly 100% coupling as well as coupling out any light propagating ballistically down the rod 300 .
  • N 10 F i i L i P i Q i P i+1 (Fractional (Segment (Segment (Incident (Coupled Out (Transmitted Light Power Index) Length) L i /L av Light Power) Light Power) Light Power) Coupled Out) 1 1 0.08333 1.0000 0.0833 0.9167 8.33% 2 1 0.08333 0.9167 0.0833 0.8333 9.09% 3 3 0.25000 0.8333 0.2500 0.5833 30.00% 4 1 0.08333 0.5833 0.0833 0.5000 14.29% 5 1 0.08333 0.5000 0.0833 0.4167 16.67% 6 1 0.08333 0.4167 0.0833 0.3333 20.00% 7 1 0.08333 0.3333 0.0833 0.2500 25.00% 8 1 0.08333 0.2500 0.0833 0.1667 33.33% 9 1 0.08333 0.1667 0.0833 0.0833 50.00% 10 1 0.08333 0.0833 0.0833 0.0000 100.00%
  • FIGS. 3B and 3C show, respectively, where FIG. 3B shows segments of uniform length while FIG. 3C shows segments of uneven length, in which segment N 3 is twice as long as the other segments.
  • the hatched portions represent the frosted sections of each segment, where light is coupled out.
  • the equivalent number of segments is six, and N 3 couples out 1 ⁇ 3+1 ⁇ 4 of the light, or a total of 48.3% across the longer segment.
  • the rod 300 is shown as a consistent diameter down its length, other shapes and cross-sections of light rods are also acceptable.
  • tapered light rods can also be used in at least some embodiments.
  • the light rod 300 need not be straight in some embodiments, and instead can be curved in any suitable arrangement.
  • Non-circular cross-sections while harder to manufacture in some cases, may offer more uniform light distribution characteristics along the length of the rod in some embodiments.
  • the frosting is assumed to be identical for each segment in the foregoing calculations and examples, in some embodiments it is desirable to vary the optical properties of the frosting at each segment. Such variations in the frosting provides a means to extend the dynamic range over which the coupling can be varied.
  • the variation in the frosting does not need to be continuous. Having a few discrete values, such as “weak”, “medium” and “strong”, offers benefit in some embodiments, while continuously variable frosting allows fine tuning of the fractional power coupled out by each segment.
  • a plurality of carboys 400 A-n each containing a component of a predetermined nutrient mix appropriate for a specific strain of algae, are associated with a plurality of metering pumps 410 A-n, each of which is computer controlled.
  • the metering pumps thus supply a desired mix of nutrients into a mixing tank 420 , which receives water 425 via a computer controlled valve 430 .
  • a number of filters 435 and 440 can also be installed between the inlet water and the mixing tank; for example, five micron and carbon filters, respectively.
  • the outlet of the mixing tank is supplied to a computer controlled pump 445 , which supplies the mixed nutrient stream to a computer controlled valve 450 .
  • the valve 450 directs the nutrient mix either to be recirculated in the tank via recirculation line 460 or to be supplied to an associated PBR or group of PBR's as indicated at 470 .
  • Filters 455 and 465 which can, for example, be two micron filters, can be provided on the recirculate and PBR tank lines, respectively.
  • the process for preparing the growth medium using the system of FIG. 4A can be better appreciated.
  • the process starts at step 4000 , and at step 4005 the tank 420 is filled with water to a predetermined level as determined by level sensor 475 , after which the pump 445 is turned on and configured to recirculate the tank contents by valve 450 as shown at step 4010 .
  • the water in the tank is heated by heater 485 to a predetermined temperature as measured by temperature sensor 480 .
  • the nutrient constituents appropriate for the particular growth medium being developed are the supplied to the tank from carboys 400 A-n via their associated metering pumps 410 A-n at step 4020 .
  • the constituents of the growth medium can vary with the particular algae strain for which the growth medium is intended.
  • the mix of water and nutrients is then circulated, as shown at step 4025 , until the nutrients are uniformly distributed, after which the growth medium is supplied to an associated PBR at step 4030 .
  • the process either completes, as shown at step 4030 , or loops back to step 4005 to begin again.
  • FIG. 5A shows a pond 500 with a paddlewheel 505 in top plan view, and also shows the location across which the cross-sectional view of FIG. 5B is taken.
  • FIG. 5B shows the various strata of the pond.
  • an anaerobic zone 510 is located at the bottom of the pond.
  • An anaerobic/aerobic transition zone 515 is located above the anaerobic zone, at the top of which are disposed one or more CO 2 supply tubes 520 .
  • the CO 2 supply tubes are typically porous tubing for distributing CO 2 substantially uniformly across at least a substantial portion of the pond 500 .
  • the CO 2 is utilized by aerobic bacteria in an aerobic zone 525 .
  • the paddlewheel 505 creates a flow, shown from left to right in exemplary FIG. 5B , such that mixing of the effluent being remediated across the various zones is facilitated.
  • the tubes 520 can be arrayed on the bottom of the pond or lagoon.
  • a tank 600 has a sealed bottom and has disposed therein at least one light rod 605 of the type described in connection with FIGS. 3A-3C . Although a round tank 600 is shown, the tank need not be round in all instances, and instead can be any convenient shape.
  • the light rod can be centrally disposed or disposed asymmetrically, and can be configured together with the shape of the tank to provide whatever uniformity of illumination or lack thereof is desired. In an embodiment, the position of the light rod can be varied within the tank to facilitate different illumination patterns.
  • Compressed air or other gases, utilized in the manner described in connection with FIGS. 2A-2B et seq., are supplied to a diffuser 610 located at the bottom of the tank via a tube 615 , which can either enter the tank from the bottom or down an inside wall as shown.
  • the diffuser can be configured to supply gas uniformly across the bottom of the tank or in any desired pattern, but the sole agitation and mixing is through the upward movement of the bubbles through the algae-laden medium, since there is no larger tank for creating the upward and downward flows of the systems shown in FIGS. 2A-2F .
  • a supply tube 620 is provided by which algae can be introduced to the column.
  • the supply tube 620 can be located at any convenient position on the tank, including a lid 625 , or an orifice in the lid through which the light rod 605 passes, a sidewall, or the bottom of the tank.
  • the bubble column is filled with a growth medium, and algae strains are introduced.
  • a gas mixture appropriate for the particular study being conducted is introduced via the diffuser, and the resulting bubbles entrain the algae as described above.
  • the bubble column is not contained within an outer housing or tank, the fluid levels are typically maintained at levels below overflowing in most embodiments.
  • Organic waste 700 is supplied to an anaerobic digester 705 , which begins the breakdown process and generates methane 710 and an effluent stream 715 , comprised in part of CO 2 , nitrogen, phosphorus and other constituents.
  • the effluent is supplied to a multiphasic pond 720 , together with water 725 as needed.
  • the methane provides fuel for a generator/boiler 730 , which generates heat 735 that is supplied back to the anaerobic digester 705 .
  • the generator 730 also provides CO2 740 to a photobioreactor 745 , typically constructed in accordance with the aforementioned teachings, as well as the multiphasic pond 720 .
  • the generator 730 also supplies electricity and heat 750 to both the PBR 745 and the multiphasic pond 720 , and may in some implementations supply additional electricity at 775 .
  • the pond 720 receives additional atmospheric CO2 at 760 , if needed, and outputs remediated wastewater.
  • the remediated wastewater can then be given an optional final treatment, as shown at 765 , such as an ultraviolet polish, carbon filtration, or other remediation step.
  • the pond 720 can also generate usable biomass as shown at 770 .
  • a concentrator system and process can be better appreciated.
  • Some species of algae grow best under one set of conditions, but produce desired products more rapidly under different conditions.
  • One example is algae that grows best when supplied with nitrogenous nutrients, but produces higher concentrations of lipids when deprived of nitrogenous nutrients.
  • algae of a desired species is grown to a desired density at step 800 in a PBR 850 using a first growth medium designed to achieve high algae density as promptly as possible.
  • At least a portion of the algae is transferred to a concentrator tank 855 , as shown at step 810 , typically although not necessarily through a computer-controlled valve 860 .
  • the transfer process requires that a substantial amount of the first growth medium be transferred with the algae, to prevent damage to the algae.
  • the combination of algae and the first growth medium are allowed to settle as shown at step 815 , causing the growth medium, which is largely water, to clarify.
  • the clarified growth medium is removed, either from the top of the concentrator or any other suitable location that will not remove and/or damage the algae within the concentrator 855 . It will be appreciated that not all of the first growth medium can be removed, but a significant percentage, in the range of 75%, can be removed without damaging the algae.
  • the remaining growth medium and the algae are transferred to a blooming tank 870 through a valve 875 , also typically but not necessarily computer-controlled.
  • a second growth medium is used in the blooming tank 870 , formulated to stimulate development of the desired products, as shown at step 830 .
  • the second growth medium is added to the blooming tank in advance of the transfer of the algae into the blooming tank, to minimize physical damage to the algae during transfer, although these steps can be reversed depending upon the particular algae, the amount of first growth medium remaining after step 820 , and the trauma likely to be suffered by the algae during the transfer process.
  • a concentrator tank 855 having a funnel-shaped lower portion can be used, where the algae settles in the funnel-shaped portion both to permit easy removal of the first growth medium and to permit easy transfer to the blooming tank.
  • the blooming tank can be configured in substantially the same way as the PBR 850 , and in some implementations the PBR 850 can be re-used as the blooming tank.
  • the first growth medium can, for example, be nitrogen-rich and thus encourage rapid growth of selected algae.
  • the transfer to the concentrator and removal of the first growth medium rapidly reduces the levels of nitrogen and other nutrients, including trace elements, in the algae.
  • the second growth medium can be, for example, pure water, or nitrogen-depleted.
  • the selected algae begin to produce lipids or other products which can be used, for example, as biofuels.
  • the result, and benefit, of the concentration process is that it rapidly accelerates the depletion of nutrients in the growth medium which, in turn, accelerates the generation of the desired products.
  • the concentration process of the present invention can be accomplished within minutes or, at most, hours, such that the beginning of production occurs much more rapidly, resulting in increased efficiency and lower operating costs.
  • a soft-fail process is described in FIG. 9 , where a check is made at step 905 to determine whether power is at proper levels. If yes, the process loops so that checking for power failures is essentially continuous. If power is not at proper levels, the process advances to step 910 and any preparation of growth medium is halted, as is any algae transfer or discharge.
  • step 915 the LED's are turned off.
  • step 920 the temperature tolerances set into the control system are automatically expanded.
  • the pH target in the tank is adjusted for the particular species being grown to maximize culture viability, as shown at step 925 .
  • the gas stream is switched from continuous operation to intermittent, so that mixing in the tank continues although not at the same levels.
  • steps 910 to 930 can be performed either essentially concurrently, or in stages where the time increment between each step can be adjusted depending upon the particular operating conditions, the strain(s) of algae, and the projected time before power is restored.
  • step 935 the state of the power is tested again. If power has been restored, the operations of steps 910 - 930 are restored to normal conditions as shown at step 940 . If power has not been restored, the check continues until power is restored or reserve power is lost.

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EP2499230A4 (de) 2015-06-17
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US20110120944A1 (en) 2011-05-26
WO2011060107A8 (en) 2012-01-05
US20110107664A1 (en) 2011-05-12
EP2499230A1 (de) 2012-09-19
US20150156977A1 (en) 2015-06-11
US20110113682A1 (en) 2011-05-19
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US8955249B2 (en) 2015-02-17
WO2011060107A1 (en) 2011-05-19

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