Non-dispersive process for insoluble oil recovery from aqueous slurries.
Abstract
The present invention relates to a method for extracting one or more insoluble oils from a liquid source, comprising one or more organisms, using one or more membrane contactors, comprising the following steps: pumping the liquid source comprising one or more oils from a reactor to the one or more membrane contactors, where the liquid source does not contain a dispersing solvent; fusing the one or more oils within the liquid source on a first surface of the one or more membrane contactors; pumping a collection fluid through the one or more membrane contactors on a second surface of the one or more membrane contactors; contacting the one or more oils fused in the liquid source with the collection fluid pumped into the one or more membrane contactors; pumping a first stream of the one or more membrane contactors back to the reactor, wherein the first stream comprises the liquid source with one or more organisms without extracted oils; and removing the second stream from the one or more membrane contactors, wherein the second stream comprises the collection fluid and the extracted oils.

Term
4.3 yearsleft in the term
Expires 13 January 2031.
- Priority
- Filed
- Granted
- Today
- Expires
26 claims: 2 independent, 24 dependent
- 1REIVINDICACIONES 1. Un método para extraer uno o más aceites insolubles de una fuente liquida, que comprende uno o más organismos, 5 utilizando uno o más contactores de membrana, que comprende las siguientes etapas:bombear la fuente líquida que comprende uno o más aceites desde un reactor hacia los uno o más contactores de membrana, en donde la fuente líquida no contiene un solvente dispersante;10 fusionar los uno o más aceites dentro de la fuente líquida sobre una primera superficie de los uno o más contactores de membrana;bombear un fluido de recolección a través del uno o más contactores de membrana sobre una segunda superficie del uno o 15 más contactores de membrana;contactar los uno o más aceites fusionados en la fuente líquida con el fluido de recolección bombeado en los uno o más contactores de membrana;bombear una primera corriente de los uno o más contactores 20 de membrana de regreso hacia el reactor, en donde la primera corriente comprende la fuente líquida con uno o más organismos sin aceites extraídos;y IMPI msTmrro mexican· t £ LA PROPIEDAD INDUSTRIAL remover la segunda corriente del uno o más contactores de membrana, en donde la segunda corriente comprende el fluido de recolección y los aceites extraídos.
- 2El método de la reivindicación 1, en donde el reactor es un termentador, y el uno o más organismos comprenden organismos que son capaces de secretar aceite.
- 3El método de la reivindicación 1, en donde los uno o más organismos comprenden organismos capaces de realizar la fotosíntesis.
- 4El método de la reivindicación 1, en donde los uno o más organismos comprenden al menos un organismo capaz de realizar la fotosíntesis, caracterizado en gue es capaz de secretar aceite o causar la acumulación de aceite fuera de las células vivas.
- 5El método de la reivindicación 1, en donde el uno o más organismos comprenden al menos un organismo que causa la acumulación de uno o más aceites fuera de células vivas.
- 6El método de la reivindicación 1, en donde al menos un organismo es un alga.
- 7El método de la reivindicación 1, en donde la fusión se logra en presencia de células de algas. 63 ΙΜΡΙ®5 03 iNSTmni muiong DE LA RRORÍLOAL· industrial ’Wil~iqWi
- 8El método de la reivindicación 1, en‘ donde”el ΐίηό “o más aceites son definidos como un compuesto hidrofóbico que es insoluble en una fuente liquida acuosa.
- 9El método de la reivindicación 1, en donde la fuente líquida es seleccionada del grupo que consiste en agua industrial, salmuera, agua residual, efluentes industriales o naturales, mezclas hídricas y oleosas, suspensiones acuosas que comprenden células rotas, células vivas, mezclas biocelulares, preparaciones celulares lisadas o combinaciones de los mismos.
- 10El método de la reivindicación 1, en donde el uno o más organismos comprenden algas, protistas, hongos, levadura, E. coli, cultivos mezclados de células, organismos que están modificados genéticamente, u organismos que son capaces de causar la acumulación del uno o más aceites fuera de células vivas.
- 11El método de la reivindicación 1, en donde se extrae del 95 al 100% de los uno o más aceites insolubles en la fuente líquida.
- 12El método de la reivindicación 1, en donde se extrae el 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99% o 100% de los uno o más aceites insolubles en la fuente líquida. 64 INSTITUI O MEXlCANi . DE LA PROPIEDAl. s-»»**©' industrial *
- 13El método de la reivindicación 1, en donde el finido ___ de recolección comprende uno o más solventes, un biodiesel, un aceite de algas, un aceite no polar o mezclas, o combinaciones de éstos.
- 14Un método para extraer uno o más aceites insolubles o componentes hidrofóbicos de un medio de crecimiento que comprende organismos, y los aceites insolubles utilizando uno o más contactores de membrana hidrofóbicos, que comprende las siguientes etapas:bombear el medio de crecimiento que comprende los organismos y aceites insolubles desde un reactor dentro de uno o más contactores de membrana hidrofóbica, en donde el medio de crecimiento no contiene un solvente dispersante;bombear uno o más fluidos de recolección a través de los uno o más contactores de membrana hidrofóbica, en donde los uno o más fluidos de recolección contra fluyen con el medio de crecimiento que comprende organismos en el contactor de membrana hidrofóbica;fusionar los aceites insolubles o componentes hidrofóbicos dentro del medio de crecimiento sobre una primera superficie del uno o más contactores de membrana hidrofóbica;contactar los aceites insolubles fusionados o componentes hidrofóbicos dentro del medio de crecimiento que comprende IMPI Μτπντο ΙΗ LA PWOPUDAD INDOSTX1AL organismos y aceites insolubles en el cohtáctór de membraná hidrofóbica con uno o más fluidos de recolección bombeadas a través de los uno o más contactores de membrana hidrofóbica sobre una segunda superficie del uno o más contactores de 5 membrana hidrofóbica;remover una primera corriente del uno o más contactores de membrana hidrofóbica, en donde la primera corriente comprende el medio de crecimiento y organismos;y remover la segunda corriente de los uno o más contactores 10 de membrana hidrofóbica, en donde la segunda corriente comprende los uno o más fluidos de recolección y los uno o más aceites insolubles.
- 15El método de la reivindicación 14, que además comprende alimentar o bombear la primera corriente hacia el 15 reactor.
- 16El método de la reivindicación 14, en donde el contactor de membrana hidrofóbica comprende polietileno, polipropileno, poliolefinas, polivinilcloruro (PVC), polietilentereftalato amorfo (PET), copolimeros de 20 poliolefina, polímeros tipo poli (éteretercetona), polímeros modificados en su superficie, mezclas o combinaciones de los mismos. 66 INSTITUTO míXICaNi DE LA RROPBDAD INDUSTRIAL ^»N-
- 17El método de la reivindicación 14 ,„_en_do.nd -«.l-íi ide--de recolección en contra flujo comprende solventes no polares, alcanos tales como hexano, solventes aromáticos tales como benceno, tolueno, éteres tales como dietiléter, solventes 5 halogenados tales como cloroformo, diclorometano y ásteres tales como etilacetato.
- 18El método de la reivindicación 14, en donde el fluido de recolección en contra flujo comprende aceites no polares, aceites de algas, componentes de biodiesel, monoglicéridos, 10 diglicéridos, triglicéridos o ésteres de ácidos grasos.
- 19El método de la reivindicación 14, en donde el organismo comprende organismos capaces de realizar la fotosíntesis.
- 20El método de la reivindicación 14, en donde el reactor 15 es un fermentador, y el organismo comprende al menos un organismo que es capaz de secretar uno o más aceites insolubles.
- 21El método de la reivindicación 14, en donde el organismo comprende al menos un organismo que causa la 20 acumulación de uno o más aceites insolubles fuera de células vivas.
- 22El método de la reivindicación 14, en donde el organismo comprende al menos un organismo capaz de realizar la IMPI INSTITUTO MEXICANO Oí LA MOHEDA!) INDUSTRIAL fotosíntesis, caracterizado en que es capaz de secretar componentes hidrofóbicos o causar la acumulación de componentes hidrofóbicos fuera de las células vivas.
- 23El método de la reivindicación 14, en donde la fusión se logra en presencia de los organismos.
- 24El método de la reivindicación 14, en donde el organismo comprenden algas, protistas, hongos, levadura, E. coli, cultivos mezclados de células, organismos que están modificados genéticamente, u organismos que son capaces de causar la acumulación del uno o más componentes hidrofóbicos fuera de células vivas.
- 25El método de la reivindicación 14, en donde se extrae al menos 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98%, 99% o 100% de los uno o más componentes hidrofóbicos en el medio de crecimiento.
- 26El método de la reivindicación 14, en donde el uno o más fluidos de recolección comprende uno o más solventes, un biodiesel, un aceite de algas, un aceite no polar o mezclas, aceite secretado por los organismos, o combinaciones de éstos. IMPI iIMTTTVTC . Pt LA PWRLDAP ÍWWISTXIAL
Independent claims26
299 paragraphs in 56 sections, as filed
(54) Title: NON-DISPERSIVE PROCESS FOR THE RECOVERY OF INSOLUBLE OIL FROM AQUEOUS SUSPENSIONS.
(54) Title: NON-DISPERSIVE PROCESS FOR INSOLUBLE OIL RECOVERY FROM AQUEOUS SLURRIES.
(57) Summary
The present invention relates to a method for extracting one or more insoluble oils from a liquid source, comprising one or more organisms, using one or more membrane contactors, comprising the following steps: pumping the liquid source comprising one or more oils from a reactor to the one or more membrane contactors, where the liquid source does not contain a dispersant solvent; fusing the one or more oils within the liquid source onto a first surface of the one or more membrane contactors; pumping a collection fluid through the one or more membrane contactors onto a second surface of the one or more membrane contactors; contacting the one or more fused oils in the liquid source with the collection fluid pumped in the one or more membrane contactors; pumping a first stream from the one or more membrane contactors back into the reactor, wherein the first stream comprises the liquid source with one or more organisms without extracted oils; and removing the second stream from the one or more membrane contactors, wherein the second stream comprises the collection fluid and the extracted oils.
(57) Abstract
The development and application of a novel non-polar oil recovery process utilizing a non-dispersive solvent extraction method fo coalesce and recover oil from a bio-cellular aqueous slurry is described herein. The process could apply fo recovery of algal oil from a lysed algae slurry, recovery of Omega fatty acids from a bio-cellular aqueous feed, recovery of Beta-carotene from a bio-cellular aqueous feed and for the removal from produced water in oil production and similar type applications. The technique of the present invention uses a microporous hollow fiber (MHF) membrane contactor. The novel non-polar oil recovery process described herein can be coupled fo a collecting fluid (a non-polar solvent such as heptane, a biodiesel mixture or the previously extracted oil) that is circulated through the hollow fiber membrane. In cases where the biodiesel mixture or the previously extracted oil is used the solvent recovery step (eg distillation) can be eliminated.
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PATENT TITLE No. 350472
Owner (s): BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM
Address: 201 West 7th. Street, Austin, Texas, 78701, USA
Name: NON-DISPERSIVE PROCESS FOR THE RECOVERY OF INSOLUBLE OIL FROM AQUEOUS SUSPENSIONS.
Classification: CIP: C02F1 / 40: C02F1 / 44; G02F3 / 32; C11B13 / 00
CPC: C02F1 / 40; C02F1 / 44: C02F3 / 325; C11B13 / 005
Inventor (s): FRANK SEIBERT; MARTIN POENIE
REQUEST
Number: International Presentation Date:
MX / a / 2015/000699 January 13, 2011
Divisional Patent Number: 327073
PRIORITY
Country: Date: ..... Number:
US January 15, 2010 61 / 295,607
Validity: Twenty years
Expiration Date: January 13, 2031
Issue Date: September 7, 2017
The reference patent is granted based on articles 1, 2 section V, 6 “section III, and 59 of the Industrial Property Law.
In accordance with article 23 of the Industrial Property Law, this patent has a validity of twenty years, non-extendable, counted from the filing date of the international application and will be subject to the payment of the fee to keep the rights in force. .
Whoever signs this title does so based on the provisions of articles 6, sections III and 7<sup>or</sup> bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 06/27/1991, amended on 08/02/1994, 10/25/1996, 12/26/1997, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 05/06/2009, 06/01/2010, 18/06/2010, 06/28/2010, 01/27/2012 and 0S / 04/2012); items 1<sup>or</sup>, 3<sup>or</sup> fraction V part a), 4<sup>or</sup> and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DO.F 12/14/1999, amended on 07/01/2002, 07/15/2004, 07/28/2004 and 09/07 2007); items 1<sup>or</sup>, 3<sup>or</sup>, 4<sup>or</sup>, 5th section V subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, ¢ 4 / 08/2004 and 13/09/2007); 1st, 3<sup>or</sup> and 5<sup>or</sup> Subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Titular of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).
This document is signed with an advanced electronic signature (FIEL), based on articles 7 BIS 2 of the Industrial Property Law; 3 of its Regulations, and 1 section III, 2 section V, 26 BIS and 26 TER of the Agreement establishing the guidelines for the use of the Payment and Electronic Services Portal (PASE) of the Mexican Institute of Industrial Property, in the procedures indicated.
THE DIVISIONAL DIRECTOR OF PATENTS
NAHANNY CANAL REYES
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NON-DISPERSIVE PROCESS FOR THE RECOVERY OF INSOLUBLE OIL FROM AQUEOUS SUSPENSIONS
Technical Field of the Invention
The present invention relates generally to the field of recovering insoluble oil from aqueous suspensions, and more particularly, to a microporous membrane-based method for recovering oil from a lysate algae concentrate and other aqueous suspensions.
Background of the Invention
Without limiting the scope of the invention, its background is described in relation to recovery methods for low solubility and insoluble compounds that have economic value from aqueous mixtures that may include one or more types of biological cells or cellular debris.
US Patent No. 4,439,629 filed by Ruegg (1984) describes a process for extracting both beta-carotene or glycerin from algae containing these substances, especially algae of the Dunaliella genera. According to the Ruegg patent, both beta-carotene and glycerin can be extracted from algae. If it is desired to extract beta-carotene, the algae are first treated with calcium hydroxide and then filtered. The residue of this filtration is subjected to treatment with a beta2 solvent
IMPI
INSTTTUT '> MEXICANA
FROM THE fkcpieda: »industrial
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carotene, which removes solvent beta-carotene. Beta-carotene can be recovered from the solvent by conventional means. If desired to extract the glycerin, the filtrate from the calcium hydroxide treatment of the algae is neutralized, concentrated, and the solid residue is subjected to a lower alkanol treatment to remove the glycerin from the residue.
US Patent No. 5,378,639 filed by Rose et al. (1995) describe a method for the extraction of the β-carotene solvent from an aqueous suspension of an algae biomass, whereby a vegetable oil that is immiscible with water is mixed with a suspension of the aqueous biomass, the biomass that contains the β-carotene, to form a mixture of the organic phase and the aqueous suspension, whereby the β-carotene is made to dissolve in the organic phase. This is further examined by separating the organic phase from the aqueous phase by passing the organic phase containing the dissolved β-carotene through a semipermeable membrane to effect microfiltration or ultrafiltration of the organic phase. The membrane is made of a material that is hydrophobic and the organic phase is passed through the membrane with a decrease in pressure across the membrane that is lower, and makes the aqueous phase pass through the membrane.
IMPI
INSTITUTO MiXICA NO DE LA ΕΚΟΕΙΪΟΛΓ
INDUSTRIAL
Brief Description of the Invention
The present invention describes a method for recovering insoluble oil from aqueous suspensions by using a hydrophobic microporous hollow fiber membrane followed by circulating a collection liquid through the membrane. The collection liquid, as described herein, comprises a suitable solvent for the solubility compound to be recovered, for eg heptane or a blend of biodiesel or extracted oil or combinations thereof. The extracted algae oil can be used as the collection liquid for the recovery of the additional algae oil, allowing the process to be carried out without a chemical solvent such as heptane. The novel process could be used in a wide variety of commercially significant applications such as: (i) recovery of released or secreted algal oil from an aqueous mixture, (ii) recovery of insoluble hydrocarbon and hydrocarbon-rich molecules from aqueous mixtures, (iii) recovery of Omega fatty acids from an aqueous mixture, (iv) recovery of Beta-carotene from an aqueous mixture, and (v) removal of oil from water produced in petroleum exploration and production.
In conventional liquid and liquid extraction and processes that combine and involve spacious oil droplets (greater than 1,000 microns), mixing and separation of the oil and water phases by a dispersive process
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IMPI
INSTITUI or MEXICAN
D £ LA MOHEDAL industrial
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is routinely put into practice- '<sup>1</sup> eon — The relative ease. However, when the oil droplets are considerably smaller in diameter (less than 10 microns) and the solids meet, complete separation of the immiscible liquids is very difficult, if not impossible, when using dispersive methods routinely practiced. for more spacious oil droplets. When routine methods are applied to try to recover small oily water droplets in the presence of solids (such as cells or cell debris), a layer of the solid liquid liquid emulsion forms resulting in incomplete and ineffective separation of the two liquids. . Therefore a new process is required that will allow a more efficient separation and the elimination of the emulsion-solid-liquid-liquid problem. The process of the present invention allows for the recovery of the micron and sub-micron dimensioned insoluble oil decreases from an aqueous suspension using a novel non-dispersive process.
A non-dispersive process promotes a unidirectional flow of specific compounds in and through a membrane to remove compounds from the cover side supply to the tube side. A non-dispersive separation process is currently used to remove dissolved gases from liquids such as removing dissolved oxygen from water to produce extreme distilled water for
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IMPI *
INSTITUTO MUCAMO V
BE LA HtCPI £<sub>ÜAU </sub>INDUSTRIAL microelectronics industry. The present invention is a first successful demonstration of the application for non-dispersive processes to recover insoluble oil from water or aqueous suspensions. The non-dispersive process described here uses a microporous hollow fiber membrane composed of hydrophobic fibers. The aqueous suspension containing the insoluble oil is fed into the shell side of the hollow fiber module and a solvent suitable for hydrocarbon, for example, a biodiesel, or similar oil recovered in the earlier application from the described process is fed into the tube side of the hollow fiber module as a collection liquid. The aqueous phase passes around the exterior of the spacious surface area of hydrophobic fibers containing the hydrophobic collection liquid as it passes through and finally the module. As the aqueous liquid with the insoluble oil droplets passes through the module, the insoluble oil droplets adhere to the hydrophobic fiber walls and dissolve in the suitable hydrocarbon collection liquid on the tube side of the module and are transported from the module with the collection liquid. In this process, the collection liquid on the tube side does not make prolonged contact with the aqueous phase or is dispersed in the aqueous phase. The absence of this mixing as assumed by the inventors prevents the formation of a liquid emulsion * IMPI »*
MUUCAN INSTITUTE.
The solid liquid industrial solution, when the solids are present, allow the insoluble oil to be efficiently recovered from an aqueous suspension containing solids. The largest hypothesis is successfully demonstrated here to efficiently recover insoluble oil from an aqueous mixture including cells without the formation of a solid liquid liquid emulsion.
In common membrane filtration processes, small amounts of solids rapidly accumulate on the membrane surface (commonly called membrane fouling) reducing the efficiency and cost-effectiveness of the filtration process. In the process discovered and described herein using the microporous hollow fiber membrane module, the inventors assumed that membrane fouling is not a concern within specific operating parameters. The inventors show that if the module is operated by using hydrophilic cells that are small enough to pass through the dimensions of the module, and a suitable pressure differential is maintained between the aqueous liquid and the collection liquid, that the hydrophilic cells they would flow through the module and repel themselves from the surface of the membrane because the membrane is coated with a hydrophobic collection liquid. The results presented here under the prescribed operating conditions do not indicate
ΙΜ
ΙΝίΤΓΠΓΓΓ MEXICANO DE LA MONEDAD INDUSTRIAL no evidence of membrane fouling.
The novel extraction process of the present invention uses a non-dispersive solvent extraction method of binding and recovering an insoluble oil from an aqueous suspension. As an example, the recovery of non-polar algae oil from an algae concentrate is described. The method uses a microporous hollow fiber membrane contactor. The inventors have analyzed the Liqui-Cel Extra Flow Contactor, commercially used for gas / liquid contacting, to obtain> 80% extraction efficiency and the process concentrates biocellular solids up to 10% without fouling of the membrane . The novel method of the present invention utilizes the spacious bonding area provided by the surface of the microporous hollow fibers when filled with a hydrophobic collection liquid and minimizes the actual contact of the solvent with the biomass (eg algae) and aqueous phase. .
The novel extraction process described herein can be coupled with a variety of collection fluids suitable for the recovery of insoluble compounds, depending on the types of compound or compounds to be recovered. The collection liquid option will affect both the subset of compounds replenished from the aqueous suspension as well as the downstream stages had to use economically.
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as effectively compounds of the collection fluid. Differential extraction of desired molecules, eg, recovery of non-polar oils, but not polar oils, can be achieved by the option of the collection liquid. Segregation of nonpolar oils from polar oils, specifically polar oils containing phosphorous (eg, phospholipids), is highly advantageous as phosphorus containing compounds complicates both the refining and transesterification processes used to form transport fuels. The polar oils could be recovered using the process described here using a different collection liquid, for example as a secondary recovery step once the non-polar oils are already removed.
The downstream stages had to recover the desired molecules from the collection liquid are also the specific request. If heptane is used as the collection liquid, the compounds of interest can be recovered by distillation without the need for a vapor stripper. If biodiesel (Fatty Acid Methyl Ester [FAME]) is used since the collection liquid, eg, recovered oils may not require processing prior to transesterification to FAME. Importantly, the present invention can also use an oil that has been previously extracted from an aqueous suspension as the collection liquid thus completely eliminating the need for
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and expense of the need to separate the recovered compounds from the collection liquid. In this application, the collection liquid is an amount of oil derived from an aqueous suspension previously processed or extracted by a different method. The microporous hollow fiber membrane contactor as described in the present invention is small, portable, inexpensive, and capable of handling roomy slurry feed rates.
In one embodiment the present invention describes a method for extracting one or more insoluble oils comprising lipid components from algae, algae oils or both from an aqueous (smooth aqueous suspension of algae) preparation by using one or more hydrophobic membranes or modules. membranes. The method of the present invention comprises the following steps: (i) to feed an aqueous suspension comprising the insoluble oil by pumping into a contactor or container, (ii) to pump one or more collection liquids through one or more more membranes or membrane modules. One or more collection liquid counterflows with the aqueous suspension in the contactor or container and comprise one or more solvents, a biodiesel, a non-polar oil extracted from the process (e.g. algae oil), or mixtures and combinations thereof, (iii) to contact the preparation in the contactor or container with one or more collection liquids pumped through one or more membranes or membrane modules, (iv) to withdraw a first stream from the contactor or container, where the first stream comprises the algal biomass, and (v) to remove a second stream from the contactor or container, where the second stream comprises one or more collection liquids, one or more extracted (seaweed lipids), one or more seaweed oils, or both.
In another embodiment, the present invention describes a method for extracting one or more hydrocarbons or hydrocarbon-rich molecules (eg, farnesene, squalane, aldehydes, triglycerides, diglycerides, etc.) or combinations thereof, from an aqueous preparation to the using one or more hydrophobic membranes or membrane modules. Without limiting the scope of the invention, an example includes the recovery of hydrocarbon and hydrocarbon-rich molecules produced by microbial fermentation. Microbial fermentation processes are described where organisms including algae, yeast, E. coli, fungi, etc. carbon sources (eg, sugars, sugarcane bagasse, glycerol, etc.) are used to metabolize hydrocarbons and hydrocarbon-rich molecules that are secreted from (or accumulated within) cells. Such organisms are expected, by design, to physically produce small oil droplets; the inventors guessed that these droplets will not resolve
IMPI * INSTITUTE McXiCANü DE LA PROPUDAD
INDUSTRIAL easily of water by gravity alone and that the process described here will be immediately applicable to recover insoluble oils produced by microbial platforms. Companies that market microbial fermentation to oily technologies have implied that oily product recovery is trivial, but emerging company descriptions and scientific data advise recovering oil from aqueous culture media is a mission critical problem. Technologies currently in use, for eg sufficient centrifugal force to E. cali from the tablet are not sufficient to break the oily / water emulsion that is formed in aqueous culture media by hydrocarbon-producing E. coli.
In addition to the steps listed hereinabove the method of the present invention additionally involves the steps of collecting lipid components from one or more extracted algae, algae oils or both in a collection chamber, recycling the solvent separated by pumping to through one or more membranes or membrane modules to process by subsequent batch of lysed algae, by converting lipid components of one or more extracted algae, algae oils or both in the collection chamber to Fatty Acid Methyl Esters (FAMEs) or a biodiesel by transesterification or alternatively, processing based
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IMPI
INSTITUTE MiXICA? *
BE LA FKMKDAU INDUSTRIAL in refinery stages such as hydrocracking or pyrolysis and processing of the first stream that comprises the algal biomass by drying the algal biomass to optionally be used as feed, raw material for chemical production, or for power generation. The as-turned-out one or more solvents are used as the collection liquids, the method includes an optional step to separate lipid components from one or more extracted algae, algae oils or both from one or more solvents. The lysed seaweed preparation used in the method of the present invention comprises a concentrate, an aqueous suspension, a suspension, a dispersion, an emulsion, a solution, or any combination thereof. In one aspect the hydrophobic membrane or the membrane module comprises membranes of microporous hollow fibers, selected from polyethylene, polypropylene, polyolefins, polyvinyl chloride (PVC), amorphous polyethylene terephthalate (PET), polyolefin copolymers, poly ( etheretherketone), surface modified polymers, mixtures or combinations thereof. Surface modified polymers comprise polymers chemically modified into one or more halogen groups either by corona discharge or ion fixation methods. In another aspect of the method of the present invention the algae are selected from the group comprising diatoms (bacillariophytes), algae
Green IMPIs (chlorophytes), blue-green algae (cyanophytes), golden-brown algae (chrysophytes), haptophytes, Amphipleura, Amphora, Chaetoceros, Cyclotella, Cymbella, Fragilaria, Hantzschia, Navicle, Nitzschia, Phaeodactylumus, Chistrodeslormus, Chistrodeslormus, Chistrocolasscoylumcus, , Dunaliella, Monoraphidium, Oocystis, Scenedesmus, Nanochlorposis, Tetraselmis, Chlorella, Dunaliella, Oscillatoria, Synechococcus, Boekelovia, Isochysis and Pleurochysis. In yet another aspect of the method of the present invention, the one or more counterfluidizing solvents comprise nonpolar solvents, alkanes such as hexane, aromatic solvents such as benzene, toluene, ethers such as diethyl ether, halogenated solvents such as chloroform, dichloromethane, and esters such as ethyl acetate. In one aspect the counterfluidizing non-polar oil comprises algal oils, biodiesel components selected from monoglycerides, diglycerides, triglycerides and methyl esters of fatty acid.
The present invention also provides a method of extracting one or more lipid components from algae, algae oils or both from an algae preparation. Used by using one or more hydrophobic membranes or membrane modules. In the first stage the preparation of Used algae is fed to a contactor or a container by pumping while at the same time, pumping a solvent, biodiesel, an algae oil,
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MEXICAN INSTITUTE
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a non-polar oil or mixtures thereof through one or more membranes or membrane modules. The solvent, biodiesel, algae oil, non-polar oil, or the mixture is pumped through the membrane such that it backs up with the smooth algae preparation. Non-limiting examples of the non-polar oil used in the present invention include oils from non-polar algae, palm tree, rapeseed, callus, etc. One or more lipid components from algae, the algae oils, or both bind to the surface of the membrane or membrane module. The bound algae lipid components and algae oils are removed from the surface of the membrane or membrane module by contacting the counter-fluidizing solvent, biodiesel, algae oil, non-polar oil, or the mixture. A first stream comprising an algal biomass is removed from the contactor or container, followed by the removal of a second stream comprising the counter-fluidizing solvent, biodiesel, the algal oil, the non-polar oil or the mixture, one or more lipid components. of extracted algae, one or more algae oils, or both. The method for extracting the oils from algae or lipids without using a solvent further comprises the steps of: (i) collecting lipid components from one or more extracted algae, algae oils or both in a collection chamber, (ii) recycling of counter-fluidizing oil by pumping part or all of the contents of the chamber
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INSTTTl 'TO MtXICANC r> É LA MOPIIDAL · INDUSTRIAL
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Harvesting through one or more membranes or membrane modules to process by subsequent batch of Used algae, (iii) conversion of one or more extracted lipid components from algae, algae oils, or both in the collection chamber to Fatty Acid Methyl Esters ( FAMEs) or a biodiesel by transesterification or administration of oil to a refinery to process by hydrocracking or pyrolysis, and (iv) processing the first stream comprising the algal biomass by drying the algal biomass to optionally be used as feed, biochemical feedstock, or for power generation. The method further comprises the optional step of adding one or more natural fatty acids or salt thereof to the lysed seaweed preparation to aid in lipid transfer to the harvest stream.
In one aspect of the method of the present invention the one or more natural fatty acids are designated as [X]: [Y], where X represents the number of carbon atoms in one or more fatty acids ranging from 8-22 and Y represents one or more double bonds in fatty acids spanning from 06. In another aspect the one or more natural fatty acids or salts thereof comprise myristic acid, palmitoleic acid, sapienic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid , acid
<img file="MX350472B_D0017.tif" />
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INSTITUTO MtXICANU í> £ LA PMNLJ JAI 'INDUSTRIAL docosahexaenoic acid, Lauric acid, FH ^ íatiao acid, - Palmitic acid, Stearic acid, arachidic acid and combinations thereof. In yet another aspect the algae preparation Used comprises a concentrate, an aqueous suspension, a suspension, a dispersion, an emulsion, a solution or any combination thereof.
The non-polar counterfluidizing oil used in the present invention comprises seaweed oils, various components of biodiesels selected from monoglycerides, diglycerides, triglycerides, and methyl esters of fatty acid. In a related aspect, the hydrophobic membrane or the membrane module comprises membranes of microporous hollow fibers, selected from polyethylene, polypropylene, polyolefins, polyvinyl chloride (PVC), amorphous polyethylene terephthalate (PET), polyolefin copolymers, polymers of the type of poly (etheretherketone), surface modified polymers, mixtures or combinations thereof. Surface modified polymers comprise polymers modified chemically at one or more halogen groups or by ion fixation or corona discharge methods. In one aspect the algae are selected from the group comprising diatoms (bacillariophytes), green algae (chlorophytes), blue-green algae (cyanophytes), brown algae (chrysophytes), haptophytes, Amphipleura, Amphora,
Chaetoceros, Cyclotella, Cymbella, Fragilaria, Hantzschia,
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Navícula, Nitzschia, Phaeodactylum, Tnalássiosi'ra
Ankistrodesmus, Botryococcus, Chlorella, Chlorococcum,
Dunaliella, Monoraphidium, Oocystis, Scenedesmus,
Nanochlorposis, Tetraselmis, Chlorella, Dunaliella, Oscillatoria, Synechococcus, Boekelovia, Isochysis and
Pleurochysis. In another embodiment the current invention describes a contactor or container for extracting one or more components of the insoluble oil from the aqueous biocellular suspension such as among other algae oils or both from a Used algae concentrate. The contactor or container as described herein comprises, an outer metallic, polypropylene or other polymeric sheath, one or more microporous hollow fiber membrane cartridges comprising a plurality of microporous hollow fiber membranes attached by the metallic sheath, where one or more membrane cartridges split the casing on one side of the casing and one side of the fiber, one or more baffles on the casing side of the metal casing, one or more distribution tubes on the fiber side of the metal sheath, two inlet ports connected with the outer metal sheath, where the lysed algae concentrate is pumped to the side of the sheath through the first inlet port and gas of the strip or a solvent are fed to the fiber side through the second inlet port and two
<img file="MX350472B_D0018.tif" />
IMPI
MUICANiI INSTITUTE
OF THE INDUSTRIAL RROMEDAlJ exhaust valve connected with the metallic shell, where an algae refinement comprising the algal biomass is removed from the first exhaust valve port and a lipid or oily solvent / extract mixture or strip gas is removed from the second exhaust valve port.
In one aspect the microporous hollow fiber membrane comprises polyethylene, polypropylene, polyolefins, polyvinyl chloride (PVC), amorphous polyethylene terephthalate (PET), polyolefin copolymers, poly (etherether ketone) type polymers, surface modified polymers, blends or combinations of the same. Surface modified polymers comprise polymers modified chemically into one or more halogen groups or by ion fixation or corona discharge methods. In another aspect the algae used for the extraction of the oil from algae or lipids are selected from the group comprising diatoms (bacillariophytes), green algae (chlorophytes), blue-green algae (cyanophytes), golden-brown algae (chrysophytes), haptophytes, Amphipleura, Amphora, Chaetoceros, Cyclotella, Cymbella, Fragilaria, Hantzschia, Navícula, Nitzschia, Phaeodactylum, Thalassiosira Ankistrodesmus, Botryococcus, Chlorella, Chlorococcum, Dunaliella, Monoraphidium, Oocystis, Scenedesmus, Nanochlorposis, Tetraselmis, Chlorella, Dunaliella, Oscillatoria, Synechococcus, Boekelovia, Isochysis and
<img file="MX350472B_D0019.tif" />
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Pleurochysis.
In yet another embodiment the present invention describes a method of extracting one or more algal oils from a lysed algal concentrate in a contactor by using one or more hydrophobic microporous hollow fiber membrane modules comprising a plurality of hollow fiber membranes. microporous that comprise the stages of: (i) to pump the lysed algae concentrate through a first contactor inlet port on one side of the contactor cover, (ii) to pump one or more collection fluids through a second contactor inlet port to one or more hollow fiber membranes on one side of the contactor fiber; where one or more collection liquid counterflows with the smooth algae preparation on the side of the contactor cover. One or more collection liquids comprise one or more solvents, a biodiesel, an algae oil, a non-polar oil, or mixtures thereof, (iii) to contact the lysed algae concentrate on the shell side with one or more non-polar solvents on the fiber side, (iv) to withdraw a first flow from a first exhaust valve port in the contactor, where the first flow comprises a biomass of algae, and (v) to withdraw a second flow from a second exhaust valve port on the contactor, where the second flow comprises the harvesting liquid and algae oils.
INSTITUTO MbXlCANi DE LA PROPERTY INDUSTRIAL one or more extracted. The method of pyrrarriqn Πρηγ-τΗ tn an io embodiment of the present invention further comprises the steps of: (i) collecting one or more extracted oils from algae in a collection chamber, (ii) recycling the separated solvent by pumping through one or more microporous hollow fiber membranes for subsequent batch processing of smooth algae, (iii) the conversion of one or more extracted oils from algae in the collection chamber to Fatty Acid Methyl Esters (FAMEs) or a biodiesel by transesterification or conversion to fuels by methods based on refinery stages such as hydrocracking and pyrolysis, and (iv) Processing of the first stream comprising the algal biomass by drying the algal biomass to optionally be used as feed or for power generation. In one aspect the extraction method as described herein comprises the optional step of separating one or more extracted algae oils from one or more solvents.
In another aspect counterfluidizing solvents comprise nonpolar solvents, alkanes like hexane, and aromatic solvents like benzene, toluene, and ethers like diethyl ether, halogenated solvents like chloroform, dichloromethane, and esters like ethyl acetate. In yet another aspect 45-80% of one or more algal oils in the lysate algae concentrate is extracted by the method of the present invention. According to the method described in this
IMPI
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OF THE PROPERTY
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Invention 45%, 55%, 60%, 65%, 70%, 75% and 80% of one or more algal oils in the lysate algae concentrate are extracted.
The present invention further describes a method of extracting one or more algal oils from a lysed algal concentrate in a contactor by using one or more hydrophobic microporous hollow fiber membrane modules comprising a plurality of microporous hollow fiber membranes. The first stage of the method involves pumping a lysed algae concentrate through a first contactor inlet port on one side of the contactor cover followed by pumping a solvent, biodiesel, algae oil, non-polar oil, or mixtures of the same through a second contactor inlet port through one or more membranes or membrane modules on one side of the contactor fiber. Biodiesel, algae oil, non-polar oil, or the mixture is pumped through the membrane such that it backs up with the smooth algae preparation on the cover side of the contactor. The algae oils bind onto the microporous hollow fiber membrane and are removed from the membrane surface by contacting the counter-fluidizing solvent, biodiesel, algae oil, non-polar oil, or the mixture. A first stream comprising an algal biomass is removed from a first exhaust valve port on the contactor followed by removal by a
<img file="MX350472B_D0021.tif" />
IMPI
MEXICAN INSTITUTE
Say THE SECOND INDUSTRIAL MOMTY flow from a second exhaust valve port on the contactor. The second stream comprises the counter-fluidizing biodiesel, the algal oil, the non-polar oil or the blend and one or more extracted algae oils.
The method of extracting the oil from algae as described in one embodiment of the present invention further comprises the steps of: collecting one or more extracted oils from algae in a collection chamber, counterfluidizing oil recycling by pumping part or all of the collection chamber contents through one or more microporous hollow fiber membranes for subsequent batch processing of smooth seaweed, by converting one or more algae oils extracted in the collection chamber to Fatty Acid Methyl Esters (FAMEs) or a biodiesel by transesterification or conversion to fuels by methods based on refinery stages such as hydrocracking and pyrolysis, and by processing the first stream that comprises the algal biomass by drying the algal biomass to optionally be used as feed, biochemical feedstock, or for power generation. In one aspect the method comprises the optional step of adding one or more natural fatty acids or salts thereof, hydrocarbon and hydrocarbon rich molecules, including aldehydes (flavors and fragrances), terpenes (chemical raw materials), etc. to the preparation of smooth seaweed. In another aspect the one or more natural fatty acids are designated as [XI: [Y], where X
IMPI
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
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represents the number of carbon atoms in one or more fatty acids ranging from 8-22 and Y represents one or more double bonds in fatty acids ranging from 0-6. The one or more natural fatty acids (saturated or unsaturated) or salts thereof comprise myristic acid, palmitoleic acid, sapienic acid, oleic acid, linoleic acid, α-linolenic acid, arachidonic acid, eicosapentaenoic acid, acid Erucic Acid, Docosahexaenoic Acid, Lauric Acid, Myristic Acid, Palmitic Acid, Stearic Acid, Arachidic Acid, and combinations thereof. In another aspect, counterfluidizing oil comprises non-polar oils, biodiesel components selected from monoglycerides, diglycerides, triglycerides, and methyl esters of fatty acid. In still another aspect the hollow fiber hydrophobic membrane comprises polyethylene, polypropylene, polyolefins, polyvinyl chloride (PVC), amorphous polyethylene terephthalate (PET), polyolefin copolymers, poly (etheretherketone) type polymers, surface modified polymers, mixtures or combinations thereof, where the polymers are modified chemically into one or more halogen groups or by ion fixation or corona discharge methods.
Another embodiment of the present invention describes a method for extracting one or more insoluble oils from a
<img file="MX350472B_D0023.tif" />
IMPI
MU1CANO INSTITUTE OF INDUSTRIAL PROPERTY liquid source when using one or more .hidrof óbicas_ja membranes. membrane modules comprising the stages of: (i) to feed the liquid source comprising one or more insoluble oils by pumping into a contactor or container, (ii) to pump one or more collection liquids through one or more membranes or membrane modules, where one or more collection liquid counterflows with the liquid source in the contactor or container, where one or more collection liquids comprise one or more solvents, a biodiesel, an algae oil, a non-polar oil or mixtures and combinations thereof, (iii) to contact one or more insoluble oils in the liquid source in the contactor or container with one or more collection fluids pumped through one or more membranes or membrane modules, (iv) to withdraw a first flow from the contactor or container, where the first flow comprises the liquid source without one or more insoluble oils, and (v) to withdraw a second flow from the contactor or container, wherein the second stream comprises one or more harvesting liquids and one or more insoluble oils extracted.
The extraction method as described above further comprises the steps of: collecting one or more extracted insoluble oils in a collection chamber, recycling the separated solvent by pumping through one or more membranes or membrane modules for batch processing
<img file="MX350472B_D0024.tif" />
from the liquid aqueous suspension, and by converting one or more extracted insoluble oils comprising lipid components from algae, algae oils, or both in the collection chamber to Fatty Acid Methyl Esters (FAMEs) or a biodiesel by transesterification or a process based on refinery stages such as hydrocracking or pyrolysis. The liquid source used in the method of the present invention is selected from the group comprising industrial water, brine, waste water, industrial or natural effluents, water and oil mixtures, aqueous suspensions, the aqueous suspensions comprising broken cells, cells in vivo or combinations mixtures of the same, biocellular, They used cell preparations and combinations of the same. In one aspect of the method described above the biocellual mixture comprises algae, protists, fungi, yeast, E. coli, mixed cell cultures and combinations thereof. In another easpect the method extracts 45-100% of one or more insoluble oils in the liquid source. In still another aspect 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98 %, 99% and 100% of one or more insoluble oils in the liquid source are extracted.
Brief Description of Figures
For a fuller understanding of the characteristics and
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INSTITUTO MEXICANO DE LA MEOME DAD INDUSTRIAL
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advantages of the present invention, reference is made to the detailed description of the invention together with the accompanying figures, and where:
Figure 1 is a schematic exposition of the method and principle of recovering oil from algae as described in the embodiments of the present invention;
Figure 2 is a schematic of a general algae oil production process;
Figures 3A and 3B show photographs of an algae cell before (3A) and after lysing (3B);
Figures 3C and 3D show photographs of algal cells before (3C) and after lysing (3D);
Figure 4 is a flow chart of a general process for extracting oil from algae;
Figure 5 is a flow diagram of the novel algae oil extraction process (with the solvent) of the present invention;
Figure 6 is a flow chart of the novel algal oil extraction process (without the solvent) of the present invention;
Figure 7 is a schematic of the Liqui-Cel extra flux microporous hollow fiber membrane contactor;
Figure 8 is an HPLC (chromatogram) trace of oil obtained using hollow fiber membrane extraction of a lysed suspension of Nanochloropsis. Two Mexican institute
OF THE WETLAND ·
INDUSTRIAL main peaks are observed in this sample, the first is a mixture of various long chain hydrocarbons and the second is a triglyceride; Y
Figure 9 shows an alternative process where a liquid-liquid-solid emulsion potentially derived from dispersive extraction is fed to the side of the microporous hollow fiber membrane shell to separate both liquids.
Detailed description of the invention
While the manufacture and use of various embodiments of the present invention are mentioned in detail, it should be appreciated that the present invention provides many applicable inventive concepts that can be implemented in a wide variety of specific contexts. The specific embodiments mentioned herein are merely illustrative of the specific ways of making and using the invention and do not limit the scope of the invention.
To facilitate understanding of this invention, various terms are defined less than. The terms defined herein have meanings as commonly understood by one of ordinary skill in the areas relevant to the present invention. Terms like the a, a, and being are not conceptualized to refer to only a singular entity, but include the general class of which an example
IMPIAS rNSTrn m> mexicani PROPERTY
Specific INDUSTRIAL can be used for illustration. The terminology used herein describes specific embodiments of the invention, but its use does not delimit the invention, except as detailed in the claims.
As used herein the term "aqueous suspension" encompasses water-based liquids containing any of the following in any combination; Insoluble oils (hydrocarbons and hydrocarbon-rich molecules of commercial value), living, dead, damaged and / or broken cells (or not), proteins and other cellular debris, including sugars, DNA, RNA, etc. The aqueous suspension may also contain a solvent that is used to pre-treat cells to release compounds of interest.
The term oil as used herein refers to a single hydrocarbon or hydrocarbon rich molecule that includes a complex mixture of lipids, hydrocarbons, free fatty acids, triglycerides, aldehydes, etc. The compounds included here can be<sub>C</sub>8 (compatible jet fuel) and the others can be <sub>C</sub>eo (compatible motor oil). Some compounds are pure hydrocarbons, some will have oxygen, and some will have phosphorous.
The present invention describes a method of recovering algal oil from lysed algae is concentrated by using the hydrophobic microporous hollow fiber membrane followed by the recovery of the algae oil by using a
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MEXICAN INSTITUTE
D £ LA PHOP1E0ALINDU5TRÍAL
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collection fluid that can be a solvent, biodiesel, algae oil, or mixtures thereof. The method of the present invention does not require the intimate contact of the lysed algae with concentrate and solvent. The use of a hydrophobic microporous hollow fiber membrane provides a non-dispersive method of bonding to and recovering oil from algae. The concentrated algae is fed into the shell side while the algae oil or biodiesel blend is fed into the fiber side. The algae oil acts to sweep and remove bound oil within the tube surface of the hollow fibers. A natural fatty acid perhaps added to the algae is concentrated to minimize fouling on the outer surface of the fiber and increase oil melting. A simple schematic representation of the method of the present invention is depicted in Figure 1.
Figure 1 shows an algae oil recovery unit 100. The unit 100 comprises a housing 102, within which is contained a membrane module 104 comprising a plurality of microporous hollow fiber membrane units represented as 104a, 104b, and 104c. The unit has two inlet ports 106 and 108. The slurry preparation is fed (pumped) through port 106. A collection liquid is pumped through inlet port 108. The collection fluid can <sup>30</sup> IMPI® ιηγγιττ rro mlxica nl>
OF INDUSTRIAL PROPERTY be a solvent, a biodiesel, an oil of 'Λ ^ ΪΓΒbΠ152C155<sup>1 </sup>of the same. The algae preparation counterflows with the harvesting liquid that flows into the microporous hollow fiber membranes 104a, 104b, and 104c. The algae oils or lipid are attached to the surface of the hollow fiber membranes and are entrained by and recovered by the collection liquid and exiting the unit 100 through the exhaust valve port 110. The outlet flow Obtained for further processing (eg solvent recovery) if necessary. Collection fluid spills out of unit 100 through port 112.
The method of the present invention by using a biodiesel blend as the collection liquid eliminates the need for a distillation system or a mold release to recover the solvent thereby reducing the capital expenditure and operating cost of the total oil recovery process.
A wide variety of organisms can be used to generate oils and lipids that can be extracted with the present invention. Non-limiting examples of algae and microalgae can be cultivated and used with the present invention which includes one or more members of the following divisions: Chlorophyta, Cyanophyta (Cyanobacteria) and Heterokontophyt. Non-limiting examples of classes of microalgae that can be used with the present invention include: Bacillariophyceae, Eustigmatophyceae, and
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Chrysophyceae. Non-limiting examples of Genetus' Jg microalgae used with the methods of the invention include: Nannochloropsis, Chlorella, Dunaliella, Scenedesmus, Selenastrum, Oscillatoria, Phormidium, Spirulina, Amphora and Ochromonas. Non-limiting examples of microalgal species that can be used with the present invention include: Achnanthes orientalis, Agmenellum spp., Amphiprora hyaline, Amphora coffeiformis, Amphora coffeiformis var. linea, Amphora coffeiformis var. punctata, Amphora coffeiformis var. taylori, Amphora coffeiformis var. tenuis, Amphora delicatissima, Amphora delicatissima var. capitata, Amphora sp. , Anabaena, Ankistrodesmus, Ankistrodesmus falcatus, Boekelovia hooglandii, Borodinella sp., Botryococcus braunii, Botryococcus sudeticus, Bracteococcus lesser, Bracteococcus medionucleatus, Carteria, Chaetoceros gracilis, Chaetoceros mierouelleri. subsalsum, Chaetoceros sp., Chlamydomas perigranulata, Chlorella anitrata, Chlorella Antarctica, Chlorella aureoviridis, Chlorella candida, Chlorella capsule, Chlorella desic, Chlorella ellipsoidea, Chlorella emersonii, Chlorella fusca, Chlorella fusca var. vacuolata, Chlorella glucotropha, Chlorella infusionum, Chlorella infusionum var. Actophila, Chlorella infusionum var. auxenophila, Chlorella kessleri, Chlorella lobophora, Chlorella luteoviridis, Chlorella luteoviridis var. aureoviridis, Chlorella luteoviridis var. lutescens,
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Chlorella maniata, Chlorella minutissima, Chlorella mutabilis, Chlorella nocturnal, Chlorella ovalis, Chlorella parva, Chlorella photophila, Chlorella pringsheimii, Chlorella protothecoides, Chlorella protothecoides var. acidicola, Chlorella will regulate, Chlorella will regulate var. minimum, Chlorella will regulate var. umbrácata, Chlorella reáságláá, Chlorella saccharophála, Chlorella saccharophála var. ellápsoádea, Chlorella salina, Chlorella samplex, Chlorella sorokiniana, Chlorella sp. , Chlorella sphaeráca, Chlorella stágmatophora, Chlorella vannáelláá, Chlorella vulgarás, Chlorella vulgarás fo. tertáa, Chlorella vulgarás var. autotrophica, Chlorella vulgarás var. várádás, Chlorella vulgarás var. vulgarás, Chlorella vulgarás var. you will vulgar fo. tertáa, Chlorella vulgarás var. you will vulgar fo. várádás, Chlorella xanthella, Chlorella zofángáensás, Chlorella trebouxáoádes, Chlorella vulgarás, Chlorococcum ampusáonum, Chlorococcum sp., Chlorogonáum, Chroomonas sp., Chrysosphaera sp. , Crácosphaera sp., Crypthecodánáum cohnáá, Cryptomonas sp. , Cyclotella cryptáca, Cyclotella meneghánáana, Cyclotella sp., Dunaláella sp., Dunaliella bardawál, Dunaláella bioculata, Dunaláella granulate, Dunaláella maritime, Dunaláella minuta, Dunaliella parva, Dunaliella peircei, Dunaláella sp., Dunaliella bardawál, Dunaláella bioculata, Dunaláella terriella prámolectaina viridis, Dunaliella tertiolecta, Eremosphaera viridis, Eremosphaera
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sp. , Effipsoidon sp. , Euglena spp., Franceia 'vp. , - Frag-i-Fnrio crotonensis, Fragilaria sp., Gleocapsa sp., Gloeothamnion sp., Haematococcus pluvialis, Hymenomonas sp., Isochrysis aff. galbana, Isochrysis galbana, Lepocinclis, Micractinium, Micractinium, Monoraphidium minutum, Monoraphidium sp. Nannochloris sp., Nannochloropsis salina, Nannochloropsis sp. , Navicle acceptata, Navicle biskanterae, Navicle pseudotenelloides, Navicle pelliculosa, Navicle saprophila, Navicle sp. , Nephrochloris sp., Nephroselmis sp., Nitschia communis, Nitzschia alexandrina, Nitzschia closterium, Nitzschia communis, Nitzschia dissipata, Nitzschia frustulum, Nitzschia hantzschiana, Nitzschia inconspicua, Nitzschia pusillatica, Nitzschiapuschia intermediums, Nitzschiacepensia microbe, Nitzschiacepensia puspicilla, Nitzschiacepensia microbes , Nitzschia quadrangular, Nitzschia sp., Ochromonas sp., Oocystis parva, Oocystis pusilla, Oocystis sp., Oscillatoria limnetica, Oscillatoria sp., Oscillatoria subbrevis, Parachlorella kessleri, Pascheria acidophila, Pavlova sp. , Phaeodactylum tricomutum, Phagus, Phormidium, Platymonas sp., Pleurochrysis portfolioe, Pleurochrysis dentate, Pleurochrysis sp. Prototheca wickerhamii, Prototheca stagnora, Prototheca portoricensis, Prototheca moriformis, Prototheca zopfii, Pseudochlorella aquatica, Pyramimonas sp. , Pyrobotrys, Rhodococcus opacus, Sarcinoid chrysophyte, Scenedesmus armatus, Schizochytrium, Spirogyra, Spirulina platensis,
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INSTITUTO MEXICAI *
OF THE • INDUSTRIAL PROPERTY
Stichococcus sp., Synechococcus sp., SynecliwysLisf, TugiLticai erecta, Tagetes patula, Tetraedron, Tetraselmis sp., Tetraselmis suecica, Thalassiosira weissflogii and Viridiella fridericiana.
Other sources for biomass can be a wild-type or genetically modified fungus. Non-limiting examples of fungi that can be used with the present invention include: Mortierella, Mortierrla vinacea, Mortierella alpino, Pythium debaryanum, Mucor circinelloides, Aspergillus ochraceus, Aspergillus terreus, Penicillium iilacinum, Hensenulo, Chaetomium, Cladoscheaporium, Rhizopusporium, . As the biomass source is not limited in using the devices and methods of the present invention it can be wild type or genetically modified yeast. Non-limiting examples of yeast that can be used with the present invention include Cryptococcus curvatus, Cryptococcus terricolus, Lipomyces starkeyi, Lipomyces lipofer, Endomycopsis vernalis, Rhodotorula glutinis, Rhodotorula gracilis, Candida 107, Saccharomyces paradoxomyus, Saccharomyces mikacestae bay, Saccharomyces cereus, Saccharvise, Saccharvise , any Cryptococcus, C. neoformans, C. bogoriensis, Yarrowia lipolytica, Apiotrichum curvatum, T. bombicola, T. apícola, T. petrophilum, C. tropicalis, C. lipolytica, and Candida sp., eg, Candida albicans.
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The biomass can even be any bacteria that generate lipids, oils, proteins and carbohydrates, either naturally or by genetic engineering. Non-limiting examples of bacteria that can be used with the present invention include Escherichia coli, Acinetobacter sp. any actinomycete, Mycobacterium tuberculosis, any streptomycete, Acinetobacter calcoaceticus, P. aeruginosa, Pseudomonas sp., R. erythropolis, N. erthopolis, Mycobacterium sp., B., U. zeae, U. mayáis, B. lichenformis, S. marcescens, P. fluorescens, B. subtilis, B. brevis, B. polmyma, C. lepus, N. erthropolis, T. thiooxidans, D. polymorphis, P. aeruginosa, and Rhodococcus opacus.
While the algae make the oil, there is no simple and inexpensive method to extract oil directly from an aqueous suspension. Drying the algae are usually necessary for solvent extraction and the biomass is exposed to toxic solvents. Other methods such as supercritical extraction are uneconomical for products of tangible good such as fuel. Solvent extraction is somewhat promising, but requires the distillation of an extract to separate the solvent from the oil. Also, a vapor stripper is generally required to recover residual solvent dissolved or trapped within the exiting algae concentrate. The solvent extraction method requires contactor equipment or separation equipment
<img file="MX350472B_D0031.tif" />
phases, a distillation system and a doomolder dol
IMPI • ííTTTW 'MEXICANO DI LA PKOnULAD ΙΝβΚ.ιπΜΛΙ steam along with various heat exchangers, surge tanks and pumps. Also steam and water for cooling are required. The process described here only requires a membrane system with pumps and reservoirs. No steam or water for cooling is required.
a Process alternatives: After the selection of the appropriate solvent, the next step should determine whether to algae oil from wet or dehydrated algae extract. The dehydrated process requires desiccation and evaporation of water from the algal biomass and then lysing the algae. Lisar is a process of breaking down the cell wall and opening the cell. The solvent can contact the dehydrated algae in the special counter current leaching equipment. Solvent and extracted seaweed oil is separated in a vacuum distillation tower or evaporator. The remaining algal biomass with the residual solvent is fed to a special evaporator to remove and recover the solvent and dry the algal biomass again. The dehydrated process suffers from having to dry the algae a second time when the solvent must evaporate away, handling a multi-stage high solids flow, and potentially keeping the solvent in the residual algae solids.
The wet process requires you to concentrate smooth and te
<img file="MX350472B_D0032.tif" />
IMPI fNSTTTUTí> MIX1CANO DI LA PROPIÍDAO INDUSTRIAL the extraction of algae. The wet process requires an excellent smoothing method followed by a solvent extraction process, which provides the adequate mass transfer area to dissolve / bond the non-polar lipids. The wet process offers the advantages of drying the algae only once and leaving less residual solvent in the algal biomass. To minimize the cost of processing, the wet process appears to offer significant advantages.
The present invention focuses on the wet process and the novel non-dispersive extraction contactor used to bind and dissolve the desirable non-polar lipids.
As shown in Figure 2, the oil extraction step 212 follows the algae concentration 208 and lysing 210 steps. After initial growth and harvest, from pond 202 the supply of dilute algae becomes considerably concentrated. The common algae concentration obtained from pond 202 generally ranges from 100 to 300 mg dried algae / liter. from solution. The objective of the concentration step 208 is to remove and recycle water 214 back to the pond. Concentration methods 208 range from centrifugation to algae flocculation / settlement. To maximize extraction efficiency and lysing, it is important that the concentrate that is fed to lysing is not flocculated. After the concentration step 208, the algae concentrate is sent
<img file="MX350472B_D0033.tif" />
IMPI nnSTTTUTV MtXICANÍi DE LA FiiOPlIDAD fNIWXTXIAL a Using 210 stage processing where the ... cell — d “—adyair mechanically or electromechanically breaks, thus exposing and releasing the non-polar oil. Various methods can be used to mechanically or electrically compress and decompress to rupture the cell. Generally speaking, after lysing, 212 the algal cell can disintegrate or open as shown in Figure 3A-3D. Figures 3A and 3C show that photographs of an algae cell before lysing and Figures 3C and 3D show photographs of previous algal cells after lysing.
Once oil has been released from within the algal cell, oil will simply not separate from the cellular biomass due to differences in density. Also since the equivalent diameters of most microalgae are very small and on the order of 1-5 microns, the oily droplet diameter is often much less than 1 micron. Such oily droplets do not rise or bond with other droplets very well and can form a stable emulsion. When solid algal biomass 216 is added to the mix, oil recovery is even more difficult. Therefore settlement of the simple gravitational phase is not a viable option for oily separation after lysing. After lysing, the concentrated algae is fed to separations stage 212 where algae oil 220 is separated from the wet algae biomass 216. Biomass 216 can be called
<img file="MX350472B_D0034.tif" />
IMPI
INSTITUTE MtXiCAN <> DB LA FROPitL'AD INDUSTRIAL additional drying and will be used for feed or further processed for power generation requests.
As shown in Figure 4, the common solvent extraction process involves 1) an extraction step to recover algae oil from the lysed biomass, 2) a vacuum distillation or evaporation step to separate oil and solvent where the solvent is the stage returned to, and 3) if necessary, steam stripping stage to recover the dissolved and trapped the solvent, maintaining the extraction stage with the biomass of algae.
Figure 4 is a flow chart 400 of a general algal oil extraction process using a conventional dispersive extraction column 406. The lysed algae concentrate 402 and 404 solvents are fed to an extractor in column 406 to extract the algae oils and lipids 408. Stream 406a comprises the 404 solvents containing the algae oils and lipids. Stream 406a is then fed to a 4 08 vacuum distillation unit to recover the 404 solvents and algae oil 410. The separated solvent without any oil or other components 404 is fed back to extractor 406. As it turned out, it needs Further purification (separation), the 404 solvents are fed back to vacuum distillation unit 408 (via flow 408a). A second flow
406b of the extractor 406 comprises the biomass of algae, solids
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INDUSTRIAL and residual solvent. Stream 406b is passed through a stream release 412, to separate the wet biomass 418 and other solids from the 404 solvents. The wet biomass 418 is subjected to further drying. The 414 recovered solvents are collected in a decanting vessel 416 before being recycled back to extractor 406 via flow 414a. A second stream 414b from vessel 416 recycles any solvent dissolved in the condensed vapor 414 back to stream 412 mold release.
Extraction Processing and Equipment: The extraction process desired for the recovery of oil from algae must satisfy certain requirements and avoid potential gaps for economic recovery. There are several wet extraction processes for oil recovery that are technically feasible, but not necessarily inexpensive. Minimal oil recovery costs are critical if the ultimate use of the recovered algae oil is fuel.
The optimal oil extraction process should include: (i) the processing of an aqueous biocellular suspension containing oil, (ii) when using solvent or non-polar extracted oil with very low miscibility in water, (iii) when using a solvent ( if necessary), which easily separates from oil, (iv) by using extraction equipment that can handle high processing feed rates and
IMPI
ΙΝίΤΓΠΓΤΌ MEXtCAN ·
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easily increased, (v) when using a fin · rifLiaL-cldll equipment which minimizes the carry-over of the solvent in the biomass, (vi) when using an extraction equipment that provides high contact area to the mass transfer and non-polar lipid fusion , (vii) by using extraction equipment capable of handling concentrated algae supplies and not being irreversibly fouled by algae solids, (viii) by using extraction equipment that is relatively compact and potentially portable to allow transport to different algae production sites, and (ix) by using extraction equipment that is readily available, inexpensive and safe.
Membrane-based processes for separations have been around for a long time. There are many types of membranes. Most membrane processes however use porous membranes where the membrane material undergoes separation as a result of differences in diffusion and balance between chemical components and at the molecular level. The present inventors however use a microporous membrane, which is rarely used commercially except applications involving the transfer of gases to or from a liquid such as water. Microporous membranes work very differently from porous membranes due to their relatively spacious pores. Microporous membranes do not make really separate chemical components on the molecular level that
<img file="MX350472B_D0036.tif" />
IMPI
INSTITUTO MEXICANO ut LA PHOUEDAO industrial similar porous membranes make. The present invention S ^ · is based on the fusion of the present non-polar lipids within the aqueous suspension of algae to bond on the hydrophobic surfaces provided by the hollow fibers. The enormous surface area of the membrane, combined with the ability of the hydrophobic collection fluid to wet the membrane, forms a surface capable of small lipid droplets that stick together. Once attached to the collection fluid, the lipids are transported from the membrane through the air chambers of the hollow fibers.
Membrane-based Oil Recovery Process: For example, the request for a microporous hollow fiber (MHF) membrane contactor as the optimal extraction equipment seems ideally suited for the recovery of oil from algae. The MHF contactor provides all of the optimal characteristics previously listed. The application of the MHF contactor to the recovery of oil from algae is novel, it minimizes solvent loss, eliminates the need for a vapor stripper, minimizes solid contamination and is easy to operate. The process does not involve dispersing a solvent in the algal biomass. The non-dispersive nature of the contactor is attractive in minimizing solvent loss and thus potentially eliminating the need for a vapor stripper. A
IMPI ΐΝίΙΤΠΓΤϋ MEXICANC
ΙΝΓΤΤΠΠΌ MEXICANC Γιί LA EROMDAD INDUSTRIAL collection fluid that usually involves ---— either a solvent (such as hexane) or a mixture of biodiesel or algae oil is circulated through the hollow fibers for the recovery of algae oils. The request for the MHF contactor in conjunction with a biodiesel blend circulated through the microporous hollow fibers eliminates the need for a solvent and distillation column. Two Reaction Schemes of oily extraction processing with the solvent and the biodiesel mixture are shown in Figures 5 and 6, respectively.
Figure 5 is a schematic representation of the novel algae oil extraction process (with the solvent) of the present invention. The process comprises a MHF contactor 502 comprising a plurality of microporous hollow fiber membranes 504 and a central baffle 506. The 508 solvents are fed (pumped) through the fibers of the membrane 504 and contacted with the lysate algae concentrate 512 contained in the shell portion of the MHF 502 contactor. There are two flows from the 502 contactor outlet , an algal biomass stream 510 that is further processed (dried) and a solvent stream 508a containing the extracted algal oils and lipids 516. Flow 508a is passed through a vacuum distillation unit 514 to separate oil 516 from the 508 solvents and recover the 508 solvents for recycling and
<img file="MX350472B_D0037.tif" />
IMPI
INSTITUTO MSXIGANO M LA «O» I®AL · INDUSTRIAL reuse. The flow from the outlet 508b of distillation unit 514 comprises 508 pure solvents that are recycled and fed to contactor 502 to repeat the process and solvent that requires further separation and recycled back to distillation unit 514. The flow from the outlet 508c of the distillation unit 514 comprises the algae oils 516. A portion of this stream is vaporized (518b) and returned to distillation unit 514.
Figure 6 is a 600 schematic representation of the novel algal oil extraction process (without the solvent, using a biodiesel blend) of the present invention. The process comprises a MHF contactor 602 comprising a plurality of microporous hollow fiber membranes 604 and a central baffle 606. Non-polar algal oil 608 is fed (pumped) through the fibers of membrane 604 and contacted with the lysate algae concentrate 612 contained in the cover portion of the MHF 602 contactor. The algae oil functions Nonpolar to dissolved and swept oil bound from the algae concentrate. The non-polar oil 616 binds to the surface of the hydrophobic fiber 604 and dissolves in the oil contained in the walls and the counter-fluidizing oil phase 608 and can be removed. There are two streams from the outlet of contactor 602, an algal biomass stream 610 that is further processed (dried) a stream 608a containing the algal oils and
<img file="MX350472B_D0038.tif" />
IMPI
MUICAM INSTITUTE
Say THE INDUSTRIAL ROR1AGE lipids 616 that is collected in a reservoir 614. The oil portion 616 can be removed from reservoir 614 and fed to contactor 602 to repeat the process.
Microporous hollow fiber contactors were initially developed in the 1980s. These early studies focused on laboratory scale prototype modules containing only a few fibers. These early studies promoted the possibility of liquid and liquid extraction requests. The contact of two immiscible liquids such as water and a non-polar solvent is unique to MHF contactors in that there is no dispersion of one liquid into the other. This technology is sometimes referred to as non-dispersive extraction. Hollow fibers are generally made up of a hydrophobic material such as polyethylene or polypropylene. These hollow fibers could be made of a different material but should be hydrophobic to avoid fouling the fiber surface with algae solids which are generally hydrophilic. The solvent should be hydrocarbon with very low solubility in water and is pumped through the hollow fibers. As a result of the hydrophobicity of the fiber material, the solvent will wet the microporous fibers and fill the micropores. Aqueous liquid is pumped through the contactor cover side of the membrane. Prevent solvent gap on cover side, cover or aqueous side will
IMPI
ΠΓΓΤηίΤΟ MEXICAN
OF THE INDUSTRIAL HW1EDAO
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controls at a higher pressure which side of hydrocarbon or fiber. This results in immobilizing a liquid and liquid interconnection on the porous walls of the hollow fibers. Unfortunately when these modules are progressively increased for liquid and liquid extraction, performance is generally disappointingly low. Further studies identified how low efficacy is a result of avoiding side cover. An improved version (referred to as the Liqui-Cel Extra Flow contactor) was developed that eliminated the possibility of deck side bypass by incorporating a side distributor through the deck. While the design eliminated side shoring through the cover, the new design eliminated true counter contacting. Overall performance is somewhat improved over the original design. However, the new design did not correct the fundamental limitations of lateral mass transfer resistance through the pore that would control the most commercially significant extraction requests. As a result, only a few commercial liquid extraction applications using MHF networking technology exist today.
Also, MHF contactors often required expensive filter systems to avoid plugging with solids associated with most extraction processes.
<img file="MX350472B_D0040.tif" />
IMPI
ΙΝίΤΠυΤΟ MUiCANO DE LA PROPERTY INDUSTRIAL liquids and commercial liquids. The 3el Liqui-Cel contactor used in the present invention has been applied almost exclusively to commercial processes that transfer gas to or from a liquid such as oxygen stripping of water for the microelectronics industry.
No applications for MHF contactors are known to enhance melting and remove oil droplets from the submicron of water. Surely no applications for MHF technology are known for oil recovery from submicron water involving significant solids concentration.
Figure 7 is 700 schematics of the Liqui-Cel extra flow microporous hollow fiber membrane contactor 702. Contactor 702 comprises a metal housing or polypropylene housing 706, containing a cartridge 708 comprising a plurality of microporous hollow fibers hydrophobic 712, along with a distribution tube 710, a collection tube 716, and a central baffle 714. Housing 706 has 2 inlet ports (704a and 704b) and two exhaust valve ports 704c and 704d.
As shown in Figure 7, the aqueous phase 718 is fed through port 7 04a on the shell side while the solvent (or oil) phase 722 is fed on the fiber side through port 704b. Lipids do not
<img file="MX350472B_D0041.tif" />
IMPI
MEXICAN INSTITUTE
OF THE INDUSTRIAL FROHEUAD poles are attached to the hydrophobic and moistened surface and dissolve in walls and in the counterfluidizing solvent (or oil) phase. A higher pressure is maintained on the aqueous side to prevent bleeding through the solvent (or oil) phase. However the lateral pressure by the cover remains below the gap pressure that forces the aqueous phase 718 into the solvent (or oil) phase 722. The algae are concentrated 718 and the solvent feeds 722 could be operated at room temperature or preheated up to 60 ° C. The solvent (or oil) phase along with the recovered lipids or oils is removed through the exhaust valve port 704c, and the aqueous algal raffinate containing the algal biomass and other solids is removed through the port 704d.
While not intuitive due to the presence of algae solids, the MHF contactor seems ideal for recovering oil from lysed algae. The MHF contactor provides: (i) high contact area for melting and mass transfer, (ii) non-flocculated or deflocculated algal solids processing, (iii) spacious cover-side flow capabilities, (iv) mass transfer resistance negligible in the pore due to the high equilibrium distribution coefficient of nonpolar oils in the nonpolar solvent, and (v) the low price per unit of algae flows per unit as contact area is 100X this for the
<img file="MX350472B_D0042.tif" />
IMPI
MEXICAN INSTITUTE
DI LA PRUHEDAL INDUSTRIAL conventional liquid extraction contactor (eg perforated plate column).
The MHF extractor provides four significant advantages: (i) no solvent carryover which eliminates the need for a stripper column when the appropriate solvent is selected, (ii) easy control of the liquid and liquid interconnection which controls pressures, (iii) area extremely large for melting small drops of algae oil. The MHF contactor works primarily as an oil coalescer. The solvent acts to simply remove the bound oils from the surface of the fibers, and (iv) while not the commercial, optimized MHF contactor modules used for gas transfer are available and reasonably priced. The Liqui-Cel Extra Flow contactor is a benign example.
MHF Contactor Performance Data: The present inventors characterize the performance of the MHF contactor for the extraction of oil from algae. The objectives of the studies are to determine the fraction of nonpolar algae removed from the supply and to determine if plugging of the membrane is observed. The 4-inch diameter Liqui-Cel Extra Flow Contactor, purchased from Membrana [Part # G503], uses algae oil from the extract of a current lysate algae concentrate (Figure 7). Common oily recoveries from experimentally smooth algae ranged from
<img file="MX350472B_D0043.tif" />
45-8 0% for an individual module. The rffSurE'es of the studies are shown in Table 1. Differences in oil recovery can be attributed to smoothing efficiency, algal oil polarity, differences in oil wettability and melting in the membrane fibers. Membrane plugging is not observed when the lysed algae from processing are concentrated where the algae are not flocculated or have deflocculated. The common range of conditions associated with non-polar algal oil recovery is shown in Table 1. These data are based on current lyse algae processing. Since the non-polar oil recovery efficiency is also affected by the smoothing efficiency, controlled experiments are carried out where known amounts of cane oil are injected into a recirculating algae concentrate flow. In the first set of studies, heptane is recirculated on the tube side as a specific collection liquid nonpolar oil. The results of these studies are shown in Table 2. In the initial small-scale studies, 44-64% of the oil volume injected is recovered by the microporous hollow fiber membrane when the only 25 mL of cane oil is injected. When a larger quantity of grenade oil is injected (250 mL), more than 90% of the oil volume injected is recovered as shown in Table 2. These data provide evidence that a
IMPI
ΙΝΠΤΠΓΓΟ MtUCANO OF INDUSTRIAL PROPERTY
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Fixed volume of oil is likely to be held in hollow fiber walls. In a second set of studies using the cane oil injected into used algae concentrates, the cane oil is recirculated through the hollow fiber tubes as a collection liquid instead of heptane. As shown in Table 3, 93% of 9 liters of injected cane oil is recovered, conclusively showing that a similar oil can be used as a collection liquid. The second set of studies validates the mechanism that the process relies on binding and the recovery of oil droplets from the aqueous suspension can be carried out using similar oil. The rapeseed oil series also provide data supporting the request for non-dispersive microporous hollow fiber technology in removing residual oil from produced water, as rapeseed oil / water emulsions is an accepted experimental power to mimic produced water. in a laboratory setting. Results from Table 2 and 3 indicate that near 100% oil recoveries are possible. The hollow fiber walls will always contain oil during processing.
Table 1: Typical Algal Oil Recoveries from Algae Used by the MHF Contactor.
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IMPI rNSTrrvTO msxican <· OF THE PROPERTY 'NtH ISTRIAL
<td>Parameter</td><td>Total interval</td><td>Common interval</td>
<td>Algae concentration,% by weight</td><td> 0.01-15</td><td> 1-5</td>
<td>Non-polar oil in Algae,% by weight</td><td> 0.5-10</td><td> 2-6</td>
<td>Algae flow rate, gpm</td><td> 0.5-2</td><td> 0.5-1</td>
<td>Heptane flow rate, gpm</td><td> 0.04-0.07</td><td> 0.07</td>
<td>Non-polar oil recovery,%</td><td> 40-90</td><td> 70-80</td>
Table 2: Controlled study results using Heptane flowing through tubes. Basis: Algae feed rate = 1,000 lbs / hr, Heptane feed rate = 50 lbs / hr, Total mass of re-circulating algae = 50 lbs containing approximately 1.5% by weight biocellular solids, injection rate of oil = 0.17 pounds / hr.
<td>Proof</td><td> #1</td><td> #2</td><td> #3</td><td> #4</td>
<td>Injected Oil, my</td><td> 25</td><td> 25</td><td> 210</td><td> 210</td>
<td>Recovered Oil, my</td><td> 11</td><td> 16</td><td> 198</td><td> 188</td>
<td>Oil absent</td><td> 114</td><td> 99</td><td> 12</td><td> 22</td>
<td>% of recovery oily</td><td> 44</td><td> 66</td><td> 94</td><td> 90</td>
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Table 3: Solvent-free test results with oil
IMPI institute MtxiCAN »DE LA« U'ILDAC industrial sunflower flowing through the tubes. Support side and tube side flows are recirculated.
<td>Tube side</td><td>Canola oil</td>
<td>Deck side</td><td>50 pounds of seaweed concentrate</td>
<td>% by weight of biocellular solids in algae</td><td>About 1.5% by weight</td>
<td>Tube side flow rate</td><td>10-15 lbs / hr</td>
<td>Cover side flow rate</td><td>500, pounds / hr</td>
<td>Injection speed of cane oil in algae</td><td>3 ml / min</td>
<td>Execution time</td><td>72 hours</td>
<td>% recovery of injected cane oil</td><td> 93%</td>
It should be noted that the algae concentrate supply or biocellular supply must not contain flocculated algae or solids to prevent plugging within the membrane module. For the case of the MHF contactor described in the present invention, the minimum dimension for lateral flow through the cover is 3 9 microns which is greater than the size of most individual algae. The flocculated algae will likely eventually plug the cover side of the MHF contactor.
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IMPI Mexican iNSTmrro Ok LA PRDPIEDAl 'INDUSTRIAL
In a related and alternative process, the microporous membrane could be used two separate liquids from a solid liquid liquid emulsion. The solid liquid liquid emulsion may have been derived from a process to recover oil from a biocellular aqueous supply by using a dispersive process. The microporous membrane gap fiber contactor would allow the hydrocarbon liquid to wet and adhere to the walls of the hollow fibers by preventing hydrophilic solids or aqueous phase from entering. Thus the hydrocarbon liquid will exit the membrane on the tube side when a suitable collection liquid is used, while the aqueous liquid and solids will exit on the cover side. An alternative process is shown in Figure 9.
The flow chart 900 shown in Figure 9 of the alternative algae oil extraction process comprises a dispersive extraction column 902, algae lysate concentrate 904, and 908 solvents are fed to a dispersive extractor such as a column extractor, centrifugal or settler type mixer 902. The solid liquid liquid emulsion (SLL) 912 from column 902 comprising the algae water solvent is then fed to one side of the shell of a microporous membrane extractor (contactor) 910. Any solid (algal biomass) from the column extractor 9 02 can
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directly undergo — adTviiunal --- processing (eg ·· drying) as shown by step 914. The microporous membrane gap fiber contactor 910 allows the hydrocarbon liquid to wet and adhere to the hollow fiber walls by preventing hydrophilic solids or aqueous phase from entering. The hydrocarbon liquid comes out of the membrane contactor 910 on the tube side when a suitable collection liquid (for e.g. the 908 solvents) is used on the tube side, while the aqueous liquid and solids (algae biomass) will come out on the cover side for further processing (eg drying) as shown by step 914. The liquid Hydrocarbon is then fed to distillation unit 916 (heat exchangers associated with distillation unit are shown as 918 and 920) for removal of any residual 906 solvents and recovering 924 algae oil. The recovered solvents 906 can be circulated back to the process, eg as the collection liquid on the tube side of the membrane contactor 910 or back to the dispersive extraction column 902.
The collection liquid on the side of the tube can be tailored to enhance recovery or selectively recover subsets of desired compounds and hold others. Study data show that hydrocarbons and
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IMPI rxsTmni। MEXICAN DE LA PROPERTY ni> l ISTRIAL nonpolar lipids are eliminated by using neptarium or similar material and phospholipids are not. Recovery of the phospholipid can probably be accomplished using a more polar collection fluid.
To determine the composition of the extracted oil, the inventors carried out normal phase HPLC using Sedex 75 evaporative light scattering detector. As shown in Figure 8, two main components are detected in this particular oil sample, the first peak corresponding to long chain hydrocarbons and the second corresponding to triglycerides. In some samples, 1,3 and 1,2 diglyceride has also been detected.
It will be understood by the skilled artisan that the process described above is widely applicable for the recovery of insoluble oil beyond algae to include protists, fungi, yeast, E. coli, etc., mixed cell cultures, grown by any method (not limited to photosynthetic organisms), aqueous suspensions containing broken cells and / or in vivo or no cells (in case previously treated to remove cell / cell debris or other suspended materials). The process can also be used to recover oil from any liquid source comprising insoluble oils for water e.g. industrial, brine, waste water, natural industrial effluents, hydro and oily mixtures,
IMPI
INSTITUTO MtXICANí De LA FtOPlEBAD INDUSTRIAL aqueous suspensions, aqueous suspensions that. GQmpjsejidaa. broken cells, cells in vivo or combinations thereof, biocellular, lysed cell preparations and combinations thereof. The process of the present invention has the ability to extract almost up to 100% of one or more insoluble oils in the liquid source. The process provides insoluble oil recoveries of 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% , 98%, 99% and 100% from the liquid source.
The method and process of the present invention can be expanded for the recovery of a variety of molecules depending on the collection liquid option and include individual or multi-step, differential recovery processes to e.g. specifically recover the non-polar oil with a module membrane, then treat the effluent with a second membrane module that uses a different collection liquid. Collection fluids can be selective, partially selective, or non-selective for specific compounds. In other specific examples, the present invention can be used to specifically recover the non-polar oil with a membrane module, then followed by treating the effluent from the first module with a second membrane module employing a different collection liquid.
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INSTITUTO MEXICANA DE IA INDUSTRIAL PROPERTY
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It is contemplated that any embodiment mentioned in this specification may be practiced with respect to any method, kit, reagent or composition of the invention, and vice versa. Furthermore, compositions of the invention may be used to accomplish methods of the invention.
It will be understood that the particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The main features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to find out using other than routine experimentation, various equivalents with the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention belongs. All publications and patent applications are incorporated herein by reference to the same degree as if each individual publication or patent application is specifically and individually indicated to be incorporated by reference.
The use of the word ao when used in conjunction with the term to be understood in the claims and / or the specification can mean a, but is also
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MEXICAN INSTITUTE
Dt LA FROmOAi 'INDUSTRIAL TbÍ consistent with the meaning of one or more, at least one, and one or more than one. The use of the term or in the claims is used mean and / or unless explicitly not indicated to refer to alternatives only or the alternatives are mutually exclusive, although the description supports a definition that refers to only alternatives and and / or. Throughout this application, the term "envelope" is used to indicate that a value includes the inherent variation of error for the device, the method that is used to determine the value or variation that exists between study patients.
Used as in this specification and claim (s), the words comprising (and any form of comprising, such that they comprehend and comprehend), having (and any form of having, such that they have and have), including (and any form of the including, such that it includes and includes) or containing (and any form of containing, such that it contains and contains) are global or without certain limits and do not exclude additional elements, not mentioned or steps of the method.
The term or combinations thereof as used herein refer to all permutations and combinations of the listed items that precede the term. For example, A, B, C, or combinations of the same intended include at least one of: A, B, C, AB, AC, BC or ABC, and if order is important in a particular context, also BA,
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CA, CB, CBA, BCA, ACB, BAC or CAB. To continue with this example, expressly included is combinations that contain repetitions of one or more article or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so on. The skilled technician will understand that there is generally no limit to the number of articles or terms in any combination, unless otherwise not apparent from the context.
All the compositions and / or methods described and claimed herein can be made and formalized without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that variations can be applied to the compositions and / or methods and in the steps or sequence of steps of the method described herein. without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are considered to be within the spirit, scope and concept of the invention as defined by the appended claims.
References
US Patent No. 4,439,629: Extraction Process for Beta-Carotene.
US Patent No. 5,378,639: Solvent Extraction.
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Contents56
63 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43 Sheet 44 Sheet 45 Sheet 46 Sheet 47 Sheet 48 Sheet 49 Sheet 50 Sheet 51 Sheet 52 Sheet 53 Sheet 54 Sheet 55 Sheet 56 Sheet 57 Sheet 58 Sheet 59 Sheet 60 Sheet 61 Sheet 62 Sheet 63
49 members in 8 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 29560710 | United States of America | P | |
| 29560710 | United States of America | P | |
| 61295607 | United States of America | – | |
| 2011021185 | United States of America | W | |
| 2011021185 | United States of America | W | |
| 61295607 | – | – | – |
| PCTUS2011021185 | – | – | – |
| US20100295607P | – | – | – |
| WO2011US21185 | – | – | – |
Members49
| Document | Office | Kind | |
|---|---|---|---|
| CA2786709A1 | Canada | A1 | |
| CA2835930A1 | Canada | A1 | |
| US2011174734A1 | United States of America | A1 | |
| WO2011088242A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US2012184759A1 | United States of America | A1 | |
| MX2012007901A | Mexico | A | |
| AU2011205246A1 | Australia | A1 | |
| US2012208247A1 | United States of America | A1 | |
| IL220837A0 | Israel | A0 | |
| IL220837D0 | Israel | D0 | |
| EP2523737A1 | European Patent Office (EPO) | A1 | |
| US8486267B2 | United States of America | B2 | |
| US8491792B2 | United States of America | B2 | |
| AU2011205246B2 | Australia | B2 | |
| US2013270187A1 | United States of America | A1 | |
| AU2013245504A1 | Australia | A1 | |
| CA2874012A1 | Canada | A1 | |
| WO2013188837A1 | World Intellectual Property Organization (WIPO) | A1 | |
| US8617396B2 | United States of America | B2 | |
| CA2786709C | Canada | C | |
| US2014131279A1 | United States of America | A1 | |
| US2014243573A1 | United States of America | A1 | |
| WO2014133619A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU2013245504B2 | Australia | B2 | |
| IL220837A | Israel | A | |
| AU2015200363A1 | Australia | A1 | |
| US2015087877A1 | United States of America | A1 | |
| EP2861331A1 | European Patent Office (EPO) | A1 | |
| MX2014014942A | Mexico | A | |
| EP2861331A4 | European Patent Office (EPO) | A4 | |
| US9149772B2 | United States of America | B2 | |
| EP2523737A4 | European Patent Office (EPO) | A4 | |
| EP2961519A1 | European Patent Office (EPO) | A1 | |
| US2016008762A1 | United States of America | A1 | |
| MX2015011088A | Mexico | A | |
| AU2015200363B2 | Australia | B2 | |
| EP2961519A4 | European Patent Office (EPO) | A4 | |
| CA2835930C | Canada | C | |
| BR112012017563A2 | Brazil | A2 | |
| AU2016222461A1 | Australia | A1 | |
| US9643127B2 | United States of America | B2 | |
| US9688921B2 | United States of America | B2 | |
| MX350472BThis record | Mexico | B | |
| US9782726B2 | United States of America | B2 | |
| CA2874012C | Canada | C | |
| EP2961519B1 | European Patent Office (EPO) | B1 | |
| IL237061A | Israel | A | |
| IL237061B | Israel | B | |
| US10773212B2 | United States of America | B2 |
Numbers
- Publication
- 350472
- Publication, DOCDB
- 350472
- Publication, EPODOC
- MX350472
- Application
- 2015000699
- Application, DOCDB
- 2015000699
- Application, EPODOC
- MX20150000699
Titles2
- Spanish
- PROCESO NO DISPERSIVO PARA LA RECUPERACION DE ACEITE INSOLUBLE A PARTIR DE SUSPENSIONES ACUOSAS.
- English
- NON-DISPERSIVE PROCESS FOR THE RECOVERY OF INSOLUBLE OIL FROM AQUEOUS SUSPENSIONS.
Classification
- CPC, 14
- C10G1/04
- B01D61/58
- B01D63/02
- B01D67/0093
- C10G2300/1014
- C10G2300/4081
- C10G2300/44
- C10L1/026
- C12M47/10
- Y02W10/37
- B01D61/246
- B01D2323/04
- Y02E50/10
- Y02P30/20
- IPC, 4
- C02F1 40
- C02F1 44
- C02F3 32
- C11B13 00