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    • 专利摘要:
    METHOD FOR RECOVERING BIO-OIL FROM A FERMENTATION PROCESS, COMPOSITION OF SEPARATION AID, TREATED VINEYARD, METHOD FOR RECOVERING OIL FROM SEAWEED AND BIO-OIL RECOVERY SYSTEM. A method and system for recovering bio-oil from biomass is provided which includes adding at least one separation aid to make the vinasse containing oil to form a treated vinasse before centrifuging the vinasse, and centrifuging the treated vinasse in at least one centrifuge to separate at least a portion of the oil from the treated vinasse. The separation aid may contain at least one lecithin and at least one oil and, optionally, at least one surfactant having an HLB value of at least 6. The treated vinasse products are also provided which may contain the indicated separation aid and recovered oil.
    公开号:BR112015014194B1
    申请号:R112015014194-3
    申请日:2013-09-26
    公开日:2021-02-17
    发明作者:Donald G. Jenkins；William C. Ganus；Carlton E. Hagen
    申请人:Buckman Laboratories International, Inc；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a method and system for recovering bio-oil. A separation aid that can be used in these methods and systems, and products containing them, are also provided. History of the invention
    [0002] [0002] Ethanol production from biomass has received significant attention in recent years as a source of alternative fuel or biofuel. Ethanol burns cleaner than fossil fuels, and can be produced using renewable sources, such as grains or other renewable biomass containing starch. A widely used method of producing ethanol from grains is known as "dry milling," and is usually practiced using corn in the United States. The dry milling process normally uses starch in corn or other renewable biomass to produce ethanol through fermentation, which creates a disposal stream comprised of by-products called "integral vinasse." Integral vinasse can also be separated by centrifuge in products known as "wet distillers grains" (WDG) and "fine vinasse." Despite containing valuable oil, whole vinasse and fine vinasse were usually treated as waste or used mainly to supplement animal feed, mostly in the form of dried grains from distillers with soluble (DDGS). DDGS is typically produced by evaporating the fine vinasse, and recombining the resulting concentrate or syrup with moist distiller grains, and the drying of the product should have a low moisture content.
    [0003] [0003] Efforts to recover valuable vinasse oil have encountered significant obstacles. For example, the previous use of melting point hydrocarbon solvents, alcohols or polyhydroxy alcohols as extraction solvents for bio-oils has disadvantages. These compounds, while effective, require high concentrations for the separation of bio-oil which results in potential safety issues. Regulatory requirements for animal feed also prevented the use of these compounds in the separation of bio-oil, especially in the fermentation of corn. Another approach involves trying to separate the oil directly from the fine vinasse before the evaporation stage, such as using a centrifuge. However, turning the fine vinasse at this stage does not produce the usable oil, however, instead, it merely creates an undesirable emulsion phase requiring further processing. US Patent No. 5,250,182 shows the use of multiple filters to remove solids and recover lactic acid and glycerol from fine vinasse without the need for evaporation. Filters, and especially the types of microfiltration and ultrafiltration proposed for use in the '182 patent, are susceptible to blockage and therefore require monitoring and maintenance for that reason. US Patent Application Publication No. 2007/0238891 shows a method of releasing the agglutinated oil present in whole vinasse and fine vinasse, which involves heating the vinasse to a temperature considered sufficient to at least partially separate the oil from the vinasse to vinasse recovery. In one embodiment, publication '891 shows the additional step of pressurizing the heated vinasse to prevent boiling as a form of pressure cooking of the vinasse.
    [0004] [0004] Seaweed is another form of biomass that has great potential as a source of bio-oil. As with fermented grains such as corn, numerous challenges previously existed to recover the usable oil in quantity and quality of the algae raw material. One challenge is to recover the desired hydrocarbon molecules from the seaweed. One option for recovering the algae hydrocarbon products may be to use a method based on solvent extraction. Unfortunately, some solvent-based methods require the use of an algae source that contains little or no water. Dehydrating a source of seaweed to a degree sufficient to allow this type of solvent extraction may require a high operating cost. Alternative solvent extraction methods may allow you to extract a sample of seaweed that contains water. However, a high-cost step usually remains, as the solvent must be separated from water, for example, by distillation.
    [0005] [0005] The present inventors recognized that there is a need for safer and more efficient, versatile and economical processes for recovering biomass oil from biomass, such as vinasse or seaweed or other biomass. Summary of the present invention
    [0006] [0006] A feature of the present invention is to provide a method for recovering bio-oil from biomass, such as vinasse or seaweed.
    [0007] [0007] An additional feature of the present invention is to provide a method for a method for recovering bio-oil from the vinasse by-product from a biomass fermentation process, in which a separation aid can be added to the vinasse containing the bio -Oil to form a treated vinasse before centrifuging the vinasse to provide efficient separation and recovery of oil when the treated vinasse is centrifuged.
    [0008] [0008] Another feature of the present invention is to provide a composition comprising lecithin oil and hydrocarbon which is useful for separating oil from vinasse or other biomass.
    [0009] [0009] An additional feature of the present invention is to provide a system with interoperable equipment to provide and apply the indicated separation aid that is useful for separating oil from vinasse or other biomass, and a separation unit for recovering oil from biomass treated.
    [0010] [00010] The additional features and advantages of the present invention will be set out partially in the description below, and will partly be apparent from the description, or may be learned from the practice of the present invention. The objectives and other advantages of the present invention will be realized and achieved by means of the elements and combinations particularly highlighted in the description and appended claims.
    [0011] [00011] To achieve these and other advantages, and in accordance with the purposes of the present invention, as carried out and widely described herein, the present invention relates, in part, to a method for recovering bio-oil from a fermentation process, comprising adding at least one separation aid to the vinasse containing the oil, to form a treated vinasse before centrifuging the vinasse, and centrifuging the treated vinasse in at least one centrifuge to separate at least a portion of the oil from the treated vinasse. The separation aid comprises at least one lecithin and at least one oil and optionally at least one surfactant having an HLB value of at least 6.
    [0012] [00012] The present invention also relates to a separation aid composition comprising a) from 20% by weight to 50% by weight of at least one lecithin; b) from 20% by weight to 50% by weight of at least one oil; and c) from 0% by weight to 20% by weight of at least one surfactant having HLB values of at least 9.
    [0013] [00013] The present invention also relates to a treated vinasse comprising the composition of separation aid and vinasse, in which the separation aid is present in an amount of at least 50 ppm.
    [0014] [00014] The present invention also relates to a method for recovering oil from seaweed, comprising adding at least a suitable separation aid to the seaweed containing the oil, to form a treated seaweed before centrifuging the seaweed, and centrifuging the seaweed treated in at least one centrifuge to separate at least a portion of the oil from the treated seaweed.
    [0015] [00015] The present invention also relates to a bio-oil recovery system, comprising a supply of biomass comprising vinasse or seaweed; a provision of the indicated separation aid; a treatment unit to combine the separation aid with the biomass to form the treated biomass; and a centrifuge to dehydrate the treated biomass to produce the concentrated bio-oil.
    [0016] [00016] As used herein, "bio-oil" refers to food grade and non-food grade oils and fats that are derived from plants and / or animals (eg, vegetable oils and animal fats ), which mainly contain triglycerides, but may also contain fatty acids, diglycerides and monoglycerides. As used herein, the term "fat" is understood to include "lipids". Examples of bio-oils derived from plants include, but are not limited to, corn oil, sugar cane oil, sunflower oil, flax seed oil, canola oil and the like. Other bio-oils include algaculture bio-oils (from seaweed).
    [0017] [00017] As used herein, "biofuel" refers to any renewable biologically produced solid, liquid or gaseous fuel, such as bio-oils, including, for example, bio-oils derived from biomass. Biofuels also include, but are not limited to, biodiesels, bioethanol (i.e., ethanol), biogasoline, biomethanol, biobutanol and the like.
    [0018] [00018] As used herein, "biomass" generally refers to organic matter harvested or collected from a renewable biological resource as an energy source. The renewable biological resource can include plant materials (eg plant biomass), animal materials and / or biologically produced materials. The term "biomass" is not considered to include non-renewable fossil fuels, such as coal, oil and natural gas, which do not normally include glycerides (eg, tri-, di-, mono-).
    [0019] [00019] As used herein, "stillage" refers to a co-product or by-product produced during the production of a biofuel. When used without qualification, the term "vinasse" can refer to integral vinasse, fine vinasse or concentrated vinasse, such as soluble condensed distillers, ie, syrup, which can be produced from biofuel process streams, p eg, bioethanol production process currents. The differences between these different forms of vinasse can be further understood with reference to their examples which are provided in FIG. 1 at present.
    [0020] [00020] As used here, a "centrifuge" is a piece of equipment, usually driven by a motor, that can put a mixture, mixture or slurry in rotation around a fixed axis, applying a force perpendicular to the axis. The centripetal acceleration generated in the centrifuge causes the denser and lighter substances in the mixture, mixture or slurry to separate. Centrifuges can be oriented horizontally, vertically or other orientations.
    [0021] [00021] As used herein, an "evaporator" is a device used to evaporate or vaporize the liquid form of a chemical or chemicals in a mixture, mixture or slurry in gaseous or vapor form. Evaporating the most volatile components of a mixture, mixture or slurry in an evaporator can concentrate the remaining less volatile liquid components in the device.
    [0022] [00022] As used herein, "surfactant" refers to a compound that can reduce the surface tension of a liquid, the interfacial tension between two liquids, or that between a liquid and a solid.
    [0023] [00023] As used herein, a "nonionic surfactant" is an organic compound that is amphipathic and has no charge group at its terminal end group, where the organic compound can reduce the surface tension of a liquid, the tension interfacial between two liquids, or that between a liquid and a solid.
    [0024] [00024] It should be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide a further explanation of the present invention, as claimed.
    [0025] [00025] The accompanying drawings, which are incorporated and constitute a part of this application, illustrate some of the features of the present invention and, together with the description, serve to explain the principles of the present invention. Brief description of the drawings
    [0026] [00026] FIG. 1 is a process flow chart for the production of biofuel and ethanol by-products from corn (or other biomass containing fermentable starch) that includes the recovery of bio-oil from vinasse treated with a separation aid in accordance with an example of this application;
    [0027] [00027] FIG. 2 is a process flow chart showing a method for recovering bio-oil from vinasse treated with a separation aid according to an example of the present application;
    [0028] [00028] FIG. 3 shows a subsystem comprising a multi-stage evaporator and centrifuge configuration for use in recovering bio-oil from vinasse treated with a separation aid according to an example of the present application;
    [0029] [00029] FIG. 4 is a process flow chart for the production of biofuel and ethanol by-products from corn (or other fermentable biomass) which includes the recovery of bio-oil from vinasse treated with a separation aid in accordance with an example of the present application ;
    [0030] [00030] FIG. 5 is a process flow chart showing a method for recovering bio-oil from oil-containing seaweed treated with a separation aid according to an example of the present application;
    [0031] [00031] FIG. 6 are photographs showing the corn oil test according to an example of the present application in which a product (13864) that has been treated with a separation aid from an example of the present application has been compared with a Basal product treated with a formulation of comparison, in the variable dosages of 200 ppm, 300 ppm and 400 ppm; and
    [0032] [00032] FIG. 7 are enlarged photographs of the product (13864) at a dosage of 400 ppm as indicated in FIG. 6 which was treated with a separation aid from an example of the present application and the resulting product was compared with that of the Basal product. Detailed description of the present invention
    [0033] [00033] The present invention provides a method for recovering bio-oil in which the oil-containing biomass is treated with a separation aid that allows the recovery of bio-oil from the raw material by separation processing, such as, centrifugation. The separation aid can increase the separation between the oil and non-oil components of the biomass, in which the oil can be recovered in high concentration fractions from the biomass by simple separation processes. The separation aid can also increase the clarity in the recoverable oil supplied in the treated biomass. In addition, the separation of oil from biomass can be achieved at relatively lower dosage levels than some comparative treatment products, such as shown in the examples described herein.
    [0034] [00034] In general, the present invention relates to a method for recovering bio-oil from a fermentation process. The method may include, understand, essentially consist of or consist of: adding at least one separation aid to the vinasse containing the oil, to form a treated vinasse before centrifuging the vinasse. The method also includes centrifuging the treated vinasse in at least one centrifuge (eg, one, two, three or more) to separate at least a portion of the oil (eg, separate at least 0.1% by weight) up to 100% by weight of available oil present in the treated vinasse based on the weight of the oil present in the treated vinasse) from the treated vinasse. The separation aid can comprise, essentially consist of, include or consist of at least one lecithin and at least one oil and optionally at least one surfactant having an HLB value of at least 6.
    [0035] [00035] In the method of the present invention, the separation aid can be added before and / or in at least one evaporator located upstream from the centrifuge.
    [0036] [00036] In the present invention, the fermentation process can comprise, consist essentially of, include or consist of a series of evaporators that the vinasse can enter sequentially and located upstream from the centrifuge. The addition of the separation aid can occur well before or in at least one of the evaporators located closest to the centrifuge. The method may involve a series of evaporators which may include from 1 to 8 or more evaporators, such as at least 8 evaporators, in which the addition of the separation aid occurs well before or at the 5th, 6th, 7th ° and / or 8 ° evaporator.
    [0037] [00037] The separation aid of the present invention can be a composition comprising lecithin and an oil. The composition may optionally also include at least one surfactant having an HLB value of at least 6. These compounds may meet the criteria required for animal feed regulations, as well as, have higher boiling points compared to the previous extraction components indicated here , but without its disadvantages. For example, the separation aid may comprise components of lecithin and mineral oil, which are listed as GRAS approved products and are individually found in many food applications. As some of its advantages, the separation aid can comprise higher boiling point components, GRAS approved starting materials, can be used in lower dosage requirements with improved oil separation and / or oil clarity and / or with decreased subject of centrifuge and improved post-separation. The separation aid can work as an oil-breaking additive to reduce emulsification or its tendencies in vinasse and other biomass and / or increase the separation capacity of oil and aqueous phase and / or separation in the treated biomass.
    [0038] [00038] In one example, the separation aid for recovering bio-oil, such as for treating a vegetable oil resulting from a biomass fermentation process or algae oil resulting from algaculture, may comprise a lecithin, a hydrocarbon oil, and optionally a surfactant with an HLB of at least 9. For example, lecithin can be a modified lecithin, the hydrocarbon oil can be based on a mineral sealing oil, and the surfactant, if included, it may be a nonionic surfactant based on ethoxylated sugar alcohol ester or triglycerides. When these components of lecithin, oil and surfactant options are used in combination when treating a biomass, the product aids resulting in oil separation and clarity at low dosage levels. The separation aid can be particularly effective in promoting the separation of oil in a biomass treated with the composition after a biomass fermentation process. Although the separation aid is advantageously used in the recovery of bio-oil, it can be used for many purposes and functions, such as defoamer, oil separation aid, fermentation aid, demulsifier and / or break aid of Oil.
    [0039] [00039] The indicated separation aid can be used, for example, in a method of recovering oil from a vinasse by-product resulting from the production of ethanol from corn, such as when using a milling technique dry, as described in United States Patent No. 5,250,182, which is incorporated herein in its entirety by reference. The vinasse by-product can be whole vinasse, fine vinasse or syrup from the evaporator. As is generally known, fine vinasse is recovered by separating the humid grain from distillers from the leftover "whole vinasse" after fermentation is complete. As also generally known in the art, this mechanical separation can be accomplished using a press / extruder, a decanter centrifuge (also simply known as a "decanter") or a screen centrifuge. The moisture is then removed from the unfiltered fine vinasse to create a concentrate or syrup, such as through evaporation. The separation aid of the present invention makes it possible to easily recover the usable oil from integral vinasse, fine vinasse, syrup (concentrate) or any of its combinations, without the need to pressure cook the vinasse or use multiple stages of filtration that can be expensive and complicated ways of processing.
    [0040] [00040] With reference to FIG. 1, a process 100 for the production of biofuel and ethanol by-products from corn includes the recovery of bio-oil 107 from vinasse treated with the aid of separation. Several process by-products 101, 102, 103 are identified in this figure for the purpose of exemplifying several types of "vinasse" that can be used at least partially in at least one, two or all three process streams 104, 105, and 106 , respectively, for use as raw material in the recovery of bio-oil 107. As indicated in FIG. 1, after distillation, the integral vinasse is separated by centrifuge, such as a decanter centrifuge, in moist grains and fine vinasse. Evaporator 108 can concentrate fine vinasse in evaporative syrup, and the syrup can be combined with wet grains to produce still and soluble grains (DGS), or can be dried to produce dried and soluble grains (DDGS) ), or both. Bio-oil recovery 107 can be implemented as a subsystem or as integrated in the primary process line shown in the figure. Bio-oil recovery, for example, can be a part of the process in which the vinasse is bypassed or removed from the main process line to be treated with a separation aid in combination with an evaporator and a centrifuge in a subsystem which is different from the main system line shown in FIG. 1 which includes evaporator 108. The recovery of bio-oil 107, alternatively, can be integrated more directly into the main process line. For example, a treatment of fine vinasse with the aid of separation can occur in combination with the evaporation carried out on the evaporator 108 of the main process line and together with an added centrifuge used to recover the oil (shown in other figures at present). In this example, evaporator 108 from the main process line and the indicated added centrifuge are used in the bio-oil recovery subsystem. Corn is shown as the biomass material in FIG. 1 for purposes of illustration, and other biomass materials can be used, such as, other fermentable starch-containing biomass materials.
    [0041] [00041] With reference to FIG. 2, a bio-oil recovery method as applied to oil-containing vinasse is shown. Vinasse 201 is shown to be fed to the recovery of bio-oil 200 (which may be the same as 107 shown in FIG. 1), where the vinasse is treated with a separation aid 202, which may have a composition described herein. The resulting treated vinasse 203 is centrifuged 204 to provide a concentrated oil product 205 and a depleted oil syrup 206. The depleted oil syrup 206 can optionally be combined in step 207 with the wet distiller grains (WDG) for further processing, such as, the WDG shown in the process flow of FIG. 1.
    [0042] [00042] With reference to FIG. 3, a subsystem 300 for bio-oil recovery comprises a multi-stage evaporator 302 and centrifuge 306 for use in recovering bio-oil 308 from vinasse containing oil 301 as a raw material. The multi-stage evaporator 302, for example, can be a series arrangement of a plurality of evaporators that can remove water and / or other volatiles from the vinasse to concentrate the fine vinasse and increase its solids content. The multi-stage evaporator 302 may, for example, be a multi-stage ignition evaporator, which may have equipment designs generally known in the bioethanol production industry. Downward film evaporators, or forced circulation or multiple effect, or other types of evaporators, can be used for the concentration of vinasse in this regard. The raw material 301, for example, can be any of the sources of vinasse indicated with respect to FIG. 1. In an example where fine vinasse is the raw material, the initial processing of whole vinasse produced as a by-product of corn fermentation and distillation can be carried out in a conventional manner, such as using a centrifugal decanter (not shown) , and mechanically separated fine vinasse can be delivered to the multi-stage evaporator 302 forming part of the subsystem 300. To increase efficiency, the temperature difference between heating and the heated media can be reduced using such multi-stage evaporators. In FIG. 3, steam 310 is increased in at least one of the individual evaporators 303A, 303B and 303C of the multiple stage evaporator 302, and volatiles 313B and 313A are discharged as a suspension from the succession of evaporators and can be used in a next evaporator to heat the vinasse in such a unit. As shown in FIG. 3, live steam can be introduced to the evaporator 303C through the valve 316G. For example, steam can be introduced into a steam side (non-product side) of a 303C evaporator heat exchange design, and volatile 313B from the heated vinasse can be discharged from the vinasse side of the 303B evaporator. Condensed heating steam 317 can be removed from the evaporator 303C. The volatile vinasse 313B produced in the evaporator 303C can be fed to a steam side of a heat exchange design of an upcoming evaporator 303B and used to heat the vinasse in such a unit. In turn, the volatiles 313A discharged from the vinasse side of the evaporator 303B can be fed into a steam side of a heat exchange design from another evaporator 303A and used to heat the vinasse in such a unit. A vapor / volatile stream 311 can be discharged from the vinasse side of the evaporator 303A. Live steam can also be used at least partially to heat vinasse in a plurality or all evaporators. The pumps can be used between the evaporators in the multi-stage evaporation process to conduct the non-volatile liquids containing oil ("bottoms") successively from one evaporator to the next evaporator in the multi-stage evaporator process flow.
    [0043] [00043] The multi-stage evaporator 302 used in FIG. 3, for example, can have a plurality of stages (i.e., "n" stages, where n> 2). The number of stages "n" can be, for example, 2 or more stages, or 5 or more stages, or 8 or more stages, or from 2 to 8 stages, or from 2 to 9 stages, or a from 2 to 10 stages, or other numbers, arranged in series. The evaporator 302, for example, can have 8 stages with 7 intervening pumps used to pump vinasse from the first evaporator or stage 1 to stage 2, from stage 2 to stage 3, from stage 3 to stage 4, from stage 4 to stage 5, from stage 5 to stage 6, from stage 6 to stage 7, and from stage 7 to stage 8. An additional pump, eg an eighth pump, can be used to pump the funds from the final evaporator. The oil content of the vinasse bottoms in the evaporator can become progressively higher and the content of aqueous and volatile organic solubles progressively lower, as the vinasse progresses through the succession of evaporator stages. For example, FIG. 3 shows a multi-stage evaporator 302 with n evaporator stages, including evaporators 303A, 303B and 303C. The 316A-F valves can be used to control the flow of liquid vinasse through the evaporator system 302. The 304A pump pumps the bottoms from the first evaporator 303A to a next evaporator, such as evaporator 303B or another intervening evaporator (no shown). The 304A pump can also be used to recirculate the bottom of the 303A evaporator back to such an evaporator. Pump 304B pumps the bottom from evaporator 303B to evaporator 303C. The 304B pump can also be used to recirculate funds back to the 303B evaporator. The 304C pump can be used to recirculate bottoms from the evaporator 303C back to the evaporator and / or can pump the bottoms 307 from the final evaporator 303C to the centrifuge 306. A separate oil slip supply pump 304D can pull from the suction of a chosen evaporator, such as evaporator 303B, and pump 304D can supply vinasse / syrup 312 from the chosen evaporator to the oil centrifuge 306. The evaporator 303B is shown as chosen for this purpose in the illustration of FIG. 3, but another evaporator, such as, 303A, 303C and etc., could be chosen. As indicated, additional evaporators and pumps can be installed and used between the first 303A evaporator and its 304A discharge pump and 303B evaporator and its 304B discharge pump. The raw materials 301A, 301B and 301C to the respective different evaporators 303A, 303B and 303C are shown. As indicated in FIG. 3, valve placement can be included to optionally recycle some or none of the bottoms from a respective evaporator back to the same evaporator. The separation aid 305A can be added to the raw material of vinasse 301, or separation aid 305B can be added at pump 304A, or separation aid 305C can be added at pump 304B or pump 304D, or the separation aid can be added to the pump powered bottoms from any other evaporator to the next in the evaporator series, or any combinations of these separation aid addition points may be used. The separation aid can also be directly introduced into an evaporator and / or via a side current (not shown).
    [0044] [00044] In a process flow through a bio-oil recovery subsystem, vinasse can have a solids content, for example, below 30% by weight, or from about 5% by weight to about 20% by weight, or from about 7% by weight to about 18% by weight, or other values (based on the weight of the vinasse), when the separation aid is added to the vinasse before or in the evaporator of the multiple stage. As indicated, the separation aid can be mixed with the vinasse prior to introduction to the evaporator, or added to the vinasse on or between the evaporators of the multiple stage evaporator, or any combination thereof. The separation aid can be added predominantly during one or more intermediate stages of a multiple stage evaporator. The separation aid can be introduced, for example, in an 8-stage multi-stage evaporator in any of the pumps 5 through 8, or directly in any of the evaporators 5 through 8, or any combination thereof. The pumps can provide convenient points of introduction for the separation aid. As indicated, pumps 1-7 are the pumps between the next evaporators in a series of 8-stage evaporator and the 8th pump is used to pump the bottoms from the final evaporator to the centrifuge. For example, in FIG. 3, the concentrate or syrup 307 discharged from the final evaporator 303C is pumped to the centrifuge 306 for separation processing to recover the oil. The concentrate or syrup is separated by the centrifuge 306 in the oil concentrate product 308 and an exhausted oil syrup 309. The centrifugation separates the oil from non-oil liquids for oil capture. The solids content of the concentrated oil product can be, for example, at least about 95% by weight, or at least about 96% by weight, or at least about 97% by weight, or at least about 98 % by weight, or at least about 99% by weight, or from about 95% by weight to 100% by weight, or from about 98% by weight to about 99, 5% by weight, or other values, based on the weight of the product. These quantities can be represented entirely (100%) by oil solids, or smaller quantities including the same indicated numerical ranges provided for the solids content in general. The balance of the concentrated oil product can be water, organic non-oil compounds, or both. The solids content of the depleted oil syrup can be, for example, from about 4 to about 8% by weight, or about 6% by weight, or other values. The centrifuge 306 can be, for example, a decanter centrifuge, a horizontal centrifugal solid bowl decanter, a disc stack centrifuge, a hermetically sealed centrifuge or another type of centrifuge or gravity separator. As indicated in FIG. 2, the exhausted oil syrup 309 discharged from the centrifuge can be combined with the wet distillers' grains for further processing.
    [0045] [00045] With reference to FIG. 4, bio-oil recovery is shown as performed on a 410 subsystem that is integrated into a main process line of a bioethanol production facility. The production of biofuel and ethanol by-products from corn includes the recovery of bio-oil from fine vinasse 401 which has been treated with the aid of 403 separation in an evaporator 402 (as shown in FIG. 3), and then the oil 406 is separated from the syrup product 404 of the evaporator 402 with a 405 centrifuge. The evaporator 402 can be a multi-stage unit, such as an 8-stage evaporator, arranged to concentrate the fine vinasse 401 in syrup 404 via a evaporation before mixing this 404 syrup with the wet grains before thermal drying. A multi-stage evaporator 402 may have the design, as shown for evaporator 302 in FIG. 3. Subsystem 410 incorporates centrifuge 405 into the process flow to separate oil 406 from syrup product 404 discharged from evaporator 402. As also shown in FIG. 4, the depleted oil syrup 407 discharged from the centrifuge 405 can be combined with the grains from moist distillers and dried in the production of DDGS.
    [0046] [00046] The separation aid may comprise, for example, a) 30% by weight to 70% by weight of lecithin; b) 30% by weight to 70% by weight of oil; and c) 0% by weight to 40% by weight of surfactant. All weight percentages provided for the separation aid components shown here are based on the total weight of the composition. The separation aid may comprise a) 30% by weight to 50% by weight of said lecithin; b) 20% by weight to 50% by weight of said oil; c) 0% by weight to 20% by weight of said surfactant. The separation aid may comprise a) 30% by weight to 50% by weight of said lecithin; b) 20% by weight to 50% by weight of said oil; c) 1% by weight to 20% by weight of said surfactant. The separation aid may comprise a) 30% by weight to 50% by weight of said lecithin; b) 20% by weight to 50% by weight of said oil; c) 3% by weight to 15% by weight of said surfactant. Lecithin and oil can be present in a weight / weight ratio of lecithin: oil from 0.8: 1 to 1: 0.8, or from 0.85: 1 to 1: 0.85, or from 0.9: 1 to 1: 0.9, or 1: 1, or other values. The separation aid can be effective in providing high quality oil at low dosage levels. The separation aid can be added to the biomass being treated in an amount to be present in a range of ppm, for example, from about 200 ppm to about 800 ppm, or from about 250 ppm to about 750 ppm, or from about 300 ppm to about 700 ppm, or from about 350 ppm to about 650 ppm, or another from about 400 ppm to about 600 ppm, or other values above , within and below the ranges provided. The ppm values given here are based on the weight / weight values.
    [0047] [00047] The separation aid can be used substantially clean, for example, comprising less than 1% by weight of water, or less than 0.5% by weight of water, or less than 0.1% by weight of water, or less than 500 ppm of water, or less than 100 ppm of water, or 0% by weight of water. The separation aid can be formulated as very low in aromatic content or free of aroma. The separation aid can be formulated, for example, as comprising less than 1% by weight of aromatics, or less than 0.5% by weight of aromatics, or less than 0.1% by weight of aromatics or 0% by weight of aromatics. The separation aid can be formulated as being very low in alcohol content or without alcohol. The separation aid can be formulated, for example, as comprising less than 1% by weight of alcohol, or less than 0.5% by weight of alcohol, or less than 0.1% by weight of alcohol or 0 % by weight of alcohol. The separation aid can be a grade of food or composition approved by GRAS or mixture.
    [0048] [00048] The bio-oil recovery processes of the present invention can be applied to other types of biomass, in addition to grains, such as corn. For example, the processed can be applied to recover bio-oil from algae. The processes to produce biofuels from algae include, for example, those that pump nutrient-rich water through plastic tubes or borosilicate glass (called "bioreactors") that are exposed to sunlight (and called photobioreactors or PBRs) ). Seaweed farms can also be set up on marginal land, such as in desert areas where groundwater is saline, instead of using water. They can also be grown on the surface of the ocean. Because seaweed strains with a lower lipid content can grow as much as thirty times faster than those with a high lipid content, efficient biodiesel production from seaweed may depend on finding a seaweed strain with a high content combination. of lipid and fast growth rate, which is not very difficult to harvest and an economic cultivation system (ie, type of photobioreactor) that is better suited for such a strain. Concentrated CO2 is used to increase the production rate. The lipid, or oily part of the algae biomass, can then be extracted. In the examples of the present invention, the removal of bio-oil is optimized by treating the algae biomass with the indicated separation aid composition, before centrifuging the treated algae biomass. The concentrated oil product or fraction discharged from the centrifuge can be used in accordance with biofuel or other purposes. After the oil is separated from the seaweed, the seaweed residue can be used as an animal feedstock or as a soil fertilizer.
    [0049] [00049] With reference to FIG. 5, bio-oil recovery is applied to recover bio-oil from algae like biomass. The oil-containing water 501 is used as a feedstock for the bio-oil recovery process flow 500 shown in FIG. 5. The oil-containing raw material is treated with a separation aid 502, and the resulting treated seaweed 503 is centrifuged 504, to provide a concentrated oil product 505 and an exhausted oil product 506.
    [0050] [00050] The lecithin used in the separation aid can be of natural, modified or synthetic origin. The lecithin that can be used in the present invention can be lecithin derived from any plant, animal or microbial source. Suitable lecithin starting materials are commercially available, and include available soy lecithin and egg yolk lecithin products. Lecithin can be obtained from natural sources, such as egg yolk, and plants, such as soy, corn, rapeseed and the like, where it is a by-product of vegetable oil refining. Soy oil is the biggest source of commercial lecithin. The composition of commercial lecithin depends on the source, preparation methods and degree of purification, however, for the most part, the pure form is mainly comprised of phosphatides. Commercial lecithin, for example, is a co-product of processing oil obtained during the degumming step. For example, soy lecithin is a complex mixture and comprises phospholipids and triglycerides, with smaller amounts of other constituents, such as phytoglycolipids, phytosterols, tocopherols and fatty acids. The main phospholipids present in plant lecithins are phosphatidylcholine, phosphatidylethanolamine and phosphatidylinositol. Egg yolk lecithin contains phosphatidylcholine and phosphatidylethanolamine as the main phospholipids. Lecithin can be extracted chemically (using hexane) or mechanically from readily available sources, such as soybeans. Lecithin has low water solubility. In the aqueous solution, its phospholipids can form liposomes, bilayer sheets, micelles or lamellar structures, depending on hydration and temperature. This results in a type of material that is normally classified as amphipathic. As used herein, "modified lecithin" refers to, but is not limited to, acetylation, hydroxylation, hydrogenation, lecithin hydrolysis products, chlorination, bromination, iodination, halogenation, phosphorylation and sulfonation, as well as, any other modification known to those in the technique. Acetylated lecithins can be produced, for example, using an anhydride carboxylic acid as acetic anhydride for the acetylation of phospholipids from vegetable lecithins, as shown in United States Patent No. 3,301,881, which is incorporated herein by reference in its entirety. An enzymatic process can be used to prepare an acetylated phospholipid from vegetable lecithins, such as soy lecithin, rapeseed lecithin and animal lecithins, such as egg yolk lecithin or pure phosphatidylethanolamine isolated from the above lecithins. Commercial lecithins can be acetylated, for example, by using vinyl acetate as an acylating agent in the presence of lipase from Mucor miehei having 1,3-position specificity as a catalyst, as shown in U.S. Patent No. 6,403 .344, which is incorporated herein by reference in its entirety. In acetylated lecithin, for example, acetylation occurs mainly in the amino group of phosphatidylethanolamine. The extent of acetylation in the modified lecithin, if used, can be partial or complete. The extent of acetylation in a modified lecithin can be, for example, from about 5% to 100%, or from about 10% to about 99%, or from about 15% to about 95%, or from about 20% to about 90%, or from about 25% to about 75% or other values. Lecithin additionally contains a number of chemical functional groups that make it susceptible to a variety of chemical reactions. These groups include carbon-carbon double bonds, esters, phosphonate esters, amine and hydroxyl groups. The modification can also result in interesterified lecithin. In addition, lecithins can be modified by enzyme. As used herein, "phosphatides" (Phospholipids) refers to, but is not limited to mixtures of phosphatidyl choline, phosphatidyl ethanolamine, phosphatidyl serine, phosphatidyl inositol, phosphatidic acid, N-acylphosphatidyl ethanolamine and other related minor constituents. Commercial sources of lecithin or modified lecithin that can be used in the separation aids of the present invention include, for example, Solec HR 2B from Solae LLC (Memphis, Tennessee USA).
    [0051] [00051] The oil included in the indicated separation aid can be, for example, mineral oil, vegetable triglyceride oil, hydrocarbon oil or any combination thereof. Mineral oil can be, for example, white mineral oil or mineral seal oil. Examples of mineral oil may be atmospheric residue oil obtained from the distillation of crude oil, vacuum gas oil and vacuum residue oil obtained by vacuum distillation of atmospheric residue oil, its hydrotreated oils, pyrolysis oils and / or their mixtures. Among such mineral oils, atmospheric residue oil, vacuum residue oil and its hydrotreated products or pyrolysis products are mentioned as waste oils in the present invention. Vegetable triglyceride oil can be, for example, triglyceride corn oil. The hydrocarbon oil can be, for example, white mineral oil, or any of its combinations. Commercial sources of oil that can be used in the separation aids of the present invention include, for example, Clarion 70 White Mineral Oil, CITGO Petroleum (Houston, USA).
    [0052] [00052] Surfactants optionally included in the indicated separation aid composition can be, for example, non-ionic surfactants, cationic surfactants or anionic surfactants. The surfactant (which can be one or more) can be a nonionic surfactant, for example, ethoxylated castor oil, an ethoxylated sorbitan ester, a PEG, a poloxamer, an acetylenic glycol or a sulfonate, or combinations thereof. Nonionic surfactants can be, for example, nonionic polyethylene glycols, such as carboxylic acid ethoxylate, mono-, di- or triglyceride ethoxylate, sorbitan mono-, di- or triester esters or fatty alcohol ethoxylates. The ethoxylated sorbitan esters can be commercially obtained as TWEEN or polysorbate series surfactant. Other suitable nonionic surfactants are mono-, di- or triglycerides based on fatty acids having 12-22 carbon atoms, or mono-, di- or triesters of sorbitan based on fatty acids having 12-22 carbon atoms. Commercial sources of the nonionic surfactant that can be used in the separation aids of the present invention include, for example, Lumisorb Polysorbates from Lambent Technologies Corporation (Gurnee, III USA). The nonionic surfactant can be at least one poloxamer. Poloxamers can be non-ionic triblock copolymers that comprise a central block of a hydrophobic polyalkyleneoxide block, which is flanked on both sides with hydrophilic polyalkyleneoxide blocks. Poloxamers are commercially available and are food grade. A commercial source of poloxamers is, for example, PLURONIC® copolymers from BASF Corporation (Florham Park, New Jersey, USA).
    [0053] [00053] The water solubility of surfactants, such as nonionic surfactants, can be related to their hydrophilic-lipophilic balance (HLB) value or number. Nonionic surfactants can have an HLB value of at least about 6, or at least about 9, or at least about 12, or from about 6 to 20, or from about 7 to about from 19, or from about 8 to about 18, or from about 9 to about 17, or from about 10 to about 16 or other values. The water solubility of non-ionic surfactants can be related to their hydrophilic-lipophilic balance (HLB) value or number. The HLB value can be calculated in a conventional manner. For example, the HLB value of a nonionic surfactant can be calculated by dividing the percentage of the molecular weight of the hydrophilic portion of the nonionic surfactant to five. For example, a nonionic surfactant containing 80 mole% hydrophilic portion (total) would have an HLB value calculated to be 16 (i.e., 80/5 = 16). HLB values that exceed 20 are relative or comparative values.
    [0054] [00054] The separation aid composition may contain additional optional additives. For example, the separation aid may contain silica, as well as vaporized silica. The vaporized silica can be hydrophobic or hydrophilic. Vaporized silica is food grade and may be more desirable for that reason. If used, the vaporized silica can be contained in the separation aid in an amount, for example, from about 1% by weight to 10% by weight.
    [0055] a) 30 % em peso até 70 % em peso da referida lecitina; b) 30 % em peso até 70 % em peso do referido óleo; c) 0 % em peso até 40 % em peso do referido surfactante. 7. O método de qualquer seguinte realização/recurso/aspecto, onde o referido auxílio de separação compreende menos do que 1 % em peso de água.8. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação compreende menos do que 1 % em peso de compostos aromáticos.9. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação compreende menos do que 1 % em peso de compostos de álcool.10. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação é um grau alimentar ou composição ou mistura aprovada por GRAS.11. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida lecitina e referido óleo estão presentes em uma razão de peso de lecitina: óleo a partir de 0,8:1 até 1:0,8.12. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação é adicionado em uma quantidade a estar presente em uma faixa de ppm a partir de cerca de 200 ppm até 800 ppm.13. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido óleo é o óleo mineral, óleo vegetal ou qualquer de sua combinação.14. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido óleo é um óleo de triglicerídeo ou óleo com base em hidrocarboneto.15. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida lecitina é uma lecitina acetilada.16. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida lecitina é lecitina de soja ou lecitina de fava de soja.17. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido surfactante é pelo menos um óleo de rícino etoxilado ou surfactante PEG ou sulfonato ou glicol acetilênico.18. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido surfactante é um surfactante não iônico.19. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido surfactante é um surfactante catiônico ou aniônico.20. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido surfactante tem um valor de HLB a partir de 9 até 20.21. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação é adicionado à referida vinhaça utilizando uma corrente lateral.22. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação é adicionado diretamente ao referido evaporador contendo a referida vinhaça.23. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação é misturado com a referida vinhaça antes de entrar no referido evaporador.24. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde o referido auxílio de separação ainda compreende sílica.25. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida vinhaça tem um conteúdo de sólidos a partir de 5 % em peso até 20 % em peso quando o referido auxílio de separação é adicionado à referida vinhaça.26. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida vinhaça tem um conteúdo de sólidos abaixo de 30 % em peso quando o referido auxílio de separação é adicionado à referida vinhaça.27. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida vinhaça é um subproduto a partir de um processo de fermentação de milho.28. O método de qualquer realização/recurso/aspecto precedente ou seguinte, onde a referida vinhaça é um subproduto a partir de um processo de fermentação de cana de açúcar.29. Uma composição de auxílio de separação compreendendo a) a partir de 20 % em peso até 50 % em peso de pelo menos uma lecitina; b) a partir de 20 % em peso até 50 % em peso de pelo menos um óleo; e c) a partir de 0 % em peso até 20 % em peso de pelo menos um surfactante tendo valores de HLB de pelo menos 9. 30. Uma vinhaça tratada compreendendo o auxílio de separação de qualquer realização/recurso/aspecto precedente ou seguinte e vinhaça caracterizada pelo fato de que o auxílio de separação está presente em uma quantidade de pelo menos 50 ppm.31. A vinhaça tratada de qualquer realização/recurso/aspecto precedente ou seguinte, caracterizada pelo fato de que o referido conteúdo de sólidos da referida vinhaça tratada é a partir de 5 % em peso até 40 % em peso.32. Um método para recuperação de óleo a partir de alga, compreendendo adicionar pelo menos um auxílio de separação à alga que contém óleo, para formar uma alga tratada antes de centrifugar a referida alga e centrifugar a referida alga tratada em pelo menos uma centrífuga para separar pelo menos uma porção do referido óleo a partir da referida alga tratada, onde o referido auxílio de separação compreende pelo menos uma lecitina e pelo menos um óleo e opcionalmente pelo menos um surfactante tendo um valor de HLB de pelo menos 6.33. Um sistema de recuperação de bio-óleo, compreendendo um fornecimento de biomassa que compreende vinhaça ou alga; um fornecimento de auxílio de separação, onde o referido auxílio de separação compreende pelo menos uma lecitina e pelo menos um óleo e opcionalmente pelo menos um surfactante tendo um valor de HLB de pelo menos 6;uma unidade de tratamento para combinar o auxílio de separação com a biomassa para formar a biomassa tratada; e uma centrífuga para desidratar a biomassa tratada para produzir o bio-óleo concentrado.[00055] The present invention includes the following aspects / achievements / resources in any order and / or in any combination: 1. A method for recovering bio-oil from a fermentation process, comprising add at least one separation aid to the vinasse containing the oil, to form a treated vinasse before centrifuging the vinasse and centrifuging said treated vinasse in at least one centrifuge to separate at least a portion of said oil from said treated vinasse, wherein said separation aid comprises at least one lecithin and at least one oil and optionally at least one surfactant having an HLB value of at least 6. 2. The method of any previous or next realization / feature / aspect, where said addition occurs in at least one evaporator located upstream from said centrifuge. 3. The method of any previous or next realization / resource / aspect, where the said fermentation process comprises a series of evaporators that the said vinasse enters sequentially and located upstream to the said centrifuge, and where said addition is at least an aid separation occurs well before or in at least one of said evaporators located closest to said centrifuge. 4. The preceding or next method of any realization / feature / aspect, where the series of evaporators comprises at least 8 evaporators and said addition occurs well before or on the 5th, 6th, 7th or 8th evaporator. 5. The method of any previous or next realization / feature / aspect, where said at least one surfactant is present. 6. The method of any previous or next realization / feature / aspect, where the aforementioned separation aid a) 30% by weight to 70% by weight of said lecithin; b) 30% by weight to 70% by weight of said oil; c) 0% by weight to 40% by weight of said surfactant. 7. The method of any following realization / feature / aspect, where said separation aid comprises less than 1% by weight of water. 8. The method of any previous or next realization / feature / aspect, where said separation aid comprises less than 1% by weight of aromatic compounds. 9. The method of any previous or next realization / feature / aspect, where said separation aid comprises less than 1% by weight of alcohol compounds. 10. The method of any preceding or following realization / feature / aspect, where said separation aid is a food grade or GRAS approved composition or mixture. 11. The method of any preceding or following realization / feature / aspect, where said lecithin and said oil are present in a weight ratio of lecithin: oil from 0.8: 1 to 1: 0.8. 12. The method of any previous or next realization / feature / aspect, where said separation aid is added in an amount to be present in a range of ppm from about 200 ppm to 800 ppm. 13. The method of any previous or next achievement / feature / aspect, where the said oil is mineral oil, vegetable oil or any combination thereof. 14. The method of any preceding or next realization / feature / aspect, where said oil is a triglyceride oil or oil based on hydrocarbon. 15. The method of any preceding or next realization / feature / aspect, where said lecithin is an acetylated lecithin. 16. The method of any previous or next achievement / feature / aspect, where said lecithin is soy lecithin or soybean lecithin. 17. The method of any previous or next realization / feature / aspect, where said surfactant is at least an ethoxylated castor oil or PEG surfactant or sulfonate or acetylenic glycol. 18. The method of any previous or next realization / feature / aspect, where said surfactant is a nonionic surfactant. 19. The method of any previous or next realization / feature / aspect, where said surfactant is a cationic or anionic surfactant. 20. The method of any previous or next realization / feature / aspect, where said surfactant has an HLB value from 9 to 20. 21. The method of any previous or next realization / feature / aspect, where said separation aid is added to said vinasse using a side chain. 22. The method of any previous or next realization / feature / aspect, where said separation aid is added directly to said evaporator containing said vinasse. 23. The method of any previous or next realization / feature / aspect, where said separation aid is mixed with said vinasse before entering the said evaporator. 24. The method of any preceding or following realization / feature / aspect, where said separation aid still comprises silica. 25. The method of any preceding or following realization / feature / aspect, where said vinasse has a solids content from 5% by weight to 20% by weight when said separation aid is added to said vinasse. 26. The method of any previous or next realization / feature / aspect, where said vinasse has a solids content below 30% by weight when said separation aid is added to said vinasse. 27. The method of any previous or next performance / feature / aspect, where the aforementioned vinasse is a by-product from a corn fermentation process. 28. The method of any preceding or following achievement / feature / aspect, where said vinasse is a by-product from a sugar cane fermentation process. 29. A separation aid composition comprising a) from 20% by weight to 50% by weight of at least one lecithin; b) from 20% by weight to 50% by weight of at least one oil; and c) from 0% by weight to 20% by weight of at least one surfactant having HLB values of at least 9. 30. A treated vinasse comprising the separation aid of any preceding or following realization / feature / aspect and vinasse characterized by the fact that the separation aid is present in an amount of at least 50 ppm. 31. The vinasse treated from any preceding or next realization / feature / aspect, characterized by the fact that the said solids content of the aforementioned treated vinasse is from 5% by weight to 40% by weight. 32. A method for recovering oil from seaweed, comprising adding at least a separation aid to the oil-containing seaweed, to form a treated seaweed before centrifuging said seaweed and centrifuging the treated seaweed in at least one centrifuge for separating at least a portion of said oil from said treated seaweed, where said separation aid comprises at least one lecithin and at least one oil and optionally at least one surfactant having an HLB value of at least 6. 33. A bio-oil recovery system, comprising a supply of biomass comprising vinasse or seaweed; a separation aid supply, wherein said separation aid comprises at least one lecithin and at least one oil and optionally at least one surfactant having an HLB value of at least 6; a treatment unit to combine the separation aid with the biomass to form the treated biomass; and a centrifuge to dehydrate the treated biomass to produce the concentrated bio-oil.
    [0056] [00056] The present invention can include any combination of these various features and achievements above and / or below as set out in the phrases and / or paragraphs. Any combination of the features disclosed herein is considered part of the present invention and no limitations are intended with respect to the combinable features.
    [0057] [00057] The present invention will be further clarified by the following examples, which are intended to be only examples of the present invention. Unless otherwise indicated, all amounts, percentages, ratios and the like used herein are by weight. EXAMPLES Example 1:
    [0058] [00058] The bench test was carried out on vinasse (16-18% by weight of solids) from a fifth evaporator from an 8-stage evaporator used in a bioethanol production facility using the corn raw material, such as shown in FIGS. 1 and 3 of the present and generally as described in the incorporated '182 patent. The samples taken from the vinasse were mixed with several treatment compositions indicated in Table 1 by manually stirring the vinasse with selected dosages of the treatment composition, then pouring the resulting mixtures into the measuring tubes, and the recovered oil products were observed and compared for clarity and volume. In Table 1, treatment compositions 1 and 2 contained at least lecithin and oil. Such compositions are separation aids which represent the examples of the present invention. the other treatment compositions contained other combinations of chemicals and are examples of comparison.
    [0059] [00059] Treatment compositions 1 and 2 have been observed to provide better oil separation volume at lower dosage levels and comparable or better oil quality than comparison test compositions 1, 2, 3 and 6 applied at levels dosage levels. Treatment compositions 1 and 2 were observed to provide better oil separation and oil quality than comparison test compositions 4 and 5 at the same dosage levels. The results indicate that a synergism is obtained in the separation of oil by a combination of lecithin and oil as compared to oils used in combination with each other and / or the indicated surfactants used in the comparison formulations. Example 2:
    [0060] [00060] The additional bench test was carried out on vinasse (16-18% by weight of solids) from a fifth evaporator from an 8-stage evaporator used in a bioethanol production facility using the raw material of corn, such as as shown in FIGS. 1 and 3 at present and generally as described in the incorporated '182 patent. The samples taken from vinasse were mixed with several treatment compositions indicated in Table 2 (quantities provided in% by weight) by manually stirring the vinasse with the added treatment composition, pouring the resulting mixtures into measuring tubes and visually comparing the recovered oils for clarity and volume with a Basal product. The basal product was a sample of vinasse treated with the treatment composition of Comparison 1 as described in Example 1. Product 33 was treated by vinasse with treatment composition 2 described in Example 1. All samples of vinasse were dosed with 30 μl of the treatment composition which is equivalent to approximately 550 ppm. Table 2 shows the results of the percentage oil recovered compared to the indicated basal sample. Trans 402 is from Trans-Chemco; Dow FC 114 and FC-149 are Volatile Cane Deformers which are E0-130 glycols from Dow Chemical; Agrol 2.0, 3.6, 4.3 is the hydroxylated soybean oil from BioBased Technologies; Suppressor Strainers 3583 and 9905 are from Hydrite Inc .; HDP products are from Harcros; and Dow Corning Defoamer and FG-10 products are silicone based.
    [0061] [00061] As can be seen from the results in Table 2, product 33, in which the vinasse was treated with the composition including lecithin and oil performed 10% better than the Basal product in which the vinasse was treated with the composition Comparison 1, and 11 times better in magnitude (ie, 110% versus 10%) than using unmodified lecithin alone as the treatment composition in the product 30. In addition, in additional tests, the composition including lecithin and oil has been observed to perform best in a wide variety of conditions. Example 3:
    [0062] [00062] The additional bench test was carried out on vinasse (16-18% by weight of solids) from a fifth evaporator from an 8-stage evaporator used in a bioethanol production facility using the raw material of corn, such as as shown in FIGS. 1 and 3 at present and generally as described in the incorporated '182 patent. The samples removed from vinasse were mixed with several treatment compositions by manually shaking in the same dosage, pouring the resulting mixtures into the measuring tubes and visually comparing the recovered oils for clarity and quantity with a Basal product. The Basal product was a sample of vinasse treated in line in an evaporator pump with the treatment composition of Comparison 1 as described in Example 1. The treated products designated 13864, 13865, 13866 and 1991 were prepared by treating samples taken from the vinasse from the evaporator with four different separation aid compositions of the present invention. The Basal product had its treatment composition added with the aid of a pump, which added the treatment composition directly to the vinasse. The samples treated with the treatment compositions in products 13864, 13865, 13866 and 1991 were manually mixed by hand from the vinasse collected from the evaporator, so there was a mixing factor involved that would be expected to provide an advantage to the comparison treatment carried out in the basal product with in-line addition at the pump. The treatment composition used for product 13864 was the same as treatment composition 2 described in Example 1. The treatment composition used for product 13865 was 40% soy lecithin, 40% mineral sealing oil and 20 Polysorbate 80%. The 1991 product received a similar treatment composition according to product 13864, in which the treatment composition also contained 5% vaporized silica.
    [0063] [00063] FIG. 6 shows the photographs of the product 13864 compared to the Basal product in the dosages of 200 ppm, 300 ppm and 400 ppm. FIG. 7 shows the photographs that compare the Basal product with the 400 ppm dosage product of 13864. As can be seen, the 13864 product has a distinct layer of oil product on top of the product material in the tube which is essentially the same corn oil level than the Basal product sample. Substantially similar results were observed for products 13865, 13866 and 1991 compared to Basal products at similar dosage levels to treat the composition, where the amount of oil recovered was comparable or less. Products 13864, 13866 and 1991 particularly produced very good oil recovery results at 400 ppm. The combinations of vinasse and separation aid representing the examples of the present invention that were tested could produce the same oil or slightly more oil than the Basal product, and in lower dosages.
    [0064] [00064] Depositors specifically incorporate the entire content of all references mentioned in this disclosure. In addition, when an amount, concentration or other value or parameter is provided as a range, preferred range or a list of upper preferable values and lower preferable values, this should be understood as specifically revealing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values is mentioned here, unless otherwise stated, the range is intended to include its end points, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values mentioned when defining a range.
    [0065] [00065] Other embodiments of the present invention will be apparent to those of skill in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples are considered to be only exemplary with a true scope and spirit of the invention being indicated by the following claims and their equivalents.
    权利要求:
    Claims (20)
    [0001]
    Method to recover bio-oil from a fermentation process, characterized by the fact that it comprises: - add at least one separation aid to the vinasse containing oil, to form a treated vinasse before centrifuging said vinasse, said separation aid being added in an amount to be present in a range of 200 ppm ppm at 800 ppm, said separation aid comprising at least one oil and 30% by weight to 70% by weight of at least one lecithin, and at least one surfactant having an HLB value of at least 6, the auxiliary being separator works as an oil-breaking / demulsifying additive to reduce emulsification or the tendency to emulsify in vinasse, and - centrifuge said treated vinasse in at least one centrifuge to separate at least a portion of said oil from said treated vinasse.
    [0002]
    Method according to claim 1, characterized in that said addition occurs in at least one evaporator.
    [0003]
    Method according to claim 1, characterized in that said fermentation process comprises a series of evaporators in which said vinasse enters sequentially, said addition of said at least one separation aid occurring before or in at least one of said evaporators.
    [0004]
    Method according to claim 3, characterized in that said series of evaporators comprises at least 8 evaporators and said addition occurs before or in any of the 5 °, 6 °, 7 ° or 8 ° evaporator.
    [0005]
    Method according to claim 1, characterized in that said separation aid comprises: a) 30% by weight to 70% by weight of said lecithin; b) 30% by weight to 70% by weight of said oil; c) 1% by weight to 40% by weight of said surfactant.
    [0006]
    Method according to claim 5, characterized in that said separation aid comprises less than 1% by weight of water and / or less than 1% by weight of aromatic compounds and / or less than 1% by weight of compounds of alcohol.
    [0007]
    Method according to claim 1, characterized in that said lecithin and said oil are present in a weight ratio of lecithin: oil from 0.8: 1 to 1: 0.8.
    [0008]
    Method according to claim 1, characterized in that said oil is mineral oil, vegetable oil or any combination thereof, preferably a triglyceride oil or oil based on hydrocarbon.
    [0009]
    Method according to claim 1, characterized in that said lecithin is an acetylated lecithin, soy lecithin or soybean lecithin.
    [0010]
    Method according to claim 1, characterized in that said surfactant is ethoxylated castor oil or PEG surfactant.
    [0011]
    Method according to claim 1, characterized in that said surfactant has an HLB value from 9 to 20.
    [0012]
    Method according to claim 1, characterized in that said separation aid is added to said vinasse using a side chain.
    [0013]
    Method according to claim 2, characterized in that said separation aid is added directly to said evaporator containing said vinasse, or is mixed with said vinasse before entering said evaporator.
    [0014]
    Method according to claim 1, characterized in that said separation aid still comprises silica.
    [0015]
    Method according to claim 1, characterized in that said vinasse has a solids content below 30% by weight when said separation aid is added to said vinasse.
    [0016]
    Method according to claim 1, characterized in that said vinasse is a by-product from a corn fermentation process or a by-product from a sugar cane fermentation process.
    [0017]
    Treated vinasse, comprising the separation aid and vinasse, characterized by the fact of understanding: a) from 20% by weight to 50% by weight of at least one lecithin; b) from 20% by weight to 50% by weight of at least one oil; and c) from 1% by weight to 20% by weight of at least one surfactant having HLB values of at least 9, said separation aid being present in an amount of 50 ppm to 800 ppm.
    [0018]
    Treated vinasse according to claim 17, characterized in that said solids content of said treated vinasse is from 5% by weight to 40% by weight.
    [0019]
    Bio-oil recovery system, characterized by the fact that it comprises: - a supply of biomass comprising vinasse; - a separation aid supply, wherein said separation aid comprises at least one oil and 30% by weight to 70% by weight of at least one lecithin, and at least one surfactant having an HLB value of at least 6, the separation aid works as an oil-breaking / demulsifying additive to reduce emulsification or the tendency to emulsify in vinasse; - a treatment unit for combining the separation aid with the biomass to form the treated biomass; and - a centrifuge to dehydrate the treated biomass to produce the concentrated bio-oil.
    [0020]
    Method according to claim 1, characterized in that said surfactant is at least a sulfonate or at least an acetylenic glycol.
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    同族专利:
    公开号 | 公开日
    WO2014099078A2|2014-06-26|
    WO2014099078A3|2014-08-14|
    ZA201504299B|2016-04-28|
    AU2013364289A1|2015-07-09|
    EP2935544A2|2015-10-28|
    AU2013364289B2|2016-07-14|
    NZ708863A|2019-04-26|
    MX364476B|2019-04-24|
    US20140171670A1|2014-06-19|
    EP2935544B1|2017-11-08|
    ES2650394T3|2018-01-18|
    CN105026537B|2020-04-21|
    CA2895684A1|2014-06-26|
    MX2015007501A|2015-12-11|
    JP2016506440A|2016-03-03|
    US9328311B2|2016-05-03|
    PT2935544T|2017-12-19|
    CA2895684C|2020-04-14|
    CN105026537A|2015-11-04|
    BR112015014194A2|2017-07-11|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2018-03-20| B06I| Technical and formal requirements: publication cancelled|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-07-14| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-11-24| B09A| Decision: intention to grant|
    2021-02-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261739218P| true| 2012-12-19|2012-12-19|
    US61/739,218|2012-12-19|
    PCT/US2013/061781|WO2014099078A2|2012-12-19|2013-09-26|Methods and systems for bio-oil recovery and separation aids therefor|
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