WO2014039613A1 - Procédés et système pour convertir un flux hétérogène de déchets de corps gras, d'huiles et de graisses (fog) en biodiesel - Google Patents

Procédés et système pour convertir un flux hétérogène de déchets de corps gras, d'huiles et de graisses (fog) en biodiesel Download PDF

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Publication number
WO2014039613A1
WO2014039613A1 PCT/US2013/058148 US2013058148W WO2014039613A1 WO 2014039613 A1 WO2014039613 A1 WO 2014039613A1 US 2013058148 W US2013058148 W US 2013058148W WO 2014039613 A1 WO2014039613 A1 WO 2014039613A1
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WO
WIPO (PCT)
Prior art keywords
stage
water
fog
stream
heat
Prior art date
Application number
PCT/US2013/058148
Other languages
English (en)
Inventor
Paul Marshall
Arthur Jonas RAGAUSKAS
Matthew J. REALFF
Original Assignee
Fogfuels, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fogfuels, Inc. filed Critical Fogfuels, Inc.
Publication of WO2014039613A1 publication Critical patent/WO2014039613A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
    • C11C1/08—Refining
    • C11C1/10—Refining by distillation
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the present disclosure relates generally to production of alternative burning fuels, and more particularly to the eon-version of renewable resources such as fats, oils, and grease ⁇ FOG) that are typically present in residential and Industrial waste -streams into clean burning bio- egradable, imiHnxie alternative fuels, a/k/a biodiesei.
  • renewable resources such as fats, oils, and grease ⁇ FOG
  • the lipid rich material resent in the waste water of cooking and food processing operations is frequeritly referred to as p ' OO (be,, Fats, Oils and Greases) and is present in grease imp waste (GTW),
  • GTW grease imp waste
  • p ' OO be,, Fats, Oils and Greases
  • GTW grease imp waste
  • Biodiesei is usu lly defined as mono-alkyl esters of long chain fatty acids derived t1 ⁇ 4m vegetable oils or speeifkadons for use in diesel engines.
  • Fuel-grade biodiesei typically has to meet industry specifications (ASTM 06751 ⁇ k order to ensure proper performance, Biodiesei is now a. widely accepted alternative ibeh at least in par because of its com liance with t e health, effects testing recphrenients of the 1 90 Clean Air Act Amendments,
  • Neat (i.e., 1.00 percent) biodiesei has been designated as an alternative fuel by the Department of Energy (DOE) and the US Department of Transportation (DOT).
  • DOE Department of Energy
  • DOT US Department of Transportation
  • raw vegetable oil cannot mee biodiesei fuel specifications, is not registered with the EPA, and. is not a legal, motor foci
  • biodiesei is an attractive fuel resource as it has a higher eetane numbe than diesel fuel has no aromaties, and is approximately 10% oxygen by weight.
  • biodiesei has been repotted to reduce the emissions of carbon monoxide, hydrocarbons, and particulate matter in the exhaust ga : when compared to diesel fuel exhausts.
  • Biodiesei generally refers to the pure fuel before blending with diesel fuel
  • Biodiesei blends are dene ted as "B X" whh "XX” representing the percentage of biodiesei contained in the blend (i.e., 20 is 20% biodiesei, 8(1% petroleum diesel).
  • biodiesei has been shown, to have fuel properties very close to diesel fuel and thus can be used, in diesel engines with little or no modifications to die engine or (he fuel system.
  • Biodiesei has a solvent effect that may release deposits accumulated on tank walls and pipes from, previous diesel fuel storage. The release of deposits m clog filters initially and precautions should be taken to ensure that only fuel meeting the biodiesei specification is used.
  • Biodiesei emissions have decreased levels of polycyclic aromatic hydrocarbons (PAH) and nitrited.
  • PAH compounds which have been identified as potential cancer causing compounds.
  • Test results indicate PAH compounds were reduced by 75 to 85 percent, with the exception, of benzo(a)anthracene, which was reduced by roughly 50 percent.
  • Targeted nPAH compounds were also .reduced dramatically with biodiesei fuel, with 2- nitmtluorene and 1 untropyrene reduced by 90 percent,, and the rest of the nPAlI om ounds reduced to onl trace levels.
  • varions FOG bioresources melade hot are not limited to) trap grease * municipal slodge/seurn, dissolved air fiotatiotxT!otation grease, waste fats, brown pease, animal grease, skimmings, or generally any FOG hioresouree comprising up to 100% FFA (free fa tty acid) con e t - even if the POO bioresource is watery and eontammated.
  • aspects of the present disclosure include methods to convert animal fats, tallo and waste vegetable oil, and other bioresources into biodiesei.
  • processes ar optimised for municipal and industrial waste stream byproducts that are typically highl contaminated, watery, and have very high FFA levels.
  • the disclosed methods can directl process up to 100% FFA and remove suilhr to ensure the resultant fuel is fully ASTM quality for on-road use. It will be appreciated that benefits of the disclosed met hods incl ude elimination, (or redaction) of caustic ehernieals, inexpensive preprocessing., etc. Eve further, the methods render economically- viable biodiesei production achievable and durable.
  • One embodiment of the Invention contemplates a system and method lor converting a waste stream comprising an admixture of fats, oiL and/or grease (FOG), water, and waste solids into hiodiese! fuel, comprising:
  • a first stage comprising apparatus for at least partially dewatering the FOG waste stream and apparatus for removing solids remo val of the FOG waste stream, the first stage comprising a succession of first, stage processing stages comprising one or more of a solids removal stage, a water/oil separation stage, (an optional acid deguouning stage), and a fiUerin ; g/porificatio stage, producing a concentrated FOG stream:
  • At least one of said first stage processing stages involving the introduction of water, heat, and/or an alcohol
  • the present invention further contemplate embodiments, wherein excess heat from a. di still ation column in the second stage may be milke in. a dryer in the first stage.
  • the present invention also contemplate- embodiments wherein, further comprising, a heat exchanger for collecting excess eat from components in the second stage for use in the first stage.
  • the present invention also contemplate embodime ts wherein water collected from a nretharml/water distillation process In stage 2 is used to feed water washes in the first stage.
  • Embodiments of the present invention also contemplate systems and methods wherein a component in the second stage generates crude glycerin, and wherein the crude glycerin is used I» the first stage instead of an alcohol,
  • PIG. I illustrates the basic chemistry Involved in the processing of plant arid animal triglycerides to hiodiesel.
  • FIG. 2 illustrates one embodiment of a first stage aud/or process of a FOG- to-biodiesel conversion process according to the present disclosure
  • FIG. 3. illustrates another embodiment of a first stage and/or process of a FOG-io- hiodicsel con ersion process according to the present disclosure
  • FIG. 4 illustrates a embodiment of a second stage and/or process of a FOG-to- ' biodlesel conversion process according to the present disclosure.
  • aspects of the present, disclosure include method to convert animal fats, tallow and waste vegetable oil, and other bioresoorces into biodiesel
  • suc processes are optimized .for municipal and industrial waste stream byproducts that a e: typically highl contaminated, watery, and have very high FFA levels, in contrast to die limitations of traditional, esterification, die disclosed methods can directly process u to 100% FFA and remove sulfur to ensure the resultant fuel is folly AST quality for on-road use, it wit! be appreciated that benefits of the disclosed methods include elimination (or reduction) of caustic chemicals, inexpensive preprocessing, etc. Even farther, the methods render economically-viable biodiesel production achievable and. durable.
  • the biodiesel. is produced in a micto-rellnery that is co-located with Waste Water Treatment Plants (W WTPs), wherein the FOG bioresources are collected and processed, ⁇ » alternate e b dime ts, a kro-refmery can be constructed as a ortable anil (e.g. deployed on a flat-bed taikr) so that the bkxiiesei production can be deployed rapidly * allowing for reduced transportation, costs and localized .fuel production.
  • W WTPs Waste Water Treatment Plants
  • FOG bioresources as received from various sources typicailyeontain several mm- triglyceride components (e.g,, phosphatides, tree fatty acids, etc. ⁇ which most be removed prior to conversion to biodiesei
  • the primary process for FOG-to-biodleael involves a first stage tor solids removal and de watering* wuh a resultant.
  • grease stream and certain byproducts solids, water tent and a second stage that processes the grease stream into biodiesel and certain byproducts (additional solids, methanol water, glycerin).
  • the overall process (an embodiment of which Is shown In FIG, 2) comprises four stages: a solids removal stage, a water/oil separation stage, an acid degummmg stage, and a filteritig/porihcation stage.
  • the conversion process separates the FOG bioresouree Into a solids stream, a water stream, and a grease stream, t will be understood tha the solids stream is generally an unusable byproduct (at least for biodiesel production), that the water stream Is there-after treated by a municipal water treatment process, and the grease stream used tor biodiesel. production..
  • PKF 2 is one embodiment of a first stage that for solids removal, de atering to provide a grease .stream for use in a second ester ipestioo slage.
  • a solid removal stage comprises junk screening, grinding,
  • a traveling screen to remove large solids.
  • the temperature of the FOG bioresouree e.g., trap grease shown flowing into point A in FIG, 2
  • a magnetic trap removes ferrous metals.
  • a grinding process involves grinding tire solids that remain after the junk screening process Into a i iforai size via a grinde pum . These solid are primarily food waste. Afte the grinding process and. according to one en:rbodlmeni these .remaining solids undergo a
  • cooking/hydrolysis proces wherein they are heated, to coagulate proteins and promote separation of tats and solids.
  • a caustic may be added to hyrlrolyxe hair and other proteins.
  • a horizontal centrifuge decanter is used to separate solids irons liquids daring a typical decanting process.
  • separated solids are dried to a..meal In. a dram dryer.
  • the liquid stream resulting from the decanting process undergoes; a water/oil. separation process, according to one embodiment Accordin to one aspect, the liquid stre m is separated through a series of two disc centrifuges into a water stream and a grease stream.
  • a degurmning process in volve the removal of gums and phospholipids from the oil. through an acid degurnming process.
  • an acid degurnming process Involves removal of phosphatide content, be, ums and phospholipids, thereb leading to lower residual phosphorus content
  • the grease stream may not undergo an acid deguunning process.
  • FIG. a One such, embodiment is illustrated by FIG. a.
  • the first stage of both mbod me ts Involve the introduction of beat si various locations, e.g. in FIG. 2 a dram dryer 210, a cooker between streams C and D, a reactor vessel between streams 0 and F, and the siearn heater between streams J and M as well as the introduction of additional water, e.g. at step 230, and in FIG. 3 re-melier at the initial entry point, a. vacuum dryer.
  • excess heat and/or water from later process steps e.g. from stage 2 are introduced to stage 1 to effect energy and water savings, in accordance with inventive aspects of the disclosure.
  • FIG. 4 illustrates an. embodiment of a second stage and/or process of a FfXi-to-biodiesei conversion, process according to the present disclosure.
  • the second stage of the. process shown, i n FIG . - begins after (lie dewatermg process at step 1, which corresponds to the first stage as described herein.
  • the grease stream ai step 4 is fir provided to an.
  • esterifkatiors stage which comprises a reactor that Introduces sulphuric acid at step 6 arid an alcohol ai step 5, such as .methanol or glycerol, Alterirati vely, cra.de glycerine could be used.
  • This step of methauoiysis or glycolysis converts the free fatty acids into their ester form.
  • the reactor output is provided at 7 to a water wash at 9 where add tional water is introduced, whose output 1.0 is provided to a centrifuge.
  • the centrifuge output is an acidic waste stream 12 that is provided, with other waste byproducts; at 17 to neutralization stage at 18, where NaOH is introduced, ' Ore concentrated FOG components f om the centrifuge ate provided at 1 1 to a first evaporator, which, boils off volatile ⁇ materials at 13 which are introduced into the acidic waste stream at 17.
  • stream 13 is condensed before it Is mixed with stream 16 to form stream 17,
  • condensation requires remo val of heat and is another benefit to the disclosed aspects of heat integration (otherwise other means of removing the heat such, as cooling water would be required) .
  • the same will he true for streams 34 and 41.
  • the concentrated. FOG from the evaporator at 14 is introduced to a O3 ⁇ 4 «sesterifeation stage, which initially comprises a reactor that, introduces sodium methoxide at 25 nd methanol at 24, Again, advantageously, rite methanol r m the distillation ai 21 may he reintroduced at 24 for process efficiency.
  • methanol recycling is known in the art, a Is recycling of water wi thin the scope of FIG, 4,. inventive aspects of the disclosed process rela te to the point at which recycled water is introduced into earlier stages of the FOGAo-biodksei process a described herein.
  • the output, from the reactor at 26 is provided to a glycerin settling tank, fire settled glycerin byproduct is removed at 28 and treated with sulphuric acid at 23, to provide a glycerin byproduct, a 40.
  • the glycerin is provided to a second evaporator, which provides crude glycerin at 42 and vokdl.es at 41 , whic are processed by the neuiraika&ou at 18, 19.
  • the FOG from the settling tank, now .from which glycerin has been removed, is provided with ano her water wash at 27, where additional water k introduced at 29, Excess water is removed at 30 and provided to the neutralization at 18, 19.
  • the snore purified FOG is provided at 1 to a second centrifuge, which removes heavier constituems at 33 to tire acidic water rseitarallzatlon at 1 1 .
  • Hie rem a sg FOG is then provided to a third, evaporator at 32» which removes volatdes at 34 to the acidic waste stream and.
  • the ion exchange process output is provided at 36 to a biodiesei distillation vessel, which, produces the desired hiodiesel output at 37 and additional waste residue at 3S,
  • condensation f om one or more of components ⁇ evaporators 41, 13, and 34 m conjunction with condenser / disdllatioiu specificall the condenser heat in 430 (alt of which are shown, in FIG. 4),
  • the beat required to produce the steam shown in FIG. 2 as provided to the heat exchanger between streams J and M i collected from the heat energy thai is provided by condensation from one or mere of components 41, 13, and 34 in conjunction wi th condenser / distillation 21 , 22 (all of which are shown in FIG. 4).
  • condensation from one or mere of components 41, 13, and 34 in conjunction wi th condenser / distillation 21 , 22 (all of which are shown in FIG. 4).
  • water collected from, the methaooi/wa er distillation, process shown as 22 FIG, 4 is be used to Iced the w : ater washes a 8 and 2 , also shown i « FIG. 4.
  • the integration cap also be made with the water stream fed to the mixer, situated between streams N and 0, prior to the degmnmifcg reaction vessel l beled 2 0 OP f 10. 2,
  • the reuse / recycling of water results in lowered overall water usage, as well as improved ultimate wafer quality when water Is eventuall removed from the process and introduced into municipal wastewater treatment
  • an output of the solids removal mid water/oil separation processes described above can be combined with, crude glycerin produced by coniponent 42 (as shown ia FIGS, 2. 4), such combination used to iced glycerin instead of methanol into component 5 (as shown In FIGs,. 2 twist 4),

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

La présente invention porte sur la production de carburants domestiques alternatifs, et plus particulièrement sur la conversion de ressources de déchets renouvelables telles que des corps gras, des huiles et des graisses (FOG), qui sont, habituellement présents dans des flux de déchets domestiques et industriels, en carburants de substitution combustibles et biodégradables, non toxiques et brûlant sans résidu, en biodiesels a.k.a. Les matières à haute teneur en lipides présentes dans les eaux usées de cuisson et de transformation des aliments sont fréquemment qualifiées de FOG (c.-à-d. corps gras, huiles et graisses) et se trouvent dans les eaux de séparateurs de graisse (GTW):
PCT/US2013/058148 2012-09-05 2013-09-05 Procédés et système pour convertir un flux hétérogène de déchets de corps gras, d'huiles et de graisses (fog) en biodiesel WO2014039613A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261697162P 2012-09-05 2012-09-05
US61/697,162 2012-09-05

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WO2014039613A1 true WO2014039613A1 (fr) 2014-03-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9476009B2 (en) 2015-03-05 2016-10-25 Drexel University Acidic methanol stripping process that reduces sulfur content of biodiesel from waste greases

Citations (6)

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Publication number Priority date Publication date Assignee Title
US7528272B2 (en) * 2004-09-24 2009-05-05 Artisan Industries, Inc. Biodiesel process
US20100126060A1 (en) * 2007-01-24 2010-05-27 Best Energies, Inc. Biodiesel production with reduced water emissions
US7806945B2 (en) * 2003-01-27 2010-10-05 Seneca Landlord, Llc Production of biodiesel and glycerin from high free fatty acid feedstocks
US7834203B2 (en) * 2003-03-28 2010-11-16 Korea Institute Of Energy Research Manufacturing method of bio-diesel oil
US20100293840A1 (en) * 2006-10-20 2010-11-25 Owen Matthew Davies Biodiesel synthesis
US8192696B2 (en) * 2008-11-18 2012-06-05 Stephanie Marie Gurski System and process of biodiesel production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7806945B2 (en) * 2003-01-27 2010-10-05 Seneca Landlord, Llc Production of biodiesel and glycerin from high free fatty acid feedstocks
US7834203B2 (en) * 2003-03-28 2010-11-16 Korea Institute Of Energy Research Manufacturing method of bio-diesel oil
US7528272B2 (en) * 2004-09-24 2009-05-05 Artisan Industries, Inc. Biodiesel process
US20100293840A1 (en) * 2006-10-20 2010-11-25 Owen Matthew Davies Biodiesel synthesis
US20100126060A1 (en) * 2007-01-24 2010-05-27 Best Energies, Inc. Biodiesel production with reduced water emissions
US8192696B2 (en) * 2008-11-18 2012-06-05 Stephanie Marie Gurski System and process of biodiesel production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9476009B2 (en) 2015-03-05 2016-10-25 Drexel University Acidic methanol stripping process that reduces sulfur content of biodiesel from waste greases

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