US008841469B2
`
`(12) United States Patent
`Shepperd et al.
`
`(10) Patent N0.:
`(45) Date of Patent:
`
`Us 8,841,469 B2
`Sep. 23, 2014
`
`(54) CHEMICAL ADDITIVES AND USE THEREOF
`
`(56)
`
`References Cited
`
`IN STILLAGE PROCESSING OPERATIONS
`
`U S PATENT DOCUMENTS
`
`(75)
`
`1‘“'e“‘°‘53 P"“' W‘ Sh°PP"dv Ne“"“1‘= DE (U329
`MeCord Pankonen, Marshall, MN
`(US); Jeffrey T. Gross, Lacenter, WA
`(US)
`
`(73) Assignee: Solenis Technologies, L.P.. Wilmington,
`| )1 1, (us)
`
`3/2009 Scheirnann et al.
`7,497,955 B2 *
`10/2009 Dauy
`7,502,353 132
`l/2006 Schcimann ct al.
`2006/0006116 A1
`9/2007 Scheimann et al.
`2007/0210007 Al
`7/2008 Randhava et al.
`2008/0176298 Al
`12/2010 Rldgley
`2010/0321580 Al
`OTHER PUBLICATIONS
`
`210/709
`
`( * ) Notice:
`
`Sultject to any disclaimer, the term ofthis
`patcnt is extended or adjusted under 35
`U'S'C' 1540)) by 337 days‘
`(21) APP1- N04 13/370,456
`(22) Filed:
`Feb. 10, 2012
`(Under 37 CFR 147)
`
`(65)
`
`Prior Publication Data
`US 2012/0245370 Al
`Sep. 27, 2012
`
`Related US_ Application Data
`(60) Provisional application No. 61/454,634, filed on Mar.
`21, 2011.
`
`(51)
`
`(2006.01)
`(2()()6.()1)
`
`Int CL
`Cl 1]) 13/00
`CIIB I/III
`(52) U.S. Cl.
`C/PC ~ CIIB 1/10 (201301)? CIIB 13/00 (201301);
`w
`Y{)2E 50/7 7 (2013,-0] 2
`USP9 """""""""" " 554/123 334/83 554/93 554/204
`(58) Field 0f Classlficatmn Search
`None
`See application file for complete search history.
`
`“C[:m\IM:rl.lting‘ Cpmgessmg ajfndhiénelrglmn Uf.CU_
`gel?’
`11° §1::,sj‘00lln;1:S'?g:S‘ u “On on creme’ 69
`lea
`ymposmm’
`Taherzadeh, lvl.J,, and Karimi, K., “Enzyme-based hydrolysis pro-
`cess
`for ethanol
`from lignocellulosic materials:
`a
`review”,
`BioResources,Vo1. 2, No. 4, 2007, pp. 707-738,
`International Search Report , Form PCT/USN210, dated Apr. 13,
`2012, pp. 2
`Klinkesorn, Utai et :11, “Stability and rheology of corn oil-in-water
`emulsions containing rnaltodextrin”, Food Research International,
`V0‘) 37 (3904) PP- 85 '-35"-
`_
`_
`VVa.ng, Hui et al., “Effect of Low-Shear Extrusion on Corn Fermen-
`tation and Oil Partition”, J, Agricultural and Food Chemistry, vol. 57
`(2009) pp, 2302-2307.
`Kadioglu, Sezin lslamoglu et al., “Surfactant-Based Oil Extraction of
`
`Corn Germ , JArr1 011 Chm Soc (2011) Vol. 88 pp. 863-869.
`* cited by examiner
`
`Yate K Cutliff
`Primary Examiner
`(74) Atzornegv, Agent, or Firm — Joanne Rossi; Michael
`Herman
`
`ABSTRACT
`(57)
`A method is provided for the use of a chemical additive to
`improve the separation of oil from the process stream (Whole
`stillage, thin stillage or syrup) generated as a byproduct in
`corn to ethanol production.
`
`20 Claims, 1 Drawing Sheet
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`HYDRITE EXHIBIT 1030
`
`Hydrite V. Solenis
`Trial IPR2015-1592
`
`(1 of 8)
`
`HYDRITE EXHIBIT 1030
`Hydrite v. Solenis
`Trial IPR2015-1592
`(1 of 8)
`
`

`
`U.S. Patent
`
`Sep. 23, 2014
`
`US 8,841,469 B2
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`HYDRITE EXHIBIT 1030
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`Hydrite V. Solenis
`Trial IPR2015-1592
`
`(2 of 8)
`
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`HYDRITE EXHIBIT 1030
`Hydrite v. Solenis
`Trial IPR2015-1592
`(2 of 8)
`
`

`
`US 8,841,469 B2
`
`1
`CHEl\IICAL ADDITIVES AND USE THEREOF
`IN STILLAGE PROCESSING OPERATIONS
`
`This application claims the benefit of provisional applica-
`tion number U.S. 61/454,634, filed Mar. 21, 2011, the entire
`contents of which are hereby incorporated by reference.
`FIELD OF THE INVENTION
`
`This invention pertains to recovering oil in corn to ethanol
`production.
`BACKGROUND OF THE INVENTION
`
`There are two types of corn to ethanol processing, wet
`milling and dry milling. The central difference between the
`two processes is how they initially treat the grain. In wet
`milling, the corn grain is steeped in water, and then separated
`for processing iii the first step. Dry n1illii1g, which is more
`common. requires a different process.
`The corn dry-milling process utilized in the production of
`ethanol is well known. For example see Kelly S. Davis, “Corn
`Milling, Processing and Generation of Co-Products”, Mi1me-
`sota Nutrition Conference, Technical Symposium, 11 Sep.
`2001. Ethanol plants typically treat w11ole stillage from the
`beer column via centrifugation to produce wet cake and thin
`stillage then further treat the thin stillage stream by subjecting
`it to multiple effect evaporation to produce increase the solids
`and recover the distillate for return use in the process (FIG. 1).
`As solids increase the thin stillage is typically referred to as
`syrup (see l*'I(}. 1). The syrup is typically combined with wet
`cake or distillers dry grains and sold as animal feed. These
`processes are well know in the industry and are generally
`employed in plant design in the industry.
`In an effort to take advantage of co—product streams, many
`plants have added oil removal processes in which the thin
`stillage (syrup) is subjected to processes, such as centrifuga-
`tion or extraction, to remove corn oil from the syrup. For
`example, the application of centrifuges to the separation of
`corn oil from syrup is in wide use in the fuel ethanol industry.
`\Vhile the theoretical yield ofoil per bushel ofprocessed corn
`is 1 .6 pound per bushel, many ofthe commercial installations
`fall far short of this. Thus there remains a need to improve the
`process to maximize the oil yield of the process.
`Recently there l1as been effort directed at increasing the
`value model of the corn to ethanol production process by
`extracting the oil from the thin stillage byproduct. Cantrell at
`al. in U.S. Pat. No. 7,602,858 B2 describes a mechanical
`method of separating the oil from concentrated thin stillage,
`referred to as the “syrup”, using a disk stack centrifuge.
`Randhava et al. in US. Pat. Appl. No. 2008/0176298 A1
`teaches the use of an alkyl acetate solvent for extraction of
`corn oil in an ethanol production process.
`Although the prior art references are effective, there is still
`opportunity to improve the oil extraction process to further
`maximize the commercial value of the process. Ofparticular
`interest are technologies which do not require the adoption of
`capital expenditures to implement a new mechanical solution
`and]or significant process change such as the use ofan extrac-
`tion solvent that requires recycling.
`SUMMARY OF THE INVENTION
`
`The present invention discloses a method comprising the
`step of adding a chemical additive to improve the separation
`of oil from the process streams (whole stillage and/or, thin
`stillage and/or syrup) generated as a byproduct in com to
`
`an
`
`10
`
`15
`
`30
`
`35
`
`40
`
`45
`
`:1. O
`
`u. an
`
`60
`
`65
`
`2
`ethzmol production. The method ca11 be used i11 either a wet
`milling process or a dry milling process. Preferably the
`method is employed in a dry-milling process. The method
`involves treating any of the process streams down stream of
`the distillation operation in corn to ethanol production with a
`chemical additive which enhances the mechanical separation
`of oil from said streams.
`One aspect ofthe invention is the application of a chemical
`additive to the thin stillage or syrup, prior to the oil separation
`centrifuge, to increase the yield of oil. This could comprise
`one, or a combination of, addition points in the thin stillage
`u11it operation such as: 1) at the inlet to the pre—mix or rete11—
`tion heat tanks, 2) the inlets and/or outlets of one or i11ore of
`the evaporators, and/or 3) just prior to the inlet of the centri-
`fuge.
`Another aspect of the invention is the application of the
`chemical additive to the whole stillage stream prior to sepa-
`ration of the wet cake from the thin stillage. A point of good
`mixing such as the inlet to a pump is preferred.
`Preferably the chemical additive is a material that is rec-
`ognized as safe such that it does not comprise the potential
`end use of the resulting dry distiller grain (DDG) as a feed-
`stock.
`Some embodiments of the invention provide a benefit of
`producing a cleaner oil (high quality) by minimizing the
`suspended solids and/or water content of the resultant oil.
`Some embodiments ofthe invention provide a benefit to the
`maintenance of the centrifuge iii the manner of reduced
`deposited materials thereby lessening the need for outages
`and cleanings as well as permitting extension oftime between
`backllush purges leading to increased production and less
`down time. This additionally provides the value of simpler
`and easier cleaning of the centrifuge at outages.
`Some embodiments ofthe invention provide a benefit to the
`maintenance of the evaporators in the manner of reduced
`deposited materials decreasing the frequency and complexity
`of cleanings, decreasing down time, thereby reducing costs.
`BRIEF DESCRIPTION OF THE FIGURES
`
`FIG. 1: Partial generic overview representative of corn to
`ethanol production indicating preferred addition points for
`the chemical additive: to the whole stillage prior to separation
`into wet cake and thin stillage, at or near the inlet to centrifuge
`1. poii1t 1; at or near the inlet of the evaporator. point 2;
`directly into the evaporator(s), point 3; to a point prior to or at
`the inlet of the oil centrifuge, centrifuge 2, point 4
`DETAILED DESCRIPTION OF THE INVENTION
`
`The present invention relates to a method which can be
`applied to the whole stillage, the thin stillage or the syrup
`processing operation in corn to ethanol production, preter-
`ably employing a dry-milling process,
`to provide for an
`increase i11 oil yield.
`The present invention describes a method for recovering oil
`from com to ethanol production, the method comprises the
`step of adding at least one chemical additive to a process
`stream where the. at least one chemical additive comprises a
`functionalized polyol derived from a sorbitol, a sorbitan, or
`isosorbide.
`One aspect of the method comprises application of a
`chemical additive to the thin stillage process stream and/or
`syrup concentrate prior to the oil separation step. Preferably
`the oil separation from the concentrated syrup is achieved by
`a mechanical operation such as a membrane or centrifuge.
`Most preferably the separation is achieved by a centrifuge
`
`HYDRITE EXHIBIT 1030
`
`Hydrite v. Solenis
`Trial IPR2015-1592
`
`(3 of 8)
`
`HYDRITE EXHIBIT 1030
`Hydrite v. Solenis
`Trial IPR2015-1592
`(3 of 8)
`
`

`
`US 8,841,469 B2
`
`3
`such as a disk stack or horizontal tricanter centrifuge. Other
`mechanical separators can also be used in the present inven-
`tion including, but not limited to, reverse centrifugal cleaners.
`A second aspect of the method comprises application of a
`chemical additive to the whole stillage prior to separation into
`thin stillage and wet cake.
`The chemical additive maybe added at different points in
`the separation system. Addition points for the chemical addi-
`live include, but are not limited to, to the whole stillage prior
`to separation into wet cake and thin stillage, a point after the
`oil—centrifuge feed pump but prior to the intake of the cei1tri—
`fuge, a point after the evaporators and prior to the pump that
`feeds the centrifuge, and a point after the syrup feed tank and
`before the centrifuge. Generally the syrup feed tank is located
`after the evaporators and before the centrifuge
`FIG. 1 is a partial generic overview representative of corn
`to ethanol production. In general in the corn to ethanol pro-
`cess, after a number of different mashing and fermentation
`steps the corn is converted to material referred to as “beer”.
`The beer is then processed through a distillation process to
`separate the crude ethanol fro111 the thick (whole) stillage
`byproduct. The thick stillage is subjected to a solid separation
`centrifugation process to yield distillers wet grain and thin
`stillage. The thin stillage is then typically processed through
`a number of evaporator units to yield the concentrated syrup.
`This syrup may then be further processed, for example by oil
`separation centrifugation, to separate the oil from the syrup.
`The remaining syrup is then typically combined with the
`distillers Wet grain, then dried, to yield dry distillers grain
`(DDG). The chemical additive of the present invention is
`typically added to the process stream at different poi11ts i11 the
`separation process. Some preferred addition points are shown
`in MG. 1. Addition points include the whole stillage process
`stream prior to separation into wet cake and thin stillage, the
`process stream at or near the inlet to the centrifuge or after the
`solid separation centrifuge. The chemical additive ca11 be
`added, prior to or at the inlet and/or outlet of one or more of
`the thin stillage evaporators, in the evaporators, to the syrup
`just prior to the oil separation centrifuge and/or at the inlet of
`the premix or retention heat tanks. The areas in the process
`Where the chemical additive is typically charged are desig-
`nated by the bracketed (“{. .
`. }”) area in the diagram.
`Chemical additives useful in the present invention are those
`which provide an increase in oil production if added to the
`processing of the whole stillage, prior to separation of the wet
`cake or to the thin stillage prior to the oil separation operation.
`The application of the chemical additives could comprise of
`one or more addition points within the thin stillage processing
`unit operation. Preferably the chemical additives are applied
`to the syrup resulting from concentration of the thin stillage in
`an evaporator.
`One class ofchemical additives usefirl in the present inven-
`tion are functionalized polyols derived from sorbitol, isosor-
`bide or a sorbitan, including 1,4-sorbitan“ Preferred chemical
`additives are functionalized polyols comprising alkoxylated
`sorbitan monoalkylates, alkoxylated S01‘l)lt€i11 dialkylates,
`alkyoxylated sorbitan trialkylates and mixtures thereof. Pref-
`erably the alkoxylated alkylates of sorbitan have an alkyl
`chain length of from about 6 to about 24 carbons, preferably
`from about 8 to about 18 carbons, preferable the alkoxylated
`sorbitan alkylates are alkoxylated esters of sorbitan. The
`alkoxylated alkyate of sorbitan is preferably alkoxylated with
`from about 5 to about l()() moles of alkyl oxide, preferably
`from 5 to 60 moles, preferably from 10 to 30 moles, most
`preferred from 12 to 30, the alkoxylated sorbitan alkylates are
`alkoxylated esters of sorbitan. The preferred alkyl oxides are
`ethylene oxide and propylene oxide or a combination thereof.
`
`at
`
`10
`
`15
`
`30
`
`35
`
`40
`
`45
`
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`u. an
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`60
`
`65
`
`4
`Preferred alkoxylated alkylate of sorbita11 are sorbitan mo11o—
`laurate, sorbitan monooleate, sorbitan monopalmitate or sor-
`bitan monostearate that have been alkoxylated with less than
`50 moles of ethylene oxide or propylene oxide or a combina-
`tion thereof. More preferred alkoxylated alkylates of sorbitan
`are sorbitan monolaurate, sorbitan monooleate, sorbitan
`monopalmitate or sorbitan monostearate that have been
`ethoxylated with from about 10 moles to about 30 moles of
`ethylene oxide or propylene oxide or a combination thereof,
`preferably the alkoxylated sorbitan alkylates are alkoxylated
`esters of sorbitan. More preferred alkoxylated alkylates of
`sorbitan are sorbitan monolaurate, sorbitan monooleate, sor-
`bitan monopalmitate or sorbitan mono stearate that have been
`alkoxylated with from about 12 moles to about 25 moles of
`ethylene oxide or propylene oxide or a combination thereof,
`preferably the alkoxylated sorbitan alkylates are alkoxylated
`esters of sorbitan. Particularly preferred are sorbitan mo11o—
`laurate, sorbitan monooleate, sorbitan monopalmitate or sor-
`bitan monostearate that have been alkoxylated with approxi-
`mately 20 moles of ethylene oxide or propylene oxide or a
`combination thereof. A further preference is for con1posi—
`tions/grades of this class of materials that are, or could be,
`classified as recognized as safe such that they do not comprise
`the potential end use of the resulting dry distiller grain as a
`feedstock.
`Classes of chemical additives that may be useful iii the
`present application are alkoxylated esters ofsorbitan, alkoxy-
`lated fatty alcohols, alkoxylated fatty acids, sulfonated
`alkoxylates, alkyl quaternary ammonium compounds, alkyl
`amine compounds, alkyl phenol ethoxylates and mixtures
`thereof. Additional classes of chemical additive that may be
`useful for the invention include, fatty acid salts (sodium,
`ammonium or potassium) and low molecular Weight silicone
`surfactants. The alkoxylate portion ofthe forgoing classes of
`chemicals may be any mixture of ethylene oxide and propy-
`lene oxide added i11 block or random fashion to the base
`molecule. The most preferred are the alkoxylated esters of
`sorbitan.
`The chemical additive can be a blend of materials as
`described above. Multiple functionalized polyols derived
`from a sorbitol, isosorbide, and/or sorbitan, including, 1,4-
`sorbitan, and can be mixed together and used as the chemical
`additive for the present invention. ()ther additives that may be
`useful in conjunction with the functionalized polyols include
`triglycerides, such as vegetable oil; liquid mixtures contain-
`ing up to 5% by weight hydrophobic silica; and high melting
`point (greater than 60° C.) Waxes. These additives are well
`known in the defoamer industry. Vegetable oils include but
`are not limited to soybean oil, canola and corn oil. The trig-
`lyceride or the liquidmixtures containing up to 5% by weight
`hydrophobic silica or the high melting point Wax can be added
`in an amount offrom 1 to 100% by weight based on the Weight
`ofthe chemical additive.
`The chemical additive can be added to the process stream
`(whole stillage, thin stillage or syrup) in an amount offrom 50
`to 5000 ppm based on the Weight of the process stream), or
`from 100 to 5000 ppm or fron1 200 to 2500 ppm, preferably
`from 300 to 1300 ppm, from 500 to 1100 ppm, from 500 to
`800 ppm. The chemical additive is added to the process
`stream (whole stillage, thin stillage or syrup) in an amount of
`at least 50 ppm, preferable at least 100 ppm, more preferably
`at least 200 ppm, more preferably at least 300. Preferable the
`amount of chemical additive is less than 10,000 ppm, less
`than 5000 ppm, less than 2500 ppm, less than 1500 ppm, or
`less than 1000 ppm.
`These chemistries may be applied under the normal ranges
`of temperatures and pHs found in a variety of the process
`
`HYDRITE EXHIBIT 1030
`
`Hydrite V. Solenis
`Trial IPR2015-1592
`
`(4 of 8)
`
`HYDRITE EXHIBIT 1030
`Hydrite v. Solenis
`Trial IPR2015-1592
`(4 of 8)
`
`

`
`US 8,841,469 B2
`
`5
`stream typical of conmiercial operations. For example,
`accordi11g to but not limited by the teachings of Cantrell at al.
`ir1 US. Pat. No. 7,602,858 B2 a preferred composition ofthe
`syrup, resulting from concentration of thin stillage, for cen-
`trifugal separation of the oil is a temperature between 150-
`212° l'., pl 1 between 3-6, and a moisture content greater than
`15% and less than 90% by weight.
`The chemical additive can be heated and applied to the
`process stream (whole stillage, thin stillage or syrup) in a
`temperature range of from 18° C. to 100° C., preferably from
`25° C. to 85° C., more preferably from 30° C. to 80° C. In
`some embodiments wl1er1 the heated additive is added to the
`process stream improved separation of the oil is observed as
`compared to using 65° F. (18.3° C.) chemical additive.
`A negative impact of processing the syrup at higher tem-
`peratures to improve the yield of oil, for example tempera-
`tures greater than 195° F. or 205° F. depending or1 the process,
`is that discoloration of the syrup results wl1ic11 imparts a
`negative appearance to the dry distillers grain (DDG) and
`lessens that Value of this material. The higher processing
`temperatures can cause higher color of the oil itself. As such,
`an added benefit of the invention is the ability to increase the
`oil yield at lower processing temperatures and mitigate the
`potential of the processed syrup to negatively impact the
`appearance and value of the DDG and the oil. Reducing
`processing temperatures also leads to overall energy savings.
`EXAMPLES
`
`Example 1
`
`Ashland PTV M-5309, an monolaurate ester of ethoxy-
`lated (20 moles) sorbitan was added at dosage of61 1 ppm into
`the syrup feed lir1e or1 the inlet side oftlie pur11p feeding a disk
`stack centrifuge at a n1id—West corn to ethanol producer to
`yield an approximately 29% increase in corn oil output (from
`approximately 1 .7 gpm before treatment to approximately 2. 2
`gpm after treatment). In addition, the suspended solids eon-
`ter1t of a 50 ml aliquot of the isolated oil after centrifugation
`in the laboratory was observed to drop from ~4 ml to -1 ml
`afier treatment.
`Table 1 summarizes a dose response for two 4-hour trials,
`and a result of a 5-day trial, conducted at different time frames
`at this site. The noted amount ofAsl1lar1d PTV M—5309 is on
`a product basis relative to the syrup feed. For the 4—l1our trials
`the data reported is the oil production rate after the system had
`equilibrated relative to the untreated production rate (0 ppm)
`at the initiation of the trial. For the 5-day trial the result is the
`average production rate over that time period relative to the
`untreated production rate (0 ppr11) at the initiation oftlie trial.
`
`TABLE 1
`
`l"l‘V M531 )9
`ppm
`0
`467
`861
`1242
`0
`375
`611
`847
`1242
`0
`680
`
`Oil
`Product ion
`(gal/min)
`1.22
`l .43
`1.62
`1.64
`1.7
`2.0
`2.2
`2.2
`2.2
`0.5
`1.5
`
`Oil
`l’i'odIicl ion
`Increase %
`—
`17%
`33%
`34%
`—
`18%
`29%
`29%
`29%
`—
`200%
`
`Test Duration
`4-Hours
`
`4-Hours
`
`5-Days
`
`6
`Example 2
`
`on
`
`10
`
`15
`
`30
`
`35
`
`40
`
`45
`
`u. 0
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`:1. VI
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`60
`
`65
`
`This field trial examined the difference between adding
`680 ppm ofAshland PTV M-5309, a11 alkoxylated sorbitan
`ester, to the syrup stream at a mid—West corn to ethanol
`producer at different addition points. One of the addition
`points was the inlet side of the pump feeding a disk stack
`centrifuge as i11 Example 1. The other addition poi11t exam-
`ined was after the pump and directly ir1to the inlet of the disk
`stack centrifuge. Relative to the untreated daily oil production
`rate j ust prior to the trial an increase in daily oil production of
`approximately 15% and 17% was measured after treatment,
`respectively.
`
`Example 3
`
`This field trial was similar to Example 1 except 690 ppm of
`Ashland P'1'V M-5309 was added to the syrup stream at a
`mid—West corn to ethanol producer at the inlet side of the
`pump feeding a horizontal tricanter centrifuge. Upon treat-
`ment the oil production rate was observed to increase by
`approximately 45% relative to the Lmtreated production rate
`at the initiation of the trial.
`
`Example 4
`
`This field trial examined the effect of temperature on the
`perfonnance ofthe chemical additive. Ashland PTV M—5309,
`at a temperature of65° F. (1 8 .3° C was addedjust prior to an
`oil extraction centrifuge to produce oil at a rate of 2.3 gallons
`per a minute. Ashland PTV M-5309 was then heated to a
`temperature of 120° 1’. (48.9° (1.) and was addedjust prior to
`an oil extraction centrifuge to produce oil at a rate of 2.7
`gallons per a minute. The higher temperature chemical addi-
`tive increased the oil recovery by 17%.
`
`Example 5
`
`Ashland PTV M—5309 was added at dosage of 980 ppm
`into the syrup feed line on the inlet side of the pump feeding
`a disk stack centrifuge at a n1id—West com to ethanol producer
`to yield a corn oil output of approximately 5.47 gpm. In a
`second trial phase Ashland PTV M-5309 w as added at dosage
`of 490 ppm into the syrup feed in conjunction with 490 ppm
`ofNofoam 7077 (SSC industries, llast Point, Ga.) to provide
`a corn oil production of5.76 gpm. 'l'his correspondedto a 5%
`increase of oil production.
`
`Example 6
`
`This laboratory experiment examined the e ‘ect of alkyl
`chain length on product effectiveness. Various alkoxylated
`esters of sorbitan were tested. The ethoxylated portion ofthe
`product was maintained at 20 moles. Products with varying
`alkyl chains, lauric, palmitic, stearic and oleic were tested by
`addition of 0.03 gram of additive to 100 ml of com syrup at
`185° 1’. followed by 0.5 minutes of intense mixing. 1() ml of
`each sample was transferred to a centrifuge tube and was then
`centrifuging for 10 minutes at 3000 rpm. The amount of oil
`was determined by measuring the height ofthe oil layer hi the
`centrifuge tube.
`
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`7
`TABLE 2
`
`Fatty Acid
`(1h:i.in length
`l.:1uric (‘,1 2
`Palmitie C16
`Stearie C18
`Oleie C18:1
`
`()il tnlm)
`
`I./uuvcxuv
`
`As can be seen in Table 2 comparable performance was
`observed for the various chain lengths tested.
`
`Example 7
`
`This laboratory experiment examined the effect of unsat-
`uration in the allq/l chain on product effectiveness. Various
`alkoxylated esters of sorbitan were tested. The ethoxylated
`portion of the product was maintained at 20 moles. Products
`tested were prepared from stearic and oleic acids. Tests were
`run at 0.1 2 gm, 0.15 gm and 0.18 gm ofadditive to 100 ml of
`corn syrup at 185° 1’. followed by 0.5 minutes of intense
`mixing. 10 ml of each sample was transferred to a centrifuge
`tube and was then centrifuged for 10 minutes at 3000 rpm.
`The amount ofoil was determined by measuring the height of
`the oil layer on the top of the centrifuge tube.
`
`TABLE 3
`
`Fatty Acid
`Chain Length
`Stcarie C1 8
`Oleic Cl 8: l
`
`Dosage 0.12 gm
`Oil Recovered
`(mm)
`4
`3
`
`Dosage 0.15 gm
`Oil Recovered
`(mm)
`5
`4
`
`Dosage 0.18 gm
`Oil Recovered
`(mm)
`6
`4
`
`As can be seen in Table 3 improved performance for the
`saturated chain product.
`
`llxample 8
`
`This study examined the alfectiveness of the chemistry on
`whole stillage using the method of Example 5. PTV M—5309
`was added to the whole stillage prior to the wet cake centri-
`fuge at a commercial corn to ethanol plant. Samples of the
`thin stillage coming out from the centrifuge were collected.
`The thin stillage samples were subjected to laboratory cen-
`trifugation. The results below show that addition of the prod-
`uct to the whole stillage does enhance oil separation.
`
`TABLE 4
`
`Sample
`number
`Baseline
`1
`
`2
`
`3
`
`ppm of
`product added
`0
`340
`
`630
`
`883
`
`description oil in
`centrifuge tube
`No visible oil
`A few drops ofoil — no
`distinct layer
`A distinct layer ofoil
`present
`Oil layer present
`
`Example 9
`
`This laboratory experiment examined the effect of blei1d—
`ing Various polysorbatans on oil separation. Various alkoxy-
`lated esters of sorbitan were tested. The table below shows the
`various blends of alkoxylated esters of sorbitan. In each
`example, 018 grams of blended material was added to 0.100
`ml ofcorn syrup at 185° F. followed by 0.5 minutes ofintense
`
`8
`mixing. 10 ml of each sample was transferred to a centrifuge
`tube and was then centrifuged for l() minutes at 3000 rpm.
`The amount ofoil was determined by measuring the height of
`the oil layer on the top of the centrifuge tube.
`Polysorbitan monooleate (5 moles ethylene oxide): psmo5
`Polysorbitan monooleate (20 moles ethylene oxide):
`psmo20
`Polysorbitan monolaurate (20 moles ethylene oxide):
`psml20
`Polysorbitan monostearate (20 n1oles ethylene oxide):
`psms20
`
`TABLE 5
`
`Sample
`1
`2
`3
`4
`5
`
`Blcnd
`100% psmo5
`45/55 psmliltl/psrrloi
`80/20 psmo2 0/psmo5
`75/25 psn1l20/psmoi
`89/11 psml20/psmo5
`
`Oil rclease (mm)
`0
`2
`3
`3.5
`4
`
`invention has been described with
`While the present
`respect to particular embodiments thereof, it is apparent that
`numerous other forms and modifications will be obvious to
`those skilled in the art. The appended claims and this inven-
`tion generally should be construed to cover all such obvious
`forms and modifications, which are within the true scope of
`the present invention.
`The invention claimed is:
`1. A method for recovering oil from corn to ethanol pro-
`duction, the method comprising the step ofadding at least one
`chemical additive to a process stream wherein the at lea st one
`chemical additive comprises a functionalized polyol derived
`from a sorbitol, a sorbitan. or isosorbide.
`2. The method ofclaim 1 wherein the functionalized polyol
`is derived from 1, 4 sorbita11 or isosorbide.
`3. T11e method ofclaim 1 wherein the functionalized polyol
`comprises an alkoxylated sorbitan alkylate.
`4. "he method of claim 3 wherein the chain length of the
`alkylate is fron1 6 to 24 carbons.
`5. "he method of claim 4 wherein the chain length of the
`alkylate is from 8 to 18 carbons.
`6. The method ofclaim 3 wherein the alkoxylated sorbitan
`all<ylate has been alkoxylated with from 5 to 60 moles of allql
`oxide.
`7. The method of claim 6 wherein the alkoxylated sorbitan
`alkylate has been alkoxylated with 10 to 30 moles of alkyl
`oxide.
`8. The method of claim 7 wherein the alkyl oxide is
`selected from ethylene oxide, propylene oxide and mixtures
`thereof.
`9. The method of claim 3 wherein the alkoxylated sorbitan
`alkylate comprises a sorbitan monolaurate that has been
`alkoxy ated with from about 10 to about 30 moles of an
`alkoxy ate wherein the alkoxyate is selected from ethylene
`oxide. Jropylene oxide or mixtures thereof.
`10. "he method of clair11 3 wherein the alkoxylated sorbi-
`tan alkylate comprises a sorbitan monooleate that has been
`alkoxy ated with from about 10 to about 30 moles of an
`alkoxy ate wherein the alkoxyate is selected from ethylene
`oxide, aropylene oxide or mixtures thereof.
`11. "he method of claim 3 wherein the alkoxylated sorbi-
`tan alkylate comprises a sorbitan monolaurate, sorbitan
`monooleate, sorbitan monopalrnitate or sorbitan monostear-
`ate that has been ethoxylated with from about 12 to about 25
`moles of an alkoxylate wherein the alkoxyate is selected from
`ethylene oxide, propylene oxide or mixtures thereof.
`
`an
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`:1. O
`
`u. an
`
`60
`
`65
`
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`
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`
`5
`
`15
`
`9
`12. The method of claim 1 wherein tl1e amount ofchemical
`additive added is from 300 to 1300 ppm based on weight of
`the process stream.
`13. The method of claim 12 wherein the amount of chemi-
`cal additive added is from 500 to 1100 ppm based on weight
`of the process stream.
`14. "he method ofelaim 1 wherein the chemical additive
`added is heated to at least 30° C. prior to the addition to the
`process stream.
`15. "he method of claim 1 further comprising the step of 10
`adding a triglyceride to the process stream.
`16. The method ofclaiin 15 wherein the amount oftriglyc-
`eride is from 1 to 100% by weight based on the weight ofthe
`chemical additive.
`17. "he method of claim 2 wherein the chemical additive is
`heated prior to the addition to the process stream.
`18. The method ofclaim 17 wherein the chemical additive
`is heated between 25° (7. to 85° (1.
`19. "he method ofelaim 1 wherein the addition point in the
`process stream is selected from the whole stillage process 20
`stream prior to removal of the wet cake, the thin stillage
`process stream at the inlet and/or outlets ofone or more ofthe
`evaporators, in the evaporator, at the inlet to the pre-mix or
`retention heat tanks, to the syrup just prior to the oil separa-
`tion centrifuge or any combination thereof.
`20. A method of claim 1 further comprising the step of
`adding an additional process additive wherein the additional
`process additive is selected from the group consisting of
`liquid mixtures containing up to 5% by weight hydrophobic
`silica; and high melting point (greater than 60° C.) waxes.
`=l<
`*
`$
`*
`=1‘
`
`25
`
`30
`
`10
`
`HYDRITE EXHIBIT 1030
`
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`
`UNITED STATES PATENT AND TRADEMARK OFFICE
`
`CERTIFICATE OF CORRECTION
`
`PATENT NO.
`APPLICATION NO.
`
`2 8,841,469 B2
`: 13/370456
`
`DATED
`INVENTOR('S)
`
`: September 23, 2014
`: Shepperd et al.
`
`Pagg ] Of]
`
`It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:
`
`In the claims
`
`COL. 8, claim 1, line 30, delete “to” and substitute therefor --in--; line 30, before “process”
`insert --corn to ethanol-- so that the claim reads:
`
`A method for recovering oil from corn in ethanol production, the method comprising the step
`ofadding at least one chemical additive to a corn to ethanol process stream wherein the at least one
`chemical additi