USOO8939388B1
`
`(12) Unlted States Patent
`(10) Patent No.:
`US 8,939,388 B1
`
`Beetz et a].
`(45) Date of Patent:
`Jan. 27, 2015
`
`(54) METHODS AND APPARATUS FOR LOW
`HEAT SPRAY DRYING
`
`(75)
`
`Inventors: Charles P. Beetz, Erlanger, KY (US);
`Robert Corbett, Westfield, NJ (US);
`David Salem, Rapid City, SD (US)
`
`(73) Assignee: ZoomEssence, Inc., Branchburg, NJ
`(Us)
`
`3,741,273 A
`3,805,869 A
`3,817,308 A
`g’gjg’ggg :
`a
`a
`
`6/ 1973 Meade
`4/1974 W1nter et 31.
`6/1974 Bundo
`18/1374 giii‘liitligftealéli
`.
`(Commued)
`
`AU
`CA
`
`FOREIGN PATENT DOCUMENTS
`549614 B2
`2/1986
`1162699 A
`2/1984
`
`( * ) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U~S-C~ 154(b) by 610 days.
`
`d
`.
`C
`( ont1nue )
`OTHER PUBLICATIONS
`
`(21) Appl. No.: 13/245,369
`.
`F11ed:
`
`Sep. 26, 2011
`
`(22)
`
`Jens Thousig Moller, et al., A Primer on Spray Drying, Chemical
`Engineering, pp. 34-40 (Nov. 2009).
`(Continued)
`
`Related US. Application Data
`.
`.
`.
`.
`Prov1s1onal appl1catlon No. 61/386,762, filed on Sep.
`27’ 2010'
`
`(60)
`
`Primary Examiner 7 Davis ku
`(74) Attorney, Agent, or Firm 7 Hultquist, PLLC; Steven J.
`Hultquist
`
`(51)
`
`(56)
`
`'''''''
`USPC
`
`See a
`
`pp
`
`Int- Cl-
`B05B 5/00
`(52) US. Cl.
`USPC ........................................ 239/690- 239/6901
`(58) Field of Classification Search
`a
`CPC
`B05B 5/00. B05B 5/043. B05B 5/0533.
`’
`’
`B05B 5/087
`239/690 690 1 706 707 708 398
`239/42'2’ 428', 159;4 01’ 163
`"""""""""""
`1icatio11 file for com 1ete, search hi st0'
`’
`'
`p
`ry.
`-
`References Clted
`U.S. PATENT DOCUMENTS
`
`(2006.01)
`
`(57)
`
`ABSTRACT
`
`Methods and apparatus provide for spray drying a liquid
`PmduCt into a dried POWder Whom applying heat: incmding:
`forming a slurry including a liquid solvent, a carrier, and an
`active ingredient; applying an electrostatic charge to the
`slurry; atomizing the charged slurry to produce a plurality of
`electrostatically charged, wet particles; suspending the elec-
`trostatically charged, wet particles for a sufiicient time to
`permit repulsive forces induced by the electrostatic charge on
`at least some wet particles to cause at least some of such
`articles to divide into wet sub- articles; and continuin the
`p
`p
`g
`suspending step, without the presence of any heated drying
`fluids, for a sufiicient time to drive off a sufiicient amount of
`the liquid solvent within most of the wet particles to leave a
`plurality of dried particles (the powder), each dried particle
`containing the active ingredient encapsulated within the car-
`ner.
`
`31 Claims, 11 Drawing Sheets
`
`2,954,293 A
`3,554,768 A
`3,615,723 A
`3,655,397 A
`3,677,321 A
`3,679,416 A
`
`9/1960 Rusoff
`1/1971 Feldman
`10/1971 Meade
`4/1972 Parliment et 31.
`7/1972 Felstead
`7/1972 Reich
`
`204
`
`210
`
`202
`
`
`
`
`45%’Q
`
` flnawaymé‘ ,
`
`
`
`220
`
`236
`
`International Flavors & Fragrances Inc.
` Exhibit
`l 001
`
`Page 1
`
`

`

`US 8,939,388 B1
`
`Page2
`
`(56)
`
`References Cited
`
`US. PATENT DOCUMENTS
`
`3,886,297 A
`3,920,815 A
`3,956,521 A
`3,962,321 A
`3,962,384 A
`3,963,559 A
`3,966,975 A
`4,001,437 A
`4,032,465 A
`4,062,641 A
`4,070,766 A
`4,072,570 A
`4 099 982 A
`4:141:783 A
`4,198,308 A
`4 261 793 A
`4:276:312 A
`4,281,024 A
`4,302,481 A
`4,362,273 A
`4,420,442 A
`4,422,900 A
`4,438,147 A
`4,476,042 A
`4,476,147 A
`4,481,221 A
`4,481,224 A
`4,490,403 A
`4511592 A
`4 515 987 A
`4520032 A
`4,521:613 A
`4,521,634 A
`4,522,765 A
`4,524,010 A
`4,525,364 A
`4,532,145 A
`4,532,364 A
`4,535,192 A
`4,537,704 A
`4,539,143 A
`4,539,209 A
`4,544,775 A
`4,548,821 A
`4,552 770 A
`4565707 A
`4568538 A
`4,571:344 A
`4,600,576 A
`4 613 511 A
`4:614:831 A
`4,619,780 A
`4,620,945 A
`4,623,538 A
`4,623,547 A
`4,626,440 A
`4,629,586 A
`4,629,805 A
`4,632,831 A
`4,643,903 A
`4,661,281 A
`4,677,207 A
`4,679,733 A
`4,680,142 A
`4,681,976 A
`4,724,121 A
`4,762,636 A
`4,794,193 A
`4,804,496 A
`4,840,801 A
`4,849,125 A
`4,865,853 A
`4,873,112 A
`4,883,884 A
`4,892,910 A
`
`5/1975 Parlimentetal.
`“/1975 Harvey et a1.
`5/1976 Pisecky
`6/1976 Parlimentetal.
`6/1976 Cannalonga et 31.
`6/1976 Petersen et al.
`6/1976 Hansen
`1/1977 Jaeggi
`6/1977 Bauer et al.
`12/1977 Hovmand
`1/1978 Kamphuis
`2/1978 Williams
`7/1978 Hansen
`2/1979 Pisecky
`4/1980 Micciche
`4/1981 Nakamura et 31.
`6/1981 Merritt
`7/1981 Hauberg
`11/1981 ijnitz et 31.
`12/1982 Seino et 31.
`12/1983 Sands
`12/1983 Bordelon etal.
`3/1984 Hedrick, Jr.
`10/1984 Sprecker
`10/1984 Hall
`11/1984 Mookherjee
`11/1984 Muralidhara
`12/1984 Pisecky
`4/1985 Percel et 31.
`5/1985 Boden
`5/1985 Hall
`6/1985 Pittet
`6/1985 Fujioka
`6/1985 Wiegers
`6/1985 Reuteretal.
`6/1985 Wiegers
`7/1985 Sa1eeb etal.
`7/1985 Fujioka
`8/1985 Hall
`8/1985 Sprecker
`9/1985 Boden
`9/1985 Wilson
`10/1985 Fujioka
`10/1985 Hall
`11/1985 Pittet
`1/1986 Pittet
`2/1986 Boden
`2/1986 Pittet
`7/1986 Pittet
`9/1986 Pittet
`9/1986 smoker
`10/1986 Fujioka
`11/1986 Mookherjee
`11/1986 Pittet
`11/1986 Pittet
`12/1986 Pittet
`12/1986 Wilson
`12/1986 Sprecker
`12/1986 Hall
`2/1987 Sprecker
`4/1987 Seiteretal.
`6/1987 Boden
`7/1987 Lipp
`7/1987 Pittet
`7/1987 Sprecker
`2/1988 Weyand
`8/1988 Balliello et a1.
`12/1988 Pittet
`2/1989 Lowery et a1.
`6/1989 Mookherjee
`7/1989 Seiter et a1.
`9/1989 Mookherjee
`10/1989 Mitchell et a1.
`11/1989 Boden
`1/1990 Klesse et a1.
`
`................ 159/4.01
`
`6/1990 Ahmed et a1.
`4,931,203 A
`6/1990 Surgant et al.
`4,936,901 A
`8/ 1990 Boden
`4,950,495 A
`10/1990 Boden
`4,962,089 A
`1/1991 Boden
`4,983,579 A
`4/1991 Buckholz, Jr.
`5,004,618 A
`3/1992 NeWhall
`5,094,860 A
`3/1992 Plseckx
`5,100,509 A
`6/1992 Bosk0V1c et a1.
`5,124,162 A
`7/1992 Keller
`5430449 A
`8/1992 Zarnpmo
`5,137,741 A
`10/1992 Patel et a1.
`5,153,011 A
`3/1993 H511 etal~
`5496119 A
`7/1993 Tanakaet a1.
`5,227,017 A
`8/1994 Johnson
`5,338,553 A
`10/1994 Demlng et a1.
`5,354,742 A
`2/1995 Yamamoto et a1.
`5,391,647 A
`8/1995 Kensiletal.
`5,443,829 A
`8/1995 Hagiwara ML
`5,445,839 A
`10/1995 Penzel et a1.
`5,462,978 A
`4/1996 Subramaniam
`5,506,353 A
`6/1996 King
`5,525,367 A
`1/1997 Chrlstensen
`5,593,715 A
`12/1997 Sugiura et a1.
`5,702,749 A
`6/1998 Wampler
`5,759,599 A
`6/1998 Getler
`5,773,061 A
`7/1998 Blake
`5786917 A
`11/1998 Larsen
`5,840,360 A
`4/1999 Stanler
`5,891,473 A
`10/1999 Rasmussen
`5968575 A
`40000 Getler
`6,048,565 A
`5/2000 Bach et al.
`6,058,624 A
`6/2000 Gordon et a1.
`6,077,543 A
`3/2001 Reijmer et al.
`6,200,949 B1
`6/2001 Rossy
`6,251,463 B1
`7/2001 Hansen
`6,253,463 B1
`12/2001 De R00s
`6,325,859 B1
`1/2002 Peters
`.
`6,335,045 B1
`5/2002 Gautschl
`6,387,431 Bl
`5/2002 Peters
`6,391,361 B1
`90002 Blake
`131337360 E
`11/2002 Kelly
`6,474,573 B1
`11/2002 DeRoos et a1.
`6,482,433 B1
`12/2002 Ha¥lsen_
`6,497,911 Bl
`5/2003 Chlckerlng et a1.
`6,560,897 B2
`6/2003 Platz etal.
`6,582,728 B1
`8/2003 Benczedi
`6,607,771 B2
`80003 Mutka
`6,607,778 132
`11/2003 Agawa et al.
`6,649,267 B2
`11/2003 Jensen
`6,652,898 B2
`12/2003 Kelly
`6,656,394 B2
`2/2004 Gabelet a1.
`6,689,755 B1
`4/2004 Subramaniam
`6,723,359 B2
`5/2004 Starkenmann
`6,734,158 B2
`7/2004 Beyerincket a1.
`6,763,607 B2
`8/2004 Raehse et a1.
`6,769,200 B2
`“2005 Jaeger
`6,838,100 132
`6/2005 Schlelfenbaum
`6,902,751 B1
`8/2005 Bouwmeesters
`6,929,814 B2
`8/2005 Marty _
`6,933,265 B2
`11/2005 Ch10ker1ng,IIIeta1.
`6,962,006 B2
`11/2005 Kelly
`6,964,385 B2
`4/2006 Decorzant
`7,022,665 B2
`80006 Zanqne
`7090332 132
`80006 DeWIS
`7,097,872 132
`10/2006 Hansen
`7,128,936 B1
`2/2007 Pickenhagen
`7,176,176 B2
`2/2007 Lambrecht
`7,176,177 B2
`4/2007 Holzner
`7,204,998 B2
`8/2007 Gelin
`7,252,848 B2
`1/2008 Kindel
`7,316,826 B2
`2/2008 Widder
`7,332,468 B2
`3/2008 Schleifenbaum
`7,348,035 B2
`4/2008 DeWis
`7,361,376 B2
`5/2008 Ley
`7,378,121 B2
`5/2009 DeWis
`7,534,460 B2
`1/2010 Keller
`7,651,713 B2
`12/2002 Tanaka et a1.
`2002/0187221 A1
`1/2003 Chien
`2003/0003212 A1
`International Flavors & Fragrances Inc.
`
`Exhibit 1001
`
`Page 2
`
`

`

`US 8,939,388 B1
` Page3
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`2003/0021883 A1
`2003/0082272 A1
`2003/0192815 A1
`2003/0196957 A1
`2003/0205629 A1
`2004/0062845 A1
`2004/0253343 A1
`2005/0031769 A1
`2005/0209443 A1
`2005/0282728 A1
`2006/0035008 A1
`2006/0159818 A1
`2006/0264130 A1
`2007/0054837 A1
`2007/0078071 A1
`2007/0117727 A1
`2007/0166185 A1
`2007/0184163 A1
`2007/0218179 A1
`2007/0231424 A1
`2007/0297993 A1
`2008/0008801 A1
`2008/0015264 A1
`2008/0057175 A1
`2008/0063747 A1
`2008/0064625 A1
`2008/0081779 A1
`2008/0107786 A1
`2008/0113073 A1
`2008/0199592 A1
`2008/0214675 A1
`2008/0220140 A1
`2008/0227866 A1
`2008/0241322 A1
`2008/0242585 A1
`
`1/2003 Skiff
`5/2003 Bouwmeesters
`10/2003 Kelly
`10/2003 Henningfield
`11/2003 Kelly
`4/2004 Krawczyk etal.
`12/2004 Ha etal.
`2/2005 Watanabe etal.
`9/2005 Bolen
`12/2005 Narula
`2/2006 Virgallito
`7/2006 Kunieda
`11/2006 Karles
`3/2007 Weiss
`4/2007 Lee etal.
`5/2007 Narula
`7/2007 Bartels
`8/2007 Toth
`9/2007 on
`10/2007 Castro etal.
`12/2007 Kindel
`1/2008 Barnekow
`1/2008 Schleifenbaum
`3/2008 Barnekow
`3/2008 Boghanietal.
`3/2008 Holscher
`4/2008 Holscher
`5/2008 Barnekow
`5/2008 Ley
`8/2008 Fexer
`9/2008 Ley
`9/2008 Ley
`9/2008 Ley
`10/2008 Bunge
`10/2008 on
`
`2008/0242740 A1
`2008/0292763 A1
`
`10/2008 Ley
`11/2008 Looft
`
`igggggaéggg :1 ngg: EZ§
`2009/0081140 A1
`3/2009 Brooke
`2009/0091049 A1
`4/2009 Nielsen
`2009/0092725 A1
`4/2009 Panten
`3883;81:233? :1
`ggggg Eackes
`2009/0155445 A1
`6/2009 LGger
`2009/0155446 A1
`6/2009 Reiss
`2009/0163403 A1
`6/2009 Levorse
`2009/0163404 A1
`6/2009 Levorse
`2009/0252789 A1
`10/2009 Trophardy
`2009/0291176 A1
`11/2009 Nagao et al.
`2010/0055267 A1
`3/2010 Popplewell et a1.
`581?;852333 :1
`$581? gmssonky t 31
`.
`aysms
`e
`2011/0064783 A1
`3/2011 Bang-Madsen et al.
`2013/0022728 A1
`1/2013 Popplewell et 31.
`2014/0193562 A1
`7/2014 Popplewell et 31.
`2014/0205713 A1
`7/2014 Hans et al.
`
`FOREIGN PATENT DOCUMENTS
`
`CA
`g:
`CA
`CA
`CA
`CA
`g?
`EP
`EP
`EP
`EP
`EP
`
`1334460 C
`3%335 g
`2258751 C
`2253154 C
`2321660 C
`2407614 C
`3233:? 2%
`0344375 B1
`0232313 B1
`0180366 B1
`0420509 A1
`0227486 B1
`
`3/1989
`gfiggg
`12/1997
`5/1999
`9/1999
`11/2001
`gig;
`12/1989
`5/1990
`6/1990
`4/1991
`11/1991
`
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`EP
`GB
`GB
`GB
`“3
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
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`W0
`W0
`W0
`W0
`W0
`W0
`W0
`W0
`
`0515478 B1
`0429482 B1
`0461197 Bl
`0517423 B1
`0366898 Bl
`0619075 Bl
`0832695 A2
`1064856 A2
`1106081 A1
`1280591 Bl
`1435797 Bl
`2052622 A1
`2138567 A1
`575118 A
`1015599 A
`2364714 A
`62024 Bl
`9117821 A1
`9428181 A2
`9513864 A1
`9517174 A1
`9713416 A1
`9714288 A2
`9733485 A1
`9804243 A1
`0167897 A1
`0207541 A1
`2005063032 A1
`2006082536 A1
`2007054853 A1
`2007096790 A1
`2007135583 A2
`2008047301 A1
`2008077399 A1
`2008113778 A1
`2010104713 A1
`2011121468 A1
`2012122010 AZ
`
`12/1993
`4/1994
`6/ 1994
`3/1995
`2/1996
`1/1997
`4/1998
`“2001
`6/2001
`12/2006
`8/2007
`4/2009
`12/2009
`2/1946
`“1966
`20002
`12/ 1994
`11/1991
`12/1994
`5/1995
`6/1995
`4/1997
`4/1997
`9/ 1997
`2/1998
`9/2001
`“2002
`7/2005
`8/2006
`5/2007
`8/2007
`11/2007
`4/2008
`7/2008
`9/2008
`9/2010
`10/2011
`90012
`
`OTHER PUBLICATIONS
`
`H. Leuenberger, Spray freeze-dryingithe process of choice for low
`water soluable drugs?, Journal of Nonpartical Research 4: pp. 111-
`119 (2002).
`Mukesh C. Gohel, Spray Drying: A Review, Pharmaceutical
`Reviews,vol.7Issue5,pp.1-20(Sep.2009)http://www.pharmainfo.
`net/rev1ews/spray-dry1ng-rev1ew.
`J. Broadhead, S. K. Edmond Rouan and C. T. Rhodes, The Spray
`Drying of Pharmaceuticals, Drug Development and Industrial Phar-
`macy, V01. 18, Issue ll&12, pp. 1169-1206 (1992).
`A. M. Goula and K. G. Adamopolous, Spray drying of tomato pulp:
`Effect of feed concentration, Drying Technology, vol. 22, pp. 2309-
`2330 (2004).
`A. G. Bailey, Electrostatic Spraying of Liquids, John Wiley & Sons
`_
`Inc" New Yf’rk’ pp' 1 35 (”711988)
`.
`.
`_
`Lord Rayleigh, On the equilibrium of liquid conducting masses
`Charged With electricity, Philos. Mag. vol. 14, pp. 184-186 (1882).
`A. Gomez and K. Tang, Charge and fission of drops in electrostatic
`sprays, Phys. Fluids vol. 6, Issue 1, pp. 404-414 (Jan. 1994).
`W. A. Sirignano, Fluid Dynamics and Transport of Droplets and
`Sprays, 2"d edition, Cambridge University Press NewYork, cover and
`p. 34 (2010).
`GEA Processing Engineering Inc., Powder Technology Division;
`Spray Drying, pp. 1-15, http://www.niroinc.com/ (date unknown).
`Vagn Westergaard, Dainsh Dairy & Food Industry .
`.
`. Worldwide;
`The New Niro Intergrated Filter Dryer IFDTM, cover page and pp.
`62-64 (sep. 2002).
`D. E. Dobry, D. M. Settell, J. M. Baumann, R. J. Ray, L. J. Graham
`andR.A.Beyerinck,AModel-BasedMethodologyfor Spray-Drying
`Process Development, J. Pharm. Innov. vol. 4, pp. 133-142 (Jul.
`2009)
`M.J.Killen,ProcessforSprayDryingandSprayCongealing,Pharm.
`Eng. vol. 13, pp. 56-62 (Jul/Aug. 1993).
`International Flavors & Fragrances Inc.
`
`Exhibit 1001
`
`Page 3
`
`

`

`US 8,939,388 B1
`Page 4
`
`(56)
`
`References Cited
`OTHERPUBLKHUIONS
`
`Mumenthaler and H. Leuenberger, Atmospheric Spray-Freeze Dry-
`ing: Suitable Alternative in Freeze Dry Technology, Int. J. Pharm. vol.
`72, pp. 97-110, (Jan. 1991).
`
`T.A.G. Langrish and DE Fletcher, Spray Drying of Food Ingredients
`and Applications of CFD in Spray Drying, Chem. Engineering and
`Proc., vol. 40, pp. 345-354 (2001).
`W.J. Coumans, P.J.A.M. Kerkhof and S. BrVin, Theotrical and Prac-
`tical Aspects ofAroma Retention in Spray Drying and Freeze Drying,
`Drying Technology, vol. 12, pp. 99- 149 (1994).
`
`* cited by examiner
`
`International Flavors & Fragrances Inc.
` Exhibit
`1 0 0 l
`
`Page 4
`
`

`

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`International Flavors & Fragrances Inc.
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`U.S. Patent
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`US 8,939,388 Bl
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`Y§§§ mom
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`U.S. Patent
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`US 8,939,388 B1
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`mom
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`US. Patent
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`Jan. 27, 2015
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`Sheet 5 of 11
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`US 8,939,388 B1
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`FIG. 5
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 9
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`US. Patent
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`Jan. 27, 2015
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`Sheet 6 of 11
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`US 8,939,388 B1
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 10
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`US. Patent
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`Jan. 27, 2015
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`Sheet 7 of 11
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`US 8,939,388 B1
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 11
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`U S. Patent
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`Jan. 27, 2015
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`Sheet 8 of 11
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`US 8,939,388 B1
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 12
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`US. Patent
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`Jan. 27, 2015
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`Sheet 9 of 11
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`US 8,939,388 B1
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`FIG. 9
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 13
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`US. Patent
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`Jan. 27, 2015
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`Sheet 10 of 11
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`US 8,939,388 B1
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`FIG. 10
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 14
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`US. Patent
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`Jan. 27, 2015
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`Sheet 11 of 11
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`US 8,939,388 B1
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`FIG. 11
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`100 7
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`D—Limonene Content vs Time
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`percent
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` :0
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`100
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`29:3
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`30:3
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`40:1
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`500
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`600
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`no
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`300
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`900
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`mm)
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`1100
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`Time (hrs)
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`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 15
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`US 8,939,388 B1
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`1
`METHODS AND APPARATUS FOR LOW
`HEAT SPRAY DRYING
`
`CROSS REFERENCE TO RELATED
`APPLICATIONS
`
`This application claims the benefit of US. Provisional
`Patent Application No. 61/386,762, filed Sep. 27, 2010, the
`entire disclosure of which is hereby incorporated by refer-
`ence.
`
`BACKGROUND
`
`The present invention relates to methods and apparatus for
`spray drying a liquid product into a dried powder without
`applying heat, or applying substantially low amounts of heat.
`Spray drying is a method of producing a dry powder from
`a liquid or slurry by rapidly drying with a hot gas (usually air).
`Spray drying technology has existed since the late 1800’s and
`has continually evolved over the past century.
`The spray drying process begins with a liquid solvent,
`commonly water, containing dissolved or suspended compo-
`nents such as an emulsion. The suspension includes a sub-
`stance to be encapsulated (the load) and an amphipathic car-
`rier (usually some sort of modified starch), which are
`homogenized as a suspension in the liquid solvent. The load
`is typically some constituent component(s) of a food, fra-
`grance, medicament, etc ., and the homogenized suspension is
`often referred to as a slurry.
`Spray dryers use some type of atomizer, such as a spray
`nozzle, to disperse the slurry into a controlled spray having
`some relatively controlled droplet size. Depending on the
`process requirements, droplet sizes may range from about 10
`to 500 microns in diameter. The most common applications
`require droplet sizes in the 50 to 200 micron range.
`In conjunction with atomization, the slurry is fed into a
`drying chamber, usually a tower into which heated air is also
`introduced. The temperature of the air as it enters the drying
`chamber is well over the boiling point of water, usually in the
`range of 180-200° C. The heated air supplies energy for
`evaporation of volatile components of the liquid (the water)
`from the droplets. As the water evaporates, the carrier forms
`a hardened shell around the load, producing a dried powder.
`Reference is made to FIG. 1, which illustrates a conven-
`tional spray drying system 50 and associated process. The
`process begins with making a slurry ofingredients. The ingre-
`dients include a liquid solvent, such as water 1, a carrier 2, and
`active ingredient(s) 3. In the typical process, the water 1 and
`carrier 2 are added into the solution tank 4 while stirring. The
`active ingredient 3 is then added to the tank 4 and stirred into
`the slurry. The active ingredient is either emulsified in the
`carrier fluid system or dissolved into it. In order for conven-
`tional spray drying processes to be commercially viable, typi-
`cal slurry viscosities must be in the range of about 10-300
`mPa-s.
`
`The slurry formed in the solution tank 4 is delivered to an
`atomizer 6 using a feed pump 5 or other means ofconveyance.
`The slurry enters the atomizer 6 and leaves the atomizer as a
`spray of liquid droplets 8, and the droplets 8 are introduced
`into a drying chamber 7. Concurrently, a feed of air is heated
`by a process heater 11 and supplied into the drying chamber
`7 by a blower 10. The water evaporated from the droplets 8
`enters the heated air as the atomized liquid droplets 8 dry to
`form solid particles after exposure to the incoming heated air.
`The dried powder leaves the dryer chamber 7 along with
`the water vapor laden air, and is carried to a cyclone separator
`12, which removes the dried particles from the circulating air
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`stream and deposits the particles into a collection container
`13. The water vapor laden air exits the collection container 13
`and enters a baghouse 14, where very fine particles are
`removed before the water vapor laden air is sent into a con-
`denser 9, via blower 15. The condenser 9 removes the water
`vapor from the process air, and the collected water may be
`re-used or discarded.
`
`One of the prominent attributes of the traditional spray
`drying process is the high temperature of the inlet gas (typi-
`cally on the order of 200° C.) leaving the heater 11 and
`entering the drying chamber 7, as well as the temperature of
`the outlet gas exiting the drying chamber 7, which is usually
`in excess of 100° C. Although the liquid droplets 8 are
`injected into the high temperature environment within the
`chamber 7, the droplets 8 do not actually reach the inlet gas
`temperature. The droplets 8, however, do become heated to a
`point at which considerable portions of desired constituents
`of the droplets (i.e., portions of the load) are undesirably
`modified, such as evaporated and/or oxidized. The undesir-
`able modification to the load (load loss) leads to a reduction in
`flavor (in the case of food loads), a reduction in aroma (in the
`case of fragrances), etc. Essentially, evaporation and heat
`degradation of the load lowers the performance characteris-
`tics of the final powder product, and therefore results in a
`significant degradation of performance in commercial use
`and a significant loss of revenue.
`The above disadvantageous characteristics of the conven-
`tional spray dry process have resulted in many process modi-
`fications and emulsion formulations to compensate for heat
`induced alterations in the load. This is especially true in the
`pharmaceutical
`industry, where excessive heating during
`spray drying leads to degradation of the active ingredient in a
`powdered medicament. This also presents a challenge to fla-
`vorists in the powdered flavor industry to design flavor for-
`mulations that can survive the drying process and deliver
`acceptable (although significantly flawed) flavor characteris-
`tics.
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`In view of the above, there are needs in the art for new
`methods and apparatus for carrying out the spray drying
`process, which reduce or eliminate the disadvantageous char-
`acteristics of the conventional spray dry process.
`
`SUMMARY OF THE INVENTION
`
`Methods and apparatus for spray drying a liquid product
`into a dried powder without applying heat provide for: form-
`ing a slurry including a liquid solvent, a carrier, and an active
`ingredient; applying an electrostatic charge to the slurry;
`atomizing the charged slurry to produce a plurality of elec-
`trostatically charged, wet particles; suspending the electro-
`statically charged, wet particles for a suflicient time to permit
`repulsive forces induced by the electrostatic charge on at least
`some wet particles to cause at least some of such particles to
`divide into wet sub-particles; and continuing the suspending
`step, without the presence of any heated drying fluids, for a
`sufficient time to drive off a suflicient amount of the liquid
`solvent within most of the wet particles to leave a plurality of
`dried particles (the powder), each dried particle containing
`the active ingredient encapsulated within the carrier.
`Preferably, a temperature of the non-heated drying fluid is
`less than about 100° C. at introduction into the drying cham-
`ber, such as at least one of: less than about 75° C. at introduc-
`tion into the drying chamber; less than about 45° C. at intro-
`duction into the drying chamber; less than about 35° C. at
`introduction into the drying chamber; less than about 30° C.
`International Flavors & Fragrances Inc.
` Exhibit 1001
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`Page 16
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`US 8,939,388 B1
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`3
`at introduction into the drying chamber; and at about an
`ambient temperature of a room within which the drying
`chamber is located.
`
`The methods and apparatus may further provide for sub-
`jecting the electrostatically charged, wet particles to a non-
`heated drying fluid within a drying chamber to drive off the
`liquid solvent. Alternatively or additionally, the methods and
`apparatus may further provide for dehumidifying the non-
`heated drying fluid prior to introduction into the drying cham-
`ber. Alternatively or additionally, the methods and apparatus
`may further provide for applying one or more electric fields
`within the drying chamber to urge at least one of the wet
`particles and the dry particles to travel in a direction defined
`from an inlet end ofthe drying chamber to an outlet end of the
`drying chamber.
`The methods and apparatus may further provide for con-
`trolling one or more of a viscosity of the slurry during forma-
`tion a ratio of water within the slurry during formation, such
`that one or more of: (i) the viscosity of the slurry at the
`atomization step is at least one of: greater than about 300
`mPa-s; greater than about 350 mPa-s; greater than about 400
`mPa-s; greater than about 500 mPa-s; greater than about 600
`mPa-s; greater than about 700 mPa-s; between about 500-16,
`000 mPa-s; and between about 1000-4000 mPa-s; and (ii) the
`ratio of water within the slurry at the atomization step is at
`least one of: between about 20-50 weight percentage;
`between about 20-45 weight percentage; between about
`20-45 weight percentage; between about 20-40 weight per-
`centage; about 30 weight percentage.
`The apparatus may include a drying chamber, including an
`inlet end, an outlet end, and an internal volume within which
`the liquid product is dried, where the drying chamber is
`formed from a non-electrically conductive material.
`Additionally or alternatively, a first electrode may be
`located at or near the inlet end of the drying chamber; and a
`second electrode may be located at or near the outlet end of
`the drying chamber, where application of a source of voltage
`potential between the first and second electrodes induces an
`electric field within the drying chamber sufficient to urge
`particles of the liquid product, produced by way of atomiza-
`tion, from the inlet end toward the outlet end of the drying
`chamber. Preferably, the first and second electrodes are dis-
`posed external to the drying chamber, yet induce an electric
`field within the internal volume of the drying chamber by
`virtue of the formation of the drying chamber from the non-
`electrically conductive material.
`The apparatus may additionally or alternatively include a
`nozzle operating to atomize a slurry to produce a plurality of
`wet particles, where the slurry includes a liquid solvent, a
`carrier, and an active ingredient. The apparatus may further
`include at least one electrode operating to contact the slurry
`and apply an electrostatic charge thereto, such that the nozzle
`operates to produce a plurality of electrostatically charged
`wet particles. The at least one electrode may be disposed
`within the nozzle such that the slurry contacts the electrode
`and becomes electrostatically charged while flowing from an
`inlet end to an outlet end of the nozzle.
`
`A dried powder produced using one or more aspects of the
`invention may include: a plurality of dried particles, which
`individually contain an amount of final active ingredient
`encapsulated within a carrier resulting from drying a slurry
`containing an initial active ingredient, a liquid solvent and the
`carrier, wherein: the initial active ingredient includes one or
`more constituent components, at least one of which is among
`one or more principle molecular types from which at least one
`of a desirable food, flavor, fragrance, medicament, and pig-
`ment is obtained; the final active ingredient includes one or
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`more ofthe constituent components corresponding with those
`ofthe initial active ingredient as modified by the drying ofthe
`slurry; and wherein a weight percentage of at least one of the
`one or more principle molecular types in the final active
`ingredient is within about 5% of a weight percentage of the
`corresponding principle molecular types in the initial active
`ingredient.
`Alternatively or additionally, the weight percentage of at
`least one of the one or more principle molecular types in the
`final active ingredient may be within about 3%, 2% or 1% of
`a weight percentage ofthe corresponding principle molecular
`types in the initial active ingredient.
`Additionally or alternatively, a dried powder produced
`using one or more aspects of the invention may include: a
`plurality of dried particles, which individually contain an
`amount of active ingredient encapsulated within a carrier,
`wherein: the active ingredient includes one or more constitu-
`ent components, at least one of which is among one or more
`principle molecular types from which at least one of a desir-
`able food, flavor, fragrance, medicament, and pigment is
`obtained; and wherein a weight percentage of at least one of
`the one or more principle molecular types in the active ingre-
`dient does not vary by more than about 5% during aging ofthe
`dried powder during any period of elevated temperature of
`about 95° F. up to about 1000 hours.
`Additionally or alternatively, the weight percentage of at
`least one of the one or more principle molecular types in the
`active ingredient does not vary by more than about 3%, 2% or
`1% during aging of the dried during any period of elevated
`temperature of about 95° F. up to about 1000 hours.
`Other aspects, features, and advantages of the present
`invention will be apparent to one skilled in the art from the
`description herein taken in conjunction with the accompany-
`ing drawings.
`
`DESCRIPTION OF THE DRAWINGS
`
`For the purposes of illustration, there are forms shown in
`the drawings that are presently preferred, it being understood,
`however, that the invention is not limited to the precise
`arrangements and instrumentalities shown.
`FIG. 1 is a system for spray drying a liquid product into a
`dried powder through the convention application ofheated air
`in accordance with the prior art;
`FIG. 2 is a system for spray drying a liquid product into a
`dried powder without employing heated air in accordance
`with one or more aspects of the present invention;
`FIG. 3 is a cross-sectional view of an atomizer that may be
`employed in the system of FIG. 2 in order to produce a
`plurality of droplets from a slurry in accordance with one or
`more aspects of the present invention;
`FIG. 4 is a cross-sectional view of a distal end of an atom-
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`izer that may be employed in the atomizer of FIG. 3 in
`accordance with one or more aspects ofthe present invention;
`FIG. 5 is a perspective, exploded view of certain compo-
`nents ofthe distal end ofthe atomizer of FIG. 4 in accordance
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`with one or more aspects of the present invention;
`FIG. 6 is a schematic, side view of a drying chamber that
`may be employed in the system of FIG. 2 in accordance with
`one or more aspects of the present invention;
`FIG. 7 is an image of dried powder non-fibrous particles
`produced using the system of FIG. 2;
`FIG. 8 is an image of a cross-section through one of the
`dried powderparticles of FIG. 7 showing the encapsulation of
`the load within the carrier;
`FIG. 9 is an image of dried powder fibers produced using
`the system of FIG. 2;
`International Flavors & Fragrances Inc.
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`Exhibit 1001
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`Page 17
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`US 8,939,388 B1
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`5
`FIG. 10 is an image of a cross-section through one of the
`dried powder fibers of FIG. 9 showing the encapsulation of
`the load within the carrier; and
`FIG. 11 is a graph illustrating certain properties of dried
`powder particles produced using the system of FIG. 2 as
`compared with the conventional spray drying process.
`
`DETAILED DESCRIPTION OF THE PREFERRED
`EMBODIMENTS
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`With reference to the drawings, wherein like numerals
`indicate like elements, there is shown in FIG. 2 a system 100
`for spray drying a liquid product into a dried powder without
`employing heated air in accordance with one or more aspects
`ofthe present invention. The system 100 includes some of the
`same or similar elements as in the system 50 of FIG. 1, which
`elements have the same reference designators.
`By way ofa high level description, the system 100 includes
`a drying chamber 107 into which a slurry is fed by way of a
`feed pump 5 (or equivalent conveying mechanism). The
`slurry enters an atomizer 106 and leaves the atomizer as a
`spray of liquid droplets 108, which are introduced into the
`drying chamber 7. Concurrently, a feed of non-heated fluid
`(such as air or another suitable gas) is supplied into the drying
`chamber 107 by a blower 10. The supplied air may be sub-
`jected to dehumidification (via dehumidifier 110) prior to
`introduction into the drying chamber 107. The atomized liq-
`uid droplets 108 dry to form solid particles after exposure to
`the incoming air. Water evaporates from the droplets 108 and
`enters the air within the drying chamber 107. Dried powder
`leaves the drying chamber 107 along with the water vapor
`laden air, and is carried to a cyclone separator 12, which
`removes the dried particles from the circulating air stream and
`deposits the particles into a collection container 13. The water
`vapor laden air exits the collection container 13 and enters a
`baghouse 14, where very fine particles are removed before the
`water vapor laden air is sent into a condenser 9, via blower 15.
`The condenser 9 removes the water vapor from the process
`air, and the collected water may be re-used or discarded.
`There are a number ofvery significant differences between
`the systems of FIGS. 1 and 2. Among these differences is the
`fact that the system 100 and related spray drying process does
`not use a heated fluid (e.g., air) to dry the atomized droplets
`within the drying chamber. The use of non-heated air is
`directly counter to the conventional and accepted wisdom in
`the spray drying art. Indeed, there is no known prior art spray
`drying process or system that does not use significantly
`heated air (on the order of 200° C.) in the drying process,
`despite the fact that the load loss associated with the heating
`process is well understood by skilled artisans. The reason that
`conventional spray drying processes call for heated air, how-
`ever, is that artisans have failed to develop an alternative to
`using heated air that results in suitable (albeit degraded) dried
`powder product.
`Among the reasons that non-heated air may be used in the
`spray drying system 100 and process is that the slurry is not
`conventional. In general, the slurry includes a liquid solvent,
`a carrier, and an active ingredient. The liquid solvent is