USOO7528272B2

(12) United States Patent (10) Patent No.: US 7,528,272 B2

Alasti (45) Date of Patent: May 5, 2009
(54) BIODIESEL PROCESS 6,642,399 B2 11/2003 Boocock ..................... 554,167
6,712,867 B1 3/2004 Boocock ...................... 44/389
(75) Inventor: Perry Alasti, Hopkinton, MA (US) (Continued)
(73) Assignee: Artisan Industries, Inc., Waltham, MA FOREIGN PATENT DOCUMENTS
(US) EP 1331 260 A2 7, 2003

(*) Notice: Subject to any disclaimer, the term of this (Continued)

patent is extended or adjusted under 35 OTHER PUBLICATIONS
U.S.C. 154(b) by 492 days. Connemann et al., “Biodiesel in Europe 1998, Biodiesel, Processing
and Technologies'. International Liquid Biofuels Congress, Jul.
(21) Appl. No.: 11/235,673 19-22, 1998, pp. 1-15 http://www.biodiesel.org/resources/
reportsdatabase/reports/gen, 19980722 gen-100.pdf.
(22) Filed: Sep. 26, 2005 (Continued)
(65) Prior Publication Data Primary Examiner Deborah D Carr
US 2006/OO74256A1 Apr. 6, 2006 (74) Attorney, Agent, or Firm Weingarten, Schurgin,
s Gagnebin & Lebovici LLP
Related U.S. Application Data
(57) ABSTRACT
(60) Provisional application No. 60/613,100, filed on Sep. -0
24, 2004. The present invention provides a biodiesel process capable of
s yielding a mono-alkyl ester biodiesel. In one embodiment, a
(51) Int. Cl. process for yielding biodiesel comprises providing a feed
CD7C5L/43 (2006.01) stream. Preferably, the feed stream comprises mono-alkyl
(52) U.S. Cl. ...................................................... S54/174 esters, salts, alcohol and glycerol. The process also comprises
(58) Field of Classification Search None Substantially separating alcohol from the feed stream to yield
See application file for com lete search histor a first stream. The first stream comprises mono-alkyl esters,
pp p ry. glycerol and salts. A separation of alcohol from the first
(56) References Cited stream is performed by volatility. Furthermore, the process of
U.S. PATENT DOCUMENTS
the invention comprises Substantially separating salts from
the first stream to yield a vapor stream. The vapor stream also
5,520,708 A 5/1996 Johnson et al. ............... 44,388 comprises mono-alkyl esters and glycerol. Separation of salts
5,525,126 A 6/1996 Basu et al. .................... 44, 308 of the vapor stream is also performed by volatility. Glycerol
5,532,392 A 7/1996 Gheorghiu and mono-alkyl esters of the vapor stream are also substan
5,697.986 A 12/1997 Haas ........................... 44, 308 tially separated so as to yield a biodiesel. Preferably, the
5,713,965 A 2/1998 Foglia et al. .................. 44,388 biodiesel is a fuel grade biodiesel comprising fatty acid
5,858,169 A 1/1999 Rachse et al. ... ... 159,48.1 mono-alkyl esters.
6,015,440 A 1/2000 Noureddini .................. 44,388
6,174.501 B1 1/2001 Noureddini ................. 422, 189 44 Claims, 6 Drawing Sheets
 US 7.528,272 B2
Page 2

U.S. PATENT DOCUMENTS Westfalia Separator, Inc., “Methyl Ester Processing Line' Westfalia
Separator Food Tec, Oils & Fats Processing, Single Separator, p. 1
2002fOO58827 A1 5/2002 Wollmann et al. .......... 552/545 http://www.wsus.com/en/products/single separator.html.
2002fOO82434 A1 6, 2002 Bonakdar et al. ........... 552/545
2003,0229238 A1 12/2003 Fleisher ...................... 554,174 Biodiesel Processor Encyclopedis article about Biodiesel Processor
2004.0034244 A1 2/2004 Bournay et al. pp. 1-3 http://encyclopedia.thefreedictionary.com/
2004/0231234 A1 1 1/2004 May et al. ..................... 44,388 biodiesel%20processor.
FOREIGN PATENT DOCUMENTS
Levelton Engineering Ltd. (S&T) Consultants Inc., Assessment of
Biodiesel and Ethanol Diesel Blends, Greenhouse Gas Emissions,
EP 1357 277 A1 10, 2003 Exhaust Emissions, and Policy Issues. Sep. 30, 2002, pp. 1-89 http://
WO WOO3,083020 A2 10, 2003 www.ghgenius.ca/reports/NRCanBiodiesel.pdf.
WO WOO3,087279 A2 10, 2003 Legislative, Thomas. AIM-AG/Agri-Industry Modeling & Analysis
Group Economic Feasibility of Producing Biodiesel in Tennessee,
OTHER PUBLICATIONS Appendix 1. “Congressional Activity, USDA Bioenergy Program,
Khan, “Research into Biodiesel, Kinetics & Catalyst Development”. Senate Energy Bill, and EPA Reduced Sulfur Emissions Regulation
May 17, 2002, pp. 1-39 http://www.cheque.uq.edu.au/ugrad/ Provisions' pp. A-1-A-31 http://web.utk.edu/~aimag/pubs/
chee4001/CHFE400102, Adam Khan Thesis.pdf biodiesel.pdf.
Schmidt, “Biodiesel Vehicle Fuel: GHG Reductions, Air Emissions, Goodrum et al., Biodiesel Production, Biological and Agriculyural
Supply and Economic Overview”. Discussion Paper C3-015, Mar. Engineering Department, The University of Georgia, pp. 1-33 http://
11, 2004, pp. 1-20 http://www.climatechangecentral.com/ www.georgiaitp.org/PDF/Biodiesel.pdf.
info centre/discussion papers 015Biodiesel Discussion Paper. Brevete Biodiesel, http://www.chiminform.home.ro/chim files/
pdf. patente abstract.doc. Copy Not Available.
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 US 7,528,272 B2
1. 2
BODESEL PROCESS on the density and solubility differences between glycerol
and mono-alkyl esters offatty acids. In view of the substantial
CROSS REFERENCE TO RELATED amount of excess alcohol present within fatty acid mono
APPLICATIONS alkyl esters and glycerol being separated, the physical dimen
sions of Such mechanical separation means can be consider
This application claims the priority of U.S. Provisional able. Settling vessels can also introduce extended delays in a
Application No. 60/613,100 filed Sep. 24, 2004 and entitled, biodiesel process.
METHOD FOR DESOLVENTIZING AND PURIFYING To date, biodiesel processes are generally inefficient and
METHYL ESTER AND GLYCERIN FROM CRUDE involve both time consuming and maintenance intensive
BIODIESEL, which is hereby incorporated by reference 10 mechanical separations. Such conventional biodiesel pro
herein. cesses also tend to suffer from marginal overall biodiesel
yields. These shortcomings have impeded the progress of
BACKGROUND OF THE INVENTION biodiesel as a viable source of alternative energy. The devel
opment of a biodiesel fuel as an alternative to standard petro
Biodiesel is a nontoxic and biodegradable fuel that can be 15 leum-based diesel fuels requires a process that can overcome
used in conventional diesel engines. As a fuel, biodiesel is a these shortcomings. Particularly, such a biodiesel process
renewable alternative to standard petroleum-based diesel should be capable of continuously producing fuel grade fatty
fuels. Typically, biodiesel is produced from oils and sources acid mono-alkyl esters from any conventional transesterifica
of free fatty acids such as, for example, vegetable oil, animal tion process. The process should also minimize the overall
fat and waste type greases. Biodiesel is usually obtained number of individual unit operations by providing for effi
through an esterification or, preferably, transesterification cient and continuous separations.
type process in which triglycerides derived from oil or fat are
reacted with alcohol in the presence of a catalyst. In general, SUMMARY OF THE INVENTION
the form of biodiesel yielded via a transesterification process
can depend on the types of alcohols or solvents employed. For 25 The present invention provides a biodiesel process capable
example, often methanol is employed in a transesterification of yielding a mono-alkyl ester biodiesel. In one embodiment,
process to obtain a fatty acid methyl ester biodiesel. Alterna a process for yielding biodiesel comprises providing a feed
tively, ethanol can be used in a transesterification process to stream. Preferably, the feed stream comprises mono-alkyl
yield a fatty acid ethyl ester biodiesel. Such biodiesel type esters, salts, alcohol and glycerol. The process also comprises
esters of fatty acids are commonly referred to as mono-alkyl 30 Substantially separating alcohol from the feed stream to yield
esters or monoesters. An esterification process can also a first stream. The first stream can, for example, comprise
employ cosolvents such as, for example, methanol and tet mono-alkyl esters, glycerol and salts. Separation of alcohol
rahydrofuran (THF) in order to yield a fatty acid ester biodie from the first stream is performed by volatility. Moreover, a
sel. process of the invention comprises Substantially separating
Mono-alkyl esters offatty acids comprise those fatty acids 35 salts from the first stream so as to yield a vapor stream. The
associated with the oils or fats used in the transesterification vapor stream can, for example, comprise mono-alkyl esters
process. For naturally occurring oils and fats, the fatty acids and glycerol. Separation of salts of the vapor stream is also
of a fatty acid ester biodiesel include, for example, linoleic, performed by volatility. Glycerol and fatty acid mono-alkyl
Stearic, palmitic or oleic acids. The catalyst present within a esters from the vapor stream are then Substantially separated
transesterification process can be basic or acidic in nature. A 40 to yield a biodiesel. A process of the present invention can
base catalyzed transesterification process can, for example, overcome the shortcomings of conventional biodiesel pro
use Such catalysts as Sodium methoxide, potassium hydrox cesses such as, for example, those described above.
ide, sodium hydroxide and combinations thereof. In addition The process of the invention yields a biodiesel comprising
to a mono-alkyl ester biodiesel, a transesterification process mono-alkyl esters offatty acids such as, for example, linoleic,
yields glycerol, which can be used for cosmetic and pharma 45 palmitic, stearic and oleic acids. Preferably, biodiesel from a
ceutical applications. The reaction Stoichemitry of a conven process of the invention is a fuel grade biodiesel. In another
tional transesterification type process also results in by-prod embodiment, the feed stream of the process is obtained from
ucts such as, for example, water, excess alcohol, light a product stream of an esterification type process, preferably,
organics, heavies, free fatty acids and salts. a transesterification type process. An exemplary esterification
Primarily, the products from a transesterification process 50 type process comprises Substantially reacting triglycerides
include fatty acid mono-alkyl esters and glycerol. The prod with alcohol to yield a product stream including fatty acid
ucts also consist of a Substantial amount of alcohol, which mono-alkyl esters, water, glycerol, Salts and alcohol. In addi
generally remains in excess due to, for example, the reaction tion, an esterification process can employ several types of
stoichemitry. In order to obtain “fuel grade' biodiesel, fatty alcohols, cosolvents or combinations thereof to yield a prod
acid mono-alkyl esters produced through a transesterification 55 uct stream. For example, methanol and THF can be used in an
process must be separated from glycerol and any reaction esterification process so as to yield a product stream. In one
by-products such as heavies, alcohol, light organics, water, embodiment, the process of the invention can comprise Sub
free fatty acids and salts. A fuel grade biodiesel is character stantially separating alcohol and water of the feed stream
ized by mono-alkyl esters that satisfy the specifications of the obtained from a product stream of an esterification process.
American Society for Testing and Materials (ASTM). Exem 60 Alcohol and water are, for example, Substantially separated
plary specifications set by ASTM for evaluation of fatty acid from the obtained feed stream by volatility to yield a first
mono-alkyl ester biodiesel include ASTM D 6751. Stream.
Commonly, mono-alkyl esters from a transesterification In one embodiment, the vapor stream yielded from a pro
type process are separated from glycerol via conventional cess of the invention is Substantially condensed in order to
means for liquid-liquid type separations such as, for example, 65 obtain a liquid stream. The liquid stream comprises mono
a settling vessel. With both a batch or continuous type biodie alkyl esters and glycerol. Preferably, mono-alkyl esters and
sel process, such mechanical means of separation are based glycerol of the liquid stream are substantially separated to
 US 7,528,272 B2
3 4
yield a biodiesel. Such a Substantial separation of glycerol process results in reaction by-products such as, for example,
and mono-alkyl esters is, for example, by gravity. In another heavies, salts, excess alcohol, free fatty acids and water,
embodiment, the process of the invention Substantially sepa which can also be present in the feed stream 2. In one embodi
rates fatty acid mono-alkyl esters and glycerol of the vapor ment, the extents of reaction via esterification can vary the
stream to yield a liquid stream comprising mono-alkyl esters. composition of the feed stream 2, which is obtained there
For example, such a liquid stream is produced by Substan from.
tially condensing mono-alkyl esters to produce a biodieselin, Triglycerides are substantially reacted with alcohol in a
for example, a distillation column. The biodiesel fuel com conventional esterification process to obtain the feed stream
prises mono-alkyl esters of fatty acids such as, for example, 2. The extents of reaction by esterification can vary given Such
linoleic, palmitic, Stearic and oleic acids. 10 factors as, for example, reaction Stoichemitry and conditions.
Moreover, the composition of the feed stream can vary
DESCRIPTION OF THE DRAWINGS depending on the type of catalyst used for esterification. A
feed stream 2 can be obtained from any conventional esteri
Other features and advantages of the invention may also be fication processes. Exemplary esterification processes are
apparent from the following detailed description thereof, 15 described by U.S. Pat. Nos. 6,855,838, 6,822,105, 6,768,015,
taken in conjunction with the accompanying drawings of 6,712,867, 6,398,707 or 6,642,399, which are hereby incor
which: porated by reference herein.
FIG. 1 is a representation of a process of the invention for As shown, the feed stream 2 of FIG. 1 is introduced to a first
yielding biodiesel; separation means 4. The separation means 4 substantially
FIG. 2 is a representation of a process of the invention for separates alcohol from the feed stream 2 to yield a first stream
yielding biodiesel; 6 featuring, for example, glycerol, salts and mono-alkyl
FIG. 3 is a representation of a process of the invention for esters. Preferably, the process of FIG. 1 comprises a preheat
yielding biodiesel; ing means in order to preheat the feed stream 2 prior to
FIG. 4 is a representation of a process of the invention for introduction to the first separation means 4. The separation
yielding biodiesel; 25 means Substantially separates alcohol present in the feed
FIG. 5 is a representation of a process of the invention for stream by Volatility. In general, a separation by Volatility is
yielding biodiesel; and based on differences in vapor pressure. For example, the first
FIG. 6 is a representation of a process of the invention for separation means can be used to vaporize a portion of alcohol
yielding biodiesel. from the feed stream 2 to yield the first stream. A portion of
30 alcohol in the feed stream is vaporized therefrom given its
DEFINITIONS high vapor pressure as compared to, for example, mono-alkyl
esters, glycerol and salts.
Unless otherwise stated, the following definitions provide In one embodiment, the first separation means 4 can be a
meaning and examples to terms used herein. Such definitions conventional type of thermal-based unit operation Such as, for
are also intended to encompass any meaning that may be 35 example, an evaporator. Exemplary evaporator types for the
contemplated or could be appreciated by a person of ordinary first separation means 4 can include forced-circulation, rising
skill within the art. film and falling film evaporators. For example, the first sepa
The terms “mono-alkyl ester' or “monoester” and deriva ration means can be an agitated-film evaporator. Preferably, a
tions thereof including, for example, mono-alkyl esters, process of the invention comprises a Substantially horizontal,
monoesters or esters generally refer to a type of fatty acid 40 thin or wiped rotary blade evaporator. For example, Such a
ester biodiesel or biodiesel fuel. For example, a fatty acid substantially horizontal, thin or wiped rotary blade evapora
mono-alkyl ester biodiesel comprises fatty acids such as tor is a ROTOTHERM (Artisan Industries Incorporated of
oleic, Stearic, linoleic or palmitic acids as well as any sort of Waltham, Mass. 02451) evaporator. Examples of conven
combinations of these fatty acids. tional agitated-film evaporators are described by U.S. Pat.
45 Nos. 3,561,517, 3,891,495, 3,985,606, 4,054,485, 3,678,983,
DETAILED DESCRIPTION OF THE INVENTION 3,695,327, 3,633,645 or 4,093,479, which are hereby incor
porated by reference herein.
The present invention provides a biodiesel process capable As described above, the first separation means 4 of FIG. 1
of yielding mono-alkyl ester biodiesel. In one embodiment, separates alcohol from the feed stream 2, which is provided
the process of the invention yields biodiesel comprising fatty 50 thereto. The extent of alcohol separation from the feed stream
acid mono-alkyl esters. Fatty acid mono-alkyl esters com 2 can vary depending on several factors. For example, the
prise fatty acids such as, for example, linoleic, Stearic, palm design, type, orientation or operating conditions of the first
itic and oleic acids. The process of the invention can also separation means 4 can affect the extent of separation of
produce a fuel grade fatty acid mono-alkyl ester biodiesel. alcohol. Such factors can also be modified or adjusted in order
Preferably, a process of the present invention is substantially 55 to influence the overall quantity or quality of a biodiesel
continuous. A process of the invention produces a generally produced by a process of the invention. In another embodi
continuous yield of mono-alkyl ester biodiesel from such ment, the extent of alcohol separation is adjusted as the pro
Sources of oils and fats as, for example, animal fat, waste type cess of the invention is being carried out. Preferably, alcohol
grease, vegetable oil or algae. is separated from the feed stream 2 in an evaporator Such as,
FIG. 1 is a representation of a process of the invention for 60 for example, an agitated-film evaporator.
yielding biodiesel. FIG. 1 shows a feed stream 2 that can In another embodiment, the first separation means 4 also
comprise, for example, salts, alcohol, glycerol and mono Substantially separates waterpresent in the feed stream 2 so as
alkyl esters. The feed stream is obtained from an esterification to yield the first stream 6. As shown, the first stream 6 exits the
type process Such as, for example, a transesterification pro first separation means 4 and is then introduced to a second
cess. An exemplary esterification process comprises Substan 65 separation means 8. FIG. 1 shows a vapor stream 10 exiting
tially reacting triglycerides with alcohol so as to yield glyc the separation means 4 and entering a column 12. The column
erol and mono-alkyl esters. Moreover, an esterification 12 can be any conventional type of column Such as a distilla
 US 7,528,272 B2
5 6
tion column. Exemplary distillation columns include tray or biodiesel produced by a process of the invention. In general,
packed columns that are liquid of vapor feed. The column 12 the extent of salts separation can be adjusted while the process
can also be a batch or continuous type column. Preferably, the of the invention is carried out. Preferably, salts are substan
column 12 is a distillation column used to Substantially sepa tially separated from the stream 6 within an evaporator such
rate alcohol from water present in the vapor stream 10. The as, for example, an agitated-film evaporator. The resulting
column 12 also comprises conventional components such as, vapor stream 18 comprises mono-alkyl esters and glycerol.
for example, reflux drums, condensers, reboilers or any com Salts substantially separated from the first stream comprise
bination thereof. a residue stream 20. The residue stream 20 is properly dis
FIG. 1 shows the column 12 receiving the vapor stream 10 posed of by any suitable means. Typically, the residue stream
comprising, for example, alcohol and water. In one embodi 10 comprises a Substantial portion of heavies that can be present
ment, alcohol is enriched in a column rectifying section so as in the feed stream 2. Preferably, fatty acid mono-alkyl esters
to exit the column 12 in an overhead vapor stream 14. More and glycerol of the vapor stream are substantially separated so
over, water is stripped in a stripping section of the column so as to yield a biodiesel.
as to depart the column in a bottoms stream 16. The overhead In one embodiment, the vapor stream 18 is introduced to a
vapor stream 14 is condensed via a condenser and a portion 15 condenser 22 to perform condensing thereof. Preferably, the
thereof refluxed to the column 12. Similarly, a portion of the vapor stream 18 is substantially condensed by the condenser.
bottoms stream 16 is reboiled and then returned to the col For example, a portion of the vapor stream is condensed prior
umn. Preferably, alcohol in the overhead vapor stream 14 is to separation of glycerol from mono-alkyl esters So as to yield
recycled in order to carry out, for example, the esterification biodiesel. The condenser 22 can be any conventional type of
process. In general, water in the bottoms stream 16 is sent to condenser Such as, for example, a vertical or horizontal type
Waste Water treatment. condenser. The extent of condensation of the vapor stream 18
The extent of alcohol separation from water in the vapor can vary depending on several factors such as, for example,
stream 10 can vary depending on several factors. For the type of condenser 22. Moreover, the cooling media and
example, the type of distillation column 12 can influence the operating conditions of the condenser 22 can also affect the
extent of separation of alcohol from water to yield the over 25 extent of condensation.
head vapor 14 and bottoms stream 16, respectively. The oper Such factors relating to the process of the invention can
ating conditions for the column 12 can also affect the extent of also be modified or adjusted in order to influence, for
separation. Such factors can also be modified or adjusted so as example, the overall quality of biodiesel. In one embodiment,
to influence, for example, the purity of alcohol in the overhead the extent of condensation in the condenser 22 is adjusted as
vapor stream 14 for recycling as described above. In one 30 the process of the invention is performed in, for example, a
embodiment, the extent of separation in the distillation col Substantially continuous manner. FIG. 1 also shows the con
umn 12 can be adjusted as the process of the invention is being denser 22 yields a liquid stream 24 comprising fatty acid
carried out. mono-alkyl esters and glycerol. Preferably, fatty acid mono
FIG. 1 also shows the first stream 6 introduced to the alkyl esters and glycerol are separated by gravity to yield
second separation means 8. Preferably, the separation means 35 biodiesel. A portion of mono-alkyl esters in the liquid stream
8 is any conventional type of thermal-based unit operation 24 are separated therefrom given the density and solubility
Such as, for example, an evaporator. Exemplary evaporator differences of esters as compared to glycerol. Such a separa
types for the second separation means 8 can include forced tion by gravity so as to yield a mono-alkyl ester biodiesel can
circulation, rising film and falling film evaporators. For be performed by any suitable means.
example, the separation means 8 can be an agitated-film 40 For example, separating mono-alkyl esters from glycerol
evaporator. Preferably, a process of the invention comprises a can occur in any Suitable process operation Such as, for
substantially horizontal, thin or wiped rotary blade evapora example, sedimentation, centrifugation, membrane separa
tor. For example, Such a Substantially horizontal, thin or tion or any types of combinations thereof. FIG. 1 also shows
wiped rotary blade evaporator is a ROTOTHERM (Artisan condensed mono-alkyl esters Substantially separated from
Industries Incorporated of Waltham, Mass. 02451) evapora 45 glycerol via a centrifuge 26. For example, mono-alkyl esters
tor. Examples of conventional agitated-film evaporators are exit the centrifuge 26 in a yield stream 25 and glycerol in a
described by U.S. Pat. Nos. 3,561,517, 3,891,495, 3,985,606, residual stream 27. The centrifuge 26 can be any type of
4,054,485, 3,678,983, 3,695,327, 3,633,645 or 4,093,479, conventional centrifuge such as a tubular bowl or decanter
which are hereby incorporated by reference herein. type centrifuge. The centrifuge 26 can further be of any suit
As shown in FIG. 1, the separation means 8 substantially 50 able orientation Such as generally horizontal or vertical.
separates salts from the first stream 6 to yield a vapor stream Moreover, the extent of separation of mono-alkyl esters from
18 comprising mono-alkyl esters and glycerol. In one glycerol can vary depending on several factors such as, for
embodiment, separation of salts from the first stream is by example, the type of and operating conditions for the centri
volatility. As described above, separation by volatility is fuge. In addition, Substantially separated glycerol from the
based on differences in vapor pressure. For example, the 55 centrifuge 26 can be used for any suitable applications such
means 8 is used to vaporize a portion of mono-alkyl esters and as, for example, cosmetic and pharmaceutical applications.
glycerol from the first stream 6 to yield the vapor stream 18. FIG. 2 also shows a representation of a process of the
A portion of mono-alkyl esters and glycerol in the first stream invention for yielding biodiesel. Particularly, FIG. 2 shows a
6 are vaporized therefrom given the high vapor pressure of process comprising a reactor 28. In one embodiment, the
esters and glycerol as compared to, for example, salts, which 60 reactor 28 can be used to carry out an esterification type
are essentially non-volatile. process such as a transesterification process. For example, the
The extent of separation of salts from the first stream 6 can reactor 28 is used for a transesterification type process in
vary depending on several factors. For example, the design, which a feed source of triglycerides is introduced thereto.
type, orientation or operating conditions of the second sepa Preferably, the feed source for the transesterification process
ration means 8 can affect the extent of separation of salts 65 comprises algae vegetable oil, animal fat, waste type greases
present in the first stream 6. Such factors can be modified or or combinations thereof. The feed source is provided to the
adjusted so as to influence the overall quantity or quality of a reactor in a feed 30. The feed 30 for the process of the
 US 7,528,272 B2
7 8
invention comprises a feed source of triglycerides and alco generally described above. In one embodiment, the feed
hol. Alternatively, several types of alcohols, cosolvents or any stream 2 is introduced to the first separation means 4. The
combination thereof can also be present in the feed 30 so as to separation means 4 substantially separates alcohol from the
yield a product stream via esterification. Generally, the prod feed stream 2 so as to yield a first stream 6 featuring, for
uct stream 32 exiting from the reactor varies depending on the example, glycerol, salts and mono-alkyl esters. The separa
composition of the feed 30. tion means Substantially separates alcohol from the feed
In one embodiment, the feed 30 can comprise alcohol such stream 2 by Volatility. For example, the first separation means
as methanol to yield methyl esters. Alternatively, ethanol can is used in order to vaporize a portion of alcohol from the feed
be used in the feed 30 to yield ethyl esters. As described stream 2 to yield the first stream 6. The separation means 4
above, a process of the invention can also use different types 10 also substantially separates waterpresent in the feed stream 2.
of alcohols, cosolvents or any combinations thereof in the As shown, the first stream 6 exits the first separation means
feed 30 to yield mono-alkyl esters comprising fatty acids such 4 and is then introduced to a second separation means 8. FIG.
as, for example, Stearic, linoleic, palmitic and oleic acid. The 2 shows a vapor stream 10 exiting the separation means 4 and
fatty acids of mono-alkyl esters can also vary based on the entering a column 12. The column 12 can be any conventional
feed source. As shown in FIG. 2, the feed 30 is provided to the 15 type of column such as a distillation column. Preferably, the
reactor 28 such that available triglycerides are substantially column 12 is a distillation column used to Substantially sepa
reacted with alcohol via an esterification process. The process rate alcohol from water present in the vapor stream 10. For
of esterification can occur in the presence of a catalyst. The example, alcohol departs from the column 12 in an overhead
catalyst can be basic or acidic in nature Such as, for example, vapor stream 14 as water exits therefrom in a bottoms stream
potassium hydroxide, Sodium methoxide, Sodium hydroxide 16.
and any suitable combinations thereof. FIG. 2 also shows the first stream 6 introduced to the
As described above, triglycerides from the feed source are second separation means 8. The separation means 8 substan
substantially reacted with alcohol in the reactor 28 to yield a tially separates salts from the first stream 6 to yield a vapor
product stream 32. The product stream can comprise glycerol stream 18 comprising mono-alkyl esters and glycerol. In one
and mono-alkyl esters. Furthermore, the esterification pro 25
embodiment, separation of salts from the first stream 6 is by
cess from which the product stream is yielded can produce volatility. Salts substantially separated from the first stream 6
reaction by-products such as, for example, heavies, salts, free comprise a residue stream 20. The residue stream 20 is prop
fatty acids, excess alcohol and water. The extent of esterifi erly disposed of by any suitable means. Typically, the residue
cation within the reactor 28 can also vary the composition of stream comprises a Substantial portion of heavies that can be
the feed stream 2 obtained from the product stream 32. For 30
present in the feed stream 2. Mono-alkyl esters and glycerol
example, the stream 2 can comprise alcohol, water, heavies, of the vapor stream 18 are substantially separated so as to
free fatty acids, mono-alkyl esters, salts and glycerol. The yield a biodiesel.
extent of esterification can also vary given such factors as In one embodiment, the vapor stream 18 is introduced to a
reaction Stoichemitry and conditions. condenser 22 to perform condensing thereof. Preferably, the
In one embodiment, the reactor 28 can be any given type of 35
vapor stream 18 is substantially condensed by the condenser
conventional reactor Suitable for carrying out an esterification 22. For example, a portion of the vapor stream is condensed
process. Exemplary reactors can include, for example, tubu prior to separation of glycerol from mono-alkyl esters So as to
lar, fixed bed, stirred tank and fluid bed reactors. A process of yield biodiesel. FIG. 2 also shows the condenser 22 yields a
the invention can also feature a plurality of reactors in any liquid stream 24 comprising fatty acid mono-alkyl esters and
type of configuration Such as, for example, in parallel or 40
glycerol. Preferably, mono-alkyl esters and glycerol are then
series. A process of the invention can optionally separate separated by gravity to yield biodiesel. A portion of mono
water present in the feed 30 prior to esterification by any alkyl esters in the liquid stream 24 are separated therefrom
Suitable means. For example, such means can be a conven given the density and solubility differences of esters as com
tional evaporator. Exemplary types of evaporators for Sub pared to glycerol.
stantially separating water in the feed 30 from a feed source 45
include forced-circulation, rising film and falling film evapo As shown in FIG. 2, substantially condensed fatty acid
rators. Preferably, the evaporator is an agitated-film evapora mono-alkyl esters are separated from glycerol in a centrifuge
tor such as a ROTOTHERM (Artisan Industries Incorporated 26. For example, mono-alkyl esters exit the centrifuge in a
of Waltham, Mass. 02451) evaporator. The extent of water yield stream 25 and glycerol in a residual stream 27. Prefer
present in the feed 30 depends on the feed source used. 50 ably, the process of FIG. 2 is substantially continuous and
As shown, the process of FIG. 2 comprises an optional capable of producing fuel grade biodiesel.
preheating means 34 in order to preheat the feed stream 2 FIG. 3 is a representation of a process of the invention for
prior to introduction to the first separation means 4. The feed yielding biodiesel. FIG.3 also features several of the various
stream obtained from the product stream 32 of the reactor 28 aspects of the processes in FIGS. 1 and 2. The process of FIG.
can have a composition that varies based on the type, design 55 3 can include or incorporate any suitable variations such as,
and operating conditions of the reactor 28. Such factors can for example, those generally described above. In one embodi
also be modified or adjusted so as to influence the overall ment, the feed stream 2 is obtained from any conventional
quantity or quality of the feed stream. In one embodiment, for esterification type process. The feed stream 2 is then intro
example, the extent of esterification can be adjusted as a duced into the first separation means 4. The first separation
process of the invention is continuously carried out. The 60 means 4 substantially separates alcohol and water from the
orientation of the reactor 28 can also affect the extent of feed stream 2 to yield a first stream 6 comprising, for
reaction. Moreover, as described above, the type of catalyst, example, glycerol, salts and mono-alkyl esters. The separa
alcohols, solvents, feed source and combinations thereof can tion means Substantially separates alcohol and water from the
affect the composition of the stream 2. feed stream by volatility. For example, the first separation
FIG. 2 also shows the various aspects of the process in FIG. 65 means 4 is used in order to vaporize a portion of alcohol and
1. The process of FIG. 2 can also include or otherwise incor water from the feed stream 2 to yield the first stream 6.
porate any suitable variations such as, for example, those Portions of alcohol and water in the feed stream are vaporized
 US 7,528,272 B2
10
therefrom given the high vapor pressure of each as compared cation type process in which a feed source of triglycerides is
to, for example, mono-alkyl esters, glycerol and salts. provided thereto such as described above. The feed source is
The process of FIG. 3 can optionally include a preheating provided to the reactor 28 in a feed 30.
means so as to preheat the feed stream 2 prior to introduction As described above, a feed source comprising triglycerides
to the first separation means 4. As shown, the first stream 6 is substantially reacted with alcohol in the reactor 28 to yield
exits the first separation means 4 and is then introduced to a a product stream 32. The product stream comprises glycerol
second separation means 8. FIG.3 also shows a vapor stream and mono-alkyl esters. In addition, the product stream also
10 exiting the separation means 4 and entering a column 12. includes alcohol, water, heavies, free fatty acids and salts. The
The column 12 can be any conventional type of column Such feed stream 2 is obtained from the product stream 32. As
as a distillation column. Preferably, the column 12 is a distil 10 shown, the process of FIG. 4 comprises an optional preheat
lation column used to Substantially separate alcohol from ing means 34 in order to preheat the feed stream 2 prior to
water present in the vapor stream 10. For example, alcohol introduction to the first separation means 4.
departs from the column in an overhead vapor stream 14 as The feed stream 2 is introduced to the first separation
water exits therefrom in a bottoms stream 16. means 4. The first separation means 4 Substantially separates
FIG. 3 also shows the first stream 6 introduced to the 15 alcohol and water from the feed stream 2 to yield a first stream
second separation means 8. The separation means 8 substan 6 comprising, for example, glycerol, salts and fatty acid
tially separates salts from the first stream 6 to yield a vapor mono-alkyl esters. The separation means 4 substantially
stream 18 comprising mono-alkyl esters and glycerol. In one separates alcohol and water from the feed stream by volatility.
embodiment, separation of salts from the first stream 6 is by For example, the first separation means is used in order to
volatility. Salts substantially separated from the first stream 6 vaporize a portion of alcohol and water from the feed stream
comprise a residue stream 20. The residue stream 20 is prop 2 to yield the first stream 6.
erly disposed of by any Suitable means. Typically, the residue In addition, the first stream 6 exits the first separation
stream 20 comprises a Substantial portion of heavies that can means 4 and is then introduced to a second separation means
be present in the feed stream 2. 8. FIG. 4 shows a vapor stream 10 exiting the separation
In one embodiment, the vapor stream 18 can be introduced 25 means 4 and entering a column 12. The column 12 can be any
to a column 36 Such as a conventional type of distillation conventional type of column Such as a distillation column.
column. Exemplary distillation columns include tray or Preferably, the column 12 is a distillation column used to
packed columns that are liquid of vapor feed. The column 36 Substantially separate alcohol from water present in the vapor
can also be a batch or continuous type column. Preferably, the stream 10. For example, alcohol departs from the column in
column 36 is used to separate glycerol and fatty acid mono 30 an overhead vapor stream 14 as water exits therefrom in a
alkyl esters present in the vapor stream by Substantially con bottoms stream 16.
densing mono-alkyl esters. In general, mono-alkyl esters FIG. 4 also shows the first stream 6 introduced to the
from the vapor stream are substantially condensed during second separation means 8. The separation means 8 substan
separation from glycerol in the column 36. The column 36 tially separates salts from the first stream 6 to yield a vapor
also comprises conventional components such as, for 35 stream 18 comprising mono-alkyl esters and glycerol. In one
example, reflux drums, condensers, reboilers or any combi embodiment, separation of salts from the first stream 6 is by
nations thereof. The column 36 can also feature any suitable volatility. Salts substantially separated from the first stream 6
reflux ratio. comprise a residue stream 20. The residue stream 20 is prop
FIG.3 shows the column 36 receiving the vapor stream 18 erly disposed of by any suitable means. Typically, the residue
comprising, for example, glycerol and mono-alkyl esters. In 40 stream 20 comprises a Substantial portion of heavies that can
one embodiment, glycerol can be enriched within a column be present in the feed stream 2.
rectifying section so as to exit the column 36 in an overhead In one embodiment, the vapor stream 18 can be introduced
vapor stream38. Moreover, mono-alkyl esters can be stripped to a column 36 Such as a conventional type of distillation
in a stripping section of the column so as to depart the column column. Exemplary distillation columns include tray or
36 in a bottoms stream 40. The overhead vapor stream 38 is 45 packed columns that are liquid of vapor feed. The column 36
condensed and a portion thereof refluxed to the column 36. can also be a batch or continuous type column. Preferably, the
Similarly, a portion of the bottoms stream 40 is also reboiled column 36 is used to Substantially separate glycerol and
and then returned to the column 36. mono-alkyl esters present in the vapor stream 18. As
The extent of glycerol separated from fatty acid mono described above, the column 36 comprises conventional com
alkyl esters in the vapor stream 18 can vary depending on 50 ponents such as, for example, condensers, reflux drums,
several factors such as the type of column 36. Moreover, the reboilers or any combinations thereof. The column 36 can
operating conditions of the column can influence the extent of also feature any suitable reflux ratio.
separation of glycerol from mono-alkyl esters. Such factors FIG. 4 shows the column 36 receiving the vapor stream 18
can be modified or adjusted to influence, for example, the comprising, for example, glycerol and mono-alkyl esters. In
overall quantity or quality of biodiesel produced by the pro 55 one embodiment, glycerol exits the column 36 in an overhead
cess shown in FIG. 3. Preferably, the extent of separation in vapor stream 38. Moreover, mono-alkyl esters depart the
the distillation column 36 can be adjusted as the process of the column 36 in a bottoms stream 40, which is a liquid stream.
invention is carried out in a Substantially continuous manner. Preferably, mono-alkyl esters and glycerol present in the
FIG. 4 is a representation of a process of the invention for overhead vapor stream 18 are substantially separated to yield
yielding biodiesel. FIG. 4 also features several of the aspects 60 the bottoms stream. As described above, such a separation is
of the processes in FIGS. 1, 2 and 3. The process of FIG. 4 can performed by Substantially condensing mono-alkyl esters in
include or incorporate any Suitable variations such as, for the column 36. In FIG. 4, the overhead vapor stream is con
example, those described above. Particularly, FIG. 4 shows a densed via a condenser and a portion thereof refluxed to the
process comprising a reactor 28. In one embodiment, the column so as to minimize carry over of biodiesel into the
reactor 28 can be used so as to carry out an esterification type 65 glycerol stream.
process such as, for example, a transesterification type pro The examples herein are provided to illustrate advantages
cess. For example, the reactor can be used for a transesterifi of the invention that have not been previously described and
 US 7,528,272 B2
11 12
to further assista person of ordinary skill in the art with using
400 to 800 pph. Furthermore, heavies are separated from the
a process of the invention. The examples hereincan include or first stream at about 400 to 1,600 pph.
incorporate the variations or inventive embodiments as The distillation column 12 can be operated at a pressure of
described above. The embodiments that are described above
about 350 to 760 torr and, preferably, 300 to 500 torr. The
also can each include or otherwise incorporate the variations 5 column 12 substantially separates methanol from water. For
of any or all other embodiments herein. The examples are not example, water exits from the column 12 as a bottoms stream
intended in any way to otherwise limit or narrow the disclo 16. The majority of the bottoms stream 16 can be disposed of
sure or scope thereofas provided herein. as comprising water and trace quantities of methanol. A por
EXAMPLE I 10 tion from the bottoms stream is also sent to a reboiler 46,
which heats the bottoms stream 16 to a temperature of about
FIG. 5 shows one representation of the process of the 175 to 190°F. The heated bottoms stream also comprises a
invention for yielding biodiesel. The feed stream 2 is obtained rate of reboiling from about 800 to 1,600 pph. The stream 14
from a conventional esterification process. The feed stream comprises methanol with about 0.2% or less of water. The rate
can comprise mono-alkyl esters, glycerol, alcohol, water, 15 of the overhead vapor stream 14 is from about 20,000 to
salts and heavies. Preferably, alcohol of the feed stream 2 is 26,000 pph.
methanol such that mono-alkyl esters are methyl esters. The The overhead vapor stream 14 is then introduced into a
feed stream includes the weight percentages (%) shown in condenser 48 operating at a pressure from about 300 to 500
Table 1.
2O
torr and temperature of about 120 to 150°F. The condenser 48
also provides the column 12 with reflux at a ratio of about 0.7
TABLE 1. to 1.0. The condenser 48 then sends a recycle stream 50 of
Feed Stream Weight %
substantially methanol to the esterification process. The
recycle stream also comprises a methanol makeup stream 52
Methyl Esters About 30 To 40 such that the stream 50 operates at a temperature of from
Glycerol About 1. To 5 25
Water About 1 To 2 about 90 to 110° F. and rate of about 20,000 to 26,000 pph.
Methanol About 50 To 65 The process of the invention can also comprise a reflux drum
Heavies About 1 To 4 associated with the condenser 48.
Salts About 1 To 2
As shown, the vapor stream 18 is introduced to a condenser
30 54 operating at a pressure of about 4 to 6 torr and temperature
of about 120 to 150°F. The condenser can condense glycerol
The feed stream 2 is introduced to the preheater means 34 at and methyl esters in the vapor stream to obtain a liquid stream
a temperature from about 80 to 120 degrees Fahrenheit (F.). 24 with a temperature of about 80 to 120°F. The condenser 54
The rate of the feed stream 2 is about 40,000 pounds per hour also operates at a pressure of from about 3 to 6 torr. The liquid
(pph). The preheater means 34 is also provided with heating is stream 24 from the condenser is then introduced to a centri
media to maintain a consistent temperature.
The feed stream 2 is heated by the preheater means 34 to a fuge 26 to produce methyl esters at a rate of from about
temperature from about 250 to 275° F. The feed stream 2 can 12,000 to 16,000 pph and an overall yield of from about 80 to
also be maintained at a pressure of from about 100 to 150 98.5%. Glycerol is also yielded at a rate from about 400 to 800
pounds per square inch (psi). The feed stream 2 is provided to 40 pph. The centrifuge 26 Separates methyl esters from glycerol
a first agitated-film evaporator 42 operating at a pressure of in the liquid stream 24 to produce a fuel grade biodiesel. Fatty
about 300 to 760 torr and, preferably, from about 300 to 500 acid mono-alkyl esters exit the centrifuge in a yield stream 25
torr. The evaporator 42 can include a film temperature of and glycerol in a residual stream 27.
about 370 to 390°F. Sparge media orgas such as, for example, The fatty acid methyl ester biodiesel yield comprises fatty
nitrogen or Steam are introduced to the evaporator. Preferably, 4s acids such as, for example, linoleic, Stearic, palmitic and oleic
Super heated sparge Steam is provided to the evaporator at a acids. The fuel grade biodiesel from the process in FIG. 5 can
rate of about 400 to 800 pph and temperature of about 300 to meet or exceed those specifications of ASTM D 6751. The
350°F. Heating media such as heat transfer oil is provided to process of FIG. 5 can also be a substantially continuous
the evaporator 42 to enable evaporation. In one embodiment, process. For example, the process produces a Substantially
the evaporator comprises an entrainment separator 43 asso- so continuous yield of biodiesel from such sources of oils and
ciated therewith. The vapor stream 10 passes through the fats as, for example, animal fat, waste type grease, algae and
entrainment separator 43 prior to entering the distillation vegetable oil. Such a process as shown in FIG. 5 can be
column 12. An exemplary entrainment separator can include modified so that overall production quantities and qualities of
demister type pads or short rectifying columns. methyl ester biodiesel are specific to a particular application.
The evaporator 42 substantially separates methanol and 55 For example, one type of application for the process may
water from the feed stream 2 into the vapor stream 10 by emphasize biodiesel yields rather than a biodiesel of excep
volatility. The first stream 6 departing the evaporator 42 tional quality.
includes salts, glycerol, heavies and methyl esters. As shown,
the first stream 6 is fed to a second agitated-film evaporator EXAMPLE II
44. The second evaporator 44 operates at a pressure of about 60
4 to 6 torr. The evaporator 44 can also operate at a temperature FIG. 6 also shows a representation of a process of the
of about 380 to 420 F. The second agitated-film evaporator invention for yielding biodiesel. The feed stream 2 is obtained
44 is also heated by a heat transfer media. The evaporator from a conventional esterification process. The feed stream
Substantially separates methyl esters and glycerol from the can comprise mono-alkyl esters, glycerol, alcohol, water,
first stream 6 into a vapor stream 18. Preferably, a residue 65 salts and heavies. Preferably, alcohol present in the stream 2
stream 20 separated via the evaporator 44 comprises salts and is methanol such that mono-alkyl esters are methyl esters. The
heavies. Salts are separated from the first stream 6 at about feed stream 2 includes the weight% shown in Table 2.
 US 7,528,272 B2
14
to 1.0. The condenser 48 then sends a recycle stream 50 of
TABLE 2 substantially methanol to the esterification process. The
Feed Stream Weight %
recycle stream also comprises a methanol makeup stream 52
such that the stream 50 operates at a temperature of from
Methyl Esters About 30 To 40 about 90 to 110° F. and rate of about 20,000 to 26,000 pph.
Glycerol About 1. To 5 The process of the invention can also comprise a reflux drum
Water About 1 To 2 associated with the condenser 48.
Methanol About 50 To 65
Heavies About 1 To 4 FIG. 6 shows the vapor stream 18 from the evaporator 44
Salts About 1 To 2 introduced into the distillation column36. The column 36 can
10 be operated at a pressure of about 4 to 6 torr. The column 36
Substantially separates fatty acid methyl esters from glycerol.
The feed stream 2 is introduced to the preheater means 34 at For example, methyl esters exit from the column 36 as a
a temperature from about 80 to 120 degrees F. The rate of the bottoms stream 40. The bottoms stream 40 is also sent to a
feed stream 2 is about 40,000 pph. The preheater means 34 is reboiler 58, which reboils the bottoms stream 40. A portion of
also provided with heating media in order to maintain a con 15 methyl esters exits the reboiler 58 at a temperature from about
sistent temperature. 350 to 400° F. The methyl esters yield rate is from about
The feed stream 2 is heated by the preheater means 34 to a 12,000 to 16,000. Moreover, a methyl esters yield is from
temperature from about 250 to 275° F. The feed stream 2 can about 80 to 98.5%. The fatty acid methyl esters comprise a
also be maintained at a pressure of from about 100 to 150 psi. fuel grade biodiesel.
The feed stream 2 is provided to a first agitated-film evapo The overhead vapor stream 38 of the distillation column 36
rator 42 operating at a pressure of from about 300 to 760 torr comprises glycerol. The stream 38 is introduced to a con
and, preferably, from about 300 to 500 torr. The evaporator 42 denser 60 operating at a pressure of about 4 to 6 torr and
can include a film temperature of about 370 to 390°F. Sparge temperature from about 100 to 120° F. The condenser 60
media or gas such as, for example, nitrogen or steam are provides the column 36 with reflux at a ratio of about 4.0 to
introduced to the evaporator 42. Preferably, super heated 25 8.0 and, preferably, about 5.0. Moreover, the condenser 60
sparge steam is provided to the evaporator at a rate of about provides a residual stream 27 of glycerol from about 400 to
400 to 800 pph and temperature of about 300 to 350° F. 800 pph at a temperature of about 100 to 120°F. A process of
Heating media Such as heat transfer oil is also provided to the the invention can also comprise a reflux drum associated with
evaporator 42 to enable evaporation. In one embodiment, the the condenser 60. Glycerol from the stream 27 can be used for
evaporator 42 comprises an entrainment separator 43 associ 30 any particular type of application Such as, for example, cos
ated therewith. The vapor stream 10 passes through the metic and pharmaceutical applications.
entrainment separator 43 prior to entering the distillation The fatty acid methyl ester biodiesel yield comprises fatty
column 12. An exemplary entrainment separator can include acids such as, for example, linoleic, Stearic, palmitic and oleic
demister type pads or short rectifying columns. acids. The fuel grade biodiesel from the process in FIG. 6 can
The evaporator 42 substantially separates methanol and
35 meet or exceed those specifications of ASTM D 6751. The
water from the feed stream 2 into the vapor stream 10 by process of FIG. 6 can also be a substantially continuous
volatility. The first stream 6 departing the evaporator 42 process. For example, the process produces a Substantially
includes salts, glycerol, heavies and methyl esters. As shown, continuous yield of biodiesel from such sources of oils and
the first stream 6 is provided to a second agitated-film evapo fats as, for example, animal fat, waste type grease, algae and
rator 44. A second evaporator 44 operates at a pressure of
40 vegetable oil. Such a process as shown in FIG. 6 can be
about 4 to 6 torr. The evaporator 44 can also operate at a modified so that overall production quantities and qualities of
temperature of about 380 to 420°F. The second agitated-film methyl ester biodiesel are specific to a particular application.
evaporator 44 is also heated by a heat transfer media. The For example, one type of application for the process may
evaporator Substantially separates methyl esters and glycerol emphasize biodiesel yields rather than a biodiesel of excep
from the first stream 6 into a vapor stream 18. Preferably, a tional quality.
residue stream 20 separated via the evaporator 44 comprises While the present invention has been described herein in
salts and heavies. Salts are separated from the first stream 6 at conjunction with a preferred embodiment, a person with ordi
about 400 to 800 pph. Furthermore, heavies are separated nary skill in the art, after reading the foregoing specification,
from the first stream at about 400 to 1,600 pph. can effect changes, Substitutions of equivalents and other
50 types of alterations to the process as set forth herein. Each
The distillation column 12 can be operated at a pressure of embodiment described above can also have included or incor
about 350 to 760 torr and, preferably, 300 to 500 torr. The porated therewith Such variations as disclosed in regard to any
column 12 substantially separates methanol from water. For or all of the other embodiments. Thus, it is intended that
example, water exits from the column 12 as a bottoms stream protection granted by Letter Patent hereon be limited in
16. The majority of the bottoms stream 16 can be disposed of 55 breadth and scope only by definitions contained in the
as comprising water and trace quantities of methanol. A por appended claims and any equivalents thereof.
tion from the bottoms stream is also sent to a reboiler 46,
which heats the bottoms stream 16 to a temperature of about What is claimed is:
175 to 190°F. The heated bottoms stream also comprises a 1. A process for yielding biodiesel, the process comprising:
rate of reboiling from about 800 to 1,600 pph. The stream 14 60 providing a feed stream, wherein the feed stream com
comprises methanol with about 0.2% or less of water. The rate prises mono-alkyl esters, glycerol, alcohol and salts;
of the overhead vapor stream 14 is from about 20,000 to Substantially separating alcohol of the feed stream to yield
26,000 pph. a first stream comprising mono-alkyl esters, glycerol
The overhead vapor stream 14 is then introduced into a and salts, wherein separation is by Volatility;
condenser 48 operating at a pressure from about 300 to 500 65 Substantially separating salts of the first stream to yield a
torr and temperature of about 120 to 150°F. The condenser 48 vapor stream comprising mono-alkyl esters and glyc
also provides the column 12 with reflux at a ratio of about 0.7 erol, wherein separation is by volatility; and
 US 7,528,272 B2
15 16
Substantially separating glycerol from the vapor stream to 23. A process for yielding biodiesel, the process compris
yield a biodiesel comprising mono-alkyl esters. 1ng:
2. The process of claim 1, wherein the biodiesel is fuel providing a feed stream, wherein the feed stream com
grade biodiesel. prises mono-alkyl esters, glycerol, alcohol and salts;
3. The process of claim 1, wherein mono-alkyl esters from Substantially separating alcohol of the feed stream to yield
the vapor stream are substantially condensed prior to separa a first stream comprising mono-alkyl esters, glycerol
tion from glycerol. and salts, wherein separation is by Volatility;
4. The process of claim 1, wherein mono-alkyl esters from Substantially separating salts of the first stream to yield a
the vapor stream are substantially condensed during separa vapor stream comprising mono-alkyl esters and glyc
tion from glycerol. 10 erol, wherein separation is by volatility; and
5. The process of claim 1, the process further comprising Substantially separating glycerol from the vapor stream to
prior to said step of providing: yield a liquid stream, wherein separation is by Substan
Substantially reacting triglycerides with alcohol, wherein tially condensing mono-alkyl esters.
reaction is by esterification. 15
24. The process of claim 23, wherein the liquid stream
6. The process of claim 5, wherein triglycerides are com comprises a biodiesel.
prised in a feed source selected from the group consisting of 25. The process of claim 23, wherein the liquid stream
Vegetable oil, animal fat, waste type greases and combina comprises a biodiesel, the biodiesel comprising mono-alkyl
tions thereof. esterS.
7. The process of claim 5, wherein esterification occurs in 26. The process of claim 24 or 25, wherein the biodiesel is
the presence of a catalyst. fuel grade biodiesel.
8. The process of claim 5 or 7, wherein esterification yields 27. The process of claim 23, wherein separation of mono
a product stream comprising glycerol, mono-alkyl esters, alky esters from glycerol occurs in a column.
salts and alcohol. 28. A process for yielding biodiesel, the process compris
1ng:
9. The process of claim 8, wherein the feed stream is 25
Substantially reacting triglycerides with alcohol to yield a
obtained from the product stream. feed stream comprising alcohol, glycerol, mono-alkyl
10. The of claim 7, the process further comprising: esters, water and salts, wherein reaction is by esterifica
Substantially separating water present in the feed source tion;
prior to esterification. Substantially separating alcohol and water of the feed
11. The process of claim 10, wherein separation of water is 30
by volatility. stream to yield a first stream comprising mono-alkyl
esters, glycerol and salts, wherein separation is by Vola
12. The process of claim 10, wherein separation of water tility:
occurs in an evaporator. Substantially separating salts of the first stream, to yield a
13. The process of claim 10, wherein separation of water 35 vapor stream comprising mono-alkyl esters and glyc
occurs in an agitated-film evaporator. erol, wherein separation is by volatility; and
14. The process of claim 1, wherein separation of alcohol Substantially separating glycerol from the vapor stream to
from the feed stream occurs in an evaporator. yield a biodiesel comprising mono-alkyl esters.
15. The of claim 1, wherein separation of alcohol from the 29. The process of claim 28, wherein the biodiesel is fuel
feed stream occurs in an agitated-film evaporator. 40 grade biodiesel.
16. The process of claim 1, wherein separation of salts from 30. The process of claim 28, wherein mono-alkyl esters
the feed stream occurs in an evaporator. from the vapor stream are substantially condensed prior to
17. The process of claim 1, wherein separation of salts from separation from glycerol.
the feed stream occurs in an agitated-film evaporator. 31. The process of claim 30, wherein separation of sub
18. The process of claim 1, wherein the process is substan 45 stantially condensed mono-alkyl esters is by gravity.
tially continuous. 32. The process of claim 31, wherein separation of sub
19. A process for yielding biodiesel, the process compris stantially condensed mono-alkyl esters occurs in a centrifuge.
ing: 33. The process of claim 28, wherein mono-alkyl esters
providing a feed stream, wherein the feed stream com from the vapor stream are substantially condensed during
prises mono-alkyl esters, glycerol, alcohol and salts; 50 separation from glycerol.
Substantially separating alcohol of the feed stream to yield 34. The process of claim 33, wherein mono-alkyl esters
a first stream comprising mono-alkyl esters, glycerol from the vapor stream are substantially condensed in a col
and salts, wherein separation is by Volatility; l
Substantially separating salts of the first stream to yield a 55
35. The process of claim 28, wherein separation of alcohol
vapor stream comprising mono-alkyl esters and glyc and water from the feed stream occurs in an evaporator.
erol, wherein separation is by volatility; 36. The process of claim 35, wherein separation of alcohol
Substantially condensing mono-alkyl esters and glycerol of and water from the feed stream occurs in an agitated-film
the vapor stream to yield a liquid stream; and evaporator.
Substantially separating glycerol from the liquid stream to 60 37. The process of claim 28, wherein separation of salts
yield a biodiesel comprising mono-alkyl esters. from the feed stream occurs in an evaporator.
20. The process of claim 18, wherein separation of mono 38. The process of claim 37, wherein separation of salts
alkyl esters from glycerol is by gravity. from the feed stream occurs in an agitated-film evaporator.
21. The process of claim 20, wherein separation of mono 39. The process of claim 1, wherein the process is substan
alkyl esters from glycerol occurs in a centrifuge. 65 tially continuous.
22. The process of claim 21, wherein the process is sub 40. The process of claim 28, wherein said triglycerides are
stantially continuous. from a feed source.
 US 7,528,272 B2
17 18
41. The process of claim 40, the process further compris- 43. The process of claim 42, wherein separation of water
ing: occurs in an evaporator.
Substantially separating water from the feed source prior to 44. The process of claim 42, wherein separation of water
esterification. occurs in an agitated-film evaporator.
42. The process of claim 41, wherein separation of water is 5
by volatility. k . . . .
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION

PATENT NO. : 7,528,272 B2 Page 1 of 1

APPLICATIONNO. : 1 1/235673
DATED : May 5, 2009
INVENTOR(S) : Perry Alasti
It is certified that error appears in the above-identified patent and that said Letters Patent is
hereby corrected as shown below:

Column 15, line 26, claim 10, “The of should read --The process of.-:
Column 15, line 37, claim 15, “The of should read --The process of -, and
Column 16, line 33, claim 28, “Stream, should read --Stream--.

Signed and Sealed this

First Day of December, 2009

David J. Kappos
Director of the United States Patent and Trademark Office