(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property

Organization
International Bureau
(10) International Publication Number
(43) International Publication Date WO 2014/098874 Al
26 June 2014 (26.06.2014) PO PCT

(51) International Patent Classification: (74) Agent: PUNDSACK, Scott, R.; Borden Ladner Gervais
C05F 5/00 (2006.01) C02F 3/30 (2006.01) LLP, World Exchange Plaza, 100 Queen Street, Suite
C02F 3/12 (2006.01) C05F 17/00 (2006.01) 1100, Ottawa, Ontario KIP 1J9 (CA).
C02F 3/28 (2006.01)
(81) Designated States (unless otherwise indicated, for every
(21) International Application Number: kind of national protection available): AE, AG, AL, AM,
PCT/US20 12/070992 AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY,
BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
(22) International Filing Date: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
20 December 2012 (20. 12.2012)
HN, HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP,
(25) Filing Language: English KR, KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD,
ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI,
(26) Publication Language: English NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU,
(71) Applicant: GENERAL ELECTRIC COMPANY RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ,
[US/US]; 1 River Road, Schenectady, New York 12345 TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA,
(US). ZM, ZW.

(72) Inventors: CARTHERY, JR., Luis Arnoldo; Rodovia (84) Designated States (unless otherwise indicated, for every
Raposo, Tavares 22900 Granja, 0671 1-030 Cotia (BR). kind of regional protection available): ARIPO (BW, GH,
BONKOSKI, William A.; 3239 Dundas Street West, Oak- GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,
ville, Ontario L6M 4B2 (CA). VALLERO, Marcus Vini- UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
cius Guerini; Rodovia Raposo Tavares, 22901, Cotia, Sao TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
Paulo, 0671 1-030 Sao Paulo (BR). LIMA, Fernando Car¬ EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
los Barata; Ed. Eldorado - Av. Das Nacoes Unidas 8501 1
TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
ao, 4 andar - Pinheiros, 05425-070 Sao Paulo (BR). ZA-
ML, MR, NE, SN, TD, TG).
BEU, Clayton; Rua Dr. Marcos Fiuza Silva, 46, Urbanova
- Sao Jose dos Campos - SP, 12244-853 Sao Jose dos Published:
Campos (BR). ARNTSEN, Brian; 3239 Dundas Street
— with international search report (Art. 21(3))
West, Oakville, Ontario L6M 4B2 (CA).

(54) Title: VINASSE TREATMENT FOR WATER REUSE, FERTILIZER AND BIOGAS PRODUCTION

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© 10 J
(57) Abstract: A system for treating vinasse combines an anaerobic digester (AD), a membrane bioreactor (MBR) and a salt concen
o trator such as an electrodialysis (ED) or reverse osmosis (RO) unit. The AD consumes part of the organic matter in vinasse and gen -
erates methane. Effluent from the AD is treated in the MBR to remove additional organic matter. Effluent from the MBR is treated in
the salt concentrator to separate a salt solution from the remaining effluent. The salt solution contains mineral nutrients and may be
used as a fertilizer. The remaining effluent may be re-used. The methane can be sold as a product or used as a source of power.
VINASSE TREATMENT FOR WATER REUSE. FERTILIZER AND BIQGAS PRODUCTION

BACKGROUND
[0001] Vinasse is an aqueous waste product produced while making ethanol by
fermentation. The term vinasse is often applied to waste produced when making fuel ethanol
from sugarcane. However, similar waste products are produced when making fuel ethanol
from other feedstock such as sugar beet or corn, when producing drinking alcohol, and when
making wine. In these applications, a similar waste product may be called spent wash, slop,
stillage, dunder, wet distiller's grains with solubles (WDGS) or other words. For the
purposes of this specification, the word vinasse will be used to include waste produced when
making fuel ethanol from sugarcane and other similar aqueous waste products from alcohol
production unless a specific source of the vinasse is specified.
[0002] 10 or more liters of vinasse are produced for every liter of alcohol distilled.
Vinasse has high concentrations of organic and inorganic matter. Vinasse has been applied
as fertilizer to fields near distilleries. However, the organic compounds in the vinasse
decompose on the land and create offensive odors. Further, unless vinasse is applied at a
low rate, the amount of salts provided by the vinasse is more than the plants can take up.
The soil becomes saturated over time which results in lower crop yields and, in some cases,
groundwater or surface water contamination. As distilleries continue or expand their
operations, the vinasse must be trucked longer distances to avoid saturating local fields and
the trucking costs become prohibitive. Vinasse trucking costs for an average size mill can
exceed $1000 (US) per hour of production.
[0003] The vinasse may be condensed in an evaporator to reduce trucking costs.
For example, an evaporation plant in Karnataka uses an evaporator to increase solids
concentration from 12 to about 55-60 wt%. However, the evaporator consumes energy. The
distillate has a high concentration of organic contaminants and is recycled to the fermenter.
[0004] Anaerobic treatment has been proposed as an alternative for treating stillage.
For example, a paper by R . Tomczak-Wandzel et al., "Anaerobic Treatment of Distillery
Wastewater", suggests using anaerobic digestion as a primary stillage treatment. In
laboratory experiments, an Upflow Anaerobic Sludge Blanket (UASB) reactor achieved a
90% COD removal rate.
[0005] In another approach, a plant installed by Rochem Separation Systems treats

spent wash from a molasses based distillery with a single stage reverse osmosis system.
The spent wash flow is 450 cubic meters per day and the recovery rates is 50%. This is a
very small system. In comparison, a typical fuel ethanol plant in Brazil may produce over
500 cubic meters per hour of vinasse.

INTRODUCTION TO THE INVENTION

[0006] A system for treating vinasse described in this specification combines an
anaerobic digester, a membrane bioreactor and a salt concentrator such as an
electrodialysis or reverse osmosis unit. Preferably, the anaerobic digester is placed
upstream of the membrane bioreactor which is upstream of the concentrator.
[0007] In a process described in this specification, an anaerobic digester consumes

part of the organic matter in vinasse and generates methane. Effluent from the anaerobic
digester is treated in a membrane bioreactor to remove additional organic matter. Effluent
from the membrane bioreactor is treated in a salt concentrator to separate a salt solution
from the remaining effluent. The salt solution contains mineral nutrients and may be used as
a fertilizer. The remaining effluent is well treated and may be re-used, for example for
fermentation, irrigation, cooling tower make up water or boiler feed water. The methane, or
electricity generated from the methane, may be sold as a product. Alternatively, the methane
may be used to produce power for an associated distillery or for the vinasse treatment
system.

BRIEF DESCRIPTION OF THE FIGURES

[0008] Figure 1 is a schematic process flow diagram for a vinasse treatment system.
[0009] Figure 2 is a process flow diagram of an example of a vinasse treatment
system according to a design example.

DETAILED DESCRIPTION
[0010] Figure 1 shows a vinasse treatment system 10 comprising an anaerobic
digester 12, a membrane bioreactor 14 and a salt concentrator 16.
[001 1] The anaerobic digester 12 may be in the form, for example of a continuously
stirred tank reactor (CSTR). The digester 12 may be located near a distillery, preferably near
the outlet of distillation columns where the vinasse 18 is produced. The vinasse 18 leaves
the distillation columns at about 90 degrees C . Preferably, the vinasse 18 passes through a
heat exchanger to cool it before it enters the digester 12. For example, the vinasse 18 may
be cooled to about 25 to 45 degrees C, or about 35 degrees C .
[0012] Vinasse 18 enters a covered tank of the digester 12 and is mixed with
digestate in the digester 12. The mixing may be intermittent, but is continuous in the sense
that there is mixing throughout the digestion process. The digester 12 is preferably a low
rate digester. The hydraulic residence time (HRT) of the digester 12 may be in a range of
about 15 to 25 days, for example about 20 days. Enzymes may be added to the digester 12
to improve the digestion.
[0013] The digester 12 consumes organic compounds and produces methane 20.
The methane 20 can be sold as a product, used to generate heat on site, used to generate
electricity for sale or use on site, or a combination of one or more of these uses. For
example, the methane can be burned in a combined heat and power (CHP) unit having a gas
turbine. The CHP unit creates electricity and heat for use in the vinasse treatment system 10
or an associated distillery, or for sale to an electrical grid or local heating grid.
[0014] The digester 12 retains part of the solids in the vinasse 18 and accumulates
biomass. Some of these solids are removed in a waste sludge 22 drawn from the digester
12. Optionally, solids may be removed from digester effluent 24 by a solid-liquid separation
device 26, for example a lamellar decanter, to reduce the solids level to the limits of the
membrane bioreactor 14. Separated solids 28 from the solid-liquid separation device 26 may
be mixed with the waste sludge 22 for further processing, for example de-watering and
disposal.
[0015] The digester effluent 24 is fed to the membrane bioreactor 14. The
membrane bioreactor 14 is operated aerobically and consumes organic content remaining in
the digester effluent 24. Waste activated sludge 30 generated in the membrane bioreactor
14 is preferably returned to the anaerobic digester 12. The membrane bioreactor 14 may
use, for example, immersed hollow fiber ultrafiltration or microfiltration membranes such as
ZeeWeed ™ 500 membrane units sold by GE Water and Process Technologies. The
membrane units may be immersed in an aeration tank, or in a separate membrane tank in a
recycle loop with an aeration tank. Permeate 32 may be withdrawn from the membrane units
by suction pump.
[0016] The permeate 32 is sent to the salt concentrator 16. The salt concentrator 16
separates the permeate 32 into a final effluent 36 and a concentrate 34, alternatively called
retentate or brine. The concentrate 34 is rich in potassium and may be used as a fertilizer.
Optionally, the concentrate 34 can be dried to further reduce its volume and reduce
transportation costs to fields where the concentrate 34 will be applied as fertilizer. The final
effluent 36 is high quality water suitable for re-use, although it may also be polished further if
required for specific applications. The final effluent 36 may be used, for example, as
irrigation water, in an industrial process such as cane washing, in fermentation, in a cooling
tower or for juice dilution, among other possible uses.
[0017] The salt concentrator 16 may be, for example, an electrodialysis unit. The
term electrodialyis unit is intended to include other electrically driven membrane devices
such as electrodialysis reversal units and supercapacitive desalination units. Alternatively,
the salt concentrator 16 may be a reverse osmosis or nanofiltration unit. Optionally, two or
more of these devices may be combined. For example, if the final effluent 36 is to be used
as boiler feed water, the salt concentrator 16 may be a reverse osmosis unit, or an
electrodialysis unit followed by a reverse osmosis unit, depending on the quality of the
permeate 32 produced by the membrane bioreactor 14.
[0018] The permeate 32 may be softened before it is sent to the salt concentrator 16.
Softening the permeate 32 inhibits scaling in the salt concentrator 16 and so allows for a
higher recovery rate. Softening may be done, for example, in a lime softener or by ion
exchange.
Example
[0019] Figure 2 provides a calculated design example 40 of a vinasse treatment
system 10 according to the description above. In the example 40, the salt concentrator 16 is
a reverse osmosis unit. In addition to the digester 12 and membrane bioreactor 14, there is

a lime softener 42 and a filter 44. Lime or soda ash 46 are added to the lime softener 42 or
to allow precipitates containing hardness to form in the permeate 32. A softener effluent 48
is then filtered in the filter 44 to remove the precipitates and produce softened permeate 50.
The filter 44 may be, for example, a multi-media filter, a microfiltration membrane filter or a
candle filter such as a One-Pass™ filter sold by GE Water & Process Technologies. A n acid
52 may be added to the softener effluent 48 flowing to the filter 44. Alternatively, a clarifier,
flotation device or other solid-liquid separation device may be used in place of the filter 44.
A n anti-scalant 54 may be added to the softened permeate 50. A coagulant 56 may be
added to the digester 12 and membrane bioreactor 14. Optionally, powdered activated
carbon may also be added to the membrane bioreactor 14.
[0020] Water is recovered from the waste sludge 22 and the waste activated sludge
30 such that the digester 12 and membrane bioreactor 14 operate at nearly complete liquid
recovery. Liquid separated from the waste sludge 22 and the waste activated sludge 30 is
returned to the digester 12. Recovery rates for the lime softener 42, filter 44 and salt
concentrator 16 are 93%, 98% and 78% respectively.
[0021] The vinasse 18 has a total suspended solids (TSS) concentration of about
3300 mg/L and a chemical oxygen demand (COD) of about 22000 mg/L. Both of these
concentrations are reduced by 90% in the digester 12. Digester effluent 24 has a TSS
concentration of about 330 mg/L and a COD of about 2200 mg/L. The TSS in the digester
effluent 24 is almost completely removed in the membrane bioreactor 14 such that the
permeate 32 has a TSS concentration of about 1 mg/L. COD is also removed in the
membrane bioreactor 14 to a concentration of about 90 mg/L in the permeate 32.
[0022] This written description uses examples to disclose the invention, including the
best mode, and also to enable any person skilled in the art to practice the invention, including
making and using any devices or systems and performing any incorporated methods. The
patentable scope of the invention is defined by the claims, and may include other examples
that occur to those skilled in the art. Such other examples are intended to be within the
scope of the claims if they have structural elements that do not differ from the literal language
of the claims, or if they include equivalent structural elements with insubstantial differences
from the literal languages of the claims.
CLAIMS:

1. A system for treating vinasse comprising,

a) an anaerobic digester;
b) a membrane bioreactor; and,
c) a salt concentrator.

2. The system of claim 1 wherein an inlet to the anaerobic digester is connected to a

source of vinasse, an effluent outlet from the anaerobic digester is connected to an inlet of
the membrane bioreactor, and a permeate outlet from the membrane bioreactor is connected
to an inlet of the salt concentrator.

3. The system of claim 1 or 2 wherein the salt concentrator comprises an electrodialysis

unit.

4. The system of any preceding claim wherein the salt concentrator comprises a reverse
osmosis unit.

5. The system of any preceding claim wherein the salt concentrator comprises an
electrodialysis unit followed by a reverse osmosis unit.

6. The system of any preceding claim comprising a solid-liquid separation device

between the effluent outlet of the anaerobic digester and the inlet of the membrane
bioreactor.

7. The system of any preceding claim comprising a recycle loop between from a waste
activated sludge outlet of the membrane bioreactor to the anaerobic digester.

8. The system of any preceding claim wherein the membrane bioreactor comprises an
aeration tank.

9. The system of any previous claim wherein the anaerobic digester is a continuously
stirred tank reactor.
10. A process for treating vinasse comprising,
a) digesting organic compounds in the vinasse anaerobically to produce a first
effluent;
b) digesting organic compounds in the first effluent aerobically to produce a mixed
liquor;
c) filtering the mixed liquor through an ultrafiltration or microfiltration membrane to
produce a permeate; and,
d) separating the permeate into a concentrate and a second effluent.

11. The process of claim 20 wherein step a) comprises treating the vinasse in a
continuously stirred tank reactor maintained under anaerobic conditions at a hydraulic
retention time of 15 to 25 days.

12. The process of claim 10 or 11 further comprising a step of cooling the vinasse before
step a).

13. The process of any of claims 10 to 12 further comprising removing solids from the first
effluent prior to step b).

14. The process of any of claims 10 to 13 further comprising a step of removing waste
activated sludge from the mixed liquor and mixing the waste activated sludge with the
vinasse in step a).

15. The process of any of claims 10 to 14 wherein step d) comprises treating the
permeate with an electrodialysis unit.

16. The process of any of claims 10 to 15 further comprising treating the permeate by
reverse osmosis.

17. The process of any of claims 10 to 16 wherein the vinasse is produced in a distillery
and the second effluent is returned to the distillery.
18. The process of any of claims 10 to 16 wherein the second effluent is sent to a sugar
cane processing operation.

19. The process of any of claims 10 to 18 further comprising using the concentrate as
fertilizer.
 International application No

PCT/US2012/07Q992
A . CLASSIFICATION O F SUBJECT MATTER
INV. C05F5/Q0 C02F3/12 C02F3/28 C02F3/30 C05F17/00
ADD.

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED
Minimum documentation searched (classification system followed by classification symbols)
C05F C02F

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal , WPI Data

C . DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2004/025715 A l (BONDE TORBEN [DK] ET 1,2,4,

AL) 12 February 2 4 (2004-02-12) 6-10,
12-14,
16,19
paragraph [0268]
paragraph [0309] paragraph [0311]
paragraph [0354] paragraph [0356]
paragraph [0378] paragraph [0379]
paragraph [0381]
paragraph [0384]
figures 5 ,6

US 2010/243544 A l (TAKEMURA KIY0KAZU [JP] 1,4,6,8

ET AL) 30 September 2010 (2010-09-30)
paragraph [0039]
paragraph [0040]

/ -

X Further documents are listed in the continuation of Box C . See patent family annex.

* Special categories of cited documents :

"A" document defining the general state of the art which is not considered
to be of particular relevance
"E" earlier application or patent but published o n or after the international
filing date
"L" document which may throw doubts on priority claim(s) orwhich is
cited to establish the publication date of another citation or other
special reason (as specified)
"O" document referring to a n oral disclosure, use, exhibition or other
means
"P" document published prior to the international filing date but later than
the priority date claimed
"T" later document published after the international filing date or priority
date and not in conflict with the application but cited to understand
the principle or theory underlying the invention
"X" document of particular relevance; the claimed invention cannot be
considered novel or cannot be considered to involve an inventive
step when the document is taken alone
" document of particular relevance; the claimed invention cannot be
considered to involve an inventive step when the document is
combined with one or more other such documents, such combination
being obvious to a person skilled in the art
"&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

10 September 2013 23/09/2013

Name and mailing address of the ISA/ Authorized officer

European Patent Office, P.B. 5818 Patentlaan 2
NL - 2280 HV Rijswijk
Tel. (+31-70) 340-2040,
Fax: (+31-70) 340-3016 Rodriguez Fontao, M
 International application No

PCT/US2012/07Q992
C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category * Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 2005/109694 Al (YOU HUEY-SONG [TW] ET 1 ,6-8

A L YOU HUEY SONG [TW] ET AL)
2 6 May 2005 (2005-05-26)
c l aims; f i gures

F R 2 945 039 Al (ONDEO IND SOLUTIONS [FR] ; 1-19

AIAT ANSTALT [CH] )
5 November 2010 (2010-11-05)
the whole document

EP 2 147 714 Al (MITSUBISHI RAYON ENG [JP] 1-19

MITSUBISHI RAYON CO [ P] )
2 7 January 2010 (2010-01-27)
c l aims
f i gures
 International application No
Information on patent family members
PCT/US2012/07Q992
Patent document Publication Patent family Publication
cited in search report date member(s) date

US 2004025715 Al 12-02-2004 AT 309001 T 15-11 2005

AT 448801 T 15-12 2009
AU 8175401 A 04-03 2002
AU 2001281754 B2 30-11 2006
BG 107663 A 30-01 2004
CA 2420064 Al 28-02 2002
CN 1471409 A 28- 1 2004
CN 101913926 A 15-12 2010
CZ 20030829 A3 12-11 2003
DE 60114863 Dl 15-12 2005
DE 60114863 T2 14- 09 2006
DK 1320388 T3 27- 3 2006
DK 200300205 Ul 06-08 2003
EE 200300076 A 15- 12 2004
EP 1320388 Al 25-06 2003
EP 1595551 Al 16- 1 1 2005
ES 2256280 T3 16-07 2006
HU 0303562 A2 29- 03 2004
P 2004506487 A 04-03 2004
MX PA03001611 A 01-11 2004
NO 20030833 A 22-04 2003
NZ 524883 A 25-06 2004
PL 361391 Al 04-10 2004
SI 1320388 Tl 30- 04 2006
SK 3702003 A3 03-02 2004
US 2004025715 Al 12-02 2004
O 0215945 Al 28- 02 2002

US 2010243544 Al 30-09-2010 AU 2010201168 Al 14-10-2010

CN 101844854 A 29-09-2010
EP 2236465 A2 06-10-2010
JP 5077586 B2 21-11-2012
JP 2010221195 A 07-10-2010
US 2010243544 Al 30-09-2010

US 2005109694 Al 26-05-2005 CA 2470450 Al 21--05·-2005

DE 102004019669 Al 16--06·-2005
JP 4233479 B2 04--03·-2009
JP 5213647 B2 19--06·-2013
JP 2005152878 A 16--06·-2005
JP 2009050852 A 12--03·-2009
KR 20050049311 A 25--05·-2005
T 1313187 B 11--08·-2009
US 2005109694 Al 26--05·-2005
US 2006243661 Al 02 -11--2006

FR 2945039 Al 05 -11- 2010 NONE

EP 2147714 Al 27 -01- 2010 AU 2007353014 Al 20- 11--2008

CN 101820980 A 01--09·-2010
EP 2147714 Al 27- 01--2010
US 2010200481 Al 12--08--2010
O 2008139617 Al 20- 11--2008