Rex B.

Demafelis
Chemical Engineering
Department
CEAT, UPLB
June 15 2010
SEARCA Drilon Hall
College, Laguna
•Biofuels Act of 2006
• Projected demand
• Incentives and support
•Wastewater Generation Potential
•Bioethanol wastewater management
•Biodiesel wastewater management
•Recommendations
TRANSPORT SECTOR
Biodiesel
Bioethanol

INDUSTRIAL SECTOR
Biogas
Biomass
 BIOFUELS ACT OF 2006
Republic Act 9367
Mandates blending of biofuels

Objectives:

 To reduce the Philippine’s

dependence on imported oil
 To increase the economic activity
in the country & boost
employment
 To mitigate Toxic and Green
House Gas Emissions
PROJECTED DEMAND
 BIOETHANOL -PEP 2007
Year Projected Mandated Bioethanol Forex
Gasoline Blend Requirement Savings**
Demand* (In Million (Php Million)
(In Liters)
Million
Liters)
PEP 2007
A B C D=BxC
2010 5,650 5% 283 20,339
2011 5,939 10% 594 21,380
2012 6,239 10% 624 22,460
2013 6,549 10% 655 23,578
2014 6,872 10% 687 24,738
2015 7,210 10% 721 25,955
PROJECTED DEMAND
 BIODIESEL - PEP2007
Year Mandated Diesel Biodiesel Forex
Blend (%) Demand* Requirement Savings**
(In Million (In Million (Php
Liters) Liters) Million)
PEP 2007
2010 2 8,653 173 5,538
2011 2 9,030 181 5,779
2012 2 9,411 188 6,023
2013 2 9,794 196 6,268
2014 2 10,122 202 6,478
2015 2 10,461 209 6,695
INCENTIVES & SUPPORT FOR BIOFUELS
PROVIDED BY THE LAW
 Provides various incentives
 Income tax holiday
 Tax and Duty-free Importation
 Zero specific tax
 Priority financing project classification\
 Exemption from waste discharge fees and
provision for reuse

 Creation of the National Biofuels Board

 WASTEWATER REUSE OPTION

All water effluents, such as, but not

limited to distillery slops from the
production of biofuels used as liquid
fertilizer and for other agricultural purposes
are considered “reuse”, and are therefore,
exempt from wastewater charges under the
system provided under Section 13 of R.A. No.
9275, also known as the Philippine Clean
Water Act.
Safeguard to Reuse Option

Provided, however, That such application shall

be in accordance with the guidelines issued
pursuant to R.A. No. 9275, subject to the
monitoring and evaluation by DENR and
approved by DA.
BIOETHANOL WASTEWATER

WHAT ARE THE TECHNOLOGIES

CURRENTLY USED IN FOOD
GRADE ETHANOL DISTILERY
WASTEWATER MANAGEMENT ?
 Sources of Wastewater
Rice Straw

Dilute NaOH, steam Dilute alkali pretreatment, steam

explosion
Cellulase
Enzymatic
Saccharomyces hydrolysis
cerevisiae/
Zymomonas
mobilis
Fermentation Sugar
Saccharafication

distillation and dehydration Distillery slops

Starch

ETHANOL
 WASTEWATER GENERATION

o Bioethanol

 10 to 18 liters distillery slops is

produced per liter ethanol

 75,000 – 120,000 mg/li COD

 Estimated Generation, MLi
14000

12000

10000

8000

6000

4000

2000

0
2007 2008 2009 2010 2011 2012 2013 2014 2015
Bioethanol Requirement Waste Volume (LowerLimit) Waste Volume (Higher Limit)

Graph volume ethanol requirement v.s. wastewater

generation max and minimum curves
WASTEWATER CHARACTERISTICS
Chemical Composition of Distillery Slops from Molasses
Characteristic/ Fresh
Composition Slops
pH 4.55
Absorbance (475 mm) 18.02
TOC (X 104 ppm) 3.18
F- (ppm) 710.00
Cl- (ppm) 3786.00
S042- (ppm) 2741.00
Na+ (ppm) 133.00
K+ (ppm) 7614.00
Ca2+ (ppm) 2746.00
Mg2+ (ppm) 384.00
Fe3+ (ppm) 74.00
Al3+ (ppm) 112.00
Total N (ppm) 1644.00
Total P (ppm) 131.00
Reducing sugars g/L 10.02
Total sugars (g/L) 16.00
(Source: Migo et al., 1993 as cited by Sison et al, n.d.).
 WASTEWATER MANAGEMENT
34,000 m3 / day Biogas

Emergency
Flare
CO
Methane CO22
Scrubber H2S
Reactor Scrubber Scrubber
Degassing
Tank
31,000 m3
Recirculation
Pump Biogas / day
To Steam
Blower Generating
Unit
Equalization
Pond

Effluent

Primary Aeration/Secondary
Primary
Settling Settling Pond
Slops Settling
Pond Pond
holding Decanter
Tank
Sludge

Dried Solids
1,139 m3 / day
Distilling Cooled slops To Solid
Column
Storage
Ranola et al, 2008 Bin
Anaerobic Digestion
For 100,000 Liters/day Ethanol

 1,139,000 Liters distillery slops

per day
 34, 000,ooo Liters3 Biogas
generated per day
 30 gas productivitity
 up to 40 % boiler fuel
substitution
BIOETHANOL WASTEWATER

WHAT ARE NEW TECHNOLOGIES

USED IN THE EMERGING FUEL
ETHANOL PRODUCTION?
PHILIPPINES’ BEST OPTION?
ANAEROBIC DIGESTION FOR THE
PRODUCTION OF BIOGAS COUPLED
WITH

 DRYING or CONCENTRATION OF SLOPS for FUEL

 COMPOSTING
 LIQUID FERTILIZATION
ROXOL Bioenergy Corp
ROXOL Bioenergy Corp
CHARACTERISTICS OF DISTILLERY STILLAGE FROM MOLASSES,
CANE JUICE & MIXED (JUICE +MOLASSES)
Chemical Data *Molasses Juice Juice + Molasses
pH 4.2-5.0 3.7-4.6 4.4 -4.6
Temperature (oC) 75-95 75-95 75-95
BOD (mg O2/li) 45,000 6,500-16,500 19,800
COD (mg O2/li) 120,000 15,000-33,000 45,000
Total Solids (mg/li) 90,500 23,700 52,700
Volatile Solids (mg/li) 65,000 20,000 40,000
Fixed Solids (mg/li) 25,500 3,700 12,700
Nitrogen (mg N/li) 450-1,600 150-700 480-710
Phosphorous (mg 100-290 10-210 9-200
P2O5/li)
Potassium (mg K2O/li) 3,740-7,830 1,200-2,100 3,340-4,600
Calcium (mg CaO/li) 450-5,180 130-1,540 1,330-4,570
Magnesium (mg MgO/li) 420-1,520 200-490 580-700
Sulphate (mg SO4/li) 6,400 600-700 3,700-3,730
Carbon (mg/li) 11,200-22,900 5,700-13,400 8,700-12,100
C/N Rate 16.0-16.27 19.7-21.07 16.4-16.43
Organic Matter (mg/li) 63,400 19,500 38,000
Reducing Matter (mg/li) 9,500 7,900 8,300

*Continuous fermentation process

 METHANE CAPTURE & ZERO WASTE MANAGEMENT - ROXOL
MOLASSES

SLOPS
UTILIZED
BIOGAS UTILIZED
AS FUEL FERTIGATION
AS FUEL

CONDENSATES
RECYCLED

SPRAY/CONDUCTION
TREATED
DRYING SLOPS
SLOPS TREATMENT PLANT
(BIOMETHANATION)
CONCENTRATED EVAPORATION/
CONCENTTRATION
SLOPS
ROXOL METHANE RECOVERY PROJECT

Alternative Wastewater Management Option

Worth Considering (Conduction Dryer)

Forced-circulation Evaporators Scraped Evaporators and Dryers

ROXOL METHANE RECOVERY PROJECT

Alternative Wastewater Management Option Worth

Considering (Spray Dryer)
 Alternative Wastewater Management
Option Worth Considering (Spray Dryer)
Final Product – Dry Vinasse Powder
San Carlos Bioenergy Inc.
San Carlos Bioenergy Inc.
Material Balance
Distillation Column
 Distillery Slops Utilization
As Process
Water (cooling
BIOLER
& cleaning)
(Steam Prd’tn)

Permeate Fertigation
Biogas 200m3/day (40m3/day)
10, 000m3/day

DISTILLERY SLOPS Anaerobic Reverse

Digestion Osmosis
400m3/day
Other wastewater
1, 400m3/day
Compost
Production
(160m3/day)
Fermentation
UPLB BIOTECH TECHNOLOGY
Distillery slops application of 200 cu m per
hectare-year ( Migo et. al .)

Basis:
65 Tons cane per hectare and
67 liters ethanol per ton cane
Slops generation volume ratio to ethanol is
12.5
Distillery slops as Fertilizer
 7,000 hectares is needed to produce 30M li per
year ethanol
 375,000 cu m slops generated
 1,875 hectares will be needed for slops fertilization
 60 hectares will be needed for slops fertigation
( San Carlos Bioenergy Incorporated)
 Area is within a 5 km radius or 27% of the total
land area requirement
CAPITAL REDUCTION FROM BIOGAS
PRODUCTION COUPLED WITH
FERTILIZATION

WASTEWATER TREATMENT PLANT

 Capital Investment Requirement- P 70M

 2.33-5% of the Total Capital Investment
BIODIESEL WASTEWATER

WHAT BIODIESEL PRODUCTION

TECHNOLOGIES CURRENTLY USED
WITH BEST WASTEWATER
MANAGEMENT OPTION ?
 Process Characteristics

LURGI Technology
Leading Global
Commercial Technology
for Biodiesel Production
 Lurgi Process
-Packed coaslescing tank
-Hold-up time: 2-3 hours
-Efficiency > 99%
-NaOCH3 catalyst
-No need for centrifuge

-Packed column
-Countercurrent

-Vacuum distillation
-Max MeOH in heavy key: 3% w/w
CHEMREZ TECHNOLOGIES
WASTEWATER PROBLEM ?
 VILLAGE SCALE BIODIESEL PRODUCTION SYSTEM

 SMALL BIODIESEL PRODUCTION SYSTEM

 BATCH BIODIESEL PRODUCTION SYSTEM

 Sources of Wastewater
Oil

Biodiesel
 WASTEWATER GENERATION
o Village Scale Biodiesel Production

Up to 6 liters wastewater per liter

biodiesel

60,000 mg/li COD

 Estimated Generation,MLi
1400

1200

1000

800

600

400

200

0
2007 2008 2009 2010 2011 2012 2013 2014 2015

Biodiesel Requirement Waste Volume (lower limit) Waste Volume (higher Limit)

Graph volume biodiesel requirement v.s. wastewater

generation Max and minimum
ANAEROBIC DIGESTION
No literature on biogas digestion of biodiesel wastewater

UPLB Preliminary work on Treatability

( Demafelis , R. B. et al)

 Methane increases with OLR up to 2,500 mg/l-d

 55.84 % methane
Characterization and Treatment

Combined Wastewater
from Acid Esterification
and Transesterification
(Upflow Filter Bed
Reactor)
Upflow Filter Bed Reactor

Source: Alonzo, Movillon, Demafelis et al, April 2009

Combined Acid Esterification and
Transesterification Wastewater
Initial Characterization Alonzo, Movillon, Demafelis et al April 2009

Parameter Value
BOD, ppm 35563
COD, ppm 61465
BOD/COD 0.58
pH 4.23
Oil and Grease, ppm 485
Combine Acid Est. And Trans.
Wastewater Treatment Results
Organic Loading Rate Mean Cumulative Gas
Alkalinity
(mg COD/L-day) Volume

Control
1000 1685.5 – 1798.8 63.5 – 496.8
800 1356.4 – 1574.8 0 – 747.2
1200 (pH=7.0) 991.2 – 1121.4 102.5 – 880.5
1200 (pH=7.4) 751 – 1098.5 129 – 969.5
Filter Bed Reactor
1000 2267.5 – 2698.2 0 – 386.5
800 1236.1 – 1831.6 0 – 800.2
1200 (pH=7.0) 881.1 – 862.7 129 – 1135.5
1200 (pH=7.4) 660.8 – 734.2 265 – 1093.9

Source: Alonzo, Movillon, Demafelis et al April 2009

Characterization and Treatment

Combined Wastewater
from Acid Esterification
and Transesterification
(Upflow Anaerobic
Fixed-Film Bed Reactor)
 Upflow Anaerobic
Fixed-Film Reactor

Source: Manalo, Movillon, Demafelis et al April 2009

Combined Acid Esterification and
Transesterification Wastewater
Initial Characterization Manalo,Movillon ,Demafelis et al April 2009

Parameter Value
BOD, ppm 35563
COD, ppm 61465
BOD/COD 0.58
pH 4.23
Oil and Grease, ppm 485
Combine Acid Est. And Trans.
Wastewater Treatment Results
Organic Loading Mean
Rate Alkalinity Cumulative Gas COD
(mg COD/L-day) Volume
Control
1000 986.4 – 1884.5 0 – 795.5 3469.7 – 4478.4
800 734.2 – 963.1 795.5 – 2536.5 2692.2 – 4512
1200 (pH=7.0) 587.4 – 835.2 2671.5 – 4405.5 2884.8 - 4126.5
1200 (pH=7.4) 477.2 – 541.5 4822.5 – 6414.5 2841.3 – 6137.1
Filter Bed Reactor
1000 1237.6 – 1970.1 0 – 571.5 2868.7 – 7200
800 1156.4 – 1340.5 747.5 – 2950.5 954 – 4960
1200 (pH=7.0) 853.5 – 1110.5 3178.5 – 5975.5 688.2 – 1296.9
1200 (pH=7.4) 587.4 – 761.7 6353.5 – 8208.5 802.9 – 2159.4

Source: Manalo, Movillon, Demafelis et al April 2009

 Biogas Potential
BASIS:
For a 1,000 li per day village scale production system

REQUIREMENT
75 ,000 liter biogas reactor ( min )
Php 2.4M TCI

INCOME
Php 0.8 M Total Annual Income
DRY WASHING TECHNOLOGY
Purification of biodiesel using dry
washing

UPLB Research works on Dry Washing

( Demafelis , R. B. et al)

 Using Magnesol
 Using Amberlite
 DRY WASHING
Jatropha Seeds

Methanol
Sodium Hydroxide
Residue

Mechanical Presser
Transesterification Vessel

Crude Jatropha Oil Crude Jatropha Biodiesel

Glycerine
Cake

Glycerine Layer Separator

Centrifuge

Methanol
Cake

Dryer

Rotary Filter 1

Magnesol
or
Amberlite
Water Gums

Mixer

Degumming Tank
Waste
Degummed Jatropha Oil Magnesol or
Amberlite

Methanol, Rotary Filter 2

FFA
Sodium
Removal Trace Magnesol
Hydroxide or
Waste Residual Traces of
Sulfuric acid
Production
Residues
Soaps and Moisture
Acid Esterification/ Caustic Refining Tank
Rotary Filter 3
Refined Jatropha Oil

Purified Jatropha Biodiesel

Dry Washing
Initial Characterization of unwashed
Jatropha curcas L. biodiesel

Component %(wt)
Jatropha Methyl Ester 95.7194

SOURCE:Gelasin,,Demafelis et al April 2010

 Magnesol™ Properties
 synthetic magnesium silicate
 fine, white, powder
 used in some industrial plants for biodiesel
purification
 high affinity to polar compounds
(e.g. excess methanol, free glycerin, glycerides, metal
contaniminants, free fatty acids, and soap)
 Optimized Dry Washing
Using Magnesol™
Upper
PARAMETER Goal Lower Limit
Limit
Importance Optimum

Temperature (°C) Minimize 42 66 1 42

Ratio (% wt) Minimize 1 2 1 1

Reaction
Minimize 20 40 1 20
Duration (min)

Mixing Speed
Minimize 200 400 1 200
(rpm)

Purity of
Maximize 5 99.0563
Biodiesel (%)

SOURCE: Gelasin, Demafelis et al April 2010

 Amberlite™ Properties
 a type of ion exchange resin
 effective in removing both soap and glycerine
 absorbs impurities
(e.g. excess water, glycerol, KOH-catalyst)
 How ever it does not remove methanol, which is very
essential to maximize its recovery
 Optimized Dry Washing
Using Amberlite™
Upper
PARAMETER Goal Lower Limit
Limit
Importance Optimum

Residual
Minimize 1 3 1 1.01
Methanol (mol)

Ratio (% wt) Minimize 1.75 2.25 1 1.84

Reaction
Minimize 30 60 1 59.4
Duration (min)

Mixing Speed
Minimize 200 400 1 201.63
(rpm)

Purity of
Maximize 5 99.86%
Biodiesel (%)

SOURCE: Roma, Demafelis et al, April 2010

RECOMMENDATIONS
FINANCIAL AND POLICY SUPPORT

 R and D on energy recovery from biodiesel

wastewater
 R and D on reused options for biodiesel
wastewater
 R and D on waste minimization in the
pretreatment stage
 R and D on production of high value
products from wastewater
END OF PRESENTATION

THANK YOU VERY MUCH !!