Rex B. DemafelisChemical Engineering

DepartmentCEAT, UPLB

June 15 2010SEARCA 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 2006Republic Act 9367

Mandates blending of biofuels

Objectives:

To reduce the Philippine’sdependence 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 Gasoline Demand*

(In Million Liters)

PEP 2007

Mandated Blend

BioethanolRequirement(In Million

Liters)

ForexSavings**

(Php Million)

A B C D = B x C

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 Blend (%)

Diesel Demand*(In Million

Liters) PEP 2007

Biodiesel Requirement (In Million

Liters)

Forex Savings**

(Php Million)

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 notlimited to distillery slops from theproduction of biofuels used as liquidfertilizer and for other agricultural purposesare considered “reuse”, and are therefore,exempt from wastewater charges under thesystem provided under Section 13 of R.A. No.9275, also known as the Philippine CleanWater 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 ?

Dilute alkali pretreatment, steam

explosion

Enzymatic

hydrolysis

Fermentation

distillation and dehydration

Cellulase

Saccharomyces

cerevisiae/

Zymomonas

mobilis

Dilute NaOH, steam

Distillery slops

Saccharafication

Starch

Sugar

Sources of Wastewater

Rice Straw

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

Graph volume ethanol requirement v.s. wastewater generation max and minimum curves

0

2000

4000

6000

8000

10000

12000

14000

2007 2008 2009 2010 2011 2012 2013 2014 2015

Bioethanol Requirement Waste Volume (LowerLimit) Waste Volume (Higher Limit)

WASTEWATER CHARACTERISTICS

Characteristic/Composition

FreshSlops

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

Chemical Composition of Distillery Slops from Molasses

(Source: Migo et al., 1993 as cited by Sison et al, n.d.).

WASTEWATER MANAGEMENT

To Solid

Storage

Bin

Effluent

Dried Solids

Primary

Settling

Pond

Blower

CO2

Scrubber

Slops

holding

Tank

Methane

Reactor

Degassing

Tank

H2S

Scrubber

Emergency

Flare

To Steam

Generating

Unit

Aeration/Secondary

Settling Pond

Ranola et al, 2008

1,139 m3 / day

Cooled slops

34,000 m3 / day Biogas

31,000 m3

Biogas / day

Sludge

Decanter

Primary

Settling Pond

CO2

Scrubber

Distilling

Column

Equalization

Pond

Recirculation

Pump

Anaerobic DigestionFor 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

P2O5/li)

100-290 10-210 9-200

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

ROXOL Presentation-2009

SLOPS TREATMENT PLANT (BIOMETHANATION)

SLOPS

FERTIGATION

TREATED SLOPS

EVAPORATION/ CONCENTTRATION

CONCENTRATED

SLOPS

UTILIZED

AS FUEL

CONDENSATES

RECYCLED

BIOGAS UTILIZED AS FUEL

METHANE CAPTURE & ZERO WASTE MANAGEMENT - ROXOL

MOLASSES

SPRAY/CONDUCTION DRYING

Alternative Wastewater Management Option Worth Considering (Conduction Dryer)

ROXOL METHANE RECOVERY PROJECT

Forced-circulation Evaporators Scraped Evaporators and Dryers

Alternative Wastewater Management Option Worth Considering (Spray Dryer)

ROXOL METHANE RECOVERY PROJECT

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

Anaerobic

Digestion

Reverse

Osmosis

Compost

Production

(160m3/day)

Fertigation

(40m3/day)Biogas

10, 000m3/day

BIOLER(Steam Prd’tn)

Permeate

200m3/day

As Process Water (cooling

& cleaning)

400m3/dayOther wastewater

1, 400m3/day

Fermentation

DISTILLERY SLOPS

UPLB BIOTECH TECHNOLOGYDistillery 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-Hold-up time: 2-3 hours

-NaOCH3 catalyst

-Packed coaslescing tank

-Efficiency > 99%

-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

Graph volume biodiesel requirement v.s. wastewater generation Max and minimum

0

200

400

600

800

1000

1200

1400

2007 2008 2009 2010 2011 2012 2013 2014 2015

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

Estimated Generation,MLi

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 WastewaterInitial Characterization

Parameter Value

BOD, ppm 35563

COD, ppm 61465

BOD/COD 0.58

pH 4.23

Oil and Grease, ppm 485

Alonzo, Movillon, Demafelis et al April 2009

Combine Acid Est. And Trans. Wastewater Treatment Results

Organic Loading Rate(mg COD/L-day)

AlkalinityMean Cumulative Gas

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 AnaerobicFixed-Film Bed Reactor)

Upflow Anaerobic Fixed-Film Reactor

Source: Manalo, Movillon, Demafelis et al April 2009

Combined Acid Esterification and Transesterification WastewaterInitial Characterization

Parameter Value

BOD, ppm 35563

COD, ppm 61465

BOD/COD 0.58

pH 4.23

Oil and Grease, ppm 485

Manalo,Movillon ,Demafelis et al April 2009

Combine Acid Est. And Trans. Wastewater Treatment Results

Organic Loading

Rate(mg COD/L-day)

Alkalinity

Mean

Cumulative Gas

Volume

COD

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 PotentialBASIS:

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

Methanol

Sodium Hydroxide

Crude Jatropha Biodiesel

Refined Jatropha Oil

Degummed Jatropha Oil

Crude Jatropha Oil

Centrifuge

Acid Esterification/ Caustic Refining Tank

Transesterification Vessel

Mixer

Dryer

Mechanical Presser

Degumming Tank

Glycerine Layer Separator

Rotary Filter 2

Rotary Filter 3

Rotary Filter 1

Jatropha Seeds

Purified Jatropha Biodiesel

Water Gums

FFA

Removal

Waste

Methanol,

Sodium

Hydroxide or

Sulfuric acid

Magnesol

or

Amberlite

Waste

Magnesol or

Amberlite

Methanol

Glycerine

Trace Magnesol

Residual Traces of

Production

Residues

Soaps and Moisture

Cake

Cake

Residue

Dry WashingInitial 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™

PARAMETER Goal Lower LimitUpper

LimitImportance Optimum

Temperature (°C) Minimize 42 66 1 42

Ratio (% wt) Minimize 1 2 1 1

Reaction

Duration (min)Minimize 20 40 1 20

Mixing Speed

(rpm)Minimize 200 400 1 200

Purity of

Biodiesel (%)Maximize 5 99.0563

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™

PARAMETER Goal Lower LimitUpper

LimitImportance Optimum

Residual

Methanol (mol)Minimize 1 3 1 1.01

Ratio (% wt) Minimize 1.75 2.25 1 1.84

Reaction

Duration (min)Minimize 30 60 1 59.4

Mixing Speed

(rpm)Minimize 200 400 1 201.63

Purity of

Biodiesel (%)Maximize 5 99.86%

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 !!