Biodiesel

Ion Exchange in
Biodiesel Production

Prepared by
Terrence Heller
Purolite Company

Page 1
 Purolite® for Biodiesel Purification

Resins used in Biodiesel Production

Catalysis
Strong Acid Resin for Esterification of Fatty Acids (Developing)
Strong Basic resins for trans-esterification (Not efficient)
Biodiesel Purification
Absorption of
Free Glycerin
Waters and Methanol
Ion Exchange of Salts, Soaps and Catalyst
Glycerin Purification
Chromatographic separation of salts (Not used at this time)
Color and ash removal (Not used at this time)
Page 2
 Trans-Esterification

Transesterification Converts Triglyceride (animal of vegetable oils)

Soybean to Methyl-ester (BIODIESEL)
Canola
CH2 – OCOR1
Palm CH2 –OH
R1 – COOCH3
Rape seed
Jatropha CH – OCOR2
+ CH3 OH R2 – COOCH3
+ CH –OH
Sunflower Methylate R3 – COOCH3
Coconut CH2 – OCOR3 CH2 –OH

Used Triglyceride Methanol Catalyst Biodiesel Free Glycerin

cooking
(Methyl Esters)
Animal fats

• Temperatures of 60-70 oC (140-160 oF), at atmospheric pressure

• Temperatures of 60-70 oC (140-160 oF), at atmospheric pressure
• •Crude
Crudeglycerin
glycerinand
andcrude
crudebiodiesel
biodieselare
areseparated
separated

Page 3
 Purolite® PD206 Advantages
Purolite PD206 Water Wash
Operating Cost Reported cost $0.08/gal
$0.014/gal ($0.021/litre)
($0.0037/litre) for water and disposal
Medium to High maintenance
Low maintenance dry system Multiple washes, difficulty
attaining < 500 ppm water
No need to filter Minimal filtration still
necessary
Low energy High pumping and drying
energy
No waste disposal costs Waste water treatment or
water disposal issues
No water required Several water wash stages
required.
Page 4
Inorganic Anhydrous Salts
Reported cost $0.12+ /gal
($0.032/litre)
due to filter equipment needed
High maintenance replacing
filters and removing sludge
Heavy Filtration needed
Medium energy to circulate, settle
and filter solids
Disposal costs for spent media
plus fire hazard
No water required
 General Technical Data
PUROLITE® PD 206
PHYSICAL AND CHEMICAL PROPERTIES

Appearance Hard spherical beads

Functional R-SO-3
Group
Ionic form (as H+
shipped)
Moisture <3 %
Holding
Capacity
Bulk Density 800-830 g/dm3 (litre)
(48-50 lbs/ft3)

Specific Gravity 1.20

Chemical Insoluble in all

Resistance common solvents
Operating <150 ºC (<300 ºF)
Temperature
Page 5
 Purolite® PD206 functions

CH2 –OH
CH3OH
CH –OH
O
CH2 –OH
S O H+
O Absorption
H20

Soap
and
Na-OCH3 O
O
+ CH3OH +
S O S O Na+
FFA
H-OCH3 & FFA O
O

Ion Exchange
Page 6
 Purification Towers

Lead Vessel Lag Vessel Final Polishing

PUROLITE® PUROLITE® PUROLITE® Evacuation

Evacuation Evacuation
Port
PD206 Port PD206 Port PD206

Purified
Crude B100
Biodiesel

OPERATING
OPERATINGINFORMATION
INFORMATION
Freeboard >150%
Freeboard >150%
Flow
Flowrates 2.5-3.0
rates 2.5-3.0BV/h
BV/h
o
Temperature Ambient C (140 oF)
Temperature Ambienttoto60
60o C (140 oF) Page 7
Minimum
Minimumbed
beddepth 60cm
depth 60cm(24
(24inches)
inches)
Screen
Screensize <150
size <150microns
microns
 Polish before demethylation
Feeds Final De-methylation
Polishing Storage
Purolite
PD206

Phase
Trans-esterification
Separation
Vegetable Oils
Or Animal fats, Biodiesel
Catalyst & (Methyl Ester)
Methanol

Methanol
Removal
Glycerin
Neutralization
Glycerin
Crude
Glycerol Purification and refining
Methanol Storage

Page 8
 Polish after Demethylation
Final
Feeds De-methylation
polishing
Purolite
Storage PD206

Phase
Trans-esterification
Separation
Vegetable Oils
Or Animal fats, Biodiesel
Catalyst & (Methyl Ester)
Methanol

Glycerin
Methanol
Neutralization
Removal

Glycerin
Crude
Glycerol Purification and refining
Methanol Storage

Page 9
 Operating Cost for Purolite® PD206

Polishing Vessels Before Demethylation

Influent glycerin is commonly 2000ppm (0.2%)
Lead tower
Washed with Methanol every 5-6 days
Replaced with new or regenerated resin every 2-3 months
Attrition is <5-15% due to handling
Capacity loss negligible
Resin life estimated 5-7 years.
Operating cost will be $.014/gal ($0.0037/litre) biodiesel using
regenerated PD206

Polishing Vessels After Demethylation

No Methanol washing only replacement of resin due to flashpoint
criteria
Columns in final position after Demethylation has been reported to
cost greater than $0.10/gal ($.026/L)
Page 10
 Methanol Wash removes free Glycerin
Cleaned Vessel Glycerin Removal Glycerin Removal
In Stand-by Lead Vessel Lag Vessel

Methanol Service Flow

Wash
Flow

PUROLITE® PUROLITE® PUROLITE®

PD206 PD206
Methanol
PD206
Strip

Heat
to > 70 0C
To Reactor (>160 0F)

Vessel Operation
Vessel Operation
• Lead Vessel washed with methanol to remove glycerin at breakthrough
• Lead Vessel washed with methanol to remove glycerin at breakthrough
• After methanol wash lag vessel moves to lead position To Storage
• After methanol wash lag vessel moves to lead position
• Methanol and glycerin are returned and used in the Transesterification process
• Methanol and glycerin are returned and used in the Transesterification process
•Catalyst loading on PD206 will reduce its holding capacity for free glycerin.
•Catalyst loading on PD206 will reduce its holding capacity for free glycerin.
•Ionic exhaustion of resin is indicated by elevated sodium or pH inPage
the11
biodiesel.
•Ionic exhaustion of resin is indicated by elevated sodium or pH in the biodiesel.
•Exhausted resin should be removed from the vessel and replaced with new or regenerated
•Exhausted resin should be removed from the vessel and replaced with new or regenerated
Purolite PD206
Purolite PD206
 Washing Glycerin from Resin
Service Cycle - IN MeOH Wash Cycle - IN
Biodiesel with Dry MeOH
trace Glycerin

PUROLITE® Evacuation
PD206 Port

Service Cycle- OUT MeOH Wash Cycle - IN

Biodiesel “FREE” of MeOH + Glycerin
Glycerin and catalyst
goes to demethylation To MeOH stripping or
Transesterification
After several methanol washes Purolite PD206 will
After several methanol washes Purolite PD206 will
exhaust
exhaustononSodium
Sodiumand
andwill
willno
nolonger
longerremove
removetrace
trace
soaps and catalyst. The resin is either disposed of or Page 12
soaps and catalyst. The resin is either disposed of or
regenerated
regenerated
 H+ form vs. Na+ Form Resin
Property H+ Form
Viscosity of glycerin Reduces viscosity for better
absorption into the bead
Catalyst removal Absorption with glycerin
then ion exchanges in bead
MeOH requirement for 2-3 BV for 95% free glycerin
washing removal
MeOH wash frequency Approx 3-5 days depending
on glycerin loading
H+ Regeneration Approximately 3-6 months
to restore performance
Capacity .4-.6 g Free Glycerin / g dry
PD206
Process downtime good
Page 13
Na+ Form
High Viscosity glycerin
absorbs on resin surface
Absorption only with free
glycerin
4 BV suggested due to thicker
glycerin
For similar sized towers
Approx. twice as often as H+
form resin
None
.1-.1.5 g FG / g Wet resin
Fair
 Meet ASTM / EN
Specifications

Before After
Turbidity high Turbidity low
Glycerin .05 - .4% Glycerin .001 - .01% (ASTM .02%)
Water .05% Water .002% (ASTM .05%)

Methanol 1-5% Methanol 1-5% no change

Before After
Catalyst 25-300 mg/kg PD206 PD206 Catalyst <2 mg/kg
Soap .1 - 3.0 mgKOH/g TAN = Soap (ASTM .5 mg KOH/g)

Page 14
 Returning Resin for Regeneration

When PD206 exhausts with catalyst of soap functional sites

are converted to Na of K.
Conversion back to H form not possible at plant
Where regeneration facilities are convenient as in the eastern
USA resin can be returned to Purolite and convert to H form
This reduces operating cost by approx 25%
Reduces solid waste generation
Resins can be used several years with negligible lose of
operating capacity
No solid or liquid waste disposed at the plant.
Shipping used resin requires flamable solid placard.
Page 15
 Summary / Status
Ion Exchange is a prominent component for purification of
Biodiesel
Primarily for Dry polishing Process
Best application is free glycerin removal before demethylation
A 3 tower lead lag application is most effective
Methanol wash will extend operating life of resin and reduce cost
Catalyst removal is achiever with resin polishing before and after
demethylation
Regeneration offered (USA and Canada)
reduce waste resin
Purolite recognized as a full service supplier
Handling and shipping details must be followed
Green Technology reduces demand on petroleum based raw
materials
Page 16