Biodiesel and Glycerine Purification With Lewatit GF-Resins

1 22 April 2008

Lewatit® Ion Exchange Resins

Tailor-made solutions forGreenFuels production

2 22 April 2008

Lewatit®

iex resins

Pure biodiesel & glycerine with Lewatit® ion exchange resins

Pure BiodieselPure BiodieselPure GlycerinePure Glycerine

3 22 April 2008

The Lewatit® GreenFuels product line for biodiesel / glycerine

Polisher, anion removal, decolorizationGF 505

Polisher, cation removalGF 404

Separation of salts from glycerineGF 303

Adsorber for glycerine, soaps, salts, water, MeOHGF 202

Esterification catalyst for FFA removal from triglyceridesGF 101

4 22 April 2008

Biodiesel and glycerine purification with Lewatit GF-Resins

Transesterification

FFA

Glycerine+ salts

GF 303(salts remova)

GF 101(esterification)

GF 404(polishing)

GF 505(polishing)

Pure Glycerine

FAMEFAME

TriglyceridesTriglycerides

BiodieselBiodiesel+ impurities+ impurities

GF 202(purification) Pure biodieselPure biodiesel

GF 101(FFA removal)

Glycerine+ soap Acid Split

5 22 April 2008

Biodiesel molecular structure

Major fatty acid methyl ester components of biodiesel

O

OCH3

Methyl linoleate

O

O CH3

Methyl palmitate

O

O CH3

Methyl oleate

6 22 April 2008

High viscosityPoor combustion

PalmRape seedSoyabeanSunflower

CanolaCoconut Jatropha

Used cookingAnimal fats

Conversion

Low viscosityGood combustion

Raw oil sources for biodiesel production

Oil types

BiodieselBiodiesel

7 22 April 2008

Triglycerides

Fatty-Acids:

Micelles, phospholipids, proteins, mineral salts Others:

> 95%

0.1- 5%

< 1%

Raw oils chemical composition

O

O

O

O

O

O

O

OH

8 22 April 2008

Property ASTM Limits UnitsFlash point 93 100 min. °CWater sediment 2709 0.05 max. vol. %Carbon residue 4530 0.050 max. w t. %Kin. viscosity 40°C 445 1.9 - 6.0 mm²/sec.Sulfur 5453 0.05 max. w t. %Cetane 613 40 min.Cloud point 2500 by customer °CCopper corrosion 130 No 3 max.Acid number 664 0.08 max. mg KOH/gSulfated ash 874 0.020 max. w t. %Free glycerine 6584 0.020 max. w t. %Total glycerine 6584 0.240 max. w t. %

Biodiesel quality standards ASTM

9 22 April 2008

Property Limits Units Test methodFlash point > 101 °C ISO CD 3679eWater content 500 mg/kg EN ISO 12937Alkali metals 5 max. mg/kg pr EN 14108Viscosity 40°C 3.5 - 5.0 mm²/sec. EN ISO 3104Sulfur 10 max. mg/kgCetane 51 min. EN ISO 5165Acid number 0.5 max. mg KOH/g pr EN 14104Sulfated ash 0.02 max. % (m/m) ISO 3987Free glycerine 0.02 max. %(m/m) pr EN 14105Monoglycerides 0.8 max %(m/m)Diglycerides 0.2 max. %(m/m)Triglycerides 0.2 max. %(m/m) pr EN 14105Total glycerine 0.25 max. w t. % pr EN 141101Methanol content 0.2 max. %(m/m)

Biodiesel quality standards Europe: EN 14214 *

* As specified for BD from rape seed oil (not all specs. listed)

10 22 April 2008

Degumming, cleaning of triglycerides

Raw Triglycerides

Phosphoric acid

Heat

Centrifuge I

Phosphatide waste

Centrifuge II

Water

Pure Triglycerides

Filter

Bleaching earth

11 22 April 2008

Purified Triglycerides

Recommended purity> 95%

OCH3

O

OHHO OH

Biodiesel phase

Glycerine phase

Transesterification catalyst CH3OH

Triglyceride transesterification

Top Layer

Bottom Layer

O

O

O

O

O

O

12 22 April 2008

Transesterification catalysts

The most commonly used transesterification catalysts are NaOH, KOH and their methanolicalkoxides NaOCH3, KOCH3.

Currently >90% of all large scale industrial plants world-wide use alkoxide catalysts:

• Reduced soap formation

• Better separation of glycerine and biodiesel phases.

• Good drying agents

The most commonly used transesterification catalysts are NaOH, KOH and their methanolicalkoxides NaOCH3, KOCH3.

Currently >90% of all large scale industrial plants world-wide use alkoxide catalysts:

• Reduced soap formation

• Better separation of glycerine and biodiesel phases.

• Good drying agents

13 22 April 2008

• NaOH, KOH react with FFA to form soap + water• Additional soap is formed by the OH-catalysed hydrolysis of ester• NaOH, KOH double the formation of soap relative to NaOMe, KOMe

• NaOH, KOH react with FFA to form soap + water• Additional soap is formed by the OH-catalysed hydrolysis of ester• NaOH, KOH double the formation of soap relative to NaOMe, KOMe

Enhanced soap formation with NaOH / KOH

FFAOH

O

NaOH

ONa

O

Soap

+

H2O +

OCH3

O

+

OH-

ONa

O

Soap

H2O

CH3OH +

FAME

14 22 April 2008

FFAOH

O

NaOCH3

With alkoxides, soaps are only formed by neutralisation of FFA:With alkoxides, soaps are only formed by neutralisation of FFA:

ONa

O

Soap

+

+

Reduced soap formation with alkoxides

CH3OH

In order to reduce alkoxide catalyst costs, Lewatit GF 101 can be utilised to effectively eliminate FFA from the triglyceride feedstocks.

In order to reduce alkoxide catalyst costs, Lewatit GF 101 can be utilised to effectively eliminate FFA from the triglyceride feedstocks.

15 22 April 2008

Free fatty acid (FFA*)

1 – 100%

OH

O

HOCH3

H2O

OCH3

O

Fatty acid methyl ester(FAME)

+

+

GF 101

Esterification of free fatty acids with catalyst Lewatit® GF 101

*The FFA feeds must be degummed and cleaned prior to passage through the GF 101*The FFA feeds must be degummed and cleaned prior to passage through the GF 101

16 22 April 2008

Transesterification

FFA

Glycerine+ salts



GF 404(polishing)

GF 505(polishing)

Pure Glycerine

FAME

Triglycerides



GF 101(FFA removal)



17 22 April 2008

Design for an 8,000 to/a esterification unit for

reduction of free fatty acids (FFA´s) from triglycerideswith

Catalyst Lewatit GF 101

Design for an 8,000 to/a esterification unit for

reduction of free fatty acids (FFA´s) from triglycerideswith

Catalyst Lewatit GF 101GF 101

FFA conversion

3 yearsCatalyst lifetime

Oil feed (kg/h)

900 kg / h (upflow)Oil + MeOH feed

Triglycerides with FFA´sOil-Feed

MeOH feed (kg/h)

FFA content in oil

90-110°CTemperature

4.0 m Bed depth

1.0 m Diameter

3.0 m3 Resin volume:


250

650

95%

10-50%

350

600

95%

50-100%

200

700

95%

1-10%

Upflow operation preventsbed plugging and enables long catalyst life

Upflow operation preventsbed plugging and enables long catalyst life

Industrial applications Pilot plants

18 22 April 2008


Prior to the esterification step it is recommendable to include a guard bed with GF 101 forremoval of any potential cationic and amine catalyst poisons, especially in conjunction withused oils from the foodstuffs industries.

Guard bed sizing: 20-30% of the resin volume in the esterification reactorBed height: 2 mReplacement: 6-9 monthly intervals (once-use / non-regeneration resin)

Prior to the esterification step it is recommendable to include a guard bed with GF 101 forremoval of any potential cationic and amine catalyst poisons, especially in conjunction withused oils from the foodstuffs industries.

Guard bed sizing: 20-30% of the resin volume in the esterification reactorBed height: 2 mReplacement: 6-9 monthly intervals (once-use / non-regeneration resin)

Triglyceride + FFA

MeOH

Triglyceride + FFA-Methyl ester

Guard - bed Esterification reactor

19 22 April 2008

• Lewatit GF 202 removes glycerine, soaps, waxes, salts, water, methanol.

• It can replace the conventional water-wash, eliminate costly water stripping

and reduce investment and operating costs.

• Lewatit GF 202 removes glycerine, soaps, waxes, salts, water, methanol.

• It can replace the conventional water-wash, eliminate costly water stripping

and reduce investment and operating costs.

Biodiesel purification with Lewatit® GF 202

20 22 April 2008

• Fulfills the stringent specification requirements of the fuel industries

• One liter of GF 202 will typically purify 10 tons biodiesel / year

• Regenerable, long resin lifetimes

• Can be retrofitted into existing plants using water-wash

• All biodiesel qualities irrespective of the triglyceride source can be treated

• Usable in plants ranging from 100 1,000,000 to/a

• The most cost-effective resin-based purification system in the market

• Fulfills the stringent specification requirements of the fuel industries

• One liter of GF 202 will typically purify 10 tons biodiesel / year

• Regenerable, long resin lifetimes

• Can be retrofitted into existing plants using water-wash

• All biodiesel qualities irrespective of the triglyceride source can be treated

• Usable in plants ranging from 100 1,000,000 to/a

• The most cost-effective resin-based purification system in the market

Features of Lewatit® GF 202 in biodiesel purification

21 22 April 2008

Transesterification

FFA

Glycerine+ salts



GF 404(polishing)

GF 505(polishing)

Pure Glycerine

FAMEFAME




GF 101(FFA removal)


Biodiesel purification with Lewatit® GF 202

22 22 April 2008

Glycerine +Salts

Transesterification

Low-acidtriglycerides

MeOH MeONa HCl

Separation

MeOH +Gly. + salts

Water +Glycerine +

Salts

Water

Water strip

Puremethyl esters

(Biodiesel)

BaynoxAntioxidant

Water wash

Water strip

MeO

H Strip

Raw oils withfree fatty acids

Esterification Methyl ester phase

Glycerine phase

Glycerine purification

Classical biodiesel production process

MeO

H Strip

23 22 April 2008

Adsorption / desorption

Puremethyl esters

(biodiesel)

Transesterification

Glycerine +Salts

MeOH MeONa

Separation

MeOH +glycerine

Methyl ester phase

Glycerine phase

BaynoxAntioxidant

MeO

H Strip

Lewatit GF 202

Glycerine purification

Esterification

Raw oils withfree fatty acids

Low-acidtriglycerides

Lewatit GF 303, 404, 505

HCl

Purification with Lewatit® GF 202

MeO

H Strip

24 22 April 2008

Water w

ash

Water +glycerine +

salts

Water

Water strip

Water strip

Purification with water wash Purification with Lewatit® GF 202

One column of resincompletely replaces the water washing system!!

Lewatit® GF 202 vs water wash

Glycerine adsorption / desorption

25 22 April 2008

Purification with water washPurification with water wash Purification with Lewatit GF 202Purification with Lewatit GF 202

Lewatit® GF 202 vs water wash

Many biodiesel plants already use NaOCH3 for transesterification, i.e. the streams are already very dry.

Water efficiently removes impurities but needs tobe stripped down down to <500 ppm in thepurified biodiesel.

In classical biodiesel plants, dry streams arewetted and redried at subtantial cost.

Many biodiesel plants already use NaOCH3 for transesterification, i.e. the streams are already very dry.

Water efficiently removes impurities but needs tobe stripped down down to <500 ppm in thepurified biodiesel.

In classical biodiesel plants, dry streams arewetted and redried at subtantial cost.

With GF 202, dry biodiesel streams remaindry.

Only methanol is required as a washingagent to regenerate the resin. The washingeffluent is recycled to the transesterification.

With GF 202, dry biodiesel streams remaindry.

Only methanol is required as a washingagent to regenerate the resin. The washingeffluent is recycled to the transesterification.

26 22 April 2008

Mechanism of glycerine adsorption

GF 202 SO

OO

Glycerine

OH

OHOH

OH

OH

OH

OH

OH

OH

Na+

Hydrogen bonding

Dry Lewatit GF 202 is hygroscopic and strongly hydrogen-bonds to alcohols and water.

Glycerine is a polar tri-alcohol and is very efficiently removed from low polarity biodiesel esters.

Dry Lewatit GF 202 is hygroscopic and strongly hydrogen-bonds to alcohols and water.

Glycerine is a polar tri-alcohol and is very efficiently removed from low polarity biodiesel esters.

27 22 April 2008

GF 202

Glycerine layer

Mechanism of salts and soaps adsorption on GF202

Typical impurities in raw BD to resin (MeOH-stripped)

conc. (ppm)Glycerine < 1500Soaps < 500Water < 500MeOH < 1000Salts < 1000

K+

Na+

Ca++

Mg++

SO42-

Cl-

-O2C

-O2C

H2O

MeOH

The glycerine layer on the GF 202 adsorbs polar and ionic impurities.Impurities are not as efficiently adsorbed if no glycerine is present.

28 22 April 2008

Important notice

Prior to passage through GF 202, the ester phase should

not be pretreated

to remove the glycerine, either by water wash, dry resins,

or inorganic filtration media.

The presence of glycerine is essential for the adsorption of soaps and salts!!

Mechanism of salts and soaps adsorption on GF202

29 22 April 2008

Adsorption of glycerine & soaps from rape seed biodiesel at 2 BV/h, 28°CAdsorption of glycerine & soaps from rape seed biodiesel at 2 BV/h, 28°C

0

100

200

300

400

500

600

700

800

5 10 15 20 25 30 35Bed volumes biodiesel from rape seed oil

ppm

glycerine inletsoaps inletglycerine outletsoaps outlet

Plant operating data for Lewatit® GF 202

30 22 April 2008

Biodiesel phase

clean

Glycerine phase+

High concentrations ofionic impurities + soaps

Biodiesel phase+

Small concentrations ofionic impurities + soaps

GF 202+

Glycerine phase+

High concentrations ofionic impurities + soaps

Transesterificationphase separation

Transesterificationphase separation

Capture of ionic impurities on glycerine phase of GF 202

Capture of ionic impurities on glycerine phase of GF 202

Impurities adsorption in glycerine

31 22 April 2008

GF 202 “sponge-structure“

Monodisperse bead sizing, hexagonal closest packing

Structure of Lewatit® GF 202

32 22 April 2008

Alternate loading and regeneration

Biodiesel + glycerine Washing with dry MeOH

Purified biodiesel MeOH + glycerine (+ water traces*)

• MeOH is either recycled to the transesterification reactor, the MeOH storage tank, or a MeOH strip column, depending on the water concentration in the effluent from Lewatit GF 202

The water concentration is dependent on whether NaOMe or NaOH / KOH is used in the transesterification (ref. following slides)

• The MeOH regeneration is effectively cost neutral !!

• MeOH is either recycled to the transesterification reactor, the MeOH storage tank, or a MeOH strip column, depending on the water concentration in the effluent from Lewatit GF 202

The water concentration is dependent on whether NaOMe or NaOH / KOH is used in the transesterification (ref. following slides)

• The MeOH regeneration is effectively cost neutral !!

LewatitGF 202

Application mode of Lewatit® GF 202

The feed must be MeOH-stripped!!

33 22 April 2008

MeOH +

glycerine +

salts & soaps

Methanol

GF 202+

glycerine +

salts & soaps

GF 202

clean

Regeneration / cleaning with methanol

Methanol

Raw oils

Transesterification

34 22 April 2008

• Fresh GF 202 is water-wet and needs to be preconditioned by drying with 3-4 bed volumes MeOH at 2BV/h. The MeOH is then drained and the biodieselpassed into the reactor. Before the MeOH wash, thebiodiesel is also drained.

• (If required, GF202 can be delivered predried!!)

• After preconditioning, GF 202 is only subjected to alternate MeOH / biodiesel treatments and neverwashed with water.

• 100% bed volume water-wet, shrinks to 95% in MeOH,further shrinks to 90% in biodiesel + glycerine

• Fresh GF 202 is water-wet and needs to be preconditioned by drying with 3-4 bed volumes MeOH at 2BV/h. The MeOH is then drained and the biodieselpassed into the reactor. Before the MeOH wash, thebiodiesel is also drained.

• (If required, GF202 can be delivered predried!!)

• After preconditioning, GF 202 is only subjected to alternate MeOH / biodiesel treatments and neverwashed with water.

• 100% bed volume water-wet, shrinks to 95% in MeOH,further shrinks to 90% in biodiesel + glycerine

Preconditioning of GF 202Preconditioning of GF 202

Operating conditions

Refined biodieselRefined biodiesel

Lewatit®

GF 202

Raw BD (MeOH-stripped)

Impurities Typical conc. (ppm)Glycerine < 1500Soaps < 500Water < 500MeOH < 1000Salts < 1000



35 22 April 2008

• Throughput (LHSV) 1.5 – 2 (BV* biodiesel / hr)

• Temperature: 30°C – 50° – 70°C

• Bed height: 1 – 2 m**

• Freeboard: 20%

• Operating capacity: 250 g glycerine / liter (max.)

*BV = bed volumes

** Please refer to us for specific design details

• Throughput (LHSV) 1.5 – 2 (BV* biodiesel / hr)

• Temperature: 30°C – 50° – 70°C

• Bed height: 1 – 2 m**

• Freeboard: 20%

• Operating capacity: 250 g glycerine / liter (max.)

*BV = bed volumes

** Please refer to us for specific design details

Operating conditionsGlycerine adsorption by GF 202Glycerine adsorption by GF 202


Lewatit®

GF 202





36 22 April 2008

• Temperature: 20 – 60°C

• Regeneration volume: 3 - 4 BV.MeOH at 2 BV

• Cycle time between regen.: 8-10 days

• Resin life: 4-5 years (average)

• Temperature: 20 – 60°C

• Regeneration volume: 3 - 4 BV.MeOH at 2 BV

• Cycle time between regen.: 8-10 days

• Resin life: 4-5 years (average)

Operating conditionsRegeneration with methanolRegeneration with methanol


Lewatit®

GF 202





37 22 April 2008

• The reactor is first drained then blown through withnitrogen to displace residual methanol from the voidvolume between the beads.

• Biodiesel is introduced from the bottom of the reactorat 2 BV/h. As MeOH is less dense than biodiesel, it is initially carried out of the reactor as a separate phase.

• The first 5-7 bed vols of biodiesel can either be passedupflow or downflow through the bed at 2 BV/h, or downflow at 4 BV/h, at temperatures in the range 25-50°C. This biodiesel should be MeOH-stripped.

•The next approx 8-20 bed volumes can be sent tostorage for further dilution with subsequently eluted BD(ref. MeOH elution profile on next page)

• The reactor is first drained then blown through withnitrogen to displace residual methanol from the voidvolume between the beads.

• Biodiesel is introduced from the bottom of the reactorat 2 BV/h. As MeOH is less dense than biodiesel, it is initially carried out of the reactor as a separate phase.

• The first 5-7 bed vols of biodiesel can either be passedupflow or downflow through the bed at 2 BV/h, or downflow at 4 BV/h, at temperatures in the range 25-50°C. This biodiesel should be MeOH-stripped.

•The next approx 8-20 bed volumes can be sent tostorage for further dilution with subsequently eluted BD(ref. MeOH elution profile on next page)

Operating conditionsMeOH displacement after regenerationMeOH displacement after regeneration


Lewatit®

GF 202





38 22 April 2008

0

0,2

0,4

0,6

0,8

1

1,2

0 5 10 15 20 25Bed volumes biodiesel

MeO

H c

once

ntra

tion

in B

D e

fflue

nt (%

)

Elution profile of GF 202 after regeneration with methanol

MeOH specification level

Biodiesel to: 1. storage for dilution 2. or to second column GF 202

MeOH strip

Throughput at 2 BV/h.

39 22 April 2008

Plant configuration

A: Single unit B: 1x in operation, 1x in standby C: 2 units in series: lead-lag

• Depending on the the amount of biodiesel produced and manufacturing siteinfrastructure, any of the configurations A-C can be used.

• We recommend the classical lead-lag setup, whereby the freshly MeOHregenerated reactor is switched to the lag-position.

• Depending on the the amount of biodiesel produced and manufacturing siteinfrastructure, any of the configurations A-C can be used.

• We recommend the classical lead-lag setup, whereby the freshly MeOHregenerated reactor is switched to the lag-position.

GF 202 GF 202 GF 202 GF 202 GF 202

40 22 April 2008

mio. gal/a30

years5Resin lifetime

h156Cycle time

ppm800Glycerine conc

g/liter resin**150-250Glycerine capacity

bar0.4Pressure drop

meter2Bed height

liters GF 2027,800Bed volume

bed vols/h2LHSV

gal./min.69

l/h15,600

to/h12.5Throughput

h8,000Annual operation

to/a*100,000Capacity This basic design can be scaled linearly for plant sizing ranging from 100 1,00,000 to/a

**Variable, depending on the influent glycerine concentration.

Basic design for a 100,000 to/a biodiesel purification unit

41 22 April 2008

Summary biodiesel purification with Lewatit® GF 202

• Substitutes conventional water-wash

• Generates specification-grade BD

• pH neutral operation, no impurities emitted by the resin

• Regenerable system

• Cost-neutral regeneration

• Applicable in 100 – 1,000,000 to/a plants

• > 10 years production experience

• Substitutes conventional water-wash

• Generates specification-grade BD

• pH neutral operation, no impurities emitted by the resin

• Regenerable system

• Cost-neutral regeneration

• Applicable in 100 – 1,000,000 to/a plants

• > 10 years production experience

42 22 April 2008

90% utilization of reactor volume No swelling relative to delivery formNo regular BD lossClean, smooth operationResin disposal every 5 yearsLewatit GF 202

Regular opening of reactor & waste handlingResin disposal several times / year

Resin swelling of 100-150%Regular BD loss in resin during dispoal

30% utilization of reactor volume

Dry resins

Cost comparison: Lewatit® GF 202 vs alternative technologies

Alternatives to Lewatit GF 202 for biodiesel purification are conventional water wash, once-use inorganic silicate-based filtration media and once-use dried ion exchange resins.

Handling- and cost-comparisons are summarised in the following tables.

43 22 April 2008

Cost / ton biodiesel ($)Application

20.00Inorganic filtration media (one way application)

13.00Dry resins (one way application)

0.35Lewatit GF 202 (lifetime 5 years minimum)

25.00Water wash

Cost comparison: Lewatit® GF 202 vs alternative technologies

44 22 April 2008

Reactor configuration: Lewatit vs dry resin in BD purification

Lewatit purification unit Lewatit purification unit

2 reactors / train2 reactors / train

GF 202 GF 202

Dry resin purification unitDry resin purification unit

4 reactors / train4 reactors / train

45 22 April 2008

Lewatit® GF 202 reference plantsCompany Oil.BLocation Solbiate Olona, Milano, ItalyCapacity 250,000 to/a (3 x 8 cbm reactors, 2 trains)Startup 2001

Company Oil.BLocation Solbiate Olona, Milano, ItalyCapacity 250,000 to/a (3 x 8 cbm reactors, 2 trains)Startup 2001

Lewatit GF 202 has been used in

industrial-scale biodiesel purification since

1996.

Of the numerous companies using Lewatit

biodiesel purification know-how,

Oil.B located near Milano, Italy, has

generously permitted the citation of its

plant as a reference.

The first batch of GF 202 was used for

7 years.

For further information please contact

your local Lewatit agent.

Lewatit GF 202 has been used in

industrial-scale biodiesel purification since

1996.

Of the numerous companies using Lewatit

biodiesel purification know-how,

Oil.B located near Milano, Italy, has

generously permitted the citation of its

plant as a reference.

The first batch of GF 202 was used for

7 years.

For further information please contact

your local Lewatit agent.

46 22 April 2008

Transesterification

FFA

Glycerine+ salts



GF 404(polishing)

GF 505(polishing)

Pure Glycerine

FAMEFAME




GF 101(FFA removal)


Glycerine processing with GF 303, GF 404, GF 505

47 22 April 2008

Salts-removal from glycerine with Lewatit® GF 303

RI & µS

Lewatit GF 303 is a chromatography resin designed for salts removal from glycerine by ion exclusion.

Raw glycerine from the acid split is introduced into the top of the resin bed.

The glycerine is then eluted with demineralised water.

The effluent is fractionated and monitored by refractive index (RI) and conductivity (µS).

Salts are eliminated first through ion exclusion, followed by glycerine.

Lewatit GF 303 is a chromatography resin designed for salts removal from glycerine by ion exclusion.

Raw glycerine from the acid split is introduced into the top of the resin bed.

The glycerine is then eluted with demineralised water.

The effluent is fractionated and monitored by refractive index (RI) and conductivity (µS).

Salts are eliminated first through ion exclusion, followed by glycerine.

48 22 April 2008

The principle of Ion Exclusion

SO3-

Na+

SO3-Na+

SO3-

Na+

SO3-

Na+

SO3-

Na+SO3-

Na+

SO3-

SO3-

Na+

+=

+-

+

+

-

-

-

+ +-

-

GF 303 GF 303

49 22 April 2008

+

+-

+

+

-

-

-

+ +-

-+

+-

+

+

-

-

-

+ +-

-

Na+ Cl- Na+ Cl- Na+ Cl- Na+ Cl- Na+ Cl-


50 22 April 2008

+

+-

+

+

-

-

-

+ +-

-

Net effect = ions pass around the resin beads

GF 303

Na+Cl- Na+Cl-

Na+

Cl-

Na+

Cl-

Cl-Na+

Cl-

+

+-

+

+

-

-

-

+ +-

-

Na+Cl- Na+Cl-

Na+

Cl-

Na+

Cl-

Cl-Na+

Cl-


51 22 April 2008

+

+-

+

+

-

-

-

+ +-

-

Ion Exclusion

OH OHOH

OH OHOH

Glycerine hydrogen bonds to the water in the GF 303

52 22 April 2008

Ion Exclusion with Lewatit GF 303

GF 303

HO OHOH

Na+Cl-

HO OHOH

Na+Cl-

Glycerine and saltare pushedthrough the bedwith demineralisedwater at 0.5 bedvolumes/hThis dilutes the Glycerine.

Glycerine is retained and elutes later

Salt is charge-repelled andelutes first

Glycerine and saltfrom the acid split are pulsed as an80% concentratein demineralisedwater every 0.8bed volumes ofthroughput ontothe top of thecolumn

HO OHOH

Na+Cl-

GF 303

53 22 April 2008

Separation of glycerine and salts from acid split

0

10

20

30

40

50

60

0,2 0,4 0,6 0,8

Filtered bed volume

Salts

[*10

0 µS

/cm

]

0

10

20

30

40

50

60

(%)G

lyce

rine

GF 303

Glycerine purification with Lewatit® GF 303

54 22 April 2008

50,000ppmNaCl

80minTotal cycle length

2560mlTotal volume/cycle

18Cycles / day

80°CTemperature

0.48bv/h

0.98m/h

1920ml/h

32ml/minFlow rate

3926mlResin volume

2000mmResin bed depth

19.63sqcmColumn square area

5,0cmColumn diameter

2,360ml/cycle

80%Glycerol conc. feed

200ml/cycleGlycerol injection

250g/cycle

200glyc/cycle

50g gly /l resin

73.75minutesWater injection

32ml/minRinse water flow

6.25minutes

Feed

Glycerol injection

20

1,260

NaCl ppm

ml/fract

16

Fractions

%

1,300ml/fract

49,980NaCl ppm

Lab arrangement for glycerine purification

1 to/d glycerine requires 1 cbm resin

55 22 April 2008

Deashing of glycerine from rape seed oil glycerine

Test procedure

column glas column with heating jacket, diameter 50 mm, filling height 200 cm = 3930 ml resin

temperature 70 °Cfeed glycerine from rape seed oil

83 % Glycerol 4.7 % NaCl

eluent demineralised water

Injection / pulse: 200 ml glycerine solution

flow rate 32 ml/ min = 100 cm/h

RI & µS

56 22 April 2008

0

500

1.000

1.500

2.000

2.500

0 200 400 600 800 1000 1200

time (min)

µS

1,335

1,34

1,345

1,35

1,355

1,36

1,365

RI

Conductivity NaCl Refractive index glycerine

Test result of glycerine-NaCl separation

57 22 April 2008

Strongly acidic,monodisperse

gel-typecation exchange

resin

GF 303

Glycerine purification with Lewatit® GF 303

80% in waterGlycerine

50,000 ppmNaCl

650 IUColor


100 ppmNaCl

200 IUColor

Raw glycerine 99.8% deashed glycerine

58 22 April 2008

demin. waterEluent

5 yearsResin lifetime

Glycerine from BD transesterificationFeed

80 °C Temperature

0.5 LHSV (bed vol./h)

5-7 wt% Salts conc. in raw glycerine

1.8 to. glycerine in 0.5 to. water Loading / cycle

1.8 to. glycerine in 7.2 to. water [ø]Effluent concentration

6.0 m Bed depth

2.5 m Diameter

30 m3 Resin volume

Design for a 10,000 to/a glycerine purification unit via

Ion Exclusion Chromatographywith

Lewatit GF 303

Plant for a 10,000 to/a fixed-bed glycerine deashing unit

GF 303

59 22 April 2008

Glycerine polishing with Lewatit® GF 404 / GF 505

GF 404

Strongly acidic,monodisperse macroporous

cation exchange resin

GF 505

Intermediate-basicmonodisperse macroporous

anion exchange resin


< 1 ppmNaCl

< 1 IUColor


100 ppmNaCl

200 IUColor

Salts-free glycerine Polished glycerine

60 22 April 2008

Plant for a 10,000 to/a glycerine polishing unit

3000 cbm / cycleCapacity

150 hCycle time

60°CTemp.

20 cbm/hFlow rate


200 ICUColor

100 ppmNaCl

GF 5056 cbm

GF 4045cbm


<1 ICUColor

<1 ppmNaClHCl NaOH

Waste

61 22 April 2008

Glycerine phase

Biodiesel phase

GF 202Transesterification

Biodiesel and glycerine purification with Lewatit® iex resins

GF 101

GF 303

GF 404

GF 505

62 22 April 2008

For additional Information

www.lewatit.com

63 22 April 2008

This information and our technical advice - whether verbal, in writing or by way of trials - are given in good faith but without warranty, and this also applies where proprietary rights of third parties are involved. Our advice does not release you from the obligation to verify the information currently provided (especially that contained in our safety data and technical information sheets) and to test our products as to their suitability for the intended processes and uses. The application, use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and, therefore, entirely your own responsibility. Our products are sold and our advisory service is given in accordance with the current version of our General Conditions of Sale and Delivery.

Lewatit® is a registered trademark of Lanxess Deutschland GmbH.

Legal note

Documents

Biodiesel and Glycerine Purification With Lewatit GF-Resins