Lewatit® Ion Exchange ResinsTailor-made solutions for GreenFuels production 1 22 April 2008 Pure biodiesel & glycerine with Lewatit® ion exchange resins Lewatit® iex resins Pure Biodiesel Pure Glycerine 2 22 April 2008 The Lewatit® GreenFuels product line for biodiesel / glycerine GF 101 GF 202 GF 303 GF 404 GF 505 Esterification catalyst for FFA removal from triglycerides Adsorber for glycerine, soaps, salts, water, MeOH Separation of salts from glycerine Polisher, cation removal Polisher, anion removal, decolorization 3 22 April 2008 Biodiesel and glycerine purification with Lewatit GF-Resins Triglycerides GF 101 (FFA removal) Glycerine + salts Transesterification Glycerine + soap Acid Split FFA GF 303 (salts remova) GF 404 (polishing) FAME GF 101 (esterification) GF 505 (polishing) Biodiesel + impurities GF 202 (purification) Pure biodiesel Pure Glycerine 4 22 April 2008 . Biodiesel molecular structure Major fatty acid methyl ester components of biodiesel Methyl palmitate O O CH3 Methyl oleate O O CH3 Methyl linoleate O O CH3 5 22 April 2008 . Raw oil sources for biodiesel production Oil types Palm Rape seed Soyabean Sunflower Canola Coconut Jatropha Used cooking Animal fats Conversion Biodiesel High viscosity Poor combustion Low viscosity Good combustion 6 22 April 2008 . Raw oils chemical composition O O Triglycerides > 95% O O O O Fatty-Acids: 0. phospholipids. proteins. mineral salts 7 22 April 2008 .1.5% O OH Others: < 1% Micelles. viscosity 40°C Sulfur Cetane Cloud point Copper corrosion Acid number Sulfated ash Free glycerine Total glycerine ASTM 93 2709 4530 445 5453 613 2500 130 664 874 6584 6584 Lim its 100 min.Biodiesel quality standards ASTM Property Flash point Water sediment Carbon residue Kin. 0.08 max.05 max.05 max.020 m ax. by customer No 3 max.0 0. 0. 40 min.020 m ax. 0. w t. 0. % w t.9 . Units °C vol. 1. % w t. 0. 0. % °C mg KOH/g w t. % 8 22 April 2008 .6.050 max. % mm²/sec. % w t.240 max. 0.2 max. 0. 0.8 max 0.5.0 10 max.02 m ax.Biodiesel quality standards Europe: EN 14214 * Property Flash point Water content Alkali metals Viscosity 40°C Sulfur Cetane Acid number Sulfated ash Free glycerine Monoglycerides Diglycerides Triglycerides Total glycerine Methanol content > 101 500 5 max. mg/kg Test method ISO CD 3679e EN ISO 12937 pr EN 14108 EN ISO 3104 EN ISO 5165 pr EN 14104 ISO 3987 pr EN 14105 * As specified for BD from rape seed oil (not all specs. 0.25 max. 0.02 m ax. % %(m/m) pr EN 14105 pr EN 141101 Limits Units °C mg/kg mg/kg mm²/sec. listed) 9 22 April 2008 .2 max. 0. mg KOH/g % (m /m ) %(m /m ) %(m/m) %(m/m) %(m/m) w t. 0.5 max.5 .2 max. 51 min. 3. cleaning of triglycerides Phosphoric acid Raw Triglycerides Water Heat Pure Triglycerides Centrifuge II Centrifuge I Filter Bleaching earth 10 22 April 2008 Phosphatide waste .Degumming. Triglyceride transesterification Purified Triglycerides Recommended purity > 95% O O O O O O Transesterification catalyst Top Layer CH3OH O OCH3 Biodiesel phase Glycerine phase Bottom Layer HO OH OH 11 22 April 2008 . phases. KOCH3.Transesterification catalysts Themost mostcommonly commonlyused usedtransesterification transesterificationcatalysts catalystsare are NaOH. alkoxidesNaOCH 3. Currently>90% >90%of ofall alllarge largescale scaleindustrial industrialplants plantsworld-wide world-wideuse usealkoxide alkoxidecatalysts: catalysts: Currently Reducedsoap soapformation formation • • Reduced Betterseparation separationof ofglycerine glycerineand andbiodiesel biodieselphases. NaOH.KOH KOHand andtheir theirmethanolic methanolic The NaOCH. • • Better Gooddrying dryingagents agents • • Good 12 22 April 2008 . alkoxides 3 KOCH3. KOH KOHdouble NaOH.KOMe KOMe NaOH.Enhanced soap formation with NaOH / KOH •• •• •• NaOH.KOH KOHreact reactwith withFFA FFAto toform formsoap soap++water water NaOH. Additionalsoap soapis isformed formedby bythe theOH-catalysed OH-catalysedhydrolysis hydrolysisof ofester ester Additional doublethe theformation formationof ofsoap soaprelative relativeto toNaOMe. O NaOH + O H2O + OH FFA ONa O Soap CH3OH + OHO H2O + ONa Soap OCH3 FAME 13 22 April 2008 . NaOMe. alkoxides.soaps soapsare areonly onlyformed formedby byneutralisation neutralisationof ofFFA: FFA: With O NaOCH3 + O CH3OH + ONa OH FFA Soap LewatitGF GF101 101can canbe beutilised utilisedto toeffectively effectively Inorder orderto toreduce reducealkoxide alkoxidecatalyst catalystcosts.Lewatit In eliminateFFA FFAfrom fromthe thetriglyceride triglyceridefeedstocks.Reduced soap formation with alkoxides Withalkoxides. costs. feedstocks. eliminate 14 22 April 2008 . Esterification of free fatty acids with catalyst Lewatit® GF 101 O Free fatty acid (FFA*) 1 – 100% + HOCH3 OH GF 101 O Fatty acid methyl ester (FAME) OCH3 + H2O *TheFFA FFAfeeds feedsmust mustbe bedegummed degummedand andcleaned cleanedprior priorto topassage passagethrough throughthe theGF GF101 101 *The 15 22 April 2008 . Esterification of free fatty acids with catalyst Lewatit® GF 101 Triglycerides GF 101 (FFA removal) Glycerine + salts Transesterification Glycerine + soap Acid Split FFA GF 303 (salts remova) GF 404 (polishing) FAME GF 101 (esterification) GF 505 (polishing) Biodiesel + impurities GF 202 (purification) Pure biodiesel Pure Glycerine 16 22 April 2008 . 0 m3 1.0 m 4.000to/a to/aesterification esterificationunit unit Design for for reductionof offree freefatty fattyacids acids(FFA´s) (FFA´s)from fromtriglycerides triglycerides reduction with with CatalystLewatit LewatitGF GF101 101 Catalyst GF 101 Oil-Feed Resin volume: Diameter Bed depth Temperature Oil + MeOH feed FFA content in oil Oil feed (kg/h) Upflow operation prevents Upflow operation prevents bed plugging and enables bed plugging and enables long catalyst life long catalyst life MeOH feed (kg/h) FFA conversion Catalyst lifetime Triglycerides with FFA´s 3.Esterification of free fatty acids with catalyst Lewatit® GF 101 Designfor foran an8.000 8.0 m 90-110°C 900 kg / h (upflow) 1-10% 700 200 95% 3 years Industrial applications Pilot plants 10-50% 650 250 95% 50-100% 600 350 95% 17 22 April 2008 . bed Triglyceride + FFA Esterification reactor Triglyceride + FFA-Methyl ester MeOH Priorto tothe theesterification esterificationstep stepititis isrecommendable recommendableto toinclude includeaaguard guardbed bedwith withGF GF101 101for for Prior removalof ofany anypotential potentialcationic cationicand andamine aminecatalyst catalystpoisons. poisons.especially especiallyin inconjunction conjunctionwith with removal usedoils oilsfrom fromthe thefoodstuffs foodstuffsindustries. used Guardbed bedsizing: sizing: Guard Bedheight: height: Bed Replacement: Replacement: 18 22 April 2008 20-30%of ofthe theresin resinvolume volumein inthe theesterification esterificationreactor reactor 20-30% m 22m 6-9monthly monthlyintervals intervals(once-use (once-use/ /non-regeneration non-regenerationresin) resin) 6-9 . industries.Esterification of free fatty acids with catalyst Lewatit® GF 101 Guard . and 19 22 April 2008 .soaps.waxes. soaps. salts.methanol.water. costs. Lewatit canreplace replacethe theconventional conventionalwater-wash. glycerine. water.salts.eliminate eliminatecostly costlywater waterstripping stripping ItItcan andreduce reduceinvestment investmentand andoperating operatingcosts. water-wash.Biodiesel purification with Lewatit® GF 202 •• •• LewatitGF GF202 202removes removes glycerine. methanol. waxes. 000.000 1.long longresin resinlifetimes lifetimes •• Regenerable.000.Features of Lewatit® GF 202 in biodiesel purification Fulfillsthe thestringent stringentspecification specificationrequirements requirementsof ofthe thefuel fuelindustries industries •• Fulfills Oneliter literof ofGF GF202 202will willtypically typicallypurify purify10 10tons tonsbiodiesel biodiesel/ /year year •• One Regenerable.000to/a to/a •• Usable Themost mostcost-effective cost-effectiveresin-based resin-basedpurification purificationsystem systemin inthe themarket market •• The 20 22 April 2008 . Canbe beretrofitted retrofittedinto intoexisting existingplants plantsusing usingwater-wash water-wash •• Can Allbiodiesel biodieselqualities qualitiesirrespective irrespectiveof ofthe thetriglyceride triglyceridesource sourcecan canbe betreated treated •• All Usablein inplants plantsranging rangingfrom from100 100Æ Æ1. Biodiesel purification with Lewatit® GF 202 Triglycerides GF 101 (FFA removal) Glycerine + salts Transesterification Glycerine + soap Acid Split FFA GF 303 (salts remova) GF 404 (polishing) FAME GF 101 (esterification) GF 505 (polishing) Biodiesel + impurities GF 202 (purification) Pure biodiesel Pure Glycerine 21 22 April 2008 . Classical biodiesel production process Low-acid triglycerides MeOH MeONa HCl Water Baynox Antioxidant MeOH Strip Raw oils with free fatty acids Glycerine purification Esterification Water strip Water strip Transesterification Methyl ester phase Separation Glycerine phase Water wash MeOH Strip MeOH + Gly. + salts Water + Glycerine + Salts Glycerine + Salts Pure methyl esters (Biodiesel) 22 22 April 2008 . 404.Purification with Lewatit® GF 202 Low-acid triglycerides MeOH MeONa HCl Baynox Antioxidant Adsorption / desorption MeOH Strip Raw oils with free fatty acids Glycerine purification Lewatit GF 303. 505 Esterification Transesterification Methyl ester phase Separation Glycerine phase Lewatit GF 202 MeOH Strip MeOH + glycerine Glycerine + Salts Pure methyl esters (biodiesel) 23 22 April 2008 . Lewatit® GF 202 vs water wash Purification with water wash Water Purification with Lewatit® GF 202 Glycerine adsorption / desorption One column of resin completely replaces the water washing system!! Water + glycerine + salts Water wash Water strip Water strip 24 22 April 2008 . i. 25 22 April 2008 . dry. In classical biodiesel plants. Only methanol is required as washing Only methanol is required as aa washing agent to regenerate the resin. the streams are already very dry.Lewatit® GF 202 vs water wash Purificationwith withwater waterwash wash Purification Purificationwith withLewatit LewatitGF GF202 202 Purification Many biodiesel plants already use NaOCH3 for Many biodiesel plants already use NaOCH 3 for transesterification.e. The washing effluent is recycled to the transesterification. The washing agent to regenerate the resin. With GF 202. dry biodiesel streams remain dry.e. Water efficiently removes impurities but needs to Water efficiently removes impurities but needs to be stripped down down to <500 ppm in the be stripped down down to <500 ppm in the purified biodiesel. dry biodiesel streams remain With GF 202. effluent is recycled to the transesterification. wetted and redried at subtantial cost. i. dry streams are In classical biodiesel plants. the streams are already transesterification. purified biodiesel. dry streams are wetted and redried at subtantial cost. very dry. water. biodiesel HO HO OH Glycerine HO O GF 202 S O O HO Na+ HO OH Hydrogen bonding HO HO 26 22 April 2008 .Mechanism of glycerine adsorption DryLewatit LewatitGF GF202 202is is Dry hygroscopicand andstrongly strongly hygroscopic hydrogen-bondsto toalcohols alcohols hydrogen-bonds andwater. and Glycerineis isaapolar polartri-alcohol tri-alcohol Glycerine andis isvery veryefficiently efficiently and removedfrom fromlow lowpolarity polarity removed biodieselesters. esters. Mechanism of salts and soaps adsorption on GF202 The glycerine layer on the GF 202 adsorbs polar and ionic impurities. Impurities are not as efficiently adsorbed if no glycerine is present. Glycerine layer Mg++ K+ -O2C Cl- Typical impurities in raw BD to resin (MeOHstripped) conc. (ppm) Glycerine < 1500 Soaps < 500 Water < 500 MeOH < 1000 Salts < 1000 H2O Na+ GF 202 -O2C MeOH SO42.Ca++ 27 22 April 2008 . or inorganic filtration media. dry resins. the ester phase should not be pretreated to remove the glycerine. either by water wash.Mechanism of salts and soaps adsorption on GF202 Important notice Prior to passage through GF 202. The presence of glycerine is essential for the adsorption of soaps and salts!! 28 22 April 2008 . Plant operating data for Lewatit® GF 202 Adsorptionof ofglycerine glycerine& &soaps soapsfrom fromrape rapeseed seedbiodiesel biodieselat at22BV/h.28°C 28°C Adsorption 800 700 600 500 ppm glycerine inlet soaps inlet glycerine outlet soaps outlet 400 300 200 100 0 5 10 15 20 25 Bed volumes biodiesel from rape seed oil 30 35 29 22 April 2008 . BV/h. Impurities adsorption in glycerine Transesterification Transesterification phaseseparation separation phase Captureof ofionic ionicimpurities impuritieson on Capture glycerinephase phaseof ofGF GF202 202 glycerine Biodiesel phase + Small concentrations of ionic impurities + soaps Biodiesel phase clean GF 202 + Glycerine phase Glycerine phase + High concentrations of ionic impurities + soaps + High concentrations of ionic impurities + soaps 30 22 April 2008 . hexagonal closest packing GF 202 “sponge-structure“ 31 22 April 2008 .Structure of Lewatit® GF 202 Monodisperse bead sizing. following slides) (ref. following slides) •• The MeOH regeneration is effectively cost neutral The MeOH regeneration is effectively cost neutral !!!! Purified biodiesel MeOH + glycerine (+ water traces*) 32 22 April 2008 . the MeOH storage tank. or aa MeOH strip column. the MeOH storage tank. depending on the water concentration in the effluent from Lewatit GF 202 effluent from Lewatit GF 202 The water concentration is dependent on whether The water concentration is dependent on whether NaOMe or NaOH KOH is used in the transesterification NaOMe or NaOH // KOH is used in the transesterification (ref. or MeOH strip reactor. depending on the water concentration in the column.Application mode of Lewatit® GF 202 Alternate loading and regeneration Biodiesel + glycerine The feed must be MeOH-stripped!! Lewatit GF 202 Washing with dry MeOH •• MeOH is either recycled to the transesterification MeOH is either recycled to the transesterification reactor. Regeneration / cleaning with methanol Raw oils MeOH Methanol + glycerine + salts & soaps GF 202 + glycerine + salts & soaps Transesterification GF 202 clean Methanol 33 22 April 2008 . Before Beforethe theMeOH MeOHwash. preconditioning. water-wet. biodiesel (Ifrequired. required. water. 2BV/h.GF GF202 202 is isonly onlysubjected subjectedto to • •After never alternateMeOH MeOH/ /biodiesel biodieseltreatments treatmentsand andnever alternate washedwith withwater. (ppm) Typical conc. wash. washed 100%bed bedvolume volumewater-wet.The TheMeOH MeOHis isthen thendrained drainedand andthe thebiodiesel biodiesel at passedinto intothe thereactor. MeOH. (ppm) 1500 << 1500 500 << 500 < 500 < 500 1000 << 1000 < 1000 < 1000 Preconditioningof ofGF GF202 202 Preconditioning FreshGF GF202 202is iswater-wet water-wetand andneeds needsto tobe be • •Fresh preconditionedby bydrying dryingwith with3-4 3-4bed bedvolumes volumesMeOH MeOH preconditioned at2BV/h.GF202 GF202can canbe bedelivered deliveredpredried!!) predried!!) • •(If Lewatit® GF 202 Afterpreconditioning.the the passed biodieselis isalso alsodrained.Operating conditions Raw BD (MeOH-stripped) Raw BD (MeOH-stripped) Impurities Impurities Glycerine Glycerine Soaps Soaps Water Water MeOH MeOH Salts Salts Typical conc. • •100% furthershrinks shrinksto to90% 90%in inbiodiesel biodiesel++glycerine glycerine further Refinedbiodiesel biodiesel Refined 34 22 April 2008 . drained. reactor.shrinks shrinksto to95% 95%in inMeOH. (ppm) Typical conc.) • •Operating *BV==bed bedvolumes volumes *BV **Please Pleaserefer referto tous usfor forspecific specificdesign designdetails details ** Refinedbiodiesel biodiesel Refined 35 22 April 2008 .Operating conditions Raw BD (MeOH-stripped) Raw BD (MeOH-stripped) Impurities Impurities Glycerine Glycerine Soaps Soaps Water Water MeOH MeOH Salts Salts Typical conc.5 1.) (max.5––22(BV* (BV*biodiesel biodiesel/ /hr) hr) • •Throughput Temperature: • •Temperature: Bedheight: height: • •Bed Freeboard: • •Freeboard: Lewatit® GF 202 30°C––50° 50°––70°C 70°C 30°C m** 11––22m** 20% 20% Operatingcapacity: capacity: 250 250ggglycerine glycerine/ /liter liter(max. (ppm) 1500 << 1500 500 << 500 < 500 < 500 1000 << 1000 < 1000 < 1000 Glycerineadsorption adsorptionby byGF GF202 202 Glycerine Throughput(LHSV) (LHSV) 1. MeOH 33. (ppm) Typical conc.: regen. (ppm) 1500 << 1500 500 << 500 < 500 < 500 1000 << 1000 < 1000 < 1000 Regenerationwith withmethanol methanol Regeneration Temperature: • •Temperature: Regenerationvolume: volume: • •Regeneration Cycletime timebetween betweenregen.-44BV.: • •Cycle Lewatit® GF 202 20––60°C 60°C 20 BV.Operating conditions Raw BD (MeOH-stripped) Raw BD (MeOH-stripped) Impurities Impurities Glycerine Glycerine Soaps Soaps Water Water MeOH MeOH Salts Salts Typical conc.MeOH at22BV BV at 8-10days days 8-10 4-5years years(average) (average) 4-5 Resinlife: life: • •Resin Refinedbiodiesel biodiesel Refined 36 22 April 2008 . or or upflow downflowat at44BV/h.This Thisbiodiesel biodieselshould shouldbe beMeOH-stripped.MeOH MeOHelution elutionprofile profileon onnext nextpage) page) (ref. biodiesel. (ppm) 1500 << 1500 500 << 500 < 500 < 500 1000 << 1000 < 1000 < 1000 MeOHdisplacement displacementafter afterregeneration regeneration MeOH Thereactor reactoris isfirst firstdrained drained then thenblown blownthrough throughwith with • •The nitrogento todisplace displaceresidual residualmethanol methanolfrom fromthe thevoid void nitrogen volumebetween betweenthe thebeads. BV/h. BV/h. volume Biodieselis isintroduced introducedfrom fromthe thebottom bottomof ofthe thereactor reactor • •Biodiesel at22BV/h. •Thenext nextapprox approx8-20 8-20bed bedvolumes volumescan canbe besent sentto to •The storagefor forfurther furtherdilution dilutionwith withsubsequently subsequentlyeluted elutedBD BD storage (ref. Refinedbiodiesel biodiesel Refined 37 22 April 2008 .at attemperatures temperaturesin inthe therange range downflow 25-50°C.Operating conditions Raw BD (MeOH-stripped) Raw BD (MeOH-stripped) Impurities Impurities Glycerine Glycerine Soaps Soaps Water Water MeOH MeOH Salts Salts Typical conc. beads. MeOH-stripped.ititis is at initiallycarried carriedout outof ofthe thereactor reactoras asaaseparate separatephase. 25-50°C. BV/h.As AsMeOH MeOHis isless lessdense densethan thanbiodiesel. phase. initially Lewatit® GF 202 Thefirst first5-7 5-7bed bedvols volsof ofbiodiesel biodieselcan caneither eitherbe bepassed passed • •The upflowor ordownflow downflowthrough throughthe thebed bedat at22BV/h. (ppm) Typical conc. 4 0.Elution profile of GF 202 after regeneration with methanol 1. storage for dilution 2. or to second column GF 202 0. 0.2 MeOH concentration in BD effluent (%) 1 MeOH strip Biodiesel to: 1.6 Throughput at 2 BV/h.8 0.2 MeOH specification level 0 0 5 10 15 20 25 Bed volumes biodiesel 38 22 April 2008 . Plant configuration Dependingon onthe thethe theamount amountof ofbiodiesel biodieselproduced producedand andmanufacturing manufacturingsite site • •Depending infrastructure. Werecommend recommendthe theclassical classicallead-lag lead-lagsetup. regenerated A: Single unit B: 1x in operation. lag-position. used.whereby wherebythe thefreshly freshlyMeOH MeOH • •We regeneratedreactor reactoris isswitched switchedto tothe thelag-position.any anyof ofthe theconfigurations configurationsA-C A-Ccan canbe beused. setup. infrastructure. 1x in standby C: 2 units in series: lead-lag GF 202 GF 202 GF 202 GF 202 GF 202 39 22 April 2008 . LHSV Bed volume Bed height Pressure drop Glycerine capacity Glycerine conc Cycle time Resin lifetime 2 bed vols/h 7. depending on the influent glycerine concentration.Basic design for a 100.600 l/h 69 gal.000 to/a 40 22 April 2008 .000 to/a biodiesel purification unit Capacity Annual operation Throughput 100.000 to/a* 30 mio. This basic design can be scaled linearly for plant sizing ranging from 100 Æ 1./min.000 h 12.5 to/h 15.00.4 bar 150-250 g/liter resin** 800 ppm 156 h 5 years **Variable.800 liters GF 202 2 meter 0. gal/a 8. 000. operation.000to/a to/aplants plants •• Applicable >10 10years yearsproduction productionexperience experience •• > 41 22 April 2008 .Summary biodiesel purification with Lewatit® GF 202 Substitutesconventional conventionalwater-wash water-wash •• Substitutes Generatesspecification-grade specification-gradeBD BD •• Generates pHneutral neutraloperation.000.000 1.no noimpurities impuritiesemitted emittedby bythe theresin resin •• pH Regenerablesystem system •• Regenerable Cost-neutralregeneration regeneration •• Cost-neutral Applicablein in100 100––1. and cost-comparisons are summarised in the following tables. once-use inorganic silicate-based filtration media and once-use dried ion exchange resins. smooth operation No regular BD loss No swelling relative to delivery form 90% utilization of reactor volume Dry resins Resin disposal several times / year Regular opening of reactor & waste handling Regular BD loss in resin during dispoal Resin swelling of 100-150% 30% utilization of reactor volume 42 22 April 2008 . Lewatit GF 202 Resin disposal every 5 years Clean.Cost comparison: Lewatit® GF 202 vs alternative technologies Alternatives to Lewatit GF 202 for biodiesel purification are conventional water wash. Handling. 00 43 22 April 2008 .Cost comparison: Lewatit® GF 202 vs alternative technologies Application Lewatit GF 202 (lifetime 5 years minimum) Dry resins (one way application) Inorganic filtration media (one way application) Water wash Cost / ton biodiesel ($) 0.00 25.00 20.35 13. Reactor configuration: Lewatit vs dry resin in BD purification Lewatitpurification purificationunit unit Lewatit reactors/ / train train 22reactors Dryresin resinpurification purificationunit unit Dry reactors/ / train train 44reactors GF 202 GF 202 44 22 April 2008 . Lewatit® GF 202 reference plants Lewatit GF 202 has been used in Lewatit GF 202 has been used in industrial-scale biodiesel purification since industrial-scale biodiesel purification since 1996.B Solbiate Olona. Milano. Italy.B Oil. Milano. your local Lewatit agent.000 to/a (3 x 8 cbm reactors. 1996. 250. has Oil. Italy Italy Solbiate Olona.B located near Milano. Italy. The first batch of GF 202 was used for The first batch of GF 202 was used for years. plant as aa reference. For further information please contact For further information please contact your local Lewatit agent. biodiesel purification know-how. trains) 250.000 to/a (3 x 8 cbm reactors. Oil. has generously permitted the citation of its generously permitted the citation of its plant as reference. 22 trains) 2001 2001 45 22 April 2008 . 77 years.B located near Milano. Company Company Location Location Capacity Capacity Startup Startup Oil. Of the numerous companies using Lewatit Of the numerous companies using Lewatit biodiesel purification know-how. Glycerine processing with GF 303. GF 505 Triglycerides GF 101 (FFA removal) Glycerine + salts Transesterification Glycerine + soap Acid Split FFA GF 303 (salts remova) GF 404 (polishing) FAME GF 101 (esterification) GF 505 (polishing) Biodiesel + impurities GF 202 (purification) Pure biodiesel Pure Glycerine 46 22 April 2008 . GF 404. (µS). The Theeffluent effluentis isfractionated fractionatedand andmonitored monitoredby byrefractive refractive The index(RI) (RI)and andconductivity conductivity(µS).. RI & µS 47 22 April 2008 . salts Rawglycerine glycerinefrom fromthe theacid acidsplit splitis isintroduced introducedinto intothe thetop top Raw ofthe theresin resinbed. of Theglycerine glycerineis isthen theneluted elutedwith withdemineralised demineralisedwater. water.followed followedby by Salts glycerine. bed. exclusion. glycerine. index Saltsare areeliminated eliminatedfirst firstthrough throughion ionexclusion.Salts-removal from glycerine with Lewatit® GF 303 LewatitGF GF303 303is isaachromatography chromatographyresin resindesigned designedfor for Lewatit ionexclusion exclusion saltsremoval removalfrom fromglycerine glycerineby byion . The principle of Ion Exclusion GF 303 GF 303 Na+ Na+ SO3 - SO3Na+ Na+ SO3 - = + + SO3- + + + + - SO3- Na+ SO - SO 3 3 Na+ SO3- Na+ 48 22 April 2008 The principle of Ion Exclusion Na+ Cl- Na+ Cl- Na+ Cl- Na+ Cl- Na+ Cl- + 49 22 April 2008 + + + + + + - + - + + + + - The principle of Ion Exclusion Net effect = ions pass around the resin beads ClNa+ ClNa+ ClNa+ ClNa+ Na+ ClNa+ Cl- ClNa+ ClCl- Na+ Cl- Na+ ClNa+ Cl- + + - + + + + - + + + + + + - GF 303 50 22 April 2008 Ion Exclusion Glycerine hydrogen bonds to the water in the GF 303 HO OH OH HO OH OH + 51 22 April 2008 + + + + + - . 5 bed volumes/h This dilutes the Glycerine.Ion Exclusion with Lewatit GF 303 HO OH OH Na+ Cl- HO OH OH Na+ Cl- Glycerine and salt from the acid split are pulsed as an 80% concentrate in demineralised water every 0.8 bed volumes of throughput onto the top of the column Glycerine and salt are pushed through the bed with demineralised water at 0. HO OH OH Glycerine is retained and elutes later GF 303 GF 303 Na+ ClSalt is chargerepelled and elutes first 52 22 April 2008 . 4 0.Glycerine purification with Lewatit® GF 303 Separation of glycerine and salts from acid split 60 GF 303 60 50 40 30 20 10 0 0.6 0.2 0.8 50 Salts [*100 µS/cm] 40 30 20 10 0 Filtered bed volume 53 22 April 2008 (%)Glycerine . Lab arrangement for glycerine purification Column diameter Column square area Resin bed depth Resin volume Flow rate cm sqcm mm ml ml/min ml/h m/h bv/h NaCl ppm 5.25 Feed Fractions Rinse water flow Total cycle length Total volume/cycle Cycles / day Temperature °C min ml 80 2560 18 80 Water injection ml/min minutes ml/cycle 32 73.260 49.98 0.360 ml/fract NaCl ppm 1.980 1 to/d glycerine requires 1 cbm resin 54 22 April 2008 .0 19.48 50. feed 32 1920 0.63 2000 3926 Glycerol conc.000 Glycerol injection % ml/cycle g/cycle glyc/cycle g gly /l resin 80 200 250 200 50 % ml/fract NaCl ppm 16 1.75 2.300 20 Glycerol injection minutes 6. diameter 50 mm.Deashing of glycerine from rape seed oil glycerine Test procedure column temperature feed glas column with heating jacket. filling height 200 cm = 3930 ml resin 70 °C glycerine from rape seed oil 83 % Glycerol 4.7 % NaCl demineralised water 200 ml glycerine solution 32 ml/ min = 100 cm/h eluent Injection / pulse: flow rate RI & µS 55 22 April 2008 . 000 Refractive index glycerine 1.355 1.Test result of glycerine-NaCl separation 2.345 500 1.500 Conductivity NaCl 2.34 0 0 200 400 600 800 1000 1.500 µS 1.335 1200 time (min) 56 22 April 2008 RI .365 1.36 1.35 1.000 1. 000 ppm 80% in water Color NaCl Glycerine 200 IU 100 ppm 20% in water Strongly acidic. monodisperse gel-type cation exchange resin 57 22 April 2008 .8% deashed glycerine GF 303 Color NaCl Glycerine 650 IU 50.Glycerine purification with Lewatit® GF 303 Raw glycerine 99. Plant for a 10.0 m 1. water [ø] 5 years GF 303 58 22 April 2008 .8 to./h) Effluent concentration Resin lifetime Glycerine from BD transesterification 30 m3 2. water 80 °C 0. glycerine in 0.5 1.5 to.2 to.8 to.5 m 6.000 to/a fixed-bed glycerine deashing unit Design for a 10. in raw glycerine Eluent Temperature LHSV (bed vol. glycerine in 7.000 to/a glycerine purification unit via Ion Exclusion Chromatography with Lewatit GF 303 Feed Resin volume Diameter Bed depth Loading / cycle Salts conc. water 5-7 wt% demin. monodisperse macroporous cation exchange resin Intermediate-basic monodisperse macroporous anion exchange resin Color NaCl Glycerine < 1 IU < 1 ppm 20% in water 59 22 April 2008 .Glycerine polishing with Lewatit® GF 404 / GF 505 Salts-free glycerine Polished glycerine GF 404 GF 505 Color NaCl Glycerine 200 IU 100 ppm 20% in water Strongly acidic. Capacity Cycle time 100 ppm 200 ICU 20% in water 20 cbm/h 60°C 3000 cbm / cycle 150 h GF 505 6 cbm Waste 60 22 April 2008 .000 to/a glycerine polishing unit HCl NaOH NaCl Color Glycerine <1 ppm <1 ICU 20% in water GF 404 5cbm NaCl Color Glycerine Flow rate Temp.Plant for a 10. Biodiesel and glycerine purification with Lewatit® iex resins Transesterification GF 101 GF 202 GF 303 Biodiesel phase GF 404 Glycerine phase GF 505 61 22 April 2008 . lewatit.com 62 22 April 2008 .For additional Information www. Lewatit® is a registered trademark of Lanxess Deutschland GmbH. use and processing of our products and the products manufactured by you on the basis of our technical advice are beyond our control and. and this also applies where proprietary rights of third parties are involved.Legal note This information and our technical advice . entirely your own responsibility.are given in good faith but without warranty. therefore. 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.whether verbal. Our products are sold and our advisory service is given in accordance with the current version of our General Conditions of Sale and Delivery. The application. in writing or by way of trials . 63 22 April 2008 .
Report "Biodiesel and Glycerine Purification With Lewatit GF-Resins"