ATELIER INTERNATIONAL DEDIAGNOSTIQUE DE L´INDUSTRIE DES
RÉSINEUX DE SECONDETRANSFORMATION
“LA COLOPHANE ET SON AVENIRDANS LE DOMAINE DU SUDOE”
BORDEAUX (France), OCTOBRE 2012
CHEMICAL DIVISION
RosinRosin isis aa solid form of naturalsolid form of naturalresin obtained from conifers andresin obtained from conifers and
mainly pine treesmainly pine trees
CHEMICAL DIVISION
WhatWhat isis RosinRosin??
CHEMICAL DIVISION
RosinRosin SourcesSources●● GUM:GUM:Tapping the Oleoresin of LivingTapping the Oleoresin of LivingPine TreesPine Trees
●●Tall Oil Rosin (TOR):Tall Oil Rosin (TOR):ByBy--product of Kraft Pulpingproduct of Kraft PulpingProcessProcess
●● StumpwoodStumpwood:: Extraction/SpecialExtraction/SpecialProcessing of Oleoresin fromProcessing of Oleoresin fromStumpsStumps
CHEMICAL DIVISION
RosinRosin compositioncompositionRosinRosin isis mainlymainly composedcomposed(>90%) of(>90%) of resinresin acidsacids withwith
similarsimilar basicbasic structuresstructures
TwoTwo commoncommon familiesfamilies ofof resinresin acidsacids::CHEMICAL DIVISION
●● AbietaneAbietane skeletal class:skeletal class:
●● PimaranePimarane skeletal class:skeletal class:
RosinRosin, as natural, as natural resinresin, has a, has avariablevariable compositioncomposition
dependingdepending onon::
CHEMICAL DIVISION
●● Origin of the Rosin (sources)Origin of the Rosin (sources)
●● Types of the trees (species)Types of the trees (species)
●● Location of the trees (geographical area)Location of the trees (geographical area)
Typical composition of resin acids in rosin byTypical composition of resin acids in rosin by sourcessourcesCHEMICAL DIVISION
ResinResin AcidAcid(% of(% of acidacid fractionfraction))
GumGumrosinrosin
TallTall OilOilrosinrosin
WoodWoodrosinrosin
AbieticAbietic 3232--3737 4040--4545 2525--3535PalustricPalustric//LevopimaricLevopimaric 1818--2323 55--1010 55--1010NeoabieticNeoabietic 1515--2020 11--66 55--1515DehydroabieticDehydroabietic 88--1010 2727--3232 2020--2525PimaricPimaric 77--1212 55--1010 33--55IsopimaricIsopimaric 66--1111 44--99 22--66SandarcopimaricSandarcopimaric 11--33 <2<2 11--33
Principal resin acids of gum rosin byPrincipal resin acids of gum rosin by speciesspeciesCHEMICAL DIVISION
Species(origin)
Resin acid (%)
P. pinaster(France)
P. halepensis(Greece)
P. sylvestris(Russia)
P. massoniana(China)
P. elliotti(Brazil)
P. merkusii(Indonesia)
Abietic 35 45 35 39 37 28
Isopimaric 10 11 7 2 17 16
Neoabietic 15 13 15 16 16 5
Palustric/Levopimaric
20 23 23 25 15 27
Dehydroabietic 9 5 10 7 5 4
Pimaric 10 9 10 5
Communic 4
Mercusic 11
Principal resin acids of gum rosin from P.Principal resin acids of gum rosin from P. pinasterpinaster bybygeographical areageographical area
CHEMICAL DIVISION
P. pinastertree location
Resin acid (%)
P. pinasterFrance
P. PinasterPortugal
P. PinasterSpain
P. pinasterUSA
Abietic 35 34 26 14
Isopimaric 10 7 5 12
Neoabietic 15 19 27 18
Palustric/Levopimaric
20 21 22 39
Dehydroabietic 9 9 6 4
Pimaric 10 8 9 8
Sandarocopimaric 2 2 2 2
Rosin is not an homogenous substanceRosin is not an homogenous substance
CHEMICAL DIVISION
Typical physical andchemical properties of
rosin by sources
Gumrosin
Tall Oilrosin
Woodrosin
Acid number 164 167 166Saponificaction index 172 174 172Unsaponifiable matter 8% 7% 6%Fatty acids - <5 -Color, U.S. rosin grade WW WG WGSoftening point (R&B) 76 ºC 77 ºC 76 ºCRefractive index 1.541 1.540 1.545Density 1.07 1.07 1.07
Typical physical and chemical properties of gum rosinTypical physical and chemical properties of gum rosin
CHEMICAL DIVISION
Typical physical andchemical properties of
gum rosin by types
Cleartypes
Middletypes
Darktypes
Acid number 165-171 160-170 155-163Saponificaction index 171-177 170-176 165-174Unsaponifiable matter 4.3%-5.5% 5.3%-8% 7%-10%Color, U.S. rosin grade XC-WW WG-I H-DSoftening point (R&B) 76 ºC 77 ºC 76 ºCAshes 0.041-0.02% 0.041-0.02% 0.01-0.17%Refractive index 1.541 1.540 1.545Density 1.07 1.07 1.07
WhyWhy RosinRosin DerivativesDerivatives??CHEMICAL DIVISION
NotNot suitablesuitable rosinrosin propertiesproperties::
●● LowLow softeningsoftening pointpoint (70(70 -- 80ºC)80ºC)●● OxidationOxidation trendtrend●● HighHigh acidityacidity ((IIaa= 155= 155 –– 170)170)●● CrystallizationCrystallization trendtrend●● LowLow viscosityviscosity●● QuiteQuite darkdark colorcolor●● HighHigh solventsolvent retentionretention●● OtherOther
OxydationOxydation testtest CHEMICAL DIVISION
0
0,5
1
1,5
2
2,5
1 day 2 day 3 day 4 day 5 day 6 day 7 day
Gum RosinDismutated RosinGlycerol esterPentaester
Time
% Weight Increase
((21 Kg. of21 Kg. of pressurepressure of Oof O22 forfor 77 daysdays))
HeatHeat stabilitystability testtestCHEMICAL DIVISION
Color Gardner
Time
(Color evolution at 170 ºC)
RosinRosin ReactivityReactivityCHEMICAL DIVISION
■■ ReactionReaction ofof DoubleDouble BondsBonds::●● AdductionAdduction●● HydrogenationHydrogenation●● DisproportionationDisproportionation●● PolymerizationPolymerization●● Etc.Etc.
■■ReactionReaction ofof CarboxylicCarboxylic AcidAcid::●● EsterificationEsterification●● SaltSalt FormationFormation ((SoapsSoaps,, ResinatesResinates))●● PhenolicPhenolic modifiedmodified rosinsrosins●● Etc.Etc.
RosinRosin goodgood oror poorpoor??It depends on the particular industrial use
CHEMICAL DIVISION
some examples:some examples:
Brazilian rosin (P.Brazilian rosin (P. elliottiielliottii) is suitable for depilatory waxes) is suitable for depilatory waxes
Indonesian rosin (P.Indonesian rosin (P. merkusiimerkusii) is suitable for inks) is suitable for inks
Chinese rosin (P.Chinese rosin (P. massonianamassoniana) is suitable for adhesives) is suitable for adhesives
SUDOE rosin (P.SUDOE rosin (P. pinasterpinaster) is suitable for most uses (versatile)) is suitable for most uses (versatile)
CHEMICAL DIVISION
EUEU RosinRosin ProductionProduction ((ForecastForecast 2012)2012)
GumGum RosinRosin ++ TallTall--OilOil RosinRosin = 147,500 MT= 147,500 MT
15,3 %
84,7 %
UE Gum Rosin Production = 22,500 MT.(15.3%)UE TOR production = 125,000 MT. (84.7%)
Gum RosinTOR
EUEU RosinRosin demanddemand ((ForecastForecast 2012)2012)
GumGum RosinRosin ++ TallTall--OilOil RosinRosin = 325,000 MT= 325,000 MT
CHEMICAL DIVISION
58.5 %
41.5 %
UE Gum Rosin market= 190,000 MT.(58.5%)UE TOR market =135,000 MT. (41.5%)
Gum Rosin
TOR
EUEU RosinRosin BalanceBalance ((ProductionProduction vs.vs. DemandDemand))
DeficitDeficit == -- 177,500 MT177,500 MTEUEU DeficitDeficit ofof GumGum RosinRosin == -- 167,500 MT. (94.4%)167,500 MT. (94.4%)EUEU DeficitDeficit of TOR =of TOR = -- 10,000 MT. (5.6 %)10,000 MT. (5.6 %)
CHEMICAL DIVISION
EuropeanEuropean RosinRosin marketmarket byby applicationsapplicationsGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 325.000 MT= 325.000 MT
CHEMICAL DIVISION
SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012
EuropeanEuropean RosinRosin AdhesivesAdhesives andand SealantsSealants marketmarketGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 130.000 MT= 130.000 MT
AverageAverage annualannual marketmarket growthgrowth : 4: 4--5%5%
CHEMICAL DIVISION
SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012
45%
22%
11%
20%Packaging
PSA Labels
Construction
Other
EuropeanEuropean RosinRosin PrintingPrinting InksInks marketmarketGumGum RosinRosin ++ TallTall--OilOil RosinRosin = 100.000 MT= 100.000 MT
AverageAverage annualannual marketmarket growthgrowth : 3: 3--3,5%3,5%
CHEMICAL DIVISION
SourceSource: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012
CHEMICAL DIVISION
PinePine treestrees
PinePine tappingtapping
CrudeCrude GumGum
DistillationDistillation
GumGumRosinRosin
GumGumturpentineturpentine
ChipsChips--woodwood
KraftKraft ProcessProcess
BlackBlack liquorliquor
SulfateSulfateturpentineturpentine
TallTall OilOilRosinRosin
TerpeneTerpene ResinsResins RosinRosin ResinsResins
PetrochemicalPetrochemical
FeedstockFeedstock(Nafta, etc.)(Nafta, etc.)
CrakingCraking ProcessProcess
ByBy--productsproducts ofoffractionationsfractionations lineslines
C5, C9, DCPDC5, C9, DCPD
HydrocarbonHydrocarbonResinsResins
RosinRosin ResinsResins areare notnot alonealone
SoapSoap AcidulationAcidulation
CTOCTO
DistillationDistillation
GlobalGlobal ResinResin ProductionProduction ((ForecastForecast 2012)2012)
CHEMICAL DIVISION
53.5%
3.3%
43.2%
Total world resin production = 2,430,000 MT- Rosin resins = 1,300,000 MT.- Hydrocarbon resins = 1,050,000 MT.- Terpene resins = 80,000 MT.
Rosin resins
Terpene resins
Hydrocarbon resins
SoureSoure: PCA International: PCA International ConferenceConference, Boston, Boston SeptemberSeptember 20122012
GlobalGlobal ResinTrendResinTrend CHEMICAL DIVISION
SourceSource: PCA: PCA InternationalInternational ConferenceConference, Boston, Boston SeptemberSeptember 20122012
• Moderate growth production of hydrocarbon resins (2%)• Moderate growth production of hydrocarbon resins (2%)• Slightly more sharper growth production of rosin resins (3%)• Slightly more sharper growth production of rosin resins (3%)• Stable production of• Stable production of terpeneterpene resins (0%)resins (0%)
CHEMICAL DIVISIONRosinRosin ResinResin TrendTrendGum Rosin
• Production is closely linked to the market price and theincrease in living standards (labor costs).• Moderate growth of production in the short term (3%)and increased market demand as a renewable raw material.• Long term limited availability of crude gum rosin(Eucaliptus vs. Pinus, salary increases, etc.)
.
Wood RosinSharp decline of wood rosin production in the long term.
Small and irrelevant proportion of total rosinproduction.
Tall Oil,• Production limited by the unavailability of crudetall-oil, linked to the price of energy (biodieselproduction).• Stable production in the short and medium termand longer-term shortages.
CHEMICAL DIVISION
WorldWorld RosinRosin ResinResin TrendTrend● Moderate growth of Gum Rosin production in the coming years(3% p.y.), but high risk of decline in the longer term.
● TOR production expectied to remain flat because production ofsoftwood kraft pulp also will be flat in the long term.
● Market demand for Rosin Resins 4 to 5 % p. y., leaded byemerging countries (China, India, Brazil, etc.)
●At longer term Trend, demand for Rosin Resins will exceed theoffer.
Higher prices and limited availability in the future
CHEMICAL DIVISION
RosinRosin resinsresins advantagesadvantages● Rosin market demands the more and more for ecological,biological and green products.
● Current economy requires development of products fromrenewable resources for sustainable industrial activities.
● Development of friendly environmental products (pinechemicals industry helps to preserve pine forests and reducecarbon footprint).
Clear advantage of Rosin resins overHydrocarbon resins
CHEMICAL DIVISIONConclusionsConclusions
●● Pine chemical industry in EU has a growing raw materialPine chemical industry in EU has a growing raw materialdemand, limited only by supply difficulties. This limiteddemand, limited only by supply difficulties. This limited
availability of rosin and turpentine will probably increase in nearavailability of rosin and turpentine will probably increase in nearfuture.future.
●● The geographic pine forest area ofThe geographic pine forest area of SUSTSUST--FOREST (Portugal,FOREST (Portugal,Spain and France), has enough resources to meet their ownSpain and France), has enough resources to meet their own
industrial needs.industrial needs.
●● Pine chemical industry is sustainable and environmentallyPine chemical industry is sustainable and environmentallyfriendly.friendly.
●●Pine chemical industry generates economic, social andPine chemical industry generates economic, social andenvironmental benefits.environmental benefits.