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Leblancprocess
FromWikipedia,thefreeencyclopedia

TheLeblancprocesswasanearlyindustrialprocessfor
theproductionofsodaash(sodiumcarbonate)used
throughoutthe19thcentury,namedafteritsinventor,
NicolasLeblanc.Itinvolvedtwostages:productionof
sodiumsulfatefromsodiumchloride,followedby
reactionofthesodiumsulfatewithcoalandcalcium
carbonatetoproducesodiumcarbonate.Theprocess
graduallybecameobsoleteafterthedevelopmentofthe
Solvayprocess.

Contents
1Background
2Chemistry
3Processdetail
4Industrialhistory
5Pollutionissues
6Obsolescence
7Biodiversity
8References
9Externallinks

Leblancprocess
Processtype Chemical
Industrial
sector(s)

Chloralkaliindustry

Feedstock

sodiumchloride,sulfuricacid,coal,
calciumcarbonate

Product(s)

sodaash,hydrochloricacid

Inventor

NicolasLeblanc

Yearof
invention

1791

Developer(s) WilliamLosh,JamesMuspratt,
CharlesTennant

Background
Sodaash(sodiumcarbonate)andpotash(potassiumcarbonate),collectivelytermedalkali,arevital
chemicalsintheglass,textile,soap,andpaperindustries.ThetraditionalsourceofalkaliinwesternEurope
hadbeenpotashobtainedfromwoodashes.However,bythe13thcentury,deforestationhadrenderedthis
meansofproductionuneconomical,andalkalihadtobeimported.PotashwasimportedfromNorth
America,Scandinavia,andRussia,wherelargeforestsstillstood.SodaashwasimportedfromSpainand
theCanaryIslands,whereitwasproducedfromtheashesofglasswortplants(calledbarillaashesinSpain),
orimportedfromSyria.[1]Thesodaashfromglasswortplantasheswasmainlyamixtureofsodium
carbonateandpotassiumcarbonate.InadditioninEgypt,naturallyoccurringsodiumcarbonate,themineral
natron,wasminedfromdrylakebeds.InBritain,theonlylocalsourceofalkaliwasfromkelp,which
washedashoreinScotlandandIreland.[2][3]
In1783,KingLouisXVIofFranceandtheFrenchAcademyofSciencesofferedaprizeof2400livresfora
methodtoproducealkalifromseasalt(sodiumchloride).In1791,NicolasLeblanc,physiciantoLouis
PhilipII,DukeofOrlans,patentedasolution.ThatsameyearhebuiltthefirstLeblancplantfortheDuke
atSaintDenis,andthisbegantoproduce320tonsofsodaperyear.[4]Hewasdeniedhisprizemoney
becauseoftheFrenchRevolution.[5]
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Formorerecenthistory,seeindustrialhistorybelow.

Chemistry
TheLeblancprocesswasabatchprocessinwhichsodium
chloridewassubjectedtoaseriesoftreatments,eventually
producingsodiumcarbonate.Inthefirststep,thesodium
chloridewasheatedwithsulfuricacidtoproducesodium
sulfate(calledthesaltcake)andhydrogenchloridegas
accordingtothechemicalequation
2NaCl+H2SO4Na2SO4+2HCl
ReactionschemeoftheLeblancprocess
Thischemicalreactionhadbeendiscoveredin1772bythe
(green=reactants,black=intermediates,
SwedishchemistCarlWilhelmScheele.Leblanc'scontribution
red=products)
wasthesecondstep,inwhichthesaltcakewasmixedwith
crushedlimestone(calciumcarbonate)andcoalandfired.This
reactionhappensintwoparts.Firstthecoal(carbon)wasoxidizedtocarbondioxide,reducingthesulfateto
sulfide.Second,thecalciumandsodiumswaptheirligandstoleavethethermodynamicallyfavorable
combinationofsodiumcarbonateandcalciumsulfide.Thismixtureiscalledblackash.

Na2SO4+2CNa2S+2CO2
Na2S+CaCO3Na2CO3+CaS
Thesodaashwasthenseparatedfromtheblackashbywashingitwithwater.Thewashwaterwasthen
evaporatedtoyieldsolidsodiumcarbonate.Thisextractionprocesswastermedlixiviation.

Processdetail
Thesodiumchlorideisinitiallymixedwithconcentratedsulfuricacidandthemixtureexposedtolowheat.
Thehydrogenchloridegasbubblesoffandwasdiscardedtoatmospherebeforegasabsorptiontowerswere
introduced.Thiscontinuesuntilallthatisleftisafusedmass.Thismassstillcontainsenoughchlorideto
contaminatethelaterstagesoftheprocess.Themassisthenexposedtodirectflame,whichevaporates
nearlyalloftheremainingchloride.[6]
Thecoalusedinthenextstepmustbelowinnitrogentoavoidtheformationofcyanide.Thecalcium
carbonate,intheformoflimestoneorchalk,shouldbelowinmagnesiaandsilica.Theweightratioofthe
chargeis2:2:1ofsaltcake,calciumcarbonate,andcarbonrespectively.Itisfiredinareverberatoryfurnace
atabout1000C.[7]
Theblackashproductoffiringmustbelixiviatedrightawaytopreventoxidationofsulfidesbackto
sulfate.[7]Inthelixiviationprocess,theblackashiscompletelycoveredinwater,againtoprevent
oxidation.Tooptimizetheleachingofsolublematerial,thelixiviationisdoneincascadedstages.Thatis,
purewaterisusedontheblackashthathasalreadybeenthroughpriorstages.Theliquorfromthatstageis
usedtoleachanearlierstageoftheblackash,andsoon.[7]

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Thefinalliquoristreatedbyblowingcarbondioxidethroughit.Thisprecipitatesdissolvedcalciumand
otherimpurities.Italsovolatilizesthesulfide,whichiscarriedoffasH2Sgas.Anyresidualsulfidecanbe
subsequentlyprecipitatedbyaddingzinchydroxide.Theliquorisseparatedfromtheprecipitateand
evaporatedusingwasteheatfromthereverberatoryfurnace.Theresultingashisthenredissolvedinto
concentratedsolutioninhotwater.Solidsthatfailtodissolveareseparated.Thesolutionisthencooledto
recrystallizenearlypuresodiumcarbonatedecahydrate.[7]

Industrialhistory
LeblancestablishedthefirstLeblancprocessplantin1791inSt.Denis.However,FrenchRevolutionaries
seizedtheplant,alongwiththerestofLouisPhilip'sestate,in1794,andpublicizedLeblanc'stradesecrets.
NapoleonIreturnedtheplanttoLeblancin1801,butlackingthefundstorepairitandcompeteagainst
othersodaworksthathadbeenestablishedinthemeantime,Leblanccommittedsuicidein1806.[5]
Bytheearly19thcentury,Frenchsodaashproducersweremaking10,00015,000tonsannually.
However,itwasinBritainthattheLeblancprocessbecamemostwidelypracticed.[5]ThefirstBritishsoda
worksusingtheLeblancprocesswasbuiltbytheLoshfamilyofironfoundersattheLosh,WilsonandBell
worksinWalkerontheRiverTynein1816,butsteepBritishtariffsonsaltproductionhinderedthe
economicsoftheLeblancprocessandkeptsuchoperationsonasmallscaleuntil1824.Followingthe
repealofthesalttariff,theBritishsodaindustrygrewdramatically,andthechemicalworksestablishedby
JamesMusprattinLiverpoolandCharlesTennantnearGlasgowbecamesomeofthelargestintheworld.
By1852,annualsodaproductionhadreached140,000tonsinBritainand45,000tonsinFrance.[5]Bythe
1870s,theBritishsodaoutputof200,000tonsannuallyexceededthatofallothernationsintheworld
combined.

Pollutionissues
TheLeblancprocessplantswerequitedamagingtothelocalenvironment.Theprocessofgeneratingsalt
cakefromsaltandsulfuricacidreleasedhydrochloricacidgas,andbecausethisacidwasindustrially
uselessintheearly19thcentury,itwassimplyventedintotheatmosphere.Also,aninsoluble,smellysolid
wastewasproduced.Forevery8tonsofsodaash,theprocessproduced5.5tonsofhydrogenchlorideand7
tonsofcalciumsulfidewaste.Thissolidwaste(knownasgalligu)hadnoeconomicvalue,andwaspiledin
heapsandspreadonfieldsnearthesodaworks,whereitweatheredtoreleasehydrogensulfide,thetoxic
gasresponsiblefortheodorofrotteneggs.
Becauseoftheirnoxiousemissions,Leblancsodaworksbecametargetsoflawsuitsandlegislation.An
1839suitagainstsodaworksalleged,"thegasfromthesemanufactoriesisofsuchadeleteriousnatureasto
blighteverythingwithinitsinfluence,andisalikebanefultohealthandproperty.Theherbageofthefields
intheirvicinityisscorched,thegardensneitheryieldfruitnorvegetablesmanyflourishingtreeshave
latelybecomerottennakedsticks.Cattleandpoultrydroopandpineaway.Ittarnishesthefurnitureinour
houses,andwhenweareexposedtoit,whichisoffrequentoccurrence,weareafflictedwithcoughsand
painsinthehead...allofwhichweattributetotheAlkaliworks."
In1863,theBritishParliamentpassedthefirstofseveralAlkaliActs,thefirstmodernairpollution
legislation.Thisactallowedthatnomorethan5%ofthehydrochloricacidproducedbyalkaliplantscould
beventedtotheatmosphere.Tocomplywiththelegislation,sodaworkspassedtheescapinghydrogen
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chloridegasupthroughatowerpackedwithcharcoal,whereitwasabsorbedbywaterflowingintheother
direction.Thechemicalworksusuallydumpedtheresultinghydrochloricacidsolutionintonearbybodies
ofwater,killingfishandotheraquaticlife.
TheLeblancprocessalsomeantveryunpleasantworkingconditionsfortheoperators.Itoriginallyrequired
carefuloperationandfrequentoperatorinterventions(someinvolvingheavymanuallabour)intoprocesses
givingoffhotnoxiouschemicals.[8]Thisimprovedsomewhatlaterasprocessesweremoreheavily
mechanisedtoimproveeconomicsanduniformityofproduct.
Bythe1880s,methodsforconvertingthehydrochloricacidtochlorinegasforthemanufactureof
bleachingpowderandforreclaimingthesulfurinthecalciumsulfidewastehadbeendiscovered,butthe
LeblancprocessremainedmorewastefulandmorepollutingthantheSolvayprocess.Thesameistrue
whenitiscomparedwiththelaterelectrolyticalprocesseswhicheventuallyreplaceditforchlorine
production.

Obsolescence
In1861,theBelgianchemistErnestSolvaydevelopedamoredirectprocessforproducingsodaashfrom
saltandlimestonethroughtheuseofammonia.TheonlywasteproductofthisSolvayprocesswascalcium
chloride,andsoitwasbothmoreeconomicalandlesspollutingthantheLeblancmethod.Fromthelate
1870s,SolvaybasedsodaworksontheEuropeancontinentprovidedstiffcompetitionintheirhome
marketstotheLeblancbasedBritishsodaindustry.AdditionallytheBrunnerMondSolvayplantwhich
openedin1874atWinningtonnearNorthwichprovidedfiercecompetitionnationally.Leblancproducers
wereunabletocompetewithSolvaysodaash,andtheirsodaashproductionwaseffectivelyanadjunctto
theirstillprofitableproductionofchlorine,bleachingpowderetc.(Theunwantedbyproductshadbecome
theprofitableproducts).Thedevelopmentofelectrolyticmethodsofchlorineproductionremovedthat
sourceofprofitsaswell,andtherefollowedadeclinemoderatedonlyby"gentlemen's'agreements"with
Solvayproducers.[9]By1900,90%oftheworld'ssodaproductionwasthroughtheSolvaymethod,oron
theNorthAmericancontinent,throughtheminingoftrona,discoveredin1938,whichcausedtheclosureof
thelastNorthAmericanSolvayplantin1986.ThelastLeblancbasedsodaashplantclosedintheearly
1920s.[3]However,becauseofsolubilityofthebicarbonate,theSolvayprocessdoesnotworkforthe
manufactureofpotassiumcarbonate,andtheLeblancprocesscontinuedinlimiteduseforitsmanufacture
untilmuchlater.

Biodiversity
IronicallythereisastrongcaseforarguingthatLeblancprocesswasteisthemostendangeredhabitatinthe
UK,sincethewasteweathersdowntocalciumcarbonateandproducesahavenforplantsthatthrivein
limerichsoils,knownascalcicoles.Onlyfoursuchsiteshavesurvivedthenewmillenniumthreeare
protectedaslocalnaturereservesofwhichthelargest,atNobEndnearBolton,isanSSSIandLocalNature
Reservelargelyforitssparseorchidcalcicoleflora,mostunusualinanareawithacidsoils.Thisalkaline
islandcontainswithinitanacidisland,whereacidboilerslagwasdeposited,whichnowshowsupasa
zonedominatedbyheather,Callunavulgaris.[10]

References
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1. "LevantineAlkaliAshesandEuropeanIndustries",byE.Ashtor&G.Cevidalli,inJournalofEuropean
EconomicHistory,year1983.
2. Clow,ArchibaldandClow,NanL.(1952).ChemicalRevolution,(AyerCoPub,June1952),pp.6590.ISBN0
836919092.
3. Kiefer,DavidM.(2002)."Itwasallaboutalkali"
(http://pubs.acs.org/subscribe/journals/tcaw/11/i01/html/01chemchron.html)11(1).Today'sChemistatWork.
pp.456.Retrieved22April2007.
4. Aftalion,Fred(1991).AHistoryoftheInternationalChemicalIndustry.Philadelphia:UniversityofPennsylvania
Press.pp.1113.ISBN0812212975.
5. AHistoryoftheInternationalChemicalIndustry.
6. "HydrochloricAcidandSodiumSulphate"(http://www.lenntech.com/Chemistry/HydrochloricAcidSodium
Sulphate.htm).Lenntech.Retrieved22April2007.
7. "TheSodaIndustries"(http://www.lenntech.com/Chemistry/Soda%20industries.htm).Lenntech.Retrieved
22April2007.
8. Russell.ColinArchibald,Chemistry,societyandenvironment:anewhistoryoftheBritishchemicalindustry,
RoyalSocietyofChemistry,2000.ISBN0854045996
9. ReaderWJImperialChemicalIndustriesAHistoryVolume1TheForerunners18701926OxfordUniversity
Press1970SBN192159372
10. Shaw,PJA&HaltonW.(1998).Classicsites:NobEnd,Bolton.BritishWildlife10,1317.

Externallinks
T.HowardDeighton.Thestruggleforsupremacy:beingaseriesofchaptersinthehistoryofthe
leblancalkaliindustryinGreatBritain:32:WealthfromWaste(http://www.ebooksread.com/authors
eng/thowarddeighton/thestruggleforsupremacybeingaseriesofchaptersinthehistoryofthe
leala/page2thestruggleforsupremacybeingaseriesofchaptersinthehistoryofthele
ala.shtml)"...thisabominablerefusetippedbymillionsoftonsuponthebanksofthe..Tyne"
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Leblanc_process&oldid=661482933"
Categories: Chemicalprocesses IndustrialRevolution Frenchinventions
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