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Haberprocess
FromWikipedia,thefreeencyclopedia

TheHaberprocess,alsocalledtheHaberBoschprocess,isan
artificialnitrogenfixationprocessandisthemainindustrial
procedurefortheproductionofammoniatoday.[1]Itisnamedafter
itsinventors,theGermanchemistsFritzHaberandCarlBosch,who
developeditinthefirsthalfofthetwentiethcentury.Theprocess
convertsatmosphericnitrogen(N2)toammonia(NH3)byareaction
withhydrogen(H2)usingametalcatalystunderhightemperatures
andpressures:
N2+3H22NH3(H=92.4kJmol1)
BeforethedevelopmentoftheHaberprocess,ammoniahadbeen
difficulttoproduceonanindustrialscale[2][3][4]withearlymethods
suchastheOddaprocess,BirkelandEydeprocessandFrankCaro
processallbeinghighlyinefficient.
AlthoughtheHaberprocessismainlyusedtoproducefertilizer
today,duringWorldWarI,itprovidedGermanywithasourceof
ammoniafortheproductionofexplosives,compensatingforthe
AlliedtradeblockadeonChileansaltpeter.

FritzHaber,1918

Contents
1History
2Theprocess
2.1Sourcesofhydrogen
2.2Reactionrateandequilibrium
2.3Catalysts
3Economicandenvironmentalaspects
4Seealso
5References
6Externallinks

History
Throughoutthenineteenthcenturythedemandfornitratesandammoniaforuseasfertilizersandindustrial
feedstockshadbeensteadilyincreasing,howeverthemainsourceremainedtheminingofniterdeposits.By
thestartofthetwentiethcenturyitwasbeingpredictedthatthesereserveswouldbeunabletosatisfyfuture
demand[5]andresearchintonewpotentialsourcesofammoniabecameevermoreimportant.Themost
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obvioussourcewasatmosphericnitrogen(N2),whichmakesupnearly80%oftheair,howeverN2is
exceptionallystableandwillnotreadilyreactwithotherchemicals.ConvertingN2intoammoniais
thereforeexceedinglydifficultandposedachemicalchallengewhichoccupiedtheeffortsofchemists
acrosstheworld.
HabertogetherwithhisassistantRobertLeRossignoldevelopedthehighpressuredevicesandcatalysts
usedtodemonstratetheHaberprocessatlaboratoryscale.[6][7]Theydemonstratedtheirprocessinthe
summerof1909byproducingammoniafromairdropbydrop,attherateofabout125ml(4USfloz)per
hour.TheprocesswaspurchasedbytheGermanchemicalcompanyBASF,whichassignedCarlBoschthe
taskofscalingupHaber'stabletopmachinetoindustriallevelproduction.[3][8]Hesucceededinthisprocess
in1910.HaberandBoschwerelaterawardedNobelprizes,in1918and1931respectively,fortheirworkin
overcomingthechemicalandengineeringproblemsposedbytheuseoflargescale,continuousflow,high
pressuretechnology.[9]
AmmoniawasfirstmanufacturedusingtheHaberprocessonanindustrialscalein1913inBASF'sOppau
plantinGermany,productionreaching20tonnes/daythefollowingyear.[10]DuringWorldWarI,the
syntheticammoniawasusedfortheproductionofnitricacid,aprecursortomunitions.TheAllieshad
accesstolargeamountsofsodiumnitratedepositsinChile(socalled"Chilesaltpetre")thatbelonged
almosttotallytoBritishindustries.AsGermanylackedaccesstosuchreadilyavailablenaturalresources,
theHaberprocessprovedessentialtothecontinuedGermanwareffort.[11][9]

Theprocess
Thisconversionistypicallyconductedat1525MPa(2,200
3,600psi)or150250barandbetween400500C(752932F),
asthegasesarepassedoverfourbedsofcatalyst,withcooling
betweeneachpasssoastomaintainareasonableequilibrium
constant.Oneachpassonlyabout15%conversionoccurs,butany
unreactedgasesarerecycled,andeventuallyanoverallconversion
of97%isachieved.[1]
Thesteamreforming,shiftconversion,carbondioxideremoval,and
methanationstepseachoperateatpressuresofabout2.53.5MPa
(360510psi)or2535bar,andtheammoniasynthesisloop
operatesatpressuresrangingfrom618MPa(8702,610psi)or
60180bar,dependinguponwhichproprietaryprocessisused.[1]

Sourcesofhydrogen
Themajorsourceofhydrogenismethanefromnaturalgas.The
conversion,steamreforming,isconductedwithair,whichis
deoxygenatedbythecombustionofnaturalgas.OriginallyBosch
obtainedhydrogenbytheelectrolysisofwater.

Anhistorical(1921)highpressure
steelreactorforproductionof
ammoniaviatheHaberprocessis
displayedattheKarlsruheInstituteof
Technology,Germany.

Reactionrateandequilibrium
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Nitrogen(N2)isveryunreactivebecausethemoleculesareheldtogetherbystrongtriplebonds.TheHaber
processreliesoncatalyststhatacceleratethescissionofthistriplebond.
Twoopposingconsiderationsarerelevanttothissynthesis:thepositionoftheequilibriumandtherateof
reaction.Atroomtemperature,theequilibriumisstronglyinfavorofammonia,butthereactiondoesn't
proceedatadetectablerate.Theobvioussolutionistoraisethetemperature,butbecausethereactionis
exothermic,theequilibriumconstant(usingatmunits)becomes1around150or200C.(SeeLe
Chatelier'sprinciple.)
Abovethistemperature,theequilibriumquicklybecomesquite
unfavourableatatmosphericpressure,accordingtotheVan'tHoff
equation.Thusonemightsupposethatalowtemperatureistobeused
andsomeothermeanstoincreaserate.However,thecatalystitself
requiresatemperatureofatleast400Ctobeefficient.
Pressureistheobviouschoicetofavourtheforwardreactionbecause
thereare4molesofreactantforevery2molesofproduct(seeentropy),
andthepressureused(around200atm)alterstheequilibrium
concentrationstogiveaprofitableyield.
Economically,though,pressureisanexpensivecommodity.Pipesand
reactionvesselsneedtobestrengthened,valvesmorerigorous,and
therearesafetyconsiderationsofworkingat200atm.Inaddition,
runningpumpsandcompressorstakesconsiderableenergy.Thusthe
compromiseusedgivesasinglepassyieldofaround15%.

Kp(T)for
N2+3H22NH3[12]
Temperature(C)

Kp

300

4.34x103

400

1.64x104

450

4.51x105

500

1.45x105

550

5.38x106

600

2.25x106

Anotherwaytoincreasetheyieldofthereactionwouldbetoremovetheproduct(i.e.ammoniagas)from
thesystem.Inpractice,gaseousammoniaisnotremovedfromthereactoritself,sincethetemperatureistoo
highbutitisremovedfromtheequilibriummixtureofgasesleavingthereactionvessel.Thehotgasesare
cooledenough,whilstmaintainingahighpressure,fortheammoniatocondenseandberemovedasliquid.
Unreactedhydrogenandnitrogengasesarethenreturnedtothereactionvesseltoundergofurtherreaction.

Catalysts
ThemostpopularcatalystsarebasedonironpromotedwithK2O,CaO,SiO2,andAl2O3.Theoriginal
HaberBoschreactionchambersusedosmiumasthecatalyst,butitwasavailableinextremelysmall
quantities.Habernoteduraniumwasalmostaseffectiveandeasiertoobtainthanosmium.UnderBosch's
directionin1909,theBASFresearcherAlwinMittaschdiscoveredamuchlessexpensiveironbased
catalyst,whichisstillusedtoday.Someammoniaproductionutilizesrutheniumbasedcatalysts(theKAAP
process).Rutheniumformsmoreactivecatalyststhatallowsmilderoperatingpressures.Suchcatalystsare
preparedbydecompositionoftrirutheniumdodecacarbonylongraphite.[1]
Inindustrialpractice,theironcatalystisobtainedfromfinelygroundironpowder,whichinturnisusually
obtainedbyreductionofhighpuritymagnetite(Fe3O4).Thepulverizedironmetalisburnt(oxidized)to
givemagnetiteofadefinedparticlesize.Themagnetiteparticlesarethenpartiallyreduced,removingsome
oftheoxygenintheprocess.Theresultingcatalystparticlesconsistofacoreofmagnetite,encasedina
shellofwstite(FeO),whichinturnissurroundedbyanoutershellofironmetal.Thecatalystmaintains
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mostofitsbulkvolumeduringthereduction,resultinginahighlyporoushighsurfaceareamaterial,which
enhancesitseffectivenessasacatalyst.Otherminorcomponentsofthecatalystincludecalciumand
aluminiumoxides,whichsupporttheironcatalystandhelpitmaintainitssurfacearea.TheseoxidesofCa,
Al,K,andSiareimmunetoreductionbythehydrogen.[1]
Thereactionmechanism,involvingthe
heterogeneouscatalyst,isbelievedtoinvolvethe
followingsteps:
1. N2(g)N2(adsorbed)
2. N2(adsorbed)2N(adsorbed)
3. H2(g)H2(adsorbed)
4. H2(adsorbed)2H(adsorbed)
5. N(adsorbed)+3H(adsorbed)NH3
(adsorbed)
6. NH3(adsorbed)NH3(g)
Reaction5occursinthreesteps,formingNH,
NH2,andthenNH3.Experimentalevidencepoints

energydiagram

toreaction2asbeingtheslow,ratedetermining
step.Thisisnotunexpectedsincethebondbroken,
thenitrogentriplebond,isthestrongestofthebondsthatmustbebroken.
AmajorcontributortotheelucidationofthismechanismisGerhardErtl.[13]

Economicandenvironmentalaspects
Whenitwasfirstinvented,theHaberprocessneededtocompeteagainstanotherindustrialprocesses,the
Cyanamideprocess.However,theCyanamideprocessconsumedlargeamountsofelectricalpowerandwas
morelaborintensivethantheHaberprocess.[9]:137143
TheHaberprocessnowproduces450milliontonnes(440,000,000longtons500,000,000shorttons)of
nitrogenfertilizerperyear,mostlyintheformofanhydrousammonia,ammoniumnitrate,andurea.35%
oftheworld'snaturalgasproductionisconsumedintheHaberprocess(~12%oftheworld'sannual
energysupply).[14][15][16][17]Incombinationwithpesticides,thesefertilizershavequadrupledthe
productivityofagriculturalland:
Withaveragecropyieldsremainingatthe1900levelthecropharvestintheyear2000wouldhave
requirednearlyfourtimesmorelandandthecultivatedareawouldhaveclaimednearlyhalfofall
icefreecontinents,ratherthanunder15%ofthetotallandareathatisrequiredtoday.[18]
Duetoitsdramaticimpactonthehumanabilitytogrowfood,theHaberprocessservedasthe"detonatorof
thepopulationexplosion",enablingtheglobalpopulationtoincreasefrom1.6billionin1900totoday's7
billion.[19]Nearly80%ofthenitrogenfoundinhumantissuesoriginatedfromtheHaberBoschprocess.[20]
Sincenitrogenuseefficiencyistypicallylessthan50%,[21]ourheavyuseofindustrialnitrogenfixationis
severelydisruptivetoourbiologicalhabitat.[2][20]
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Seealso
Ammonia
Ammoniaproduction
Hydrogenproduction
Industrialgas

References
1. MaxAppl"Ammonia"inUllmann'sEncyclopediaofIndustrialChemistry2006WileyVCH,Weinheim.
doi:10.1002/14356007.a02_143.pub2(https://dx.doi.org/10.1002%2F14356007.a02_143.pub2)
2. Smil,Vaclav(2004).Enrichingtheearth:FritzHaber,CarlBosch,andthetransformationofworldfood
production(1stMITPresspaperbacked.).Cambridge,Mass.:MIT.ISBN9780262693134.
3. Hager,Thomas(2008).Thealchemyofair:aJewishgenius,adoomedtycoon,andthescientificdiscoverythat
fedtheworldbutfueledtheriseofHitler(1sted.).NewYork:HarmonyBooks.ISBN9780307351784.
4. Sittig,Marshall(1979).Fertilizerindustry:processes,pollutioncontrol,andenergyconservation.ParkRidge,
N.J.:NoyesDataCorp.ISBN0815507348.
5. K.James,,Laylin(1993).Nobellaureatesinchemistry19011992(3.printinged.).[S.l.]:Americanchemical
society.p.118.ISBN0841226903.
6. Haber,Fritz(2012).ThermodynamiktechnischerGasreaktionen(inGerman)(1.Aufl.ed.).Paderborn:
SalzwasserVerlag.ISBN9783864448423.
7. "RobertLeRossignol,18841976:ProfessionalChemist"
(http://www.ucl.ac.uk/chemistry/alumni/documents/A5booklet_020909.pdf)(PDF),ChemUCLNewsletter(UCL
DepartmentofChemistry),2009:8
8. USPat990191(http://www.google.com/patents/US990191)
9. Hager,T.TheAlchemyofAir.HarmonyBooks,NY,2008.
10. Philip&PhyllisMorris,FromFertileMinds(review)AmericanScientist2001
(http://www.americanscientist.org/bookshelf/pub/fromfertileminds)
11. "NobelAwardtoHaber"(http://query.nytimes.com/mem/archivefree/pdf?
_r=1&res=9807EEDA133BEE32A25750C0A9649C946195D6CF&oref=slogin).NewYorkTimes.3February
1920.Retrieved11October2010.
12. Brown,TheodoreL.,LeMay,Jr.,H.Eugene,Bursten,BruceE."Chemistry:TheCentralScience".TenthEd.,
UpperSaddleRiver,NJ:Pearson,2006.Table15.2.ISBN0131096869
13. F.Bozso,G.Ertl,M.GrunzeandM.Weiss(1977)."Interactionofnitrogenwithironsurfaces:I.Fe(100)and
Fe(111)".JournalofCatalysis49(1):1841.doi:10.1016/00219517(77)902378
(https://dx.doi.org/10.1016%2F00219517%2877%29902378)..R.Imbihl,R.J.Behm,G.ErtlandW.Moritz
(1982)."ThestructureofatomicnitrogenadsorbedonFe(100)".SurfaceScience123(1):129140.
Bibcode:1982SurSc.123..129I(http://adsabs.harvard.edu/abs/1982SurSc.123..129I).doi:10.1016/0039
6028(82)901352(https://dx.doi.org/10.1016%2F00396028%2882%29901352)..G.Ertl,S.B.LeeandM.
Weiss(1982)."KineticsofnitrogenadsorptiononFe(111)".SurfaceScience114(23):515526.
Bibcode:1982SurSc.114..515E(http://adsabs.harvard.edu/abs/1982SurSc.114..515E).doi:10.1016/0039
6028(82)907026(https://dx.doi.org/10.1016%2F00396028%2882%29907026)..G.Ertl(1983)."Primarysteps
incatalyticsynthesisofammonia".JournalofVacuumScienceandTechnologyA1(2):12471253.
doi:10.1116/1.572299(https://dx.doi.org/10.1116%2F1.572299).
14. Smil,Vaclav(2004).EnrichingtheEarth:FritzHaber,CarlBosch,andtheTransformationofWorldFood
Production.Cambridge,MA:MITPress.ISBN9780262693134.
15. "InternationalEnergyOutlook2007"(http://www.eia.doe.gov/oiaf/ieo/nat_gas.html).
16. Fertilizerstatistics."?"(http://www.fertilizer.org/ifa/statistics/indicators/ind_reserves.asp).
17. Smith,BarryE.(September2002)."Structure.Nitrogenaserevealsitsinnersecrets".Science297(5587):1654
5.doi:10.1126/science.1076659(https://dx.doi.org/10.1126%2Fscience.1076659).PMID12215632
(https://www.ncbi.nlm.nih.gov/pubmed/12215632).
18. Smil,Vaclav(2011)."Nitrogencycleandworldfoodproduction"(http://www.vaclavsmil.com/wp
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content/uploads/docs/smilarticleworldagriculture.pdf)(PDF).WorldAgriculture2:91.
19. Smil,Vaclav(1999)."Detonatorofthepopulationexplosion"(http://www.vaclavsmil.com/wp
content/uploads/docs/smilarticle1999nature7.pdf)(PDF).Nature400:415.doi:10.1038/22672
(https://dx.doi.org/10.1038%2F22672).
20. Howarth,R.W.(2008)."Coastalnitrogenpollution:areviewofsourcesandtrendsgloballyandregionally".
HarmfulAlgae8:1420.doi:10.1016/j.hal.2008.08.015(https://dx.doi.org/10.1016%2Fj.hal.2008.08.015).
21. Oenema,O.Witzke,H.P.Klimont,Z.Lesschen,J.P.Velthof,G.L.(2009)."Integratedassessmentof
promisingmeasurestodecreasenitrogenlossesinagricultureinEU27".Agriculture,Ecosystemsand
Environment133:280288.doi:10.1016/j.agee.2009.04.025(https://dx.doi.org/10.1016%2Fj.agee.2009.04.025).

"TheHaberProcess"(http://www.chemguide.co.uk/physical/equilibria/haber.html).
Chemguide.co.uk.

Externallinks
HaberBoschprocess(http://www.idsia.ch/~juergen/haberbosch.html),mostimportantinventionof
the20thcentury,accordingtoV.Smil,Nature,July29,1999,p415(byJrgenSchmidhuber)
BritannicaguidetoNobelPrizes:FritzHaber(http://www.britannica.com/nobelprize/article
9038696)
NobeleMuseumBiographyofFritzHaber
(http://nobelprize.org/nobel_prizes/chemistry/laureates/1918/haberbio.html)
BASFFertilizeroutofthinair(http://www.basf.com/group/corporate/en/newsandmedia
relations/sciencearoundus/ammonia/story)
UsesandProductionofAmmonia(http://www.ausetute.com.au/haberpro.html)
HaberProcessforAmmoniaSynthesis(http://www.ias.ac.in/resonance/Volumes/16/12/1159
1167.pdf)
Reviewof"BetweenGeniusandGenocide:TheTragedyofFritzHaber,FatherofChemical
Warfare"byDanielCharles(http://www.fas.harvard.edu/~hsdept/bios/docs/shapin_LRBHaber.pdf)
Retrievedfrom"https://en.wikipedia.org/w/index.php?title=Haber_process&oldid=667903306"
Categories: BASF Chemicalprocesses Industrialprocesses Equilibriumchemistry Peakoil
Catalysis HistoryofmininginChile Germaninventions Industrialgases
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