UnitedStatesPatent[191[1114,415,754

Lawrence[45]Nov.15,1983
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PROCESSFORPREPARINGANILINE
Inventor:FrederickR.Lawrence,Claymont,
Del.
Assignee:E.I.DuPentdeNemours&Co.,
Wilmington,Del.
Appl.No.:458,659
Filed:Jan.17,1983.
Int.
Cl.3..............................................
C07C85/11
U.S.Cl......................................564/423;
564/420
FieldofSearch................................
564/420,423
ReferencesCited
U.S.PATENTDOCUMENTS
1,447,5573/1923Legg...............................
564/420X
1,854,2584/1932Heroldetal....................
564/420X
2,560,5557/1951Condit............................
564/420X
2,891,0946/1959Karkalitsetal....................
564/420
3,136,8186/1964Sperberetal.......................
564/420
4,185,0361/1980Coosaboon..........................
564/423
OTHERPUBLICATIONS
Albrightetal.,Chem.Eng.,74,#33,pp.251259,

11/67.
PrimaryExamz'nerPaulF.Shaver
[57]ABSTRACT
Anilinecanbepreparedbycatalytichydrogenationof
nitrobenzenecontainingpolynitrophenolimpurities.
Thepolynitrophenolimpuritiesareconvertedtotars,
andcanbeseparatedanddisposedof.
6Claims,1DrawingFigure
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14,415,754A
PROCESSFORPREPARINGANILINE
DESCRIPTION.
1.TechnicalFieldu
Thisinventionrelatestoaprocessforpreparingani
linebythehydrogenationofnitrobenzene.Itismore
particularlydirectedtoaprocessforpreparinganiline
bycatalytichydrogenationofacidicnitrobenzenecon
tainingpolynitrophenolimpurities."
BACKGROUNDANDSUMMARYOFTHE

"INVENTION
Anilineisacommodityinthechemicalindustry,
widelyusedinthepreparationofdyes,pigmentsand
chemicalintermediates.Alargeproportionoftheani
lineconsumedisproducedbyhdrogenationofnitroben
zene(NB),whichnormallycontainspolynitrophenol
(PNP)impurities,chiey2,4dinitrophenolandpicric
acid.Itwasheretoforethoughtdesirablethatthese
PNPimpuritiesberemovedfromtheNBbeforehydro
genation,andthiswasnormallydonebyextracting
themwithalkalinewater.Althoughthisisa
satisfactory
method,thePNPimpuritiesareextremelytoxicand
disposingofthemisdifiicultandexpensive.
IthasnowbeenfoundthatthisextractionofPNP
impuritiescanbedispensedwithentirelyandthatani
linecanbepreparedbycatalytichydrogenationdi
rectlyfromNBcontainingthesePNPimpurities.This
convertsthePNPimpuritiestopolymerictarswhich
canbeeasilyseparatedfromtheanilineproductand
disposedof,mostpreferablybyincineration.Thisis
especiallyadvantageousbecausetheNB/anilinereac
tionitselfproducestars,whichmustbeseparatedfrom
theanilineanddisposedof.Thus,whentheprocessof
theinventionisused,thetwotypesoftarcanbesepa
ratedfromtheNBproductanddisposedoftogether.
ThecostlyandtimeconsumingPNPseparationstepis
therebyeliminated.'
BRIEFDESCRIPTIONOFTHEDRAWING
Thedrawingisaowsheetoftheprocessofthe
invention.7
DETAILEDDESCRIPTIONOFTHE
INVENTION
Theinventioncanbebestdescribedwithreferenceto
thedrawing.
CrudeacidicNBcontainingabout1030,000ppmof
PNPimpurities,whichcanbetakendirectlyfromaNB
preparationfacility,isfedvialine1intovessel2,
where
itiswashedsubstantiallyfreeofresidualmineralacid
withwaterfedintothevesselvialine3.Acidicwash

waterisremovedfromthevesselvialine4.
ThewashedNBisthenfedvialine5intocolumn6,
whereliquidswithlowboilingpointsareconvention
allyremovedandwithdrawnvialine7.TheNB,still
containingthePNPimpurities,isthenfedvialine8
into
thebottomofsieveplatereactor9,whereitis
continu
ouslyandcatalyticallyhydrogenatedtoanilineata
temperatureof100300C.andahydrogenpressureof
3452068kPagauge,witharesidencetimeofthereac
tantsinthereactorof230minutes,andusinga
conven
tionalliquidphasehydrogenationcatalyst,preferablya
platinum/palladium/irononcarbonsupportcatalystof
thetypedescribedinExampleXofU.S.Pat.No.
2,823,235toGrahamandSpiegler.
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2
Hydrogenisfedintothereactorvialine10,anda
O.13.0%byweightslurryofthecatalystinaniline,
preferablyrecycledfromthereactor,isfedinvialine
11
ataratewhichwillcontinuouslyprovide0.12%,by
weight,ofcatalyst(basedontheNBfeed)inthe
reactor
(recycleanilinestreamisnotshown).Alloftheliquid
feedsareheatedto75125C.toinitiatereaction.
Waterandabout80%byweightoftheanilinepro

ducedinthereactorarewithdrawninthevaporphase
vialine12.Thisvaporiscondensedandthewaterand
anilineseparated.Theanilineisdrawnoffvialine13
andthewaterisrecycledtothereactorvialine14for
temperaturecontrol.Theremainderoftheaniline,and
thetars(intowhichthePNPimpuritieshavebeencon
vertedinthereactor),arewithdrawnfromthereactor
asaliquidvialine15andpassedintocolumn16,where
theanilineandtarsareseparatedbyconventional
distil
lation.Anilineiswithdrawnfromthecolumnvialine17
andthetarsarewithdrawnvialine18anddisposedof,
preferablybyincineration.
Thereisanalternativeembodimentoftheprocessof
theinvention,usedwhenitisdesirabletobypassso_me
oftheequipmenttominimizethecorrosiveeffectsof
theacidicNB.Inthisembodiment,NBcontainingPNP
impurities,butfromwhichthemineralacidshavebeen
removed,iswithdrawnfromvessel2vialine19and
passedtovessel20,wherethePNPimpuritiesareex
tractedfromtheNBandconvertedtowatersoluble
saltsbymixingabout8partsoftheNBwithabout1
part
ofwaterandadjustingthepHofthemixtureto912
withsodiumhydroxideorammoniumhydroxide.The
NBphaseandtheaqueousphasearethenseparated.
TheNBphaseiswashedwithwaterandpassedto
column6vialine21andisthenprocessedinthe
regular
fashion.TheaqueousextractofwatersolublePNPsalts
iswithdrawnfromvessel20vialine22andpassedto
extractor23,wherethePNPsaltsareconvertedbackto
PNPbybringingtheextracttoapHof0.51withnitric
acidorsulfuricacidfedintotheextractorvialine
24.
ThePNPisthenextractedbyanddissolvedinNBfed
intotheextractorvialine25.Spentacidiswithdrawn
fromthereactorvialine26.ThePNP/NBsolutionis
washedmoderatelywithwaterandthenfedvialine27
intoreactor9,wherethePNPisconvertedtotar.This
tariswithdrawnfromthereactoranddisposedofas

before._.
EXAMPLE
Inthefollowingexample,allpartsarebyweight.
CrudeNBcontaining4061ppmofPNP(130parts
perhour)wascontinuouslyfedintovessel2,whereits
mineralacidcontentwasreducedto300ppmbywash
ingitwithwater.TheNBwasthencontinuouslyfedvia
line19intovessel20,wherethePNPimpuritieswere
convertedtowatersolublesaltsbybringingthepHof
theNBtoabout10withaqueousammoniaandthen
washingwithwatertoremoveexcessalkalinity.The
NBphasewastakenfromthevesselvialine21andfed
intocolumn6,whereliquidshavinglowboilingpoints
wereremovedandwithdrawnfromthecolumnvialine
7.TheNB(31,149partsperhour)wasthencontinu
ouslyfedvialine8intoreactor9.
TheaqueousphasecontainingthePNPsaltswas
withdrawnfromvessel20vialine22andfedintoex
tractor23,wherethePNPsaltswereconvertedtoPNP
bybringingtheaqueousphasetoaboutpH1withnitric
acid.PNPwasthenextractedfromtheaqueousphase
withNB,using1partNBtol0partsofwater.The
4,415,754
34
resulting14%PNPinNBsolution(714partsperhour)
waswashedwithwatertoremoveexcessacidityand
continuouslyfedtoreactor9vialine27.
Simultaneouslytherewerefedintoreactor9the
following:
Recyclewater'(34,264partsperhour)vialine14
Hydrogen(2346partsperhour)vialine10
Catalystslurry(15,468partsperhour)vialine11.
Slurryisa1.24%slurryofthecatalystdescribedin
ExampleXofU.S.Pat.No.2,823,235inaniline.
Allliquidfeedstreamswereheatedto75125C.to
initiatereaction.Thereactortemperatureacrossthe
columnwasheldat120230C.bymanipulatingthe
waterandcatalystfeedrates.Hydrogenpressurewas
heldatabout1723kPagauge(250psig).
Astreamofsteamandanilinewaswithdrawnfrom

thereactorvialine12,condensedandthewaterand
anilineseparated.Theaniline(29,228partsperhour)
wastakenoffvialine13andwater(34,264partsper
hour)wasrecycledtothereactorvialine14.
Liquidaniline(2282partsperhour)wastakenfrom
thereactorvialine15andfedtocolumn16,wheretars
andanilinewereseparatedbydistillation.Aniline
prod
uct(2114partsperhour)waswithdrawnfromthecol
umnvialine17.Tarswerewithdrawnvialine18and
incinerated.
Theanilineproductcontainedlessthan5ppmof
PNP.ConversionofPNPtotarwasmorethan_99%,
andanilineyieldwasmorethan99%.
Iclaim:
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1.Amethodforpreparinganilinedirectlyfrom
acidicnitrobenzenecontainingaboutl030,000ppmof
polynitrophenolimpurities,themethodcomprising
(a)removingsubstantiallyallthemineralacidfrom
thenitrobenzene,
(b)catalyticallyhydrogenatingthenitrobenzenere
sultingfromstep(a)togiveanilineandtars,and
then
(c)separatingtheanilineandthetars.
2.Themethodofclaim1inwhichthecatalystusedis
aplatinum/palladium/ironcatalyst.
3.Theprocessofclaim1inwhichstep(b)isper
formedat100300C.andahydrogenpressureof

3452068kPagauge.
4.Theprocessofclaim1inwhichstep(c)isper
formedbyfractionaldistillation.
5.Theprocessofclaim1inwhichstep(a)isper
formedbyextractionwithwater.
6.Theprocessofclaim1having,betweensteps(a)
and(b),theadditionalstepsof
(c)separatingthepolynitrophenolimpuritiesfrom
thenitrobenzeneandconvertingthemintowater
solublesalts;
(d)convertingthewatersolublesaltsbacktotheir
originalformanddissolvingtheresultingmaterial
innitrobenzene;and
(e)feedingthenitrobenzenefrom(c)andthenitro
,benzenesolutionfrom(d)separatelyintostep(b)of
claim1.
=1=*=1!=l=.=1=