12›UnitedStatesPatent (10)PatentNo.

: US8,603,324B2
Fanctal. (45)DateofPatent: *Dec.10,2013

(54)METHOD FOR HYDRO-UPGRADING oxides:EffectoftheincorporationmethodofTi,CatalysisToday,vol.109,Is

INFERIORGASOLINEVIAULTRA-DEEP sues1-4,Nov.30,2005,pp.54-60,http:www.sciencedirect.com.*
DESULFURIZATIONANDOCTANENUMBERR TatianaKlimova,DoraSolisCasados,
ECOVERY JorgeRamirez,NewselectiveMoandNiMoHDScatalystssupportedon
AI2O3—M8t^)miX8d
(75)Inventors: Yu Fan, Beijing (CN); Xiaojun Bao, oxides,CatalysisToday,vol.43,Issues1-2,Aug,13,1998,pp.
135-146,ISSN0920-5861,10.1016S0920-5861(98)00142-4.
Beijing (CN); Gang Shi, Beijing (CN); (http:www.sciencedirect.com/sciencearticlepiiS0920586198001424).*
Haiyan Liu, Beijing (CN) Yu Fan, Jun Lu, Gang Shi, Haiyan Liu, Xiaojun Bao, Effect
ofsynergism between potassium and phosphorus on
(73) Assignee: China University ofPetroleum— selectivehydrodesulfurizationperformanceofCo—
Bejing(CUPB),Beijing(CN) MoAIO3FCCgasolinehydro-
upgradingcatalyst,CatalysisToday,vol.125,Issues3-
4,Jul.30,2007,pp.220-228,ISSN0920-
5861,10.1016j.cattod.2007.02.
(*) Notice: Subject toany disclaimer, thetermofthis 022.(http:www.sciencedirect.com/.*
patentisextendedoradjustedunder35 Yu Fan, Duo Lei, Gang Shi, Xiaojun Bao, Synthesis of
U.S.C.154(b)by611days. ZSM-5/SAPO-11 composite and its application in FCC gasoline
hydro-upgrading catalyst,CatalysisToday,vol.114,Issue4, May30,
Thispatentissubjecttoaterminaldis- claimer. 2006,
pp.388-396,ISSN0920-5861,10.1016j.cattod.2006.02.050.
(http://www.sciencedirect.com/science
articlepiiS0920586106001052.*
(21)Appl.No.:12/725,939 PingLiu,lieRen,YuhanSun,InfluenceoftemplateonSidistributionofSA
PO-11andtheirperformanceforn-paraffinisomerization,
(22) Filed: Mar.17,2010 MicroporousandMesoporousMaterials,vol.114,Issues1-
3,Sep.1,2008,pp.365-372,ISSN1387-
1811,10.1016j.micromeso.2008.01.
(65) PriorPublicationData aheavycrudewithNiMocatalystssupportedonTiO2—Al2O3binary

US2010/0236978A1 Sep.23,2010

(30) ForeignApplicationPriorityData

Mar.19,2009 (CN)..............................200910080111

(51) Int.Cl.
C10G57/#6 (2006.01)
(52) U.S.CI.
USPC....................................................208/80;208/60
(58)FieldofClassificationSearch
USPC..................................................208/60;585/258
Seeapplicationfileforcompletesearchhistory.

(56) ReferencesCited

U.S.PATENTDOCUMENTS
4,062,762 A* 12/1977 Howardetal. 208211
5,308,471 A 5 1994 Apelianetal.
5,360,532 A* 11/1994 Fletcheretal. 208/89
5,411,658 A 5 1995 Chawlaetal.
5,413,697 A 5 1995 Fletcheretal.
5,770,046 A* 61998 Sudhakar.................. 208216R
5,770,047 A 61998 Salazaretal.
2005/0092655 A1 52005 Nicolaosetal.
2005/0137434 Al* 6/2005 Lietal. 585 258
2005/0269245 Al* 122005 Huve 208/89
2008/0116112 Al 5 2008 Umanskyetal.
2008/0302001 Al* 122008 Koivusalmietal. .44308

FOREIGNPATENTDOCUMENTS

CN 1465666 12004
CN 1488722 4 2004
CN 1718688 12006
CN 1743425 3 2006
OTHERPUBLICATIONS

Jorge Ramirez, Patricia Rayo, Aida Gutiérrez-Alejandre,

JorgeAncheyla,MohanS.Rana,AnalysisofthehydrotreatmentofMay
022. (http://www.sciencedirect.com/science
article/pii/S1387181108000255).*
TatianaKlimova,DoraSolisCasados,JorgeRamirez,Newselective
MoandNiMoHDS catalystssupportedonAl2O3—
MgO(x)mixedoxides, Catalysis Today, vol. 43, Issues 1-2,
Aug. 13, 1998, pp.135-146

(http:www.sciencedirect.com/sciencearticle/pii/S09205861980
01424).*

(Continued)

PrimaryExaminer—RandyBoyer
AssistantExaminer—JuanValencia
(74) Attorney,Agent, or Firm —MichaelFedrick;Loza&
Loza, LLP

(57) ABSTRACT

The present invention relates to a method of hydro-

upgrading inferior gasoline through ultra-deep
desulfurization and octane number recovery. The
method comprises the following steps : cutting inferior
full-range gasoline into light fraction gasoline and
heavy fraction gasoline;contacting the light fraction
gasoline successively with a catalyst for selective diene
removal and a catalyst for desulfurization and hydro
carbon multi-branched-chain hydro isomerization;
contacting the heavy fraction gasoline with the catalyst
for selective hydro desulfurization in a first reactor, and
contacting the effluent from the first reactor with a
catalyst for supplemental desulfurization and
hydrocarbon aromatization/single-branched-chain hydro
isomerization in a second reactor; and blending the
treated light fraction gasoline and the heavy fraction
gasoline toobtainthe ultra-clean gasoline product. The
hydro-upgradingmethod of the invention is
suitableforhydro-upgradinginferior gasoline,
especiallyfor hydro-
upgradinginferiorFCCgasolinewithultra-highsulfur
content andhigholefin content toobtain excellent
hydro- upgrading effects.

13Claims, NoDrawings
 US8,603,324B2
Page2

(56) ReferencesCited upgradingcatalyst, CatalysisToday,vol.114,Issue4, May30,2006,

pp.388-396,ISSN0920-5861,10.1016j.cattod.2006.02.050.
OTHERPUBLICATIONS (http://www.sciencedirect.com/science/article/
piiS0920586106001052).*
Ping Liu, Jie Ren,YuhanSun, Influenceof template on Sidistributionof
Jorge Ramirez, Patricia Rayo, Aida Gutiérrez-Alejandre,
SAPO-11and their performance for n-parafhn
JorgeAncheyta,MohanS.Rana,AnalysisofthehydrotreatmentofMay
isomerization,MicroporousandMesoporousMaterials,vol.114,Issues
aheavycrudewithNiMocatalystssupportedonTiO2—
1-3,Sep.1,2008,pp. 365-372 (http: Al2O3binaryoxides:EffectoftheincorporationmethodofTi,CatalysisTod
www.sciencedirect.com/sciencearticle/pii/Sl387l81108000255).* ay,vol.109, Issues 1-4, Nov.30, 2005, pp.54-60.*
YuFan,DuoLei,GangShi,XiaojunBao,SynthesisofZSM-5/
SAPO-11compositeanditsapplicationinFCCgasolinehydro-
*citedbyexaminer
 US8,603,324B2
1 2
METHOD FOR HYDRO-UPGRADING
INFERIORGASOLINEVIAULTRA-DEEP
DESULFURIZATIONAND OCTANENUMBER
RECOVERY
TECHNICALFIELD
The invention relates to a hydro-upgrading method for
inferiorgasoline,especiallytoahydro-upgradingmethodby
ultra-deepdesulfurizationandoctanenumberpreservation
for inferior gasoline, in particular for poor fluid catalytic
cracking(FCC)gasolinewithultra-highsulfurcompounds
andhigholefins inthefieldofpetroleum refining.
RELATEDART
Currently,thehighsulfur andolefincontentof FCCgaso-
linehavebecomeamainsourceoftroubleintheproduction of
cleangasolineworldwide.In thecaseofdeficientreformed
gasolineandalkylatedgasolinewithhighoctanenumber,the
hydro-upgradingofFCCgasolinebecomesoneofthekey
technologiesfortheproductionofcleanfuelsforvehiclesin
ordertomeetincreasinglystrictstandardsrequiredforclean
gasoline.
U.S.Pat.No.5,770,047,U.S.Pat.No.5,413,697,U.S.Pat.
No.5,411,658,andU.S. Pat.No.5,308,471havedisclosed a
desulfurizationandolefin-reducingprocessprimarilybased
onhydrofiningandcracking/single-branched-chainhydroi-
somerization. Thisprocessincludes cuttingfull-range FCC
gasolineintothelightandheavyfractions, deeply desulfur-
izingtheheavyfractionofFCCgasolinebyusingconven-
tionalhydrofiningcatalyststo convertolefinintoalkanecom-
pletely, then carrying out alkane cracking and
hydroisomerizationreaction over the highlyacidicHZSM-5
zeolite-basedcatalyst, andfinallyobtaining thefull-range
upgraded gasoline by blendingthelight and heavy fractions.
Accordingtothedescriptionoftheabovepatents,theliquid
yieldofthefinalblendedproduct is94wt%byweight,and
thelossofresearchoctanenumber(RON)ingasolineisabout
2.0units.
US2008116112A1hasdisclosed amethodforupgrading
gasoline withhigharomaticsand sulfur contents. The proce-
duresofsuchupgradingmethoddisclosedbythispatentare
asfollows:firstlythegasolineiscutintothelightandheavy
fractions; then thelight fraction undergoesaalkylationreac-
tionina fixed-bedreactor followedby a desulfurizationpro-
cesswithouthydrogenandtheheavyfractionissubjectedto
analkylationreactionbetweenolefinsandsulfurcompounds
tomaketheboiling point ofthesulfurcompounds therein
higher thantheendboiling pointoftheheavygasolineand the
sulfurcompoundswiththehigherboilingpointremovedby
cutting.Thismethodcannotremovethesulfurcompoundsin
gasoline,butonlyexcludestheobtainedsulfurcompounds
withthehigherboilingpointfromgasolinebycuttingand
fractionating.
US2005092655A1hasdisclosedadesulfurizationmethod
for gasoline including the following steps: firstly cutting
gasolineintothelight andheavyfractions toallow thelight
thiopheneandmethylthiophenetoremaininthelightfraction
andtheheavyaromatic sulfurcompoundstoremaininthe
heavy fraction, then subjecting the heavy fraction to
hydrodesulfurizationanddesulfurizingthelightfractionin
contactwithsolidadsorbents.Sincethefeedstockusedinthis
methodisamodelgasolinecomposedofamixture ofmono-
mersulfurcompoundsandmonomerhydrocarbons,itisdif-
ficulttopredicttheupgradingeffectofthemethodonreal
FCCgasoline.
Although desulfurizationand olefinreduction could be
achievedbytheabove-mentionedgasolinehydro-upgrading
methods,thetargetedfeedstockgenerallyhasanolefincon-
tentof20-30v%by volumeanda higharomaticscontent
5(about25v%byvolume).Forthegasolinewithhigholefin
andsulfurcontentsbutlowaromaticscontent(about15v% by
volume),suchasChinese FCCgasolinein whichtheolefin
contentisupto 40v% byvolume ormore,theabovehydro-
upgradingprocess canleadtothegreatsaturationofolefins
10viahydrogenation,substantiallyincreasingthelossingaso-
lineoctane number. Therefore, these upgrading technologies
reportedpubliclyareclearlynotapplicabletotheabovecase. In
viewofthis,aimingattheparticularityof Asian(especially
Chinese) FCCgasoline,amorescientificallyrationalmethod
15 for upgrading more inferior gasoline has always been a
researchfocus inthepetroleum refining industry.
CN1465666A (Chinese Patent Application No.
02121595.2)andCN1488722A(Chinese PatentApplication
No.02133111.1)haveprovidedamethodfordeepdesulfur-
20ization and olefin reduction of gasoline.According tothe
above-mentionedcharacteristicsofChineseFCCgasoline,
themethodinvolvessubjectingtheheavygasolinefractionto
hydrodesulfurization,hydrodenitrogenationand complete
olefinsaturationoverahydrofiningcatalyst,thencracking
2Jandhydroisomerizingoftheformedalkaneswithlowoctane
number torecovertheproduct octane number overacatalyst
withsufficientlyacidic function,andfinally mixing the light
and heavy fractions to obtain the final upgraded product.
Accordingtothedescriptionoftheabovepatent,olefinsare
30completelysaturatedbyhydrogenationinthefirstreaction
stage,soitisrequiredtoincreasethecrackingabilityofthe
second-stagecatalysttorecovertheproductoctanenumber,
whichresultsinasignificant reductionintheproduct liquid
yield(only86%)andgreatlyincreasestheprocessingcost.
35 CNl743425A (Chinese Patent Application No.
200410074058.7)has disclosed a hydro-upgrading process
forChineseFCCgasolinewithhigholefincontent.Wherein,
afterthefull-rangeFCCgasolineundergoesthethreereac-
tionsofdieneremoval,olefinaromatizationandsupplemen-
40talolefinreduction,thefull-rangeproductisobtainedwitha
desulfurizationratioat78%,thecontentofolefinsat30v%
byvolume,theRONlossat1.0unit,andtheliquidyieldat about
98.5wt%byweight. However, thismethodisonly
suitablefortheFCCgasolinewiththelowsulfurcontent,and
45hasalowdesulfurizationratioandapoorolefinreduction,
leadingtoworseproduct qualitythanthat regulatedbyEuro-
pean III and IV standard forcleangasoline. Thereby, this
methodisobviouslynot suitable forFCC gasoline feedstock
with the medium and high sulfur content.
50 CN1718688A (Chinese Patent Application No.
200410020932.9)has disclosed a hydro-upgrading method
forinferiorFCCgasoline.Thismethodincludesremoving
dienes in full-range FCC gasoline at high feeding space
velocity(6h*1)overaconventionalhydrofiningcatalyst,
followedbyolefinaromatizationathightemperature(415°
C.)usinganano-zeolitecatalystandbyselectivedesulfuriza-
tionathightemperature(415°C.)andhigherspacevelocity
(40h*')usingaCo—Mo—K—P/AltO,catalyst.Theresult- ing
producthaslowolefin andsulfurcontents,whiletheRON
60lossoftheproductisabout3.0unitsandtheproduct liquid
yieldisonlyabout94wt%byweight.Thenano-zeolitewith
complicated preparationispronetobedeactivatedathigh
temperature and has a poor regenerationperfomince. In
addition,thedesulfurizationcatalystinthethirdstagealso
65tendstobedeactivatedatveryhighspacevelocityandvery
hightemperature.Thus,thereactionstability ofthewhole
process is undesirable.
 US8,603,324B2
3 4
Insummary,forinferiorfuelssuchasFCCgasolinewith octane number. For the heavy fraction gasoline, thediffi-
highsulfurandolefincontents,ithasbeenattemptedindif- cultly-removedsulfurcompounds(alkylthiopheneandben-
ferentwaystoachievedesulfurizationandolefinreduction zothiophene) and the unstable dienes are firstly removed
whilemaintainingandimprovingtheproductoctanenumber therefrombyusingacatalystwithselectivehydrodesulfur-
asmuchaspossible,andtheeffectofsingle-branched-chain 5izationfunctioninthefirstreactor,soastoavoidpolymer-
hydroisomerizationofhydrogenatedproductontheoctane izationofdienesinthefollowingtreatmentthataffectsthe
numberrecoveryisalsomentioned.However, thedisclosed servicelifeofthecatalystinthesecondreactor,andtosolve
methodshavetheirownadvantagesanddisadvantages,espe- theproblemthatstericallyhinderedsulfurcompoundscan
ciallylackingofafurtherconcernabouttheimportanceof eco- hardlyberemovedby thesubsequentcatalystatthesame
friendly multi-branched-chain hydroisomerization of 10time.Uponentryintothesecondreactor,thereactioneffluent from
hydrocarbonsinincreasingtheoctanenumberofFCCgaso- thefirstreactorwith nodieneyetmany ofolefinsandthe
line. Thus, it is always theobject sought inthe petroleum suitablecontentofthiophenesulfurs,contactswiththecata-
refiningfieldtoprobeforamorereasonable upgrading pro- lystforsupplementaldesulfurizationandhydrocarbonaro-
cess andselectthe catalystswith suitablefunctionsandactivi-ties, matization/single-branched-chainhydroisomerization.After
inordertoachievedeepdesulfurization andolefinreduc- 15blending the treated light and heavy fractions, ultra-clean
tionwhilemaintainingoctanenumber,andtosolveproblems gasoline products withultra-low sulfur content, ultra-low
such as undesirable catalyst stability and high processing olefincontentand highoctanenumbercan beobtained,sothe
cost. objectofultra-deep desulfurization,greatolefinreduction
andgoodoctanerecoveryforinferiorgasolinecanbe
SUMMARY 20achieved.
Thehydro-upgradingmethodprovidedby theinvention is
Tosolvetheabovetechnical problems, anobject ofthe suitableforinferiorgasolineincludingoneofFCCgasoline,
inventionistoprovideamethodforhydro-upgradinginferior cokergasoline,catalytic pyrolysisgasoline,thermalcracking
gasoline bya combined process, whichincludesprefraction- gasoline,andsteampyrolysisgasolineoramixtureofthe
ating inferior full-range gasoline into the light and heavy 2Jaboveseveral kinds.
fractions, thentreatingthelightfractionandtheheavyfrac- Inthehydro-upgradingmethodprovidedby theinvention,
tionrespectively,andfinallyobtaining theultra-cleangaso- preferably, for the light and heavy fraction gasolines, the
lineproductwiththeultra-lowsulfurcontent,theultra-low cutting temperature is between 80 and 110° C. The light
olefincontentandthehighoctanenumberbyblendingthe fractiongasolinehasaboilingpoint whichislessthanthe
respectively upgraded light and heavy fraction gasolines. 30cuttingtemperature, andtheheavyfractiongasolinehasa
Thismethodisparticularly suitableforupgradinginferior boiling point whichismorethanthecutting temperature.
FCCgasoline withhigholefincontent andultra-high sulfur According tothespecifictechnical solutionoftheinven-
content,andcanachievetheeffectsofultra-deepdesulfuriza- tion, preferably,the catalystsystemusedin thehydro-upgrad-
tion,greatolefinreductionandoctanenumberrecovery. ingofthelightfractiongasolineincludesthecatalystfor
Toaccomplishtheaboveobjects,the inventionprovidesa 35selectivedieneremovalandthecatalystfordesulfurization and
methodofhydro-upgradinginferior gasolinethroughultra- hydrocarbon multi-branched-chainhydroisomerization
deepdesulfurizationandoctanenumberrecovery, compris- whichareloaded inthesamereactorsuccessivelyalongthe
ing: flow directionofthereactant. Inotherwords, thelightfrac-
cuttinginferiorfull-rangegasolineintothelightandheavy tiongasolinesuccessivelycontactswiththeabovetwocata-
fraction gasolines; 40lysts.
contactingthelightfractiongasolinewiththecatalyst for Inthehydro-upgradingmethodprovided bytheinvention, the
selective diene removaland the catalyst for desulfurization light fraction gasoline is subjected to the removal of
andhydrocarbonmulti-branched-chainhydroisomerization; unstable dienes by using the catalyst for selective diene
contactingtheheavyfractiongasolinewiththecatalystfor removal.Preferably,basedonthetotalweight ofthecatalyst,
selectivehydrodesulfurizationinafirstreactor,andcontact- 45theabovecatalystforselectivedieneremovalcomprises4-7 wt
ingthereactioneffluentfromthefirst reactorwiththecatalyst % MoO„l-3 wt % NiO, 3-5 It% Kz, and 1-4 wt %
forsupplementaldesulfurizationandhydrocarbonaromati- LaO„ with the balance ofAlO,.
zation/single-branched-chainhydroisomerizationinasecond Inthehydro-upgradingmethodprovidedbytheinvention,
reactor;and afterthedieneremoval,thelightfractiongasolineissubjected
blendingthe treated lightandthe heavy fraction gasolines 50todesulfurizationofthiophenesulfurs,olefinreduction,and
to obtain the ultra-clean gasoline product. octanenumberrecoverybyusingthecatalystfordesulfuriza-
Theinferior gasoline generally hasanolefincontent of tionand hydrocarbonmulti-branched-chainhydroisomeriza-
between 40%and 60% by volume anda sulfurcontent of tion.Preferably,basedonthetotalweightofthecatalyst,the
greaterthan1000{ig.g*1.Theinferiorfull-rangegasolinehas abovecatalystfordesulfurizationandhydrocarbonmulti-
adistillation temperature rangebetween about 30°C.and branched-chain hydroisomerization comprises 3-9 wt %
about 220° C. MoO„2-5wt%B2O„2-5wt%NiO,about50-70wt%of
Inthehydro-upgradingmethodofinferiorgasolinepro- theSAPO-IIzeolite, withthebalanceofAl—Ticomposite
videdbytheinvention,firstly,thefull-rangeinferiorgasoline oxides.
waspre-fractionated(cut),andthentheobtainedlightand Inthehydro-upgradingmethodprovidedbytheinvention,
heavyfractionsofthegasolineweretreatedbydifferentcom- 60inthefirstreactor,bycontactingtheheavyfractiongasoline
binedprocessesincludingolefinreduction,deep desulfuriza- withthecatalystforselectivehydrodesulfurization,thesulfur
tionandoctanenumberrecovery.Forthelight fraction gaso- compoundswhich arerelativelydifficulttobe removed(alkyl
line, dienes are removed using a catalyst for selectively thiophene and benzothiophene) and the unstable dienes
removingunstabledienesinthegasoline,andthefollowing thereinmayberemoved,avoidingthepolymerizationof
effluent contacts with a catalyst for desulfurization and 65dienesinthefollowing treatment thatdeteriorates theservice
hydrocarbon multi-branched-chain hydroisomerizationto lifeofthecatalyst inthesecondreactor.Preferably,basedon
eliminate thiophenesulfurs,lowerolefincontentandrecover thetotalweightofthecatalyst,theabovecatalystforselective
 US8,603,324B2
5 6
hydrodesulfurizationcomprises10-18wt %MoO„2-6wt%
CoO,1-7wt%K2Oand2-6wt%P2O„withthebalanceof Al—
Ti—Mg composite oxides.
Inthehydro-upgradingmethodprovidedbytheinvention,
preferably,based onthetotal weightofthecatalyst,thecata-
lystforsupplementaldesulfurizationand hydrocarbon aro-
matization/single-branched-chain hydroisomerizationused
in the second reactor to treat the heavy fraction gasoline
comprises 3-9wt%MoO„ 2-4wt%CoO, and50-70wt% of
hydrogen-typeZSM-5/SAPO-11in-situcompositezeolites,
with the balance of alumina binders.
Accordingtothespecifictechnical solutionoftheinven-
tion,preferably,theSAPO-11zeoliteusedintheinvention
hasamolarratioofSiO/Al2O,as0.1-2.0:1,andamolarratio of
P2O,/AI2O, as 0.5-2.5:1.
Accordingtothespecifictechnicalsolutionoftheinven-
tion,preferably,inthehydrogen-type ZSM-5/SAPO-11in-
situcompositezeoliteoftheinvention,theZSM-5zeolitehas
amolarratioofSiO2/A12O,as40-70,andispresentedata
weightcontent of 50-70 wt %;theSAPO-11zeolite has a
molarratioofSiO2/Al2O, as0.2-1.0, andispresentedata
weightcontentof30-50wt%.Themethod forsynthesizing the
ZSM-5/SAPO-11 composite zeolite includes firstly
obtainingtheZSM-5crystallizedproductaccordingtothe
synthesisprocessoftheZSM-5zeoliteandthenaddingraw
materialsforsynthesizingtheSAPO-11intotheabovecrys-
tallizedproducttofurthercrystallize,thedetailsofwhichcan be
found in the description of CN101081370A (Chinese
Patent Application No. 200610083284.0)or other related
reports for reference.
According tothespecifictechnical solutionoftheinven-
tion,preferably,theSAPO-11zeoliteusedintheinvention
may useC2-C,alkyl siliconesters asorganicsilicon sources,
andcanbesynthesizedbyaddingtheorganicsiliconsource
togetherwithanorganicalcoholthatisthesameasthealco-
holfromthehydrolysisoftheorganicsiliconsource,i.e.,a
corresponding alcohol withacarbonchainofCj•Cg› Com-
paredwiththeconventional SAPO-11zeolites,theaddition
oftheorganicalcoholemployedintheinventioncanregulate
thehydrolysisdegreeofthesiliconsourceandthussuppress
thehydrolysisoftheorganicsilicon,expanding thepore size
ofconventional SAPO-11zeolitesandthereby improving
theirmulti-branched-chainhydroisomerization performance.
Specifically,theorganicsiliconsourcecanbeselectedfrom
thelong-chainorganicsiliconssuchastetraethylorthosili-
cate,tetrapropylorthosilicate,tetrabutyl orthosilicate,tetra-
pentyl orthosilicate or tetrahexyl orthosilicate, and the
organicalcohol canbecorrespondinglyselectedfrom etha-
nol, propanol, n-butanol, n-pentanol or n-hexanol. For
example,whenthe organicsilicon source istetraethylortho-
silicate,thecorrespondingethanolischosenastheorganic
alcohol.Toadjust theporesizeoftheSAPO-11zeolite,the
templateusedintheSAPO-11synthesisispreferablyamix-
tureofdi-n-propylamineandlong-chainorganicaminewith
amolarratioof3-10:1,andthelong-chain organic amineis
selected from those alkyldiamines having a carbon chain
lengihofC,-C,.Thelong-chain organic aminecan be,for
example,oneofdi-n-butylamine,di-n-pentylamine,anddi-n-
hexylamine,inordertofacilitatetheregulationofthepore
structureofthezeolite,especiallyto increase the poresizeof
thezeolitetomeetthereactionrequirementforhydrocarbon
multi-branched-chain hydroisomerization.
TheotherrawmaterialsusedinthesynthesisoftheSAPO-
11 zeolite and the proportion thereof may be determined
accordingtotheconventionaloperations.Forexample,the
feeding ratio of the raw materials can be determined as
organicsiliconsource:aluminumsource:phosphorussource:
template: organic alcohol: water=0.1-2.0:1:0.5-2.5:0.7-2.0:
0.1-40:20-60(inmolarratio).Thespecificsynthesisprocess
can be as follows:
thephosphorussourceandthealuminumsourceareevenly
5mixedinwateraccordingtothepredeterminedproportionto
formasol,with themixingtemperaturegenerallyat20-
40°C.oroom temperature;
themixturesolutionoftheorganic siliconsourceandthe
organicalcoholisadded into theabovesol,mixedevenlyby
10stirring,and thetemplateis thenaddedtopreparean initialgel
mixture;
theobtainedinitialgel mixtureiscrystallizedbyheatingat
thecrystallizationtemperatureof150-200°C.for8-60hours.
Uponthecompletionofcrystallization,the solidproductis
15separatedfromthemothersolution,washedtillneutraland
dried (forexample,dried in airat 110-120°C.) toformthe raw
powder oftheSAPO-11zeolite thatiscalcinedat 500-600°C. for
4-6 hours.
Accordingtothe specifictechnicalsolutionoftheinven-
20tion,preferably,theweightcompositionoftheAl—Ticom-
positeoxidesusedinthecatalystoftheinvention(namely,
based ontheweight ofthecatalyst fordesulfurizationand
hydrocarbonmulti-branched-chainhydroisomerization)is
15-40wt%A,and2-15wt%TiOandtheAl—Ti
2Jcompositeoxidebinderispreparedbythefractionalprecipi-
tation of aluminum and titanium salts.
According tothespecifictechnical solutionoftheinven-
tion,preferably,theweightcompositionof theAl—Ti—Mg
compositeoxidesusedinthecatalystoftheinvention
30(namely, based on the weight of the catalyst for selective
hydrodesulfurization)is60-75wt%Al2O„5-15wt%TiO2and3-
10wt%MgO,andtheAl—Ti—Mgcompositeoxides are
prepared by the fractional precipitation of aluminum,
titanium and magnesium salts.
35Inthehydro-upgradingmethodprovidedbytheinvention,
preferably,whentreatingthelightfractiongasoline, thecata-
lystforselectivedieneremovalusesaluminaasthecarrier,
andthecatalystfordesulfurizationandhydrocarbonmulti-
branched-chainhydroisomerizationusesacarriercomposed
40of lhe SAPO-11 zeolite and theAl—Ti composite oxide;
whentreating theheavy fraction gasoline, thecatalyst for
selective hydrodesulfurizationemployed in thefirst reactor
usestheAl—Ti—Mgcomposite oxideasthecarrier,andthe
catalystforsupplementaldesulfurizationandhydrocarbon
45 aromatization/single-branched-
chainhydroisomerizationusedinthesecondreactorchoosesth
ehydrogen-typeZSM- 5/SAPO-I Iin-situ composite
zeoliteasthecarrier.
According tothespecifictechnical solutionoftheinven-
tion,apHswing method isusedforpreparingthealumina
50precipitatesandtheAl—Ti—Mgcompositeoxidecarrier,
whichincludes:addingaalkaliprecipitator(theamountof
thealkaliprecipitatorusedforthefirsttimeatabout15-30v
%byvolumeofthetotalamountofthealuminumsaltsolu-
tion),suchascommonlyusedsodiumhydroxidesolutionora
mixedammoniasolution(forexample,amixedsolutionof
NH,.H2OandNH,HCO,withamolarratioof2-10:I),con-
currentlywiththealuminum saltsolution under constantand
violentstirring, continuing toaddthealuminumsaltsolution
afterdepletingthesuitableamount ofthealkaliprecipitator
60untilthepHvalueisappropriatelyacidic(forexample,pH=2-
4),furtheraddingthealkaliprecipitatorsolution afterstirring
forawhile(5-30mins)until thepHvalueisappropriately
alkaline(for example,pH=7.5-9.5),stirring foranadditional
periodoftime(5-30mins)andrepeatingsuchpHswingfor a
65coupleoftimes(usually2-5times)toobtainaluminaprecipi-
tates;stirringforaperiodoftimeunderthesuitablealkaline
pHvalueafterdepletingthealuminumsaltsolution,then
 US8,603,324B2
7 8
addingamixedsolutionofmagnesiumsaltandtitaniumsalt (2) thelightfractiongasolinecanbeprocessedinsucha
whilemaintaininganalkalinesolutionto promote the occur- mannerthat thetwo types ofcatalystsareloaded inthesame
rence of co-precipitation reaction; continuing to stir for a reactor,whiletheheavyfractiongasolinecanbeprocessedin
period oftime(5-30mins)afterthe completionof feedingand serieswithouttheseparatingequipmentduringthetreatment;
precipitation, followed by cooling, filtering, beating and 5(3) heat is sufficiently utilized by the heat exchange
washing for a couple of times, subsequently drying, and between the high-temperature product at the exit of the
crushing andsievingthe filtercaketoobtainthe Al—Ti—Mg upgrading reactor for the heavy fraction gasoline and the
compositecarrierpowders.Inthepreparationofthecompos- untreatedfeedstockofheavyfractiongasoline,andoperating
iteoxides,thesaltsolutionsofaluminum,titaniumandmag- iseasy;
10(4)inthehydro-upgradingmethodoftheinvention,infe-
nesium can be the solutions of their nitrate, chloride, and
riorfull-rangegasolineisfirstlypre-fractionatedintothelight
sulfate.Thespecific processforpreparing alumina bythe
andheavyfractiongasolines;thenthelightfractiongasoline
abovepHswingmethodcanbeperformedaccordingtothe is treated through diene removal, and desulfurizationand
methodspubliclyreportedorapplied.Thecarrierpowders hydrocarbonmulti-branched-chainhydroisomerization,and
obtainedbythefractionalprecipitationcanbeshapedinan15theheavyfractiongasolineissubjectedtothetwo-stagetreat-
extruderusingaconventionalshapingmethod,andthen dried ment of selective hydrodesulfurization,and supplemental
andcalcined toobtainthecarrierofthecorresponding cata- desulfurization and hydrocarbon aromatization/single-
lyst. branched-chainhydroisomerization;thesemultiplereactions
Accordingtothespecifictechnical solutionoftheinven- contributetoachievetheeffectsincludingtheultra-deepdes-
tion,thepreparationmethodofAl—Ticompositeoxidepow- 20ulfurization,thegreatolefinreduction,andtheoctanenumber
dersisalmostthesameasthatoftheAl—Ti—Mgcomposite recovery oftheblendedfull-range gasoline product;
oxidementionedabove,exceptfortheonlyincorporationof (5)Thehydro-upgradingmethodoftheinventionisespe-
titanium salt solution inthesecond step ofprecipitation. cially suitable for upgrading more inferior gasoline with
Accordingtothespecifictechnical solutionoftheinven- ultra-highsulfurcontentandhigholefincontent,increasing
tion, when hydro-upgrading inferior gasoline using the 2Jtheoctanenumberthereofandmaintainingahighliquidyield of
hydro-upgradingmethod ofthe invention, preferably, the the product while significantly reducing the olefin and
reactionconditionsforthelightfractiongasolineobtainedby sulfurcontents thereof; therefore,comparedwiththeforeign
cuttingcanbecontrolledwithareactionpressure ofl-3 MPa, methods ofgasoline hydro-upgrading,thehydro-upgrading
areactiontemperatureof290-360°C.,ahydrogen/oilvolume melhodoftheinventionismoreadvantagefortreatinginfe-
ratioof200-600, aliquidvolumespacevelocityof8-14h*‘30riorgasoline.
forthecatalyst withthefunction ofselective dieneremoval,
andaliquidvolumespace velocityof 2-5 h*1forthecatalyst BESTMODESOF CARRYINGOUTTHE
withthefunctionsofdesulfurizationand hydrocarbonmulti- INVENTION
branched-chainhydroisomerization.
Inaccordance with the means of expression frequently 35Now,theembodimentsandfeaturesofthetechnicalsolu- tion
usedinthecatalystfield,thecontentsofthecarrierandactive oftheinventionwill bedescribedindetailcombinedwiththe
components (elements) onthecatalysts mentioned bythe specificexamplesin ordertohelpthe readertounderstand
invention are determined in terms of the corresponding thespirit andbeneficial effect oftheinvention,whichshould
oxides thereof. notbeconstruedasanylimitationtotherangewithinwhich
According tothespecifictechnical solutionoftheinven- 40theinventioncanbeimplemented.
tion, when hydro-upgrading inferior gasoline using the
hydro-upgradingmethod ofthe invention, preferably, the Example1
reactionconditions fortheheavyfractiongasolineobtained
bycuttinginthefirstreactorcanbecontrolledwithareaction Inthisexample,ahydro-upgradingtreatmentwascarried
pressureof1-3MPa,aliquidvolumespacevelocityof3-6 45outoninferiorFCCgasolinewithultra-highsulfurcontent and
h*’,areactiontemperatureof230-300°C.,andahydrogen high olefin content (feedstock 1), wherein the sulfur
oilvolumeratioof200-600;and,thereactionconditionsof contentis1750qg.g'andtheolefincontentis48.4v%by
thereaction effluentfromthefirstreactor inthesecondreac- volume.
torareareaction pressureof1-3 MPa,aliquidvolumespace (1)CuttingtheFull-RangeGasolineFeedstock
velocityof1-3h*',areactiontemperature of360-430°C., 50 Theaboveinferiorfull-rangeFCCgasolinewascutintothe light
anda hydrogen/oil volume ratio of 200-600. andheavyfraction gasolinesat 85°C.,andtheproperties ofthefull-
Themethodoftheinventionissuitableforhydro-upgrad- rangegasolineandthecutlightandheavyfractions
inginferior gasoline, especially forhydro-upgrading inferior areshowninTable1.
FCCgasoline withultra-high sulfurcontentandhigholefin
content, e.g.,FCCgasoline withthesulfurcontent of1400- TABLE1
2500Jig.g'andtheolefincontentof40-55v%byvolume. PropertiesofFeedstockI
Compared with the existing technologies,the method of
hydro-upgradinginferiorgasolinethroughultra-deepdes- Full-range Lightfrac- Heavy frac-
ulfurizationandoctanenumberrecoveryprovidedbythe Item gasoline tion<85°C. tion>85°C.
inventionischaracterized inthose: 60 100 42.4 57.6
Yield(wt%)
(1) FCC gasoline withthe sulfurcontent of1400-2500 Density 0.735 0.665 0.780
qg.g*'andtheolefincontentof40-55v%byvolumecanbe (g/mL)Distillationrang 33-204 31-87 82-206
hydro-upgradedtothehigh-qualitygasoline withthesulfur e(°C.)
Content of
content ofequaltoor lessthan 30qg.g*’,the typicalhydrocarbons (v %)
olefincontentofequal toorlessthan 15v%by volume,theRON 2.9
lossin 65
equal Multi-branched-
toorlessthan1.0unit,andtheproductliquidyieldofmore chainisoalkane
than orequal to 98 wt % by weight;
 US8,603,324B2
9 10
TABLEl-continued cipitate completely; the resultant was stirred for 15 mins,
filtered,beatenandwashedtwicewiththeNH,HCO,solu-
PropertiesofFeedstock1
tionof0.8mol/L,washedtwicewithdeionizedwater,driedat
Full-range Lightfrac- Heavyfrac- 120°C.for15hours,andcrushedandsievedtoobtain50gof
Item gasoline tion<85°C. tion>85°C. 5Ai—Ticompositeoxidepowderswith300meshes.

OlefinAromatic 64.0 goftheabove SAPO-11zeolites,26.0gofthe Al—Ti

sSulfur(pg- 48.4 59.6 39.8
g')Diene(gI/100 26.9 composite oxides (the weight contents ofAl 2O,
g) 1750 290 2825 andTiO2were84wt%and16wt
2.4 %,respectively)and2.5gsesbania
powdersweremixed evenlybygrinding,andthen6.0 mL
RON 91.3 94.6 89.5 10
nitricacidsolutionwiththeconcentration of65%byweight
wereaddedtherein;afterkneadingsufficiently,theresultant
(2) UpgradingtheLightFractionGasolineThroughSelec- wasshapedinanextruder,driedat120°C.,andcalcinedat 520°
tiveDieneRemovalandDesulfurizationandHydrocarbon C.to obtain theshaped catalyst carrier.
Multi-Branched-ChainHydroisomerization 60.0mLofammoniummolybdatesolutioncontaining5.0
Ina200mLhydrogenationreactor,thecatalystforselec- 15 gofMoO,wereprepared,and5.8mLammoniawiththe
tivedieneremoval wasloadedontheupperlayer,and the concentrationof17%byweightwereaddedtherein,stirring
catalystfordesulfurizationandhydrocarbonmulti-branched- sufficientlyuntilthesolidwasdissolvedcompletelysoasto
chainhydroisomerizationwasloadedonthelowerlayer. obtaintheimpregnatingsolution;then75goftheabove
Afterthereactorairtightnesswasconfirmed,thesecatalysts20 shaped catalyst carrier were impregnated in the above
werepre-sulfurizedbytheconventionalsulfurizationprocess impregnatingsolution,agedatroomtemperature for5hours,
andtheproduct wascollectedforanalysis after reactionfor dried at 120° C. for3 hours and calcined at 500° C. for4
500 hours. hours;thecalcinedcatalystcarriercontaining molybdenum
Fortheabovecatalystforselectivedieneremoval,basedon wasimpregnatedina60.0mLmixturesolutionofboricacid
stoichiometricratio,theappropriateamountsofK,MoO, 2Jandnickelnitratecontaining2.5gB2O,and2.5gNiO,aged
alongwithNiOandLa2O, wereloadedontheshapedalu- atroomtemperaturefor5hours,driedat120°C.for3hours
minacarriersuccessivelybytheconventionalisovolumetric andcalcinedat500°C.for4hourstoobtainthefinalcatalyst
impregnation method, and the steps of aging, drying and fordesulfurizationandhydrocarbonmulti-branched-chain
calciningelc.wereneededaftereachloadingofactivemetal hydroisomerization.
components;thecompositionbyweightofthiscatalystwas230 Thereaction conditionsof thelight fractiongasoline were
wt%NiO-4wt%MoO,-3wt%K2O-2wt%La2O,/89wt% areactionpressureof2.0MPa,areaction temperatureof310°
Alz3- C.,ahydrogen/oilvolumeratioof400,aliquidvolumespace
ThecompositionbyweightoftheaboveSAPO-1l-Al—Ti
velocityof9h*'forthecatalystwiththefunctionofselective
basedcatalystfordesulfurizationandhydrocarbonmulti-
dieneremoval,andaliquidvolumespacevelocityof2h*'for
branched-chainhydroisomerizationwas3wt%B2O,-6wt
thecatalystwiththefunctions ofdesulfurizationandhydro-
%35MoO,-3wt%NiO/64wt%SAPO-11•20It%Alz3•4t% TiO2;
carbon multi-branched-chain hydroisomerization. The
itwaspreparedasfollows:firstly,accordingtothe
hydro-upgradingeffectsofthelightfractiongasolinewere
feedingcomposition(molarratio)fortheSAPO-11zeoliteas
shown in Table 2.
ET(ethanol):DHA(di-n-hexylamine):DPA(di-n-propy-
lamine):Al2O,:P2O,:SiO2:H2O10:0.3:1:1:1:0.4:50,40
phosphoricacid,pseudo-boehmiteand deionizedwaterwere TABLE2
evenlymixedbystirringfor 1.0hour,andanappropriate Hydro-upgradingEffectsoftheLightFractionGasoline
amountofthemixturesolutionoftetrapropylorthosilicate
andethanolwasaddedintothemixed sol;afterstirringfor2.0 Light fraction
hours,anappropriateamountofthemixtureofdi-n-hexy-45 Upgradedproductgasoline l <85° C.
oflightfraction
Item (feedstock) gasoline1
lamineanddi-n-propylaminewasaddedtherein,andstirred
untilauniformcolloidalwasformed;thereafter,theproduct Yield(wt%) 99.6
wasloadedintoa stainless-steelautoclavelinedwithpolytet- Density(g/mL) 0.665 0.670
Distillationrange (°C.)Content 31-87 33-89
rafluoroethylenetocrystallizeat185°C.for24hours,then of typical
cooled,filtered,driedat120°C.andcalcinedat600°C.for5 hours 50hydrocarbons(v%)
to obtain the SAPO-11 zeolite.
Multi-branched-chain 17.8
312.2gAl(NO,),.9H2Owereaddedinto405.0mLdeion-
isoalkaneOlefi
ized water and stirred until complete dissolutiontoobtainan nAromatics 59.6 21.5
A, solution; 25.0 g Ti(SO,)2, were added into 285.0 mL 2.0 3.3
deionizedwaterandstirredviolentlyuntilcompletedissolu- RON 290 21
tiontoobtainaTsolution; 90.0mLprecipitator (amixed 94.6 93.4
ammoniasolutionwiththemolarratioofNH3•Hzto
NH,HCO,as8:1)andtheAsolutionwere addedconcur- (3) UpgradingtheHeavyFractionGasolineThrough
rentlyintothecontainerunderstrongstirringwhilethepH SelectiveHydrodesulfurizationandSupplementalDesulfur-
valuewascontrolledatabout9.0,andtheAsolutioncontin- 60izationandHydrocarbonAromatization/Single-Branched-
uedtobeaddedaftercompletingtheadditionofthemixed Chain Hydroisomerization
ammoniasolutionuntilthe pHvaluewas4.0; afterstirringfor In two 200 mL hydrogenation reactors of in series, the
10mins,themixedammoniasolutionwasaddedagainuntil the catalystforselectivehydrodesulfurizationwasloadedinthe
pHvaluewas9.0,and themixturewasstirredagain for10 firstreactor,andthecatalystforsupplementaldesulfurization
mins;afterrepeatingsuchpH-swingtwice,theTt solution 65 and hydrocarbon aromatization/single-branched-chain
was addedwhilethepH valuewascontrolledat about9.0with hydroisomerizationwasloadedinthesecondreactor.After
themixedammoniasolutionso astoallowtitaniumtopre- thereactor airtightnesswasconfirmed,thesecatalysts were
 US8,603,324B2
11 12
pre-sulfurizedbytheconventionalsulfurizationprocessand based catalyst was prepared according to the preparation
theproduct wascollectedforanalysisafterreactionfor500 method provided in CN101081370A (Application No.
hours. 200610083284.0).
Thecompositionbyweightoftheabovecatalystforselec- Thereactionconditionsfortheheavyfractiongasoline in
tivehydrodesulfurizationloadedinthefirstreactorwas4wt 5thefirstreactorwereareactionpressureof2.5MPa,aliquid
%CoO-12wt %MoO,-3wt %K2O-2wt%P2O,/67wt % volumespacevelocityof4h*',areactiontemperatureof240°
Al2O3-8Wt%TiO2-4wt%MgO.Thecatalystwasprepared C., a hydrogen/oil volume ratio of 500; and the reaction
asfollows:631.8gAltNO,),.9H2Oand819.7mLdeionized conditionsfor thereactioneffluentfromthe firstreactorinthe
waterwere addedtherein,andstirreduntilcompletedissolu- secondreactorwereareaction pressureof2.5MPa,aliquid
10volumespacevelocityof1.5h*’,areactiontemperatureof
tiontoobtainanA2solution;31.3gTi(SO4)2and357.7 mL 370°C.,andahydrogen/oilvolumeratio of500. Thehydro-
deionizedwaterwereaddedtherein,andstronglystirreduntil
complete dissolution to obtain a T2 solution; 32.1 g Mg upgradingeffects of theheavy fractiongasolinewereshown in
Table 3.
(NO,)2.6H2Oand55.2mLdeionizedwaterwereadded
therein,andaM2solutionwasobtainedupondissolution.The15 TABLE3
TzandMrsolutionsweremixedandstirredevenlytoobtain
aTM2solution; 180.0mL precipitator (amixedammonia Hydro-upgradingEffectsoftheHeavyFractionGasoline
solution with themolar ratio of NH,.H 2Oto NH,HCO, as
Heavy fraction
8:1)and theAusolutionwereaddedconcurrentlyintothe
Upgradedproductgasolinel>85°C.
ofheavyfraction
containerunderstrongstirringwhilethepHvalue wascon-20 Item (feedstock) gasoline1
trolledatabout9.0,andtheA2solutioncontinued tobeadded
aftercompletingtheadditionofthemixedammoniasolution Yield(wt%) 97.5
until the pH value was 4.0; after stirring for 10 mins, the Density 0.780 0.790
(g/mL)Distillationrang 82-206 84-205
mixedammoniasolutionwasaddedagainuntil thepHvalue
e(°C.)Content of
was9.0,andthemixturewasstirredagainfor10mins;after typical
repeatingsuchpH-swingthreetimes,theTMPsolutionwas 2J
addedwhenthepHwascontrolledatabout9.0withthemixed 2.9
Multi-branched-chain

ammoniasolutionsoastoallowtitaniumandmagnesiumto Olefin 39.8

precipitatecompletely;theresultantwasstirredfor15mins, Aromatics 26.9
Sulfur(big'g°') 2825
filtered,beatenandwashedtwicewiththeNH4HCO,solu- 30
RON 89.5 88.7
tionof0.6mol/L,washedtwicewithdeionizedwater,driedat
120ºC.for24hours, andcrushedandsievedtoobtain100g
ofAi—Ti—Mgcompositeoxidepowderswith300meshes. (4) BlendedProductoftheUpgradedLightandHeavy
70goftheaboveAi—Ti—Mgcompositeoxidespowders FractionGasolines
(withaboundwatercontentof25wt%byweight)and1.6g 35Based onthecutting ratio, thelight andheavyfractions
sesbaniapowdersweremixedevenlybygrinding,andthen5 upgradedthroughsteps(2)and(3)wereblendedtoobtainthe
mLnitricacidsolutionwith the concentrationof65%by ultra-cleangasolineproductwiththeultra-lowsulfurcontent,
weightwasaddedtherein;afterkneadingsufficiently,the the ultra-lowolefincontentand thehighoctanenumber. Table
resultantwas shapedinanextruder,driedat 120ºC., and 4showedthepropertiesofthefull-rangegasolinefeedstock
calcined at520ºC.topreparethecatalystcarrierofAl—Ti— 40and the blended product of the upgraded light and heavy
fraction gasolines.
Mgcompositeoxides.
40goftheaboveshaped catalyst carrierofAl—Ti—Mg
compositeoxideswereimpregnatedinthe35mLmixed TABLE4
impregnatingsolutioncomposedofpotassiumnitrateand
diammoniumphosphatewhichincluded 1.5gofK2Oand1.045 PropertiesoftheFull-rangeGasolineFeedstockandtheBlended
Productofthe UpgradedLightandHeavYFractionGasolines
gof , intermsofoxides,andthentheresultantwasaged
atroomtemperaturefor5hours,driedat120ºC.for3hours Full-range
andcalcinedat520ºC.for4hours; a32mLmixture solution
BlendedproductofthegasolineI
upgradedlightandheavy
ofcobaltnitrate and ammonium molybdate including2.0g Item (feedstock) fractiongasolines
CoOand6.1gMoO,(thecontentofeachactivecomponent 50Yield(wt%) 98.4
wasbased onthe oxideform,whichdoes not limit theactive Density(g/mL) 0.735 0.736
Distillation range (° 33-204 32-203
componentsinthemixturesolutiontopresentinoxideform
C.)Contentof
only)wasprepared,and3.3mLammoniawiththeconcen- typicalhydrocarbons(v %)
trationof17%byweightwereaddedtherein,stirringsuffi-
cientlyuntil thesolid was dissolved completely soasto obtain the Multi-branched-chainisoalkane 2.2 10.7
impregnating solution; then the above catalyst carrier Olefin
48.4 14.1
containingpotassiumandphosphoruswasimpregnatedin the ÄfO1T1fit1CS
23.4
Sulfur
solutioncontainingcobaltandmolybdate,agedatroom tem- 1750 26
(gg'g')Diene(gI/
peraturefor5hours,driedat120ºC.for3hours andcalcined at 100g) 2.4 0.0
520º C. for 5 hours to obtain thefinal catalyst. 91.3 90.4
RON
Theabovehydrogen-typeZSM-5/SAPO-11composite 60
zeolite-based catalyst forsupplemental desulfurizationand SiO2/AI2O,as50)-22wt%SAPO-11(withthemolarratioof
hydrocarbonaromatization/single-branched-chainhydroi- SizAlz3as0.3)-21•5Et%Alzsthiscompositezeolite-
somerization loadedinthesecondreactorcomprises2.5wt %
CoO-7wt%MoO,/48wt%ZSM-5(withthemolarratioof
 US8,603,324B2
11 12
Itcanbeseenfrom Table4that, withthehydro-
upgrading
methodoftheinvention,thesulfurcontentininferiorFC
C
gasolinemaybereducedfrom1750qg.g*’to<30qg.g*'wit
h
65theolefincontentfrom48.4v%to/15v%,andthecontent
ofmulti-branched-
chainisoalkaneintheproductincreases
significantlytogetherwiththeconsiderableincreaseinth
e
 US8,603,324B2
13 14
contentofaromatics,decreasingtheRONlosstobelessthan tivedieneremoval, andaliquidvolume spacevelocityof2.5 h*'
1.0unitwhile achievingultra-deepdesulfurizationand great forthecatalystwiththefunctions ofdesulfurizationand
olefinreduction. Moreover,theyield oftheblendedproductis as hydrocarbonmulti-branched-chain hydroisomerization. The
high as 98.4 wt %, and the product quality is far more hydro-upgradingeffectsofthelightfractiongasolinewere
superiorthanthatregulatedbytheEuropeanIVstandardfor 5showninTable6.
clean gasoline.
TABLE6
Example2
Hydro-upgradingEffectsoftheLightFractionGasoline
Inthisexample,thehydro-upgradingeffectsofinferior10
Light fraction
FCCgasoline withultra-highsulfurcontentandhigholefin
content(feedstock2),containing2210qg.g*’ofsulfurcom-
Upgradedproductgasoline 2 <95° C.
oflightfraction
Item (feedstock) gasoline2
poundsand51.3v%ofolefinsbyvolume,areillustrated.
(1) CuttingtheFull-RangeGasolineFeedstock Yield (wt 99.5
TheaboveinferiorFCCgasolinewascutintothelight and15 %)Density(g/m 0.680
L)
heavyfractiongasolinesat95°C.,andthepropertiesofthe full- Distillationrange(°C.) 34-98 33-99
range gasoline feedstock and the cut light and heavy Contentoftypical
fractions were shown inTable 5. mhmuser(v%)
20
TABLE5 Multi-branched-chain 2.5 19.8
isoalkaneOlefi
PropertiesofFeedstock2 n 64.7 23.9
Aromatics 3.5 5.2
Item Full-range Lightfrac- Heavyfrac-
gasoline tion<95°C. tion>95°C. Sulfu'r(Fig 8*') 360 19
2JRON 94.3 93.0
Yield (wt 100 45.6 54.4
%)Density(g/mL 0.746 0.676 0.789
) 35-206 34-98 93-209
Distillation range
(3) UpgradingtheHeavyFractionGasolineThrough
(°C.)Content of SelectiveHydrodesulfurizationandSupplementalDesulfur-
typicalhydrocarbons (v %) 30izationandHydrocarbonAromatization/Single-Branched-Chain
54 2.5 4.2
Multi-branched-
Hydroisomerization
chainisoalkane 51.3 64.7 37.1 Intwo200 mL hydrogenationreactorsofin series,the
OlefinAromati 18.l 3.5 31.4
csSulfur(p-
catalystforselectivehydrodesulfurizationwasloadedinthe
gg°')Diene(gI/ 3.5 35
firstreactor,andthecatalystforsupplementaldesulfurization and
100g)RON 92.4 94.3 91.2 hydrocarbon aromatization/single-branched-chain
hydroisomerizationwasloadedinthesecondreactor.After
(2) UpgradingtheLightFractionGasolineThroughSelec- tive thereactorairtightness wasconfirmed, thesecatalysts were
DieneRemovalandDesulfurization andHydrocarbon Multi- pre-sulfurizedbytheconventionalsulfurizationprocessand
Branched-ChainHydroisomerization theproduct wascollectedforanalysis afterreaction for500
40 hours.
Ina200mL hydrogenation reactor, thecatalyst forselec- tive
diene removalwas loaded on the upper layer, andthe Thecompositionbyweightoftheabovecatalyst forselec- tive
catalystfordesulfurizationandhydrocarbonmulti-branched- hydrodesulfurization was 2.5 wt % CoO-10 wt % MoO,-
chainhydroisomerizationwasloadedonthelowerlayer. 2wt%K2O-3wt%PRO,/60wt%Al2O3-15.5wt%
Afterthereactorairtightness TiO 2-7 wt%MgO,andthis catalystwaspreparedin asimilar way

wasconfirmed,thesecatalysts45werepre- as shown in Example 1.

sulfurizedbytheconventionalsulfurizationprocess and the The above hydrogen-type ZSM-5/SAPO-11 composite
product was collected for analysis after reaction for 500 zeolite-based catalyst for supplementaldesulfurizationand
hours. hydrocarbonaromatization/single-branched-chainhydroi-
Fortheabovecatalystforselectivedieneremoval,basedonthesto somerization comprised4.0wt%CoO-8wt% MoO,/38wt
ichiometricratio,theappropriateamountsofK2O,50MoO, along %ZSM-5(withthemolarratioofSiO2/Al2O,as60)-30wt%
with NiOandLa2O, were loaded ontheshaped alumina carrier SAPO-11(withthemolarratioofSiO2/Al2O,as0.5)-20wt%
successively bytheconventionalisovolumet- AI2O,.This compositezeolite-basedcatalystwas prepared
ricimpregnationmethod, andthestepsofaging,dryingand
calciningetc.wereneededaftereachloadingofactivemetal
components;thecompositionbyweightofthiscatalystwas2 areactionpressureof2.5MPa,areactiontemperatureof330°
wt%NiO-6wt%MoO,-5wt%K2O-1wt%La2O,/86wt% C.,ahydrogen/oilvolumeratioof300,aliquidvolumespace
Az3 velocityofIIh*'forthecatalystwiththefunctionofselec-
The compositionbyweightofthe aboveSAPO-1l-Al—Ti
based catalyst fordesulfurizationand hydrocarbon multi-
branched-chainhydroisomerizationwas2wt%B2O,-5wt%
MoO,-2wt%NiO/68 wt%SAPO-11-20wt%Al2O,-3wt%
TiO2,and thiscatalystwaspreparedin asimilarwayasshown in
Example 1.
Thereactionconditionsforthelightfractiongasolinewere
 US8,603,324B2
13 14
55accordingtothepreparationmethodprovidedin
CN101081370A(ApplicationNo.200610083284.0).
Thereactionconditions
fortheheavyfractiongasolinein
thefirstreactorwereareactionpressureof2.0MPa,aliqui 60
d volumespacevelocityof3h1,areactiontemperature
of230° C., a hydrogen/oil volume ratio of 400; and
the reaction conditionsforthereactioneffluentfromthe
firstreactorin the
secondreactorwereareactionpressureof2.0MPa,aliqui
d volume spacevelocityof2h*’,a
reactiontemperatureof380°
65C.,andahydrogen/oil volumeratioof400.Thehydro-
up-
gradingeffectsoftheheavyfractiongasolinewereshown
in Table 7.
 US8,603,324B2
15 16
TABLE7 Theinventionclaimedis:
1.Amethodof hydro-upgradinginferiorgasolinethrough
Hydro-upyadingEffectsoftheHeavyFractionGasoline
ultra-deepdesulfurizationandoctanenumberrecovery,com-
prising:
Heavyfraction 5cuttinginferiorfull-rangegasolineintolightfractiongaso-
Upgradedproductofgasoline 2 >95° C.
theheavyfraction
Item (feedstock) gasoline2 lineandheavy fraction gasoline at 80to 110° C.;
Yield(wt%) 97.1 contactingthelight fractiongasolinewith acatalystfor
Density (g/mL) selectivedieneremovalandacatalystfordesulfuriza-
0.789 0.796
Distillation range (° 93-209 91-206 tionandhydrocarbonmulti-branched-chainhydroi-
C.)Content of 10somerization;
typicalhydrocarbons(v %) contactingtheheavyfractiongasolinewithacatalystfor
Multi-branched-chain 4.2 4.9 selectivehydrodesulfurizationinafirstreactor,andcon-
isoalkane tactingaresultingreactioneffluentfromthefirstreactor
Olefin 37.1 8.5 withacatalystforsupplementaldesulfurizationand
Aromatics 31.4 40.1
Sulfur(pg-g°1) 15 hydrocarbon aromatization/single-branched-chain
2g9
RON
91.2 0.6
hydroisomerizationin a second reactor; and
blendingthetreatedlightandheavy fractiongasolines to
obtain the ultra-clean gasoline product.
(4)BlendedProductoftheUpgradedLightandHeavy 2. Thehydro-upgradingmethodaccordingtoclaim1,
FractionGasolines 20whereinthelightfractiongasolinecontactsthecatalystfor
Basedonthecuttingratio,thelightandheavyfractionsof selectivedieneremovalandthecatalystfordesulfurization
gasolineupgradedthroughsteps(2)and(3)wereblendedto and hydrocarbon multi-branched-chainhydroisomerization
obtain the ultra-clean gasoline product with the ultra-low successivelyin the same reactor.
sulfur content, the ultra-low olefin content and the high 3. Thehydro-upgradingmethodaccordingtoclaim1,
octane number. Table 8showed theproperties ofthefull- 2Jwhereinthe catalystfor selectivediene removalcomprises 4-
range gasoline feedstock and the blended product of the 7wt%MoO„ 1-3wt%NiO,3-5wt%K2O,and1-4wt%
upgraded light and heavy fraction gasolines. La2O„with the balanceof the catalystcomprisingAI2O„
basedonthetotalweightofsaidcatalyst.
TABLE8 4. Thehydro-upgradingmethodaccordingtoclaim1,
30whereinthecatalystfordesulfurizationandhydrocarbon
PropertiesoftheFull-rangeGasolineFeedstockandtheBlended multi-branched-chainhydroisomerizationcomprises3-9wt
ProductoftheUpgradedLightandHeavyFractionGasolines
%MoO3, 2-5wt%B2O3,2-5wt%NiO,and50-70wt %
SAPO-11zeolites,withthebalanceofthecatalystcompris-
Full-range FCC ingAl—Ticompositeoxides,based onthetotalweightofsaid
Blendedproductofthegasoline2
upgradedlightandheavy
Item (feedstock) fractiongasolines 35catalyst.
Yield(wt%) 98.2 5. Thehydro-upgradingmethodaccordingtoclaim4,
Density 0.746 0.754 whereinthecompositionby weightof theAl—Ticomposite
(g/mL)Distillationrang 35-206 33—207 oxidesinthecatalyst is15-40wt%Al2O3and2-15wt%
e(°C.)
Content TiO2,andwhereintheAl—Ticompositeoxidesareprepared
oftypicalhydrocarbons (v 40bylhefractionalprecipitationofaluminumandtitaniumsalts.
%) 3.4 6. The hydro-upgrading method according to claim 4,
whereintheSAPO-11zeolitesofthecatalystfordesulfuriza-
51.3 14.5 tionand hydrocarbonmulti-branched-chainhydroisomeriza-
Multi-branched- 18.1 26.4
chainisoalkane 2210 24 tionhaveamolarratioofSiO2/Al2O3of0.1-2.0,andamolar
OlefinAromatic 3.5 p.p 45ratioofP2O5/Al2O3of0.5-2.5.
sSulfur(pg- 92.4 91.4 7. The hydro-upgrading method according to claim 1,
g°1)Diene(gI/
100g)RON whereinthecatalystforselectivehydrodesulfurizationcom-
ItcanbeseenfromTable8that, withthehydro-upgrading lishinganexcellenttechnicalbasisforproducingthesulfur- free
methodoftheinvention,thesulfurcontentininferiorFCC gasoline in the future.
gasolinemaybereducedfrom2210qg.g*'to<30qg.g*'with
theolefincontentfrom51.3v%to<15v%,andthecontent
ofmulti-branched-chainisoalkaneintheproductincreases
significantlytogetherwiththeconsiderableincreaseinthe
content of aromatics, decreasing theRONloss to 1.0 unit
whileachievingultra-deepdesulfurizationandgreatolefin
reduction.Moreover,theyieldoftheblendedproductisas high
as98.2wt%, andtheproductqualityisfarmoresuperior than that
regulated by theEuropean IVstandard forclean gasoline.
Theresultsoftheabovetwoexamplesaboveshowthat,
withthemethodoftheinvention,inferiorFCCgasolinewith ultra-
highsulfurcontentof1400-2500qg.g*’andhigholefin
contentof40-55v%canbeupgradedintoanmuchcleaner
gasoline productthan EuropeanIV cleangasoline,thusestab-
 US8,603,324B2
15 16
prises10-18wt%MoO„2-6wt%CoO,1-7wt%K2Oand
2-6wt%P2O„withthebalanceofthecatalyst
comprising
50Al—Ti—
Mgcompositeoxides,basedonthetotalweightof said
catalyst.
8. The hydro-upgrading method according to
claim 7, whereinthecompositionbyweightoftheAl—Ti
—Mgcom- positeoxidesinthecatalystis60-75 wt
%Al2O„5-15wt%
TiO2 and 3-10 wt % MgO, and wherein theAl—Ti—
Mg
compositeoxidesarepreparedbythefractionalprecipitati
on ofaluminum, titanium and magnesium salts.
9. The hydro-upgrading method according to
claim 1,
whereinthecatalystforsupplementaldesulfurizationan
d
60hydrocarbonaromatization/single-branched-
chainhydroi- somerization comprises 3-9 wt %
MoO3, 2-4 wt %CoO, 50-70 wt%hydrogen-
typeZSM-5/SAPO-11in-situcompos- itezeolites,
withthebalance ofthecatalystcomprisingalu- mina
binders, based onthetotalweight of saidcatalyst.
6510. The hydro-upgrading method according to claim
9, whereininthehydrogen-typeZSM-5/SAPO-11in-
situcom- positezeolite,theZSM-
5zeolitehasamolarratioofSiO2/
 US8,603,324B2
17
AI2O3 as40-70,andis presentedataweightcontentof50-70 wt
%,andwhereintheSAPO-11zeolitehasamolarratioof
SiO2/AI2O3of0.2-1.0,andispresentedataweightcontent of
30-50 wt %.
11.Thehydro-upgradingmethod according toclaim1,
wherein:the reactionconditionsforthe lightfractiongasoline
compriseareactionpressureof1-3MPa, areaction tempera-
tureof290-360°C.,ahydrogen/oilvolumeratioof200-600, a
liquidvolumespace velocityof8-14h*'for thecatalystwith
thefunctionofselectivedieneremoval,andaliquidvolume
spacevelocityof2-5h*’forthecatalystwiththefunctionsof
desulfurization and hydrocarbon multi-branched-chain
hydroisomerization;
thereactionconditionsfortheheavyfractiongasolinein
thefirst reactorcompriseareactionpressureofl-3MPa, a
liquid volume space velocity of 3-6 h* 1,a reaction
temperature of230-300° C.,andahydrogen/oilvolume
ratio of 200-600; and
thereactionconditionsforthereactioneffluentfromthe
firstreactorinthesecondreactorcompriseareaction
pressureof1-3MPa,aliquidvolumespacevelocityof 1-
3h*’,areactiontemperature of360-430° C.,anda
hydrogen/oil volume ratio of 200-600.
12.Amethodofhydro-upgradinginferiorgasolinethrough
ultra-deepdesulfurizationandoctanenumberrecovery,com-
prising:
cuttinginferiorfull-rangegasolineintolightfractiongaso-
lineand heavy fraction gasoline at 80 to 110° C.;
contacting thelightfractiongasoline withacatalystfor
selectivedieneremovalandacatalystfordesulfuriza-
tion and hydrocarbon multi-branched-chain hydroi-
somerization, whereinthecatalystforselectivediene
removalcomprises4-7wt%MoO„1-3wt%NiO,3-5
18
wt%K2O,and1-4wt%La2O„withthebalanceofthe
catalystcomprisingAl2O,basedonthetotalweightof
saidcatalyst,andwhereinthecatalystfordesulfuriza-
tionandhydrocarbonmulti-branched-chainhydroi-
5 somerizationcomprises3-9wt%MoO3,2-5at%
B2O„2-5wt%NiO,and50-70wt%SAPO-11zeolites,
withthebalanceofthecatalystcomprisingAl—Ticom-
positeoxidesbasedonthetotalweight of saidcatalyst;
contactingthe heavyfractiongasolinewithacatalystfor
ioselectivehydrodesulfurizationinafirstreactor,wherein the
catalyst for selective hydrodesulfurization com-
prises10-18w't%MoO„2-6wt%CoO,1-7wt%K2O and
2-6 wt % P2O„ with the balance of the catalyst
comprisingAl—Ti—Mgcompositeoxides,basedon
15thetotalweight ofsaidcatalyst;
contactingaresultingreactioneffluentfromthefirstreac-
torwithacatalystforsupplementaldesulfurizationand
hydrocarbon aromatization/single-branched-chain
hydroisomerizationinasecondreactor,whereinthe
20Catalystforsupplementaldesulfurizationandhydrocar-
bonaromatization/single-branched-chain hydroisomer-
izationcomprises3-9wt%MoO3,2-4wt%CoO,50-70 wt
%hydrogen-typeZSM-5/SAPO-11in-situ compos-
itezeolites,withthebalanceofthecatalystcomprising
zsaluminabinders,basedonthetotalweightofsaidcata- lyst; and
blendingthetreatedlightandheavyfractiongasolines to
obtain the ultra-clean gasoline product.
13. Thehydro-upgradingmethodaccordingtoclaim1,
sowhereinthecatalystforselectivehydrodesulfurization
employed inthefirstreactorcomprisesacarrierfromanoxide
ofaluminum,titanium, andmagnesium.