GASOLINE RANGE ETHER SYNTHESIS FROM LIGHT NAPHTHA PRODUCTS OF.pdf

8/10/2019 GASOLINE RANGE ETHER SYNTHESIS FROM LIGHT NAPHTHA PRODUCTS OF.pdf

1/6

A

\

GASOLI NE RANGE ETHER SYNTHESI S FROM LI GHT NAPHTHA PRODUCTS OF

FLUI D CATALYTI C CRACKI NG OF FI SCHER- TROPSCHWAX.

W

J . Reagan

Amoco Oi l Company

Naperv i l l e, I l l i noi s 60566

Keywords: Fi scher - Tropsch wax, Fl ui d Cat al yti c Cr acki ng. Et her Synthesi s

The Fl ui d Catal yti c Cr acki ng of Fi scher- Tropsch wax ( Czof par aff i ns) produces

two to f our t i mes the concent r ati on of r eacti ve i so- ol ef i ns ( i sobut yl ene,

i soarnyl enes, i sohexenes) t han obser ved f romconvent i onal gas oi l f eedst ocks.

Met hanol reacts wi t h these ol ef i ns t o f orm the corr espondi ng t er t i ar y al kyl

methyl ethers: MTBE. TAME and MTHE' s. These etheri f i cati on r eact i ons ar e

ml dl y exotherm c and equi l i br i um l i m t ed. The r eact i on t emper at ure and t he

ol ef i n mol ecul ar st r uct ur e are i mport ant var i abl es f or maxi mum ether yi el ds.

The base napht ha research oct ane number i ncr eases by 2- 4 number s af t er t he

et heri f i cat i on react i on.

on ether yi el ds because of hydr ogenati on of r eacti ve ol efi ns t o par af f i ns.

The cat al yti c cr acki ng of Fi scher- Tr opsch wax pr ovi des a non-convent i onal

SOUKCe of ol ef i ns f or et her synt hesi s that can suppl ement exi st i ng and

dw ndl i ng petr ol eumsuppl i es .

I NTRODUCTI ON

Fi scher- Tropsch (F-T) synt hesi s t echnol ogy (1) pr oduces l i qui d hydrocarbons

f r om synt hesi s gas ( hydrogen and carbon monoxi de) deri ved f r omt he

gas i f i cat i on of coal O r ef orm ng of nat ur al gas.

consi st s of a br oad r ange of nor mal par aff i ns (C-C,+ and a smal l quant i t y

of oxygenates and ol ef i ns. The di st i l l ate f r act i on, C+ i s an excel l ent

qual i t y f uel . The l argest pr oduct f racti on. C, 8+ i s pr i mar i l y wax and is

usel ess as a t r anspor t at i on f uel .

convent i onal petr ol eum processes, such

as

hydr otr eat i ng, r efor m ng and

cat al yt i c cracki ng to produce convent i onal gasol i ne and di st i l l ate

f uel s .

2 )

Fl ui d Catal yt i c cr acki ng and hydr ocracki ng st udi es have been r epor t ed by

Mobi l ( 3 ) and UOP. 4 ) Heavy wax C,,+) f r act i ons have also been t r eat ed

wi t h hydroi someri zati on and hydr ocracki ng processes at Exxon. ( 5 )

Hydr odewaxi ng and cat al yt i c cr acki ng t r eatment s of heavy wax f r omsl urr y F- T

processi ng are al so repor t ed by Mobi l . ( 6 )

I n

addi t i on, pure component

cr acki ng st udi es (decanol , decanal ) over the i nter medi ate

-

pore zeol i t e

HZSM- 5 have been r epor t ed.

( 7 )

exam ned i n some detai l by Woj ci echowski Over l arge- pore f auj asi t e

(zeol i te

Y)

and over HZSM- 5 zeol i t e cat al yst s. ( 8. 9) Government al

r egul at i ons, most r ecent l y i n t he Cl ean Ai r Act Amendment s of

November , 1 9 9 0 . have r esul t ed i n the phaseout of l ead addi t i ves, l ower i ng

of t he Rei d vapor pl ; essure of gasol i ne and i n some geographi cal ar eas, t he

mandat ed use of oxygenat es.

pr oduced and used

as

gasol i ne bl endi ng component s. (10) Recent st udi es of

methyl t ert i ary but yl et her ( MTBE) and t ert i ary amyl methyl et her ( TAME)

suggest t hat t hese compounds may r educe automat i ve car bon monoxi de

em ssi ons, have hi gh bl endi ng gasol i ne oct ane r at i ngs, R+M/ 2, ( MTBE-108,

TAME- 102) and have l o w Rei d Vapor pr essure. These et her s are pr oduced

commerci al l y by t he ether i f i cat i on of t he appr opr i ate ol ef i n by methanol

( MTBE, i sobutyl ene; TAME, i soamyl enes). ( 11. 12) There i s l ess i nf ormati on i n

the open l i t eratur e about t he et her i f i cat i on r eact i ons of C, ol ef i ns that

are al so pr esent i n s i gni f i cant quanti t i es i n f l ui d cat al yt i c Cr acki ng

product napht has.

f r om C,-C, r eact i ve i so-ol efi ns i n napht has. One r eport

(14)

pr ovi des some

i nf ormati on about t he r eact i on of C, i so- ol efi ns w t h methanol t o pr oduce

the hi gher et her s, MTHE' s, methyl t ert i ary hexyl et her s. MTBE has attracted

the most att ent i on i n recent year s.

coul d reach 25%par year by 1995.

( 15. 16)

There i s e gr owi ng need f or

al t er nat i ve sour ces of ol efi ns f or ether synt heses as demand f ar t hese

materi al s escal ates beyond t he capaci t y of conventi onal petr ol eumP KOC~SS ~S.

There ar e no r eport ed st udi es of t he cat al yti c cracki ng processi ng of F-T

l i qui ds t o pr oduce C,- C8 ol ef i ns as f eedst ocks f or t he synt hesi s

of

gasol i ne

range

ethers .

EXPERI MENTAL

The f eedst ock OK t hi s wor k i s a sampl e of r eact or wax f r oma commer ci al

f i xed bed F- T uni t operated by Sasol , L i m t ed.

char acteri zat i on of t hi s f eedstock i s avai l abl e i n other st udi es. ( 4) The

smal l scal e (1 gramof f eed,

3-5 gr ams of cat al yst ) cat al yti c cr acki ng t est s

wer e perf ormed on a M cro Act i vi t y Test uni t ( MAT) si m l ar i n desi gn t o the

uni t descr i bed i n ASTM procedur e.

09907- 86. Thi s test uni t

i s

equi pped f or

detai l ed anal yses of gas and l i qui d pr oduct s and cake yi el ds.

pl ant t est s were conduct ed i n

a

c i rcul at i ng cat al ys t uni t s t m i l n r o i

desi gn descr i bed by ARCO. Thi s uni t operates wi Lh

2

to 3 ki l ogr ams < i

The presence of hydrogen has a det r i ment al ef f ect

The F- T l i qui d pr oduct

These pr oduct s ar e f urt her t r eat ed by

The cat al yt i c cracki ng of F- T l i qui ds was

Sever al t ypes of et her s are now commer ci al l y

The Et her ol process (13) produces a m xed et her product

The gr owt h r ate f ar i t s pr oduct i on

The anal yti cal

The pi l ot

337


2/6

catal yst and f eed rat es of 10- 30 gr ams/ m nut e.

exper i ment s were Car r i ed out i n a convent i onal hi gh pressure m cro- r eact or.

Tht ee FCC catal yst s,

cont ai ni ng zeol i t e

Y,

zeol i t e Beta and zeol i t e HSZM- 5

arb t he pri mary catal ysts f or t he FCC st udi es, The Y zeol i t e cat a l ys t i s an.

Ul crastabl e Y f auj as i t e ( USY) zeol i t e cat al yst taken fr om one of Amoco s

commerc i al FCC uni t s. The HZSM- 5 cat al yst

is

a commer ci al sampl e pr oduced by

I ncer cat Gor p. The Beta s ampl e was prepar ed i n our l abor at ory by spray

dr yi ng a commer ci al l y avai l abl e Beta zeol i t e and a convent i onal si l i ca-

al um na matr i x. Two commer ci al i on exchange r esi n cat al yst s, Rohmand

Haas' s Amber l yst 15 and Bayer ' s K 2 6 3 4 , were used i n t he et her s ynt hesi s

The et her synt hesi s

KU115.

RESULTS AND DI SCUSSI ON.

A. Cat al yt i c Cr acki ng Test s

I ni t i a l catal yt i c Cracki ng runs wi t h t he smal l scal e test systemprovi de

some i nsi ght s i nt o the cat al yt i c cracki ng behavi or of the wax f eedst ock.

The

i ni t i al choi ce of f l ui d c at a l yt i c c r ac ki ng

( FCC) catal yst and pr ocess

condi t i ons f ocuses on compar i sons wi t h convent i onai gas oi l , t he usual

f eedst ock t o commerc i al FCC uni t s. At t hese condi t i ons. (970' F r eacti on

t emperat ure,

3 cata l ys t

to

oi l wei ght r ati o), t he wax feedst ock readi l y

COnVeKt S

( 8 5 +

conver si on) t o hi gh yi el ds of C,- gas ( hi gh i n propyl ene and

C, ol ef i ns) and napht ha (C -430' F). A Summar y of t hi s compari son is

presented i n Tabl e

I .

The conversi on l evel i s def i ned by convent i on

as

t he

sum of t he pr oduct s: napht ha, gas and coke, Thi s hi gh cat al yt i c cracki ng

conver si on l evel

f or t he wax f eedst ock agr ees wi t h the publ i shed Mobi l dat a

3 . 6 ) on F- T wax cr acki ng. I n addi t i on. hi st ori cal pur e component

hydrocarbon cr acki ng studi es

( 17) suggest t hat l ong chai n paraf f i ns cr ack at

much gr eater Kate5 than t he short er chai n paraf f i ns.

t he wax f eedst ock wi l l be an i mport ant par amet er when commer ci al heat

bal anced Operat i ons are eval uat ed.

wax product napht ha r esul t s f r om t he hi gher concentr at i ons of l ow octane

number paraf f i ns compared t o t he gasol i ne f r om t he mor e ar omat i c gas oi l

f eedst ocks. The oct ane number s i n the Tabl e I are est i mat ed resul t s f rom

detai l ed naphtha anal yses by gas chromat ogr aphy and cor r el ati ons wi t h oct ane

engi ne t est s. The t arget of t hese st udi es i s to opt i m ze the yi el ds of

br anched ol ef i n i nter medi ates ( i sobut yl ene and i soamyl enes) f or et her

synt hesi s . Three FCC catal yst s, cont ai ni ng zeol i t e

Y,

zeol i t e Beta, and

zeol i t e HZSH- 5,

wer e test ed f or

wax C O ~ V ~ K S ~ O ~

nd product sel ect i vi t y as a

ser i es of b l ends wi t h an i ner t sol i d. Tabl e I1 pr esent s t he det ai l ed

pr oduct d i st r i but i ons f or t he t hr ee catal ysts at a s i m l ar conver s i on l evel

of about 8 3 .

of the desi r abl e ol e f i ns, However . th i s OCCUKS at t he expense of napht ha

pr oduct .

pr opyl ene. These scr eeni ng t est r esul t s show t hat FCC catal yst vari at i ons

can provi de f or w del y di f f erent pr oduct di st r i but i ons.

8. Pi l ot P l ant Cata l yt i c Cracki ng Test s .

Some i ni t i a l wax cat al yt i c cr ack i ng screeni ng t ests on the pi l ot pl ant uni t

ar e pr esent ed i n Tabl e 111.

t he pi l ot pl ant agree wi t h the smal l

scal e

test resul t s .

cat al yst convert s

a

great er f r act i on of the wax f eedstock to l i ght ol e f i ns,

i ncl udi ng propyl ene, i sobut yl ene and i soamyl enes. t han the

Y

zeol i t e

cat a l ys t .

napht ha yi el d f or t he Bet a zeol i t e cat al yst compar ed to t he st andard Y

zeol i t e cat a l ys t .

s i m l ar to the Beta zeol i t e.

Hi gh yi el ds of the t argec l i ght ol ef i ns ar e

produced but t he napht ha yi el d i s much l ower t han the Y zeol i t e cat a l ys t .

Thi s t rade- of f of l i ght ol ef i n and napht ha yi el ds can be adj ust ed by t he

amount of t he HZSM- 5 addi t i ve.

pl ant Catal yti c cr acki ng r uns were combi ned and di st i l l ed ( ASTMKethod

0 - 2 8 9 2 ) to pr oduce l i ght napht ha (QOO F) f r acti ons f or t he ether i f i cati on

studi es .

The l ow coke yi el d of

The r el at i vel y l ow oct ane number of t he

Bot h t he Bet a and HZSH- 5 cat al yst s produce much hi gher yi el ds

I n addi t i on, t he HZSH- 5 cat al yst pr oduces ver y hi gh yi el ds of

The hi gh conver si ons of the wax f eedstock i n

The Beta zeol i t e

The hi gher ol ef i n y i e l ds are off set by a s i gni f i cant l y l ower

The t est r esul t s for t he HZSH- 5 cat al yst m xture are

The total l i qui d products f romsever al p i l ot

C . Et her Synt hesi s.

Si nce the r eact i on of i sobut yl ene and methanol to f orm MTBE i s wel l known,

thi s st udy wi l l f ocus on t he producti on of TAME and KTHE ethers f r om the

l i ght napht ha pr oducts of the pi l ot pl ant wax cracki ng st udi es.

f i xed bed uni t was used f or t hese et her i f i cat i on st udi es. The i ni t i a l t est

runs i nvol ve the r eact i on of 2-Kethyl - 2- but ene wi t h methanol to pr oduce

TAKE.

i soamyl ene to TAME: mol es TAME out/ mol es i soamyl ene i n*100) .

condi t i ons are: vari abl e t emperatures, 200

PSIC

uni t pr essure, 0 . 6 6 WHSV

(ol ef i n) and 1. 2 mol rat i o of met hanol / ol ef i n.

i s Amber l yst 15,

a

commerci al ether i f i cat i on cat al yst The r eact i on

t empcr aLure is

R

m a j o r f actor I n L hf s eLher i Cl cnLi on

re.wt. Ion.

A smal l .

Tabl e I V shows t he compar i son of TAME yi el ds ( conver si on of

The test

The cat al yst f or t hese r uns

TIIV a l ~ i ~ r , ,

338


3/6

c

I

I

r i se i n TAME yi el d at 150 F and t he decl i ne at 200' F suggest s t hat

equi l i br i uml i m t at i ons exi st at t hese t emper at ur es and r eact i on condi t i ons .

The maxi mumyi el ds of et her s wi l l occur at t hese equi l i br i umcondi t i ons.

Tabl e V pr esent s t he det ai l ed composi t i on of the l i ght napht ha sampl es f r om

t he Pi l ot pl ant wax cat al yt i c cr acki ng KUnS.

sampl es, f eeds 8 and

C ,

are hi gher f r om the pi l ot pl ant wax cat al yt i c

cr acki ng runs t han t he l i ght naphtha sampl e. f eed " A".

Use Of hi gh ol ef i n sel ecti ve FCC cat al yst s, Beta and HZSM- 5.

i n the pi l ot

pl ant r uns, Nos. 940- 01, 02 and 941- 01. The same

Y

zeol i t e cata l ys t w a s used

i n the r uns f or f eed "A" and

"C"

,

r esul t s f r om the l ower conver si on l evel . The reacti ve i soamyl enes, 2-

Methyl - 2-butene and 2- Met hyl - 1- but ene f or TAME synt hesi s and the r eact i ve C,

i so- ol ef i ns. 2- Methyl - 1- pent ene. 2- Met hyl - 2- pent ene. 2. 3- Di met hyl - 1- but ene.

and Ci s and t r ans 3- Met hyl - 2- pent ene f or MTHE synt hesi s ar e t he i mpor t ant

components . Thi s l i ght napht ha. f eed "A" sampl e and met hanol are t he

f eedst ock f or a seri es of ether i f i cat i on r uns at the same pr ocess condi t i ons

f or t he 2-Hethyl-2-butene/methanol t es ts . Due to the l i m ted avai l abi l i t y

of t he napht ha, onl y t wo r eact i on t emperatures ar e avai l abl e.

t he conversi on of t he vari ous C and C, i so- ol ef i ns to t hei r r espect i ve

met hyl et her s, Tabl e VI . shows t hat r eact i on t emper at ure

i s

a maj or f actor

i n the et her i f i cat i on r eact i on. The decrease

i n conver si on

w t h the

i ncrease i n the car bon number of the i so-ol efi n agr ees wi t h ot her l i t eratur e

ether i f i cat i on s tudi es .

( 18. 20)

The r eact i on pr oduct s f r omt hese r uns have

a s i gni f i cant yel l ow col or, especi al l y at the hi gher r eact i on t emper at ur e of

150F.

tests . I t i s l i kel y that pol ymer i zat i on of o l ef i ns to

C,,+

hydr ocar bon

"col or bodi es" i s responsi bl e f or the col or ed pr oduct . The col or of t he

et her product coul d be a si gni f i cant pr oduct qual i t y i ssue.

pr esent s t he r esul t s of the et heri f i cat i on r uns wi t h t he "B" and "C"

l i ght

napht has at 15OF. I n t hese r uns, both Amber l yst 15 and another CO~e r Ci a l

et her i f i cat i on cat al yst , gayer' s K2634 ar e under st udy.

The

Bayer catal yst

cont ai ns a nobl e met al i n addi t i on to t he str ong aci d f unct i onal i t y.

nobl e metal i s avai l abl e f ar o l ef i n i somer i zat i on and di ol ef i n sat urat i on,

i n the pr esence of hydrogen.

pr evi ous set of r uns,

200

P S I G , 2. 9 gr ams of cat al yst , met hanol 1. 37 g/ hr ,

napht ha, 5 . 5 g/hr ar e t he same except t hat onl y one r eact i on t emper at ure.

150'F. i s avai l abl e. The i so- ol ef i n conver si on r esul t s are si m l ar for bot h

catal yst s and the t hree f eedstocks. i n the absence of hydrogen gas i n t he

r eact or. The cal cul ated r esearch octane val ues f or t he products of t hese

ether i f i cat i on r uns ar e 2- 4 number s hi gher t han t he st art i ng l i ght napht ha

Feedst ocks, Tabl e

VI I I .

As expect ed, t hi s oct ane i ncrease depends, t o some

ext ent upon t he concent r at i ons of t he ether s i n the pr oduct.

octane number s f or t he m xed ether l i ght napht ha f r act i ons ar e al so shown i n

Tabl e VI I I . There i s a f ai r agreement wi t h the cal cul ated ( by

G C

oct ane

numbers . When hydr ogen gas i s pres ent , Run No. 034- 1, Tabl e VI I I , t here i s

a maj or l oss of i so- ol ef i n conver s i on. These react i on condi t i ons resul t i n

the hydr ogenat i on of bot h react i ve i so- ol ef i ns and l i near o l ef i ns . Thi s i s

an undesi r abl e r esul t si nce bot h t he pr oducti on of ethers and t he octane

number of t he pr oduct decr eases si gni f i cant l y. The r un wi t h added hydrogen

gas, 034- 1, has a l ower r esear ch oct ane r ati ng ( 79. 5) t han t he f eedstock

( 84. 6) or t he r un wi t h no added hydr ogen, 034- 3, ( 8 5 . 8 ) . Thi s octane l oss

i s due t o t he conver si on of hi gh oct ane val ue ol ef i ns to l ow oct ane val ue

para f f i ns .

ether i f i cat i on products i n the pr esence of hydr ogen gas.

These et her i f i cat i on r uns cl ear l y demonst r ate t hat t he l i ght napht ha

f ract i ons f r om the cat al yt i c cracki ng of Fi scher- Tropsch wax ar e excel l ent

ether synt hesi s feedst ocks.

ACKNOWLEDGEMENT

Thi s work

was

suppor t ed by t he U S . Depar t ment of Ener gy. Pi t t sbur gh Ener gy

Technol ogy Cent er . Pi t t sbur gh. Pennsyl vani a under Cont r act No. DE- AC22-

91PC90057. D. Kovach and R. Br own per f or med t he exper i mental wor k.

3 .

Newbur y pr ovi ded the

GC

napht ha anal yses.

REFERENCES

The i so- ol ef i n content s of the

Thi s i s due to t he

The hi gh i so- ol ef i n cont ent of f eed

C

A s ummar y of

Thi s cal or i s not present f or t he pur e component 2- Met hyl butene-:

Tabl e V I 1

The

The nom nal r eact i on condi t i ons f r omt he

Bl endi ng

There i s a si gni f i cant i mpr ovement i n the col or of t he

1.

2 .

3.

4.

5

Anderson, R. B. The Fi scher - Tropsch Synthesi s; Academ c ( New York),

1984.

Stuar t , J .

S . ,

et el . Oi l h Gas J our nal , August 31. 1981, 62.

Kuo.

J .

C.

W , et al . 1988 AI ChE Annual Meet i ng (Washi ngt on, DC,

11/ 17/ 88. Pr epr i nt No. 61D) ; 1984 AI ChE Annual Meet i ng ( Anahei m

Cal i f orni a. Prepr i nt No. 11D); Depart ment of Energy. Fi nal Report ,

Oct ober, 1985,

DOE/ PC/ 60019-9A.

Shah,

P.

P.. et al . " F- T Wax Char acter i zat i on and Upgr adi ng"; Fi nal

Report . Depar t ment of Ener gy. J une

6 ,

1988. DOE/ PC/ 80017- T1.

Exxon RLE Company ,

U . S .

L. 832. 819. May 23, 1989.

339


4/6

6. Hobil

Oil Company, U.S. 4,684,75 6, August 4 1987.

7. Riley, M . ; Anthony, R. G. J . Cat.. 103, 87-94, 1987.

8. Abbot, J.: Wojciechowski. B. W . Ind. Eng. Chem. Prod, Res Dev.1985.24,

9. Kobolskis. I.; Wojciechowski. B.

W

Can.

J

Chem. Eng., 6 3, April 1985,

10

Piel,

W .

J

Energy Progress,

8.

No.

4

201.

1988; Oil

6

Gas

J . .

11.

Reychler, A. Bull. SOC . Chim. Belg. ; 21, 71 (1907).

12.

Ancillotti,

F..

et al.. J . Catalysis; 46, 49-57 (1977).

13. Halsig, C. P.. et el ., NPRA, 1986 Annual Meeting, Paper AH-86-94.

14. Krause, A.

0

I.. et al.. 8th l n t Gong. Cecal., 5 .

553,

1984.

15. Oil 6 Gas J . , January 27,1992, 21.

16. Oil 6 Gas J . , November 30,1 992, 48.

17. C o m a , A, ; Wojclechowski, B. W. Catal. Rev.-Sci. Eng ., 27(1),

501-507.

269-277.

December 4 , 1989, 60.

29-150. 1985

Convers ion,

w t X

P l O h l S t l .

r t X :

c

c.

C

430.F

43O.Ft

Coke

I r ob t y l cnc

I . O ~ l C C I

Naphtha, u r n

MOW

Gas

o i l UI)I

61.6 88.1

2.6 1.8

11.6 31.4

6.9 15.9

36.2 36.8

38.4 11.9

4 3 2.2

1.3 4.5

2.3 5.8

90.4 85.8

79.8 77.6

T M LE I1

U T IEST RESILIS--UTALIST

oDIpARIso*S

AT mLIF

Z e o l i t e Befa

042

85.3

C a t a l y s t

1

Z e o l i t e Y

u r n

Y O.

c onv e r s i on . U t % 83.0

le01 t c HLsn-5

055

85 . 8

Product Y i e l d s , Ut :

c;

c

C

C

C

;

C,.430 F

430.F

Coke

0.6

7.4

0.8

13.2

3.7

11.7

3.6

41.7

17.0

0.3

l s o b t y l e n c

l r o a m y l m e s

G-430.F

57.0

85.2

16.2

ON

K W

340


5/6

1ABLE 111

P l l O l pu*T m s

Feed IO: 92-0490-01A 93-0024-011

reed

A*

reed

B

Pilot P l a n t

939-01. +

02

v40-01. 02

m NOS. 4 us7 CDt.l St 941-01

conversion = 93.6% 8etalHZSU-5

C a t a l y s t

convers ions = 90.96%

r o t a l P a r a f f i n s w t X 6.69 8.44

T o t a l I r o - p . r a f f l n 9 U t 42.71 17.64

To t a l A r m t i c 9 wtX 1.74 2.62

T o t a l NsPhthems W t X 3.96 5.55

T ot al o l c f i m YtX 44.51 64.47

~ e a c t i v e r o - o le f in r

wtX

93-0024-01C

Feed

C

939-04

4

SY Cstalyst

C m e r . i M 3%

4.32

22.88

0.35

3.16

68.6

1.25

4.26

C6's

2 , 3 - d i m t h y l h t c n c

2-mthyL.l.pnrcne

Z-nrthyl-2-pntene

S - m t h y L - t r a n s - 2 - p n t e m

I - r e t hy l - v i s -Z -pn t em

2.15

.67

0.8 0 . n 0.97

2.35

2.49 3.02

4.01 5.27 5.46

2.49 3.13 3.29

3.98 5.48 5.35

1.76

5.64

341


6/6

I so -o le f in C 1Z'F

2~Wethyl-l-bUtene 85.4

2-nrthyl -Z-brtme

2P.P

2.3 Dimethyl-l-butene

56.5

2-Wethyl - l -pntme

65.9

2-Methyl.Z-pnttne 20.7

3-Wethyl-ci~-Z-penCene 21.7

cs

C6

3-Wethy l - t rans-Z -penfene

20.8

150'6

G

8P.P

65.5

83.4

87.5

48 6

38.6

2P.8

i r o -o le f in

c-ent

2-Methy1-l-butcne

2-Methy1-2.butane 65.5 62.2 M.2 42.9 38.2 61.2

89 9 b0.2 87.1 77.2 78.1 87.7

200.F-

Naphtha

Reaction

T a p .F

Catalyst

Feed

A

F e d B

Feed

C

P2-04P-OlA

92-0024-01A PI-0024-01C

150 150

50 150 150

50

lnberlyrt 15 Ir he r ly st 15 12634 12634 12634

K2634

No

H2 H2 H2

No

H2

TLBLE V I 1 1

2.3.0Incthyl-l-butene

C6'r

2-nechyl- l -pmtme

2-Methy1-2-pentenc

3-Mefhyl -Ci s-2-pntene

3-nc~hy l - t ranr -Z-pntenc

...

eed

A

-0-01A

15586-024-2 125.F

15586-024-6 15UF

15586-024-8 150.F

Feed

P3-0026-01A

15586-031-2 150.F

05586-033-1 150.F

15586-033-3 150.6

...

83 . 4 ... ...

87.5 85.5 84.1 72.2 78.6 86.P

48 6

56.1 62.7 44.2 31.5 51.5

38.6 31.0 43.4 23.8 7.3

25.8

2P.B

32.2 43.7 25.P 20.7

33.3

...

93-0024-OlC

15586-034-1 1W F

RV no.

Feed A

G O - O l A

15586-024-2

15586-024-6

15586-024-8

Feed

15586-031-2

15586-033-3

Feed C

ps-ooi4-OIA

05586-033.1

OCtllM

Nlnber

80.P2

w r l y r t 15 80 . OP

83.76

w r 1 y r t

15

83.88

I * O .

P araf fi ns pa raf f in s A ~ m t i ~ s aphthenes O l ef i ns OxyeCnateS V n t n o ~ n s

6 689

42.712

1.736 3.956 44.507

0.071 0.33

7.806

40.230

1.W5 4.474

33.762

11.406 0.34

6 463

40.42P

2.247 4.576

29.671

16.294 0.32

6.337 4 0 . 4 M

2.263

4.586 2'9.58

16 436 0 . 3 3

m.437

17.617 2.623

5 . 5 4 ~ 64.472

0.17 1.11

7.381

1 7 . ~ 0 3 . 6~ 1

6.583

41.716

22.44s 0 .844

7.417

17.989

3.647 6 424

41.847 21.815 0.821

8.205 1 7 . M

3.62 6.512

45 889

17.277 0.83

84.56

95.9

ayer

H2 12634 m.47

88.P

Keyer no H2 12634 85.78

95 9

...

*CBlC l.ted

342

GASOLINE RANGE ETHER SYNTHESIS FROM LIGHT NAPHTHA PRODUCTS OF.pdf

Documents

Transcript of GASOLINE RANGE ETHER SYNTHESIS FROM LIGHT NAPHTHA PRODUCTS OF.pdf