Petrochemical Industry And the Possibilities of Its

Establishment in the Developing Countries

Editions Technip

by Mercier, Claude engineer.

IV. 3. BUTADIENE PRO DU CTJON

IV . 3. 1. BuULdiene sources
The butadiene raw material situation in Europe is also somewhat different from that
!n the u.s. c4 production in the u.s. in 1962 totalled 36.106 tons, primarily as butane
from natural gas and butane-butylene refinery streams.
The biggest petrochemical market for c 4 streams is butadiene, obtained by butane
dehydrogenation, butylene dehydrogenation or as a eo-product in ethylene plants.
In Europe, butadiene production has been based on refinery butylenes and on butadlene
extraction from naphtha steam-cracking plants which are expanding rapidly. The butadiene
can be extracted relatively simply from the other C4's produced 1n the same way that the
butadiene product is extracted from the reactor effluent of a dehydrogenation plant. Typical
extraction solvents are cuprous ammonium acetate, acetonitrile and furCural.

IV . 3 . 2. Distribution of processes
In the U. S. the dehydrogenation of butylenes is still the dominant process, but t he
one-step Houdry process is making considerable strides. The choice between these processes !s largely Influenced by the availability of feed associated with large refinery

BASIC PRODUCTS OR FIRST OENERATIOII PE'IROCHEI'IICA!S

Installations . Where there is a considerable availability of cat. butyle~es, lt Is likely that

the butylenc dehydrogenation process would be chosen (EssoPetroleumatFawley,England).
In Germany, on the other hand, the Hols plant selected dehydrogenation of n- butane, since
it was Celt that there wore no adequate supplies of eat. butylenea available to form the baaia
of a fully economic plant .
In Europe, now. where ethylene productions from naphtha steam-cracking are auffieiently large. it may be well worth while to extract butadienefrom the C& cut, since it becomes a
valuable eo-product with ethylene.
IV. 3 . 3. Economics of butadiene production

IV.3 .3 .A. Butane de hydrogenation by Houdry process

The cost of butadiene ao produced in the U. S. is lower than in Europe because of
the size of the plants, the low energy costs (an important factor In dehydrogenation processes) and the large avallabillty of butane at a low price. On the other hand, the butylene
output in Europe Is low, because of limited catalytic cracking facilities, and butane Is
high- priced because of its use as domestic fuel.
Also, U . S. butadiene producers whose plants are already amortized can export to
Europe at landed prices which are be low their own domestic prices.
The elements o! the operating coat for a 44,000 tone/year butadiene plant, which could
be envisaged to be built respectively In Europe and In the U. S .. are presented In Table Xll.
The manufacturing coats for the two cases are given in T ables XlU and XIV and the
corresponding butadiene selling prices are derived.
The effect of plant size and butane feed cost on the economics of butadlene production
are shown respectively in Figures 7 and 8 tor units to ~ erected in Europe.
,.._ 1. lPrlCT OP' Pl.ANT Slzt

20

22 2-<

26 2& lO

32 3-' 36

PE'IROCHEMICAL DIOOS'mY

TABU: XII
44 , 000 TONS/iEAR BUTADI&NE PRODUCTION
HOUDRY BUTANE DEHYDROGENATION AND
PHIWPS FURPURAL EXTRACTIVE DISTILLATION

OPERATING COST ELEMENTS

10 6

us

u.s.

Europe
lnveatment (Gr ass Roots Plant)
Proceee Unite . . . . . . . . . . . . . . . . .. . . . ..
Olleltes, ineluding utilities and aux:Utartea
required tor a eel! eulficient lnatallation . . . .
Initial catalyst a.nd chemical chargee . . .. . ..
Start ...up 8XJM::D8el
0

Total . . . ... .. . .
Material balances
Raw material: n ... butanc
Product: butadiene

15.40

16.20

0.64
1.00

0.60
1.00

17.04

17.80

- -80,000
44,000

tonofyear
tone/year

By-pr oduct: fuel gas (Included In

fuel consumption) . . . . . , . ,

UWitiea regulrerneota
Fuel
Electricity
0

Hf KcaVYear

312,000
13,600, 000
290

Treated water . . . . . . . . . . . . .

KWHI,year
103 m /year

Catal:z:at and chemical regulrementa .

US $/year

Labor . .

men/ohift

18

Roya!Ueo

US $f.t on of
butadiene

13.80

650,000

630,000

'lABLt XIII
~ 4 . 000 1'0NS/VrAR

IUTADIENE PR.OOUC'l'IOK HOUDRY 6U1'A."' OEWtOROCNAl'ION At' D

PHlWPS rVR:r\JAAl. tx!IIACTM: DISTIL.L\TION (LRC1'J> I.N EU!ROPE}

PRICE

MANUFACTURING COST AND BUIAOlBNE SflLL.lNC

Un lt coal

Vnl\

Annua.l qua.nUt)'

us$

Vu-Lab!~

~al

103

eot

S/year

coc.
ltDw material
n~tane

. . . .. .. .. .. .. .. . .. . . .

Fuel

....

El~b14::1ty

6
10 Kea.l

. . . . . . . .,, . . .. .. . . . .. .

"'"'

..............

,.

..

~,.

................

'

,.

:S3

't OM

ucutue
'@.

J. 5
10

!03 KWH

'

Tua,ed watr .. ,...................

80.000

o. a

m3

ftoy&ltte

moo/year

,.t U,. ot ubJ"-1o Md ..acu

13, GOO

I'G
58

~000

12
I
I

n. e

't.ont

. . .. .. . .. ... . . .. . . ...

ar;a
GSO

<t$0

J60
ltO

.... ... . . ..... .... ... ,. ...... ' ' ..

Total Vrtablo C oU

4$8.

Labor att.t upcFVIeion

S atar,'lt and. lllttS ,
S\Jpcu~t.on

112,000

uo.ooo

c aalyal b.d ebcunJc.U. . .

2.560

.... 000

610
,,lt:J~

,, at 12. 5 4Jit of Lnvotmtn.t

.,.

IDteroet .. . . .. . .. .. .. .. .. .. . at 3. $ Yt of:

~nvo tmcnt

:..t a.ltiterta.nt f!' ..

Glt
ot J.nvotmcnl
G e.neral Plant Overbead. . . . at 2~ of uwea taoent
T axt! ud Jr~urance ,. . . ., .. . .. . . .. ,. .. .. . + .. at l 1- of lhvet cnen t
Total F~ed Co"'ta .. .. ,..
.. ..
"'
..
" ..
" ' ' " .
"
Ma.nQ/e..c ti.H"Ull Co1.

,.
..
.. ..
t'

..

..

...

..

..

..

..

..

..

...

..

. ...... .. ..............
. . . .. . . .. . .. .. .. .. . . .... .... . .. . . . ... .. .. .. .. ........
. ....

e""i
Ntol Caeh now at 20 fa.(l) ot totlltrav~stm(IAt

" ' "

~"'i:V

a,eG~

Sou~,

N 0 1 lnc:om-o after tu.e .. . . .. .. .. . , . .. . . . . ..

3. 400
1. 120
1, 280

N'C't ln~om~ bctforo t .aac

~larnlt&eturLnr c:out

s. 85:&

....

.... 4

........

jo.

....

.a ... ..

. . . . . . . . . . . . . . . ..... . . . . . . .

Ocrpr ol!a.tJora p.rov LtJea ~ ,. , . .. , ,. ,. ,. , .. .. ,. .. . . ,. . .,. ,. , ., ,.

?'

..

"

..

,..

o t ~Cl < ...... ., ... . ,. .............. . ......... , ................ , ...

....... . .... ..... .. ................. .... .. ....... ...... . ...... . .. ..
~

2.$60

Hucadien.e aalt- .. . .. .. . . . . . . . .. .,. . . . . . .

11, 4 12

9utodi4;1JI o acUln.: pri4:e US $ /.ttnL , .

~60

1/.lb . . .. . . . . . . . ...... ......... ........ .. ........

jn Rec~ ~ t:,~QutnHt I or

~~-n-~ar '!_~out.

}
t!
g
~

Flx~ ..coets
O.pre~ laU011

- --

--

11,81

i
n

TABLt XIV
44 , 000 'JON'S;'rrAR. IDlm\Dtt~t: PROD UCTrON HOU11lY !WANt OtH"'Dft.OG_EHATIOH A-ND
i'HlLUi'S fUitFUitAL 1XiRAC1'M DISTlUA1i0M (W<iitD IN U .S. GUll' Co.\SI')
~UFAC'fURING

OOST AND DUTADIENE SELLlNG PRICE

l.TnJII. coL

lfJrl'i:li

us'

VU'ilil:Jll! cclli:a

Ra~ "'ifilw~lill
n~b;;i.~G

UtW11c-
Puelt

11 ,

~ ~~

Ele~lt:ftlcity

T.re.ed

rAJ

r&;

..

"

*' i ii!
. .,

+ .:

-..to~

rt'

"

..

. ..

"

~~

~, ~ +

I!

l'f'

"

I!!

lt

lt'l

1!1'

..

ll

laJ

..

~~ ~

. . "

ArmA&l Qlll.'lllil.y

m6 IIWaJ.

~03 KWR
m~

ID$

18rO..,OOC

Z4l

lto:n

.AmJual rC:CHIIt

J.O

312~01)0

8
0.,2

2,i(Jr( ). 0CID

$/tear

li. 91:ZQ

Ut

lot

~~ 600

511

41'9.
C'a~ll: and

memtrea11 .

G'O I

Lalboro anll i111pl!ll"ViahJn

lt~:l&rl-t::

.. ~~

u-d Wll.g'C 11

S'u,pentliiiCirt .a t 2! ~

Ra;ydtlell

ll'l

,.

l'l

ll

tl

ot .8Jalal"1-eol uull

re

Tohll v.~SA: Cot. ....

Fb.edl

tl

~~

7 lj[)l)

manJ':fr!'H

12

~so

!1.317

'I!.IDS:I!!!I

tll

..

~~

11

Ill

li

il

l:l~ B.

lcnl

i'8"r I

41-t..(liOI.J

810

...."'16 1

t~lil

~Pir~el!l.1lon

,, .. .. .. .. .. at l2. !5 ~ ,.,_, irlvealrni!!'fil

+ + . . . . . . . . . . . . . . . . . . . . . . . . . . , ., Ill 3., :5 ,. or lJ:!vt".li~-f'!}t

lnw"' ..... ~

Mlli.ftten._an.ce i i " i + " "

~~] 4 ~. {o l lnva-.tmJC\nL
Gm~rliJ. Plant Ov-crtlt-.Did . . . . . . . . . . .. ,. at 2 ,_
o.t ~.V"! :I! b:neonl
11

11

Tu1U 1 ilndlln:I-\U'Ineill

11

11

. ,

fWl

t1

rl

r.l

Ill

.al

. + +

Tatal P~M Cc

ii

ltt-IL1fi111U IU:riDJ CD.I t

li

!i

il

ji

11

..

+ ._.
11

......
11

1'1

i
tl

'I

"

lE

11

I ,.

o:l'

11

rtJ

11

t1

Ill

lll

]a veil tm.e-nl

tl

Ill

11

..

rei

11

aJ

,.,ltl
8.. 426

r &o:wpg P!d!ca

( l)
.
.
Flew at m t.
gt t~;;~ILIII1 In"Ytlllrtrnl!!nt ,. ~ ~ ~ ............ . . . . ~ + +
Dtpn-c:IUoQ, PJ~Olftl:dtl
it> '! ~ ~ ~ ~ lo lo I! ~ I ... !i
I!
~
~
r-m
l'te\ illlcom tAfte~ 1ax.11 ~~ ~~ ~~ a fi! .. it fi! ., ,. + ~ ii
~
c.~ . . . . . . . . . . . . .
Nat lrtco-me beiMe 1t:U.e11 at 5~ s .,. .............
~~ ~ ~ ! ~ 8 " + + .. ! ! , + +
l8l

Ill

iil

~utur-m~:

c011l . . .

Bll\..1.dltllt ltS.-Il
Butad.tu llln..f pri'C'-

11.1

11

...

!Ill

11

tal

Ill

11

<11

lil

l rltOJt

I!

I!

11

'1'!

]T ill :Re\\11"1'1 ll"flq,m&i"td !fiOir 11

' llt:J

ii !!!i
!11

nw-~a:r ~you1.

"

11

11

(1,

il

!iil

'

'

i: oil

11

11

!Ill

11

11

us

11

11

11

~~

11!

...

ll

11

lll

r.l

ll

.....

,..

..

..

!11!

li .., il

11

..

l!i

+ +

ll'l

!111!1

llll

!I

ii ,.

..

l'l

1'1

ll

11

l'r

D&l

!Ill

11

..

lil

11

.,.

" + ,..

"

.. ,...

Ill

!111!1

191

11

~~~

SI

tel

till

Ill

11

!m

Ill

!I

r.IO

il

11

lil

!Ill

!ll

!111!1

~~

J. 51ifl

:2',.

~~0

J, ;Sot 0
3, 8:ZO
B .t2fl
u. ~ns

211

u.e
!I

lVa,.3.Ba iJu\ 4l
.xtrac\ion fro
Ct cut produco4 la etllyle11
p1odac t tOll tiy t h~ e rac: kint or nphttla
$ln.e Ol'l,y proeqt of lttr.e UOI'\ !. tavolv ~. ttto mlltLM'IITI'\ calt at I lCl\ Se !e
conomie eo ztr.a.cc ~a-product at d cm la aftlalllr LhA&'lltaAt for b.J& dl .n .)11lli1eU l.od
fnnt blr\lt~Doe or n t.u~ tit. 1"1lte rn.LI\lmltm co~of e IC'tllo d J)CIJ\dl Oil WiroJ f"G1<>.r.
bMf'ly:

.. \11

~~H'Q>

ot

o~e

d1 n. .,

U.a.bl~

ill Ult

c,. er

"tr.t t.on o! tu~L l ne Sn th total

fhe a1U'u~ ot che otber C4 coa1Ut~nca.
- Ut

eo

~;

c,. st1'

m.

Ttl~ c::ccullcioae of c rac-kl.il wb!ch l(:i'Ve botb a bla~ yJelcl or ~'bfll!tlt'

ompotSU~f\ f v~rabl to ~~
l'lL~H~ o! P~NI thy
t mtnlm'IIM
t..r1c- .tlo Uloac whl~lt ,aivo t.
oon.eclltredcll'\ ot b t.adlenr ra Q. 4 c~at.

rood

ud *ll ~xU ea.

t, r. ~y .-nd
A1.o, C'f.'pe n

producer-. ho have UM> tond eoey to so to moN- aov~roc era.ddngwhhht1bttr yl let.

o! ethrlt'GC, ar~ ln a 10od poltloa to ~pq buL'ld1 oc: a.t a. low~r vr ice.
T~ L -m l"'te of tl'l
NI\Lf\JI ~o t t prc e!'te<J l.n T t. ~'V for a6. 000 ( 1) one/
y~u b.Jtadtc.nt- extil"dioD p!.a.nt u.tinc, rcpectiv~y. lbo CM proeu.trom aao }(c-,arctl
od Enalm:e~(Qf eo . 1'he A~eCollLtrUe- proce .. Crom Shell aad 'be Furfur I extnacHve dlltUla.t on frol'!'\ P._t !Jp4J. Th m nu!acwrln eo t aQd U\e b ( d&OM a.olll.nJI pricoe .foro ttu~
eh-r~e ~e- re ctvefl ln Table XVI. The e!te~t ot C t~~~ eoat on t~ ~lUar pr e of
bul.:uHomo are 1bowo lrt !~sure 9 for tbt AettonUr-Hc J)roc.
Ae ea.nbe &C!C!D. U~t
t or bu~lil t produe tUna u , l)()() tollll/year .Gul"opeanaait byL ....
ta.n ~ll.ydi"C) lll\1.011 raoce trOmJ>Pl"'JC1m~b US f 260t\on&oUS f 2:90fton~te~rd rarto bJ
Ct.ftC fo~ cot v.nry111c t.-o11 US$ ~~oo to tiS $ $0/to,.. The
pdeeof extract LOll trot.ldac:c.c
by \t'l AettortitrH pro~. tn U'ie um t1'Qf of U\! Ct (o t. 1 m~th ~u 4 b'lf..1) for
a mill~r proctuctioo (tlt,OOO to.u/J'O'l'), and il H t. a.uumed U\a.t the cUt)' e!IIC production
b t a.ll tl~ captt.at :Y t ot tla Mph~tt~ ~"ctcer 114 tt'l eh .,~ dt n ~har. d t~ th
~xt cUCKJ pla.r:t .at tu~~ value, a b&J dl
coil of llho.tt US $ U.O/tora can b lletiJe'# d.
ettlyl~rAe

lll.n:

iAtn..t XV
16,0110 "roNS/YEAA. BUfADltNt J:X!!AACTlOH
CPLA~"T Dl&CT!D IN t~OP)
OP1\A'TlNC CO:t''T 1..1:' 1:t:NTS
A~c-tonUf'UO

Unit a

p~f'U

CAA p?oc1' 0

Sb~U

tnnttmc-flt
On.-eltfl
otf ite

'Totaa

uuuu.-.
&eam

hl'l

P'hUUpa
2. 6
0. G

i.G

0.,

e1me11t

,, l

3.1

2. ti

..

1,$

,~t

;.

... ...
._

. - ....... ..... ... .

........ .

CooJtn, wate-r

Rol!tt~"

Fnfl.lnt
extra~t.ton

. . . ..... . ...

~Jo~triC'tty

Chmlw

MM US$,

,.

. . .

reQIJlremtmla

..

..

...

....... .. .......

L.ahor .. .

\ons/hr

:u

KWft

110

so3

a.

.ttO

G, lt

"20 .~

tOO

m3f t.r

a..oao

720

\JS $/y~ar

2:5,001)

as.ooo

8. ~$4 2)

1.2$

(I)

us

$/1.()J\

mn/bUt

411 Pa tdur> ro)'~hi~ lnd1.1.ded In ln~acm~l coat.

C2l Rllllllint roptt!e pa let durlnJ t y l f"tt,

2,87G

&(). ()(JO

'8

IAIU: XVI
1', 000 TONS/VI'AR IUTADinlt CIC'J'It.ActrON (PIA>."T tRECTtD IH tUJ\0

MAJ\UFACTURlN"G COST AND SELLlNO I'RlCE

I

Aut:oftltr-1 to

Vt1l'
tiJIJt

COlt

Varla.ble culJI

Raw matorlal4

us
.
31

\Ont

Utillt.J.e.1

5 t,.~.a.~~t

f!l~trleUy

CeUca water
ChtmSC61 rf'~d'"ment.

t.abor at)tlu.Ptrvtton

S&la.r1 ~ .,
~rvie011

at 25

t. c

ao~
KW
3

ao

l0 m3

~ct.aanury

to3

IG.~OO

!)z-7

Z$tl.OCO

uo

leG

e.oeo

Cl

~5

monf .,.,.,.

6000

11

... .............
,

Sellloc prlca
Nrt Cub Flow at 20 ,. 01 !l.or.al llwutmeru , , , , ,
D~:redaUoa pro.ldu
rfet income alter
'Nt income b..tore ta.u1 at .50 ,. ,.

........................
tax ...................
,.,.

'laDufaetul'Lft&

COlt

~ ~

o o

, o

1;1uta4ltt:-tt lal~t ....... ~ ..................................

!lutadleM aoUlnr pr-t.t"o HJS U
...................... 4

I
1

Cl f

UutAw:Ue.o~ iD

C cut..

(IU-.n't 1\J

80

ao'

I6,SOO
I
I

67,000

9,100
l, 11'0

..

Annul
Cotl4

A.n:.uai

CNC

C\UMUly

lctl s

521

16.5(10

$V

,,

~.~(J

~"

lO

2. :&10

101

20

lU
1. !Sl

91&

&0

u~

eo

lG

10

20

230

I
I

.,.

ftxed cllarcu
L>tproeelallor. , , , , , , , , , , , 14 12, ~ ~ O( 'AVt~CMI'tll
In.te~ , at 3. $ " oC lnvc ltrn~.n'
lktaltlt~acee , at
oC lnvoCrq~n~
Gentl'tlS l~'.ant OV.,.._ead at a~ o t 1.1\ve~men;
Tut and l&IIU'tU'te at I ~ of lr.vntm,
...... ._ ...........
To1al FLse-d eo'
1anataetur1.rta Cost ~ .... ..

'
~

1\n~t'l:laL

~hft~al

ola.l.a.ri ucl wace

R~ tloya.1ti ,
To1a,l Variable Cl\uu

Ancual
eolt

Aanu&l

F'IU't\lral

'C AA

to

880

I
I

:1

1. Ha

420
2~

1SC
120
1.. 'Ul
2~051

no

99

?3~

tl9

l,'Ul

l. 580

no .

MO
-400
240

l10
~
~00

-.eo
us

2. :ns
140

,a. 580
010
I

I
I

115