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N e w M a r k e t s fo r A c e t y le n e
Exp and ing acry lon i t r i l e consumpt ion an d ne w
acety len ics w i l l boost chemica l consumpt ion o f acety lene
η ρ Η Ε S LI CE O F C R YL ON IT RI LE m a d e
•*- v ia a ce ty len e is expe c ted to to p 509ί
by the e nd o f ne x t ye a r , up f rom
67<
i n 1953 . Typ ic a l o f a c e ty l e ne ' s po t e n
t i a l , a c ry lon i t r i l e i s e xpe c t e d to j ump
f rom 1953 ' s 57 mi l l i on pounds to c lo se
to 190 mi l l i on in 1955 . Inc re a s e w i l l
l a r g e l y b e d u e t o A m e r i c a n C y a n a m i d ' s
ne w Fo r t i e r p l a n t i n Lou i s i a na a n d to
n o w - a b u i l d i n g B . F . G o o d r i c h C h e m i
c a l un i t , pa r t o f t he a c e ty l e ne c omple x
a t C a lve r t C i ty , K y .
C a lve r t C i ty i s a n e xa mple o f w ha t
a r e a dy supp ly o f p ipe l ine a c e ty l e ne
c a n do fo r i ndus t r y . C a pa c i ty o f A i r
R e d u c t i o n ' s c a l c i u m c a r b i d e p l a n t h a s
r e c e n t l y b e e n d o u b l e d ; p l a n t i s n o w
s u p p l y i n g c a r b i d e e q u i v a l e n t t o m o r e
tha n 2 00 rn i l l i on po un ds o f a c e ty l e ne
pe r ye a r . B e s id e s G o od r i c h p l a n t s fo r
v iny l c h lo r i de a n d a c ry lon i t r i l e , A i r
R e d u c t i o n C h e m i c a l i s p l a n n i n g a 3 0
m i l li o n p o u n d v i n y l a c e t a t e u n i t ; G e n
era l Ani l ine wi l l bu i ld a $6 mil l ion
p la n t t o u t i l i z e h igh p re ssu re t e c h
n ique s o f a c e ty l e ne c he mis t ry o r ig ina l ly
d e v e l o p e d b y J. W . R e p p e i n G e r m a n y .
G e ne ra l A n i l i ne ha s ope ra t e d a p i lo t
p l a n t i n t h e U . S . s inc e 1949 .
M o r e t h a n
75
o f p r e s e n t a c e t y l e n e
p r o d u c t i o n g o e s t o c h e m i c a l m a n u f a c
tu re r s , ba l a nc e ma in ly t o oxy -a c e ty -
l e n e c u t t i n g a n d w e l d i n g . D e v e l o p
m e n t o f e c o n o m i c m e t h o d s f o r a c e t y
l e ne syn the s i s f rom na tu ra l ga s i s now
p r o m i s i n g l a r g e q u a n t i t i e s o f t r i p l e
bon ds fo r e xp lo i t a t i on . A n d e xp lo i t e d
t h e y a r e , a t h i g h a n d l o w p r e s s u r e s ,
w e t a nd d ry , u p to 250 ° C . a nd 20 0
proof.
C a n you u se som e p ro pa r gy l a l c oho l .
iV -v iny l -2 -py r ro l idone , c yc looc ta t e t r e -
a ne , d ime thy l oc tyne d io l , i sop rope ny l
a c e t y l e n e ? T h e s e a n d m a n y o t h e r e x o
t i c sou nd in g c he mic a l s a re now , a f t e r
se ve ra l ye a r s o f i n t e ns ive ma rke t de ve l
o p m e n t a n d r e s e a r c h , t e e t e r i n g o n t h e
b r ink o f c om me r c i a l p ro duc t ion . Pa r t
o f t he now -s t a r t i ng a c e ty l e ne boom,
the y a re e xpe c t e d to boos t t o t a l a c e ty
l e ne u sa g e t e n fo ld by 197 5 , t o 3 b i l l i on
p o u n d s a y e a r .
M o r e t h a n 3 0 n e w a c e t y l e n e d e r i v a
t i v es h a v e b e e n m a n u f a c t u r e d a t G A F ' s
L inde n , N . J . , p i l o t p l a n t , i n se mi -
c o m m e r c i a l q u a n t i t i e s r a n g i n g f r om
ta nk c a r s o f bu ty ro l a c tone ( a t 60 c e n t s
a pou nd ) t o l a b sa mp le s of c yc lo -
o c t a t e t r a e n e ( a t $ 3 5 a p o u n d ) . M o s t
o f t he se de r iva t ive s w i l l be ma de a t
C a lve r t C i ty .
A i r R e d u c t i o n ' s C h e m i c a l D i v i s i o n
h a s a l so b e e n p u s h i n g d e v e l o p m e n t o f
a c e ty l e n i c c he mic a l s : r e se a rc h a t
A i r c o 's M u r r a y H i l l , N . J ., l a b ( C & E N ,
A pr i l 12 , pa ge 146 6 ) a nd p i lo t p l a n t
a t B o u n d B r o o k, N . J . D e v e l o p m e n t
qua n t i t i e s o f t e r t i a ry a c e ty l e n i c a l c o
ho l s ,
g lyc o l s , a nd o the r t r i p l e bond
c om pou nds a re be in g o f fere d . W he n
the t im e i s r i pe t h e re i s p l e n ty o f room
fo r more a c e ty l e ne c onsume rs a t C a l
ve r t C i ty .
A c r y l a t e m o n o m e r s a r e b e i n g m a n u
fa c tu re d v i a a c e ty l e ne , c a rbon mon
ox ide , a nd a n a l c oho l a t l ow p re ssu re s .
R o h m a n d H a a s ' H o u s t o n p l a n t
( C & E N , F e b . 9 , 1 9 5 3 , p a g e 5 6 0 ) u s e s
a c on t inuous , c a t a ly t i c p roc e ss ba se d
on a r e a c t ion d i sc ove re d by R e pp e ,
o r ig ina to r o f t e c hn ique s t o be u se d by
G A F a t C a lve r t C i ty .
A c e ty le ne de c o mp ose s spon ta ne o us ly
a t h igh p re ssu re s , w i th i n s t a n t p re ssu r e
r i se s up to 20 0 t ime s in i t i a l p re s su re .
R e p p e a n d h i s c o w o r k e r s d e v i s e d p r a c
t i ca l me tho ds fo r c on t ro l l i ng de c o mp o
s i t ions a nd p re ve n t ing e xp los ions . In
e r t gas d i la t ion of process ace ty lene ,
useful a t re la t ive ly low par t ia l pres
su re s , r e duc e s e xp los ion ha z a rd . W he re
d i lu t ion i s impra c t i c a l , sma l l bo re t r a ns
mission l ines a re used to reduce free
spa c e to a min imu m. A l l p roc e ss l i ne s
la rger than one inch in d iameter a re
f i l led wi th smal le r tubes; bends a re
sub divi ded wi th such f i l le rs as Rasc hig
r ings . Eq u ipm e n t is bu i l t t o s t a nd
tw e lve fo ld p re s su re i n c re a se s .
Fou r ba s i c r e a c t ions o f h igh p re ssu re
a c e ty l e ne c he m is t ry a re v iny la t io n ,
e thyny la t ion , c yc lopo lyme r i z a t ion , c a r -
bony la t ion . V iny la t ion a d ds a l c oho l s ,
me rc a p ta ns , a c id s , a min e s , a nd a m ide s
to g ive v inyl e thers , th ioe thers , este rs ,
v inylamines
>
a n d a m i d e s . D i l u t e d
a c e ty l e ne a t one to 15 a tmosphe re s i s
usua l ly reac ted a t 120° C. to 180° C.
wi th a lka l ine ca ta lysts .
E thyny la t ion r e t a in s t he va lua b le
t r i p l e bond ; a dds a lde hyde s , ke tone s ,
a mine s a t a b ou t 100° C . a nd th re e
a tmosphe re s . P roduc t s a re mono- o r
polyfunc t ion a l ace t y len ic a lcoh ols ,
a minop ropyx ie s , a nd a minobu tyne s .
A c ry l i c e s t e r s o r hyd roqu inone a re p re
pa re d by c a rbony la t ion— a dd i t i on o f
me ta l c a rbony l s , a l c oho l s t o a c e ty l e ne .
C y c l o o e t e t e t r a e n e — P o t e n t i a l
U n l i m i t e d f o r A r o m a t i c s
C yc looc ta t e t r a e n e ha s be c om e a lmos t
a c l i c he in c he mic a l de ve lo pm e n t c i r
cles . P re pa re d by c yc lopo ly me r i z a t io n
of a c e ty l e ne ( i n t e t r a hyd r o fu r a n , 60°
to 70° C , 10 to 25 a tm osp he re s , n i c ke l
c ya n ide c a t a ly s t ) , i t c ou ld be found a
t ion of a w ho le ne w f ie ld of o rga nic
chemist ry . Hig hly rea c t iv e , o le f in ic
ra the r t ha n a roma t i c , c yc looc ta t e t r a
e ne r e a d i ly r e a r ra nge s t o a roma t i c c om
pou nds . I t is e a s i l y c on ve r t e d to su
be r i c a c id , a n in t e rme d ia t e fo r po ly
me rs , dye s , d rugs . X y l e ne pu r i f i c a tion
t r o u b l e s c o u ld b e h i s t o r y w h e n C O T
ox ida t ion to t e re ph tha l i c a c id ( fo r po ly
este r f ibers) becomes commerc ia l ly
fe a s ib l e . D ie l s -A lde r a dduc t o f C O T
a nd ma le i c a nhyd r ide r e a c t s w i th a l
c oho l s t o fo rm d iba s i c e s t e r s , po t e n t i a
p l a s t ic i z e r s . Se ve n m e m be re d r ings c a n
a lso be formed from C O T . Pro cess i
s t i l l unde rgo ing l a bo ra to ry de ve lop
me n t a t G A F 's Ea s t on l a bs . Sma l l l a b
ba tc h e s a re c a use of p re se n t h igh ($3 5
a pou nd) p r i c e , e xp e c t e d to d r op to
25 to 30 c e n t s a pou nd in c om me rc i a
p roduc t ion .
H ighe s t do l l a r vo lume a nd mos
ve rsa t i l e o f ne w a c e ty l e n i c s i s ( a n d
p roba b ly w i l l be ) po lyv iny lpy r ro l ido ne
Pre pa re d by po lyme r i z a t ion o f
1-viny
2-py r ro l idone , PV P i s so lub le i n w a te r
3 3 2 C H E M I C A L A N D E N G I N E E R I N G N E W S
ACETYLENE PROSUCTION
TOTAL
ACETYLENE
CARBIDE
ACETYLENE
I
CALCIUM
— CARBIDE·
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Air Redu
V in
30 mil l ion
B. F , G oo
V i
e a n d F i l m
ion
lene Derivatives
e m i c a l s
le
p e r year
By the end of 1955, at least four plants will be receiving over-the-fence acetylene from
Air Reduction's ca rbid e plant. Mo re land and acet ylene are available; rumors are flying
and in a variety of organic solvents.
Its best known use is as a blood volume
expander . Other pharm aceutical uses
ar ise from its physio logical compati
bi l i ty , teamed with other propexties .
Used with penic i l l in , insul in, sa l icylates,
hormones, and other drugs, PVP pro
longs act iv i ty and improves dispersion.
It has a detoxify ing e ffect on some toxic
dyes and toxins. Com bined with iod ine ,
PVP makes a bacter ic ide -which is not
irritating and practically nontoxic.
Nonpharmaceutical appl icat ions for
PVP are as str ipping agent for vat ,
sulfur , and direct dyes, suspending
agent, thickening agent, and film-form
ing polymer. Th e wife 's ne w hair-do
may be s et with a hair lacquer con
taining PVP. It can substi tute for nat
ural gums in some pr inting and l i tho
graphing processes. It preve nts re-
deposit ion of dir t during washing.
PVP is a unique and ubiquitous poly-
Reactivity
o f
Derivatives
Points
t o
Uses
a s
Intermediates
Reactiv i ty of acetylene der ivatives
makes them promising candidates for
chemical raw mater ia ls or intermedi
ates. Propargyl a lcohol (ac etyle ne plus
formaldehyde) , for instance , has three
reactive centers in the mo lecu le . Be
sides the tr iple bond and the hydroxyl
group, reaction can also take place at
the act ive acetylenic methine hydrogen.
Acetylenic carbinols , made from pro
pargyl hal ides v ia Reformatsky-type
reactions, are intermediates in syn
thesis of terpenoid structures related to
plant-growth horm ones. Propargyl bro
mide is an intermediate in v i tamin A
synth esis. Pote ntial large market for
propargyl halides is in soil sterilization.
Propargyl a lcohol can be dimerized
through oxidation of the methine hy
drogen (cuprous ammonium chlor ide
c a ta ly s t s ) ,
2 H O C H
2
C = C H + V
2
0
2
- »
H O C H
2
C = C - C E E = C C H
2
O H
and the result ing dio l hydrogenated to
1 ,6-hexanediol , an intermediate in syn
thesis of polyurethan, polyamide , and
poly ester fibers. Altern ative route to
adipic ac id (for nylon) is through oxi
dation of 1 ,6-hexanediol; cyc lode hy-
drog enatio n of this diol is a route t o
caprolactam, polyamide Per lon-type
fibers.
Another versati le reagent is butyne-
diol , which can react both as a g lycol
and as a disubsti tuted acetylene . Va
riety of materials that can be made
from it are shown on page 3034.
Catalyt ic reduction of butynediol
forms butanediol , a new glycol of in
terest in plasticizers, polyesters, and
polyurethans. Butaned iol could be used
in pla ce of furfural or but adie ne i n
nylon synthesis .
Buta nediol dehydro genation g ives
excellent yield s of butyr olacton e, a
powerful solvent for acetylene and such
difficultly soluble resins as polyacrylo-
nitrile; also a possible intermediate in
synthesis of BL-methionine.
Reaction of butyrolactone with am
monia gives pyrrolidone, a monomer
in formation of linear nylon-type poly
mers.
With methyl amine , butyrolac
tone forms m ethyl pyr idine , a power
ful solvent for dyes, acetylene, syn
thetic fibers, other high polymers.
Vinyl e thers (methyl , e thyl , n-butyl ,
isobutyl) are available in tank cars
from GA F's pilot plant . Prepared b y
addition of alcohols to acetylene, they
can be polym erized or copolymerized .
Polymers vary from water soluble to
elastomeric solids. Co polym ers (w ith
acrylonitrile, acrylic esters, vinyl chlo
ride, etc.) possess im prove d flexibility
and solubi l ity . Vinyl methyl e ther-
male ic anhydride copolymer is unique;
a wh ite amorphous powd er soluble in
water or alcoho ls with con version to
corresponding polymeric acid or par
tial ester. I t has potent ial use as pap er
and textile finish, adhesiv e, and thick
ening agent.
Improved she l l molding may result
from use of polymethoxy acetals as
sand pick-up agents. Surface smooth
ness and accuracy of reproduction are
improved; mold distortion is lessened.
Polymethoxy acetals promise cast ings
requir ing very l i tt le mach ining. Th ey
are a lso c la imed to be exce l lent resin
modifiers for phenolics, urea, melamine,
and polyvinyl a lcohol .
Acetylenic Glycols
A r e
Surface Active Agents
Tertiary acetylenic glycols, made by
Air Redu ction's conventional chem ical
methods/ ' are surface act ive , can be
V O L U M E 3 2 , N O . 3 1 » » A U G U S T 2 , 1 9 5 4 3 33
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® ®Bmm
f&B&& fc
W-N«(OAc)
2
-t-TR METHYLOLBENZENE
C O ]
+-PROPARGYL A L D E H Y D E - * -
2-AM1NOPYR1 MIDI
N E
-
2 ,4-HEXADIYNE- i ,6-D OL
L6-HEXANEDI0L
J PX
3
PROPARGYL HALIDES
MELLITIC A C I D * - H N 0
3
— HEXAMETHYLOLBENZENE-—Ni(OAc>
2
-
, H
2
|,4-DIHYDROXY-2-BUTANONEw-ACET
Y L - 2 -
PYRR0L1 DONE
VINYLPYRROLIDONE-ACRYLONITRILE COPOLYMERS—n
VINYLPYRROLIDONE-MALEIC ANHYDRIDE COPOLYMERS-*H
VINYLPYRROLIDONE-VINYL ETHER COPOLYMERS — i i
VINYLPYRROLIDONE-VINYL ACETATE
C O P O L Y M E R S * ] *
VINYLPYRROLIDONE-STYRENE COPOLYMERS—-^
VINYL PYRROLIDONE-VINYL CHLORIDE COPOLYMERS—-J
x
j
eOLYVUVIYLP^YRROLlDONEXP^P);
H±C C=0
• V
I
•^—CH~CHA r VV
*
J*
PVP
IODINE
use d fo r p igme n t d i spe r s ion , v i sc os i ty
re duc t ion , ge l a t i on c on t ro l , a n t i foa m.
D ime thy l he xyne d io l i s a n a l l e th r in i n
t e r m e d i a t e . T r i p l e b o n d i m p a r t s li n e a r
r ig id i ty sa id t o p roduc e po lyme rs o f
improve d toughne ss a nd r ig id i ty .
I sop re no id s t ruc t u re o f t e r t i a ry a c e t -
y lenic a lcohols suggests use as s ta r t ing
mater ia ls in synthesis of f lavors , v i ta
mins , pha r ma c e u t i c a l s , a nd spe c i a l t y
mon ome rs . M e thy l bu tyn o l , a so lve n t
fo r ma ny h igh mo le c u la r w e igh t mo le
cules , i s sa id to be a polymeriza t ion ac
c e l e ra to r i n e mu l s ion po lyme r i z a t ion o f
v iny l ide ne a nd v iny l c h lo r ide .
Te r t i a ry a c e ty l e n i c a l c oho l s a re good
a c c e p to r s fo r t r a c e s o f hyd roc h lo r i c
a c id . Th e y c a n be u se d to r e t a rd d e g
ra da t ion in c h lo r ina t e d o rga n ic s .
V iny l s t e a ra t e , ne w ly de ve lope d by
re a c t ion o f a c e ty l e ne w i th a n ima l f a t
de r iva t ive s , fo rms in t e rna l ly p l a s t i c i z e d
po lyme rs a nd c opo lyme rs o f e x t r e me ly
low cost.
Alka l i Me t a l Acet y l ides
A r e High ly Reac t i ve
A n o t h e r b r a n c h o f a c e ty l e n e c h e m
i s t ry w i th g re a t po t e n t i a l fo r t he fu
ture i s tha t of the a lka l i me ta l a ce ty
l i de s , e spe c i a l l y sod iu m a c e ty l ide .
H igh ly r e a c t ive , a nd w i th p rove d va lue
in o rga n ic syn the s i s hypn o t i c s , a l l e
th r in ) t he y a re a p romis ing sou rc e o f
ine xpe ns ive , ve r sa t i l e r a w ma te r i a l .
St i l l def in i te ly in the specula t ive s tage ,
a pp l i c a t ions o f t he t ouc hy ma te r i a l s
a re be ing inve s t iga t e d in ma ny in t e r
e s t e d l a b s a c ro ss t he c oun t ry .
Though on ly a f e w c ompa n ie s a re
a c t ive ly de ve lop ing c he mic a l s f rom
a c e ty l e ne , t he y a re be ing w a tc he d
c lose ly by the rest of th e indu st ry . In
te rest i s not l imi ted to cur iosi ty about
ne w a nd po te n t i a l l y u se fu l subs t a nc e s .
Se ve ra l c he mic a l f i rms w ho now ha ve
o r w h o a re p l a n n ing a c e ty l e n e -p rod uc
ing fac i l i t ies have a sharp eye open for
n e w m o n e y - m a k e r s . C o n s t r u c t i o n c o m
pa n ie s a re o f fe r ing p a c ka ge a c e ty l e n e
un i t s a nd a re ga in ing know -how in
bu i ld ing a nd runn ing the p l a n t s t o u se
the gas.
Th ous a nd s of sa mp le s ha ve be e n se n t
out to labs a l l over the U. S . ; deve l
opers say there i s hardly a major lab
in t he c ou n t ry t h a t ha s no t e xp re sse d
in te rest in a t least some of the i r ace ty-
lenics . A c e ty l e n e is r e ga rde d a s t he
mos t impor t a n t r a w ma te r i a l i n t he
syn the t ic f iber fu tur e . I t is a nu c leu s to
w h ic h the c he a pe s t r a w ma te r i a l s c a n
b e a d d e d .
Ac etyle ne che mis t ry is s t i ll in th e
e a r ly de v e lop me n t s t a ge s ; i t s fu tu re
c a nno t be a c c u r a t e ly e va lua t e d . Bu t
the re is no dou b t t h a t a s t he imp la
c a b le ma rc h o f t e c hno logy ma ke s more ,
c he a pe r , pu re r a c e ty l e ne a va i l a b l e ,
c he mis t ry w i l l f i nd ma ny va lua b le u se s
for th is versa t i le , convenient gas.
3034 C H E M I C A L A N D E N G I N E E R I N G N E W S
