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Патент USA US2128126

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Patented- Aug. v23, 1938
2,128,126 .
; UNI-“Denies
I
.
,
PATENT OFFICE ,
2.12am
POLYMERIZATION or GASEOUS OLEFINES
Albert Ernest Dunstan, London, England, assign-0
or- to Anglo-Iranian Oil Company, Limited,
London, England I
No Drawing. Applicationlune 5, 1936, Serial
’ ' m. 83,697.
In Great Britain June as, 1935
16 Claims. (01; 196-10)
This invention ‘relates to the polymerization of ‘
‘gasecus'ole?nes especially for the production of
a liquid product suitable for use as a motor spirit
or as a blending material for such fuel by rea- >
“ ‘5 son of its high Octane value and its still higher
anti-knock value when used as a blending mate
when heated to 100° C. with excess of water, free
phosphoric acid being also produced in solution.
It is however also known that the reaction by
which this compound is produced from cadmium
dihydrogen ortho-phosphate is reversible, for if
the compound be evaporated in contact with free
, phosphoric acid as is the case in the production
'
a
The invention-has among its objects to use ior ' of the dried cake in the manner hereinbefore'
rial.
the purpose a catalyst whose high polymerizing described, the two re-combine and produce the
cadmium dihydrogen ortho-phosphate. This 10
efiiciency is maintained without liability to li
quefy or to disintegrate while in use, and which» compound consisting of or containing cadmium
after use for a long period is capable of being re-I dihydrogen ortho-phosphate under the condi
tions of its use as a catalyst in the polymeriza
generated, whereby its original e?iciency is re
stored. Such a catalyst is adapted for effective tion of ole?nes is maintained in substantially
use in the polymerization of gaseous ole?nes and the same dry state. The reversible‘ reaction :is
‘10
especially propylene and the butylenes which in
expressed" as follows:
‘
its use may be rapidly polymerized for the’ pro- >
' duction of a spirit
‘range.
.20
According‘
boiling‘ withinv the gasoline
'
‘
‘
‘
‘ it being understood that the reaction proceeds
to‘thei'invention'5a catalyst is em- ‘ from left to'ri'ght when the compound is heated 20
ployed for polymerizing gaseous ole?nes, consist-> to 100° C. with excess of water, and in the re
‘i ‘ ing ofor containing cadmium dihydrogen ortho
‘phosphate, thegaseous fole?nes to be polymerized
being passed through or ‘over 'thecatalyst under
‘conditions in‘which- the‘catalyst is maintained
.25 in'the substantially,
state in which it was
‘ ' 7 produced and the treatment carried out at tem
' ' peratures within a range'tha't may not substan
and at a pressure advan- -
tially exceed 250“ C.
l‘ tageously though not necessarily higher than at
mospheric pressure.
‘
"
According to the invention moreover a salt of
cadmium ‘and ortho-phosphoric acid is employed
a as catalyst that may be‘produced by combining
verse direction from right‘ to leftfwhen water is
removed from the system by drying.
In the production at such a catalyst in the
form of fragments or grains from the dried‘cake 25
the upper limit in molecular proportion of ortho
phosphoric acid to cadmium ortho-phosphate
may with‘ advantage be 3.5. The product may
however’be increased in hardness and resistance
to- disintegration by pulverizing the cake and 30
mixing with its. hinder, the mass being consoli
dated or pelleted, and then roasted for the pro
duction of especially hard pellets not liable to
under the conditions of use.
cadmium ortho-phosphate with ortho-phosphor disintegrate
For the purpose the my cake produced may 35
0 lo ‘acid in the ratio of 1 molecular proportion of .
be pulverized and mixed with from 21/2 to 5%
‘cadmium ortho-phosphate to from 2 to 4 molec
by weight of lubricating oil acid tar and/or 5%
40
ular. proportions of ortho-phosphoric acid, the ‘of graphite, and the mass pelleted and the pellets .
cadmium ortho-phosphate being in a ?nely di-‘ ?nally roasted for from 12'to 24 hours at about
vided condition intimately mixed with ortho
300? C. The period of heating is determined 40
phosphoric acid and the mixture driedand heat
ed to a moderate temperature not substantially
in excess of 100° C., whereby a solid cake is
produced that is dry, porous, hard and resistant
to disintegration under the conditions of use, the
cake being broken into fragments or grains 'with
out further treatment before use in the polymer
ization of normally gaseous ole?nes.
The catalyst is‘ thus‘producedwithout roast
ing or calcining and without addition to the mix
ture of absorbent or dehydrating substances.
The catalyst consists of or contains’ cadmium di
at the stage when the pellets are rendered dry
and su?iciently hard to be very resistantto dis
integration in use.
"
According to the invention moreover copper
ortho-phosphate in ‘a ‘?nely divided condition 45
may be mixed with cadmium Qrtho-phosphate
also in a ?nely’ divided condition and ortho-'
phosphoric acid, and the mixture heated and.
dried in the manner hereinbefore described for
the‘ production of 'a hard, dry and porous cake 50
that is resistant .to disintegration, the copper salt
being advantageously used in equi-molecular pro-'
‘hydrogen ortho-phosphate in proportion ‘corre- V portion with the cadmium salt. The molecular sponding to the molecular proportion of ortho
ratiosvof cadmium .ortho-phosphate, copper or
55 phosphoric acid to cadmium ortho—‘phosphate tho-phosphate and ortho-phosphoric acid may be 55
used in its preparation. " It is known that cad-' within the limits of 1:1:3 and 1:1:8. The prod
mium dihydrogen-ortho-phosphate is converted
‘ into the solid compound:
w
’
cdurooi-zcanrolamo
uct in the form of a dry, hard and porous cake
may be broken into fragments or grains and
used in that condition, or it may be pulverized
2
2,128,126
and~mixed~ with a binder and/or graphite‘ and
then consolidated orpeileted and ?nally roasted , ' hereinbefore described from a dry pulverized
in the manner hereinbefore'described for the pro
cake being the product of heating and drying oi’ a'
lyst containing cadmium copper dihydrogen
phosphoric acidv in the molecular proportion of
1:3, while catalyst B was a catalyst inthe form
of grains produced by heating a ?nely divided
,‘duction' of an especially hard and resistant cata- ' ' mixture of- cadmiumorthophosphate and ortho- ,
ortho-phosphate.
-
_ In carrying out the polymerizing treatment the
crude gas if its ‘condition require it, may be ‘mixture of cadmium ortho-phosphate,~-copper '
treated for desulphurizing and for removing from
ortho-phosphate and ortho-phosphoric acid in the
10 the gas any'gum or other constituents that would
molecular ratio of 1:1:4.
contaminate the catalyst used, the gas being for
the purpose treated for its cleansing and puri?
' .10
~ Example
cation in known manner as its condition and
character may require.
Catalyst A
The catalyst may be charged into towers or cas
i'ngs'in' bulk or in trays in the form of pellets or ‘as broken cake 01' grains and the gas passed
Pressure lbs/sq. inch ______________ __v__
150
150
Temperature °C _______________ ________
‘ 230‘
230
through the charge at a temperature within a
range for example of 180°-250° C. and at atmos
Inlet gas rate cu. it. at standard tem
.
catalyst per hour_;; _________ ___ .... __
4. 0
4. 0
pheric pressure or preferably at a pressure‘ higher I
Percent vol. steam in inlet gas__;_____
Weight of_pro(iuctlweiglit of catalyst“
Composition of-gas treated:
7.0
32. 5
- 7. 0
' 95
'
than atmospheric such for example as 100 to 500
,lbs. per sq. inch. The size of the pellets, broken
cake or grains and the thickness of the catalyst
bed are such that there shall be good contact
perature and pressure pe‘r lb.v of
resistance at- the high velocity of the gas ?ow.
The broken cake or grains on their being charged
may be passed through a. screen for the removal‘
used through which the gas containing the ga'se
ous ole?nes to be polymerized may be passed in
series, the gas being ?rst heated. to the deter
.
80% t?tal ole?nes, 45% 04111, 35%
liquid produced:
'
-
’
_
.
-
'
S1’). gr. at 60° F __________________ __
0. 77
0, 77
Octane No‘. (CFR motor method)_
80
81
Percent vol. at 100° C ___________ _.
15
Percent vol. at 140° C ______ __
57
60'
200
200
F. B. P.,- °C __________________ _I claim: 4
One, two or more such towers or casings may be
15'
__'_ _____________________________________
-; ‘
Properties 0| _____________
g nsoline distilled
from the
between gases - and catalyst without excessive
30
Catalyst B
14
'
l. A process for polymerizingnormally gaseous 3o
ole?nes such as propylene and the butylene's for. .
the production of a motor spirit, .in which cad
mium dihvdrogen
ortho-phosphate is used as the '
mined,tem'perature within ‘the range. indicated," catalyst, in which process the catalyst is main- '
35 by passagethrough heat exchangers or otherwise, tained in avsubstantially
drystate;
. v
and on passing from‘ the ?rst tower or casing may
2. A process for polymerizing normally-gase
be- re-heated or cooled, to be raised or lowered ous- ole?nes such as propylene and the .butylenes
to the determined temperature‘ before passage ' for the "production of a motor spirit, in which .
through the remaining
or casings
or casings.
may be - con- _
this purpose the towers .towers
structed in ‘known manner and with known'means
i‘or-the control or the gas stream and for 'cuttin'g'f
out the towers or casings ‘in succession for
the‘ '
purpose of the regeneration ‘of, the charge.
45
,
Means may also be provided for re~cycling the‘
gas as may be required: to ensure a substantially
cadmium dihydrogenortho-phosphate is used as -
the catalyst andis maintained in a ‘substantially
drystate and the gas to be? treated ‘is mixed ,with ’
a proportion of ‘from 4 to' v10% byvolume o1’ "
steam.
--
_ 3. A process for
'
-
"
"
polymerizing normally gaseous"
‘
ole?nes such as propylene and the butylenes “for
the production of a motor‘spirit, in-which cad
ih. 5
complete conversion. This re-cycling may-also -mium' dihydrogen orthoephosphate is used as,
‘ serve as means for the control of the temperature 1
of the catalyst in the-towers or casings, since the
reaction is exothermic.
‘
'
'
-
catalyst being ?rstvprepared by intimately ‘mix
ing- cadmium orthoéphosphate‘ and ortho-phos
'
phoric acid in the ratio of one molecular‘propor- .
It is found that‘ the activity of the catalyst may . tionv of ' cadmium ortho-phosphate to‘ between"2_
be maintained ,forsubstantially longer periods if and 4qmolecular proportions of ortho-phosphoric
the gas containing the ole?nes to be polymerized . acid; heating and drying the'mixed
' '
temperature ‘not substantialiy'in
r
H excess
mass
0'1 at
100°
a'
The proportionoi' steam used may be from 4‘, C. for the production ,of a dry, hard and porous
is ?rst mixed with a small proportion of steam.
'
to 10% by volume and not substantially more. _~ material resistant. to disintegration under" the "
It'is' known to use a small proportion of steam in conditions of its use ‘in- the process as a catalyst._.
processes of, conversion ofv gaseous ole?nes and
4.‘ A process forpolymerizing'normally gaseous
no novelty is claimed broadly in this condition 7 ole?nessuch as propylene and the butylenes for
60 of polymerization. .
_
the production of a'_ motor spirit, in which cad
When the activity 01’ the. catalyst has 'fallen
to such an- extent as to render its furtheruse
unec0nomical,.it may be regenerated to its origi-n
v nal activity by’heating
v
in a current of nitrogen or
mium dihydrogen orthoephosphate is used- as
catalyst being ?rst prepared by intimately mix
ing ‘cadmium, ortho-phosphate and ortho-phos- . .
phoric acid in the ratio of one molecular propor
?ue gas at‘ about 300° C. for a period of time tion. of cadmium ortho-phosphate to between 2 _
usually from 4 to 24 hours
} I depending on’ the
and 4 molecular proportions of ortho-phos'phoric
length of time the catalyst has been previously acid, heating and drying the mixed. mass at a
used. It hasbeen found that the catalyst'may be temperature not substantially in excess’of 100° C.
repeatedly regenerated with no fall from. ‘its for the production of a dry, hard and porous
70 original activity.
The following examples illustrate ‘the condi--" material, reducing the dry, hard and porous mate
tions of use of two catalysts and the nature and ' rial to a ?nely divided'state, mixing the ?nely '
,quantity‘ of the motor spirit distilled fromthe
liquid produced. In the examples catalyst A was
75 produced from material pelleted in the manner
divided material with a binder andv then consoli
products
5. A process for polymerizing normally gaseous
dating the mixture and roasting the consolidated -' I
v
-
_
~
3.
2,128,126
ole?nes such as propylene and the butylenes for
the production of a motor spirit in which cad
mium dihydrogen ortho-phosphate is used as
catalyst being ?rst prepared by intimately mix
ing cadmium ortho-phosphate and ortho-phos
phoric acid in the ratio of one molecular propor
tion of cadmium ortho-phosphate to between 2
and 4 molecular proportions of ortho-phosphorie
the production of a motor spirit, in which the
catalyst used is prepared by intimately mixing
ortho-phosphoric acid with cadmium ortho-phos
phate and copper ortho-phosphate, the molecular
proportions being within the limits of 3:121 and Cl
8:121, heating and drying the mixed mass at
a temperature not substantially in excess of
100° C. for the production of a dry, hard and
porous material resistant to disintegration under
acid, heating and drying the mixed mass at a the conditions of its use as a catalyst.
10
temperature not substantially in excess of 100° C.‘
10. A process for polymerizing normally gase
10
for the producition of a dry, hard and porous ous ole?nes such as propylene and the butylenes
material, reducing the dry, hard and porous ma
for the production of a motor spirit in.which
terial to a ?nely divided state, mixing the ?nely the catalyst used is prepared by intimately mix
divided material with 21/2 to 5% _by weight of
lubricating oil acid tar, then consolidating the
mixture and roasting the consolidated products.‘
6. A process for polymerizing normally gase
ous ole?nes such as propylene and the butylenes
for the production of a motor spirit in which
20 cadmium dihydrogen ortho-phosphate is used as
catalyst being ?rst prepared by intimately mix
15
ing. cadmium ortho-phosphate and ortho-phos
phoric acid in the ratio of one molecular pro
25
portion of cadmium ortho-phosphate to between
2 and 4 molecular proportions of ortho-phos
phoric acid, heating and drying the mixed mass
vat a temperature not substantially in excess of
100° C. for the production of a dry, hard and
porous material, reducing the dry, hard and por
30
ous material to a ?nely divided state, mixing the
?nely divided material with 21/2 to 5% by weight
of lubricating oil acid tar and about 5% of
graphite, then consolidating the mixture and
roasting the consolidated products.
7. A process for polymerizing normally gaseous
ole?nes such as propylene and the butylenes for
the production of a motor spirit in which cad
mium dihydrogen ortho-phosphate is used as
catalyst being ?rst prepared by intimately mix
ing cadmium ortho-phosphate and ortho-phos
phoric acid in the ratio of one molecular propor
tion of cadmium ortho-phosphate to between 2
and 4 molecular proportions of ortho-phosphoric
‘acid, heating and drying the mixed mass at a
temperature not substantially in excess of 100° C.
45
for the production of a dry, hard and porous
material, reducing the dry, hard and porous mate
rial to a ?nely divided state, then mixing the
50
?nely divided material with graphite, then con
solidating the mixture and roasting the consoli
dated products.
>
8. A process for polymerizing normally gaseous
ole?nes such as propylene and the butylenes for
the production of a motor spirit, in which the
m 51
catalyst used is prepared by intimately mixing
ortho-phosphoric acid with cadmium ortho-phos
phate and copper ortho-phosphate, and heating
ing ortho-phosphoric acid with cadmium ortho;
phosphate and copper ortho-phosphate, then
heating and drying the mixed mass at ‘a tem
perature not substantially in excess of 100° C.
for the production of a dry, hard and porous
material, reducing the dry, hard and porous ma
terial to a. ?nely divided state, mixing the ?nely
divided material with a binder, then consolidat
ing the mixture and roasting the consolidated
products.
11. A process for polymerizing normally gase
ous ole?nes such as propylene and the butylenes
for the production of a motor spirit in which the
gas consisting of gaseous ole?nes is_passed in
contact with a catalyst consisting of cadmium
dihydrogen ortho-phosphate as catalyst prepared 30
in a dry, hard and porous state, recovering the
liquid product of polymerization and distilling
it for the recovery of a motor spirit.
12. A process for polymerizing normally gase
ous ole?nes such as propylene and the butylenes
for the production of a motor spirit in which
the gas consisting of gaseous ole?nes is passed
in contact with a catalyst consisting of cadmium
copper dihydrogen ortho-phosphate as catalyst
prepared in a dry, hard and porous state, recov
40
ering the liquid product of polymerization and
distilling it for the recovery of a motor spirit.
13. A catalyst for use in the polymerization
of ole?nes being cadmium dihydrogen ortho
phosphate in a dray, hard, porous and ?nely di 45
vided state, incorporated with a binder, consoli
dated and roasted.
‘
‘
14. A catalyst for use in the polymerization
of ole?nes being cadmium dihydrogen ortho
phosphate in a dry, hard, porous and ?nely di 50
vided state incorporated with graphite, and
roasted.
,
15. A catalyst for use in the polymerization
of ole?nes being cadmium copper dihydrogen or
tho-phosphate in a dry, hard, porous and ?nely 55
divided state incorporated with a binder, consoli
dated and roasted.
16. A catalyst for use in the polymerization
of ole?nes being cadmium copper dihydrogen or
tho-phosphate in which the metals are present in 60
equal proportion, the salt being in a dry, hard,
to disintegration under the conditions 01' its use porous and ?nely divided state, incorporated
as a catalyst.
with a binder, consolidated and roasted.
and drying the mixed mass at a temperature not
substantially in excess of 100° C. for the produc
tion of a dry, hard and porous material resistant
9. A process for polymerizing normally gaseous
ole?nes such as propylene and the butylenes for
ALBERT ERNEST DUNSTAN.
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