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Патент USA US2122787

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" Patented July 5, 193a
'. 2,122,787 '
_ Hana 'l‘ropsch, Chicago, 11]., assignor to' Univer
sal Oil Products Company, Chicago, 111., a
poration of Delaware
No Drawing. Application January 25, 1935, Se
rial _-No. 3,474. Renewed January 14, I937
15 Claims. (or. 260-170)
This invention relates to the treatment of" ceding paragraph, have been found to be particu
para?ln hydrocarbons which are normally gas
larly valuable and e?icient.
eous including ethane, propane and the butanes.
A considerable number of alternative catalysts
>_ .In a more speci?c sense the invention is con
fall within the scope 'of the present invention.
5' cerned with a process for converting these low
In any case each combination will exert its own
particular in?uence upon the dehydrogenating
boiling members of the para?in series of hydro
carbons into their corresponding ole?ns which reactions which will not be identical with that of
contain two atoms of hydrogen less per. molecule other alternative materials of varying composi
and consequently have one double bond between ,.tionv.,- Catalysts of the present‘character may be
considered as magnesium oxide containing chro- ‘l0
10 carbon atoms.
There is a large commercial production of mates as the essential promoting catalysts, the
gaseous para?ln hydrocarbons. They occur in ‘value of which are accentuated by further addi
very large quantities in natural gas, particularly tions of other salts of the character indicated.
those gases associated with the production oi.’ Later examples will show the results‘obtained
15 crude oil and commonly [known asqcasing head 'with di?’erent combinations of this general char- 15
‘ gases and this supply is further augmented-by the acter. The alternative combinations mentioned
, gases produced in'cracking oils for the production
excludes salts of the halogen acids which as a
of gasoline although this latter type “of pyrolytically produced gas contains substantial quanti20 vties'of ole?ns as well as paraf?nic hydrocarbons.
The greater part of the para?in gas production
is used merely for domestic and industrial fuel
purposes and not as a source of hydrocarbon
derivatives on account of the unreactive char25 acter of its components in comparison with their
ole?nic counterparts.
' In one speci?c embodiment the present invention comprises the dehydrogenation of gaseous
paraiiin hydrocarbons at elevated temperatures
30 in the presence of catalysts comprising essentially
magnesium oxide supporting minor amounts of
rule have not been found to produce good promoting effects.
The mineral magnesite from which magnesium
oxide is conveniently prepared to furnish base
material for the present type of catalysts is most
commonly encountered ina massiveor earthy va
riety and rarelyincrystal form, the crystals being
usually rhombohedral. In~ many magnesites,
the magnesium oxide may be replaced to the ex
tent of several percent by ferrous oxide. The
mineral is of quite common occurrence and readily
obtainable in quantity at a reasonable ?gure.
The pure compound begins to decompose to form
the oxide at a temperature of 350° 0.. (663° F.) ,
chromates and/or dichromates of lead, zinc, m'ag-
though the rate of decomposition only reachesa
nesium, cadmium, iron, nickel, cobalt and alkali!“ practical value at considerably higher tempera
metals and'other chromates, for instance thorium
35 chromate, along with still smaller proportions of
selected sulfates, nitrates, acetates and other salts
of these same metals and preferably those of zinc,
copper and aluminum.
In the present instance the catalyst mixtures
40 which are preferred for selectively dehydrogenating the lower boiling para?inic hydrocarbons
tures, usually of the order of 800° C. (1472°‘F.)
to 900° C. (1652° F.) This n ineral is related to 35
dolomite, the mixed carbonate of calcium and
magnesium, this later mineral, however, not be
ing of as good service as the relatively pure mag
nesite in the present instance. Magnesium car
bonate prepared by precipitation or other chem- 40
ical methods may be used alternatively, in place
have been evolved as the result of a large number of experiments with catalysts having a de-
of_ the natural mineral, this permitting its use as
the active constituent of masses containing spac
hydrogenating action upon various types of hy-
ing materials of relatively inert character and in
45" drocarbons such as are encountered in the frac-
tions produced in the distillation of petroleum
and other naturally occurring hydrocarbon oil
3 mixtures.
The criterion of an acceptable dehy
drogenating catalyst is that it shall split oil.’
'50 hydrogen without inducing either carbon separa
' tion or scission of the bonds between carbon
atoms. In the concept of the present invention,
catalyst mixtures comprising major amounts of
magnesium oxide and minor amounts of the pro
55 motlng salts as generally designated in the pre
some cases allowing the production of catalysts of 45
higher e?iciency and longer life.
To prepare the magnesium oxide for use as
base material for preparing catalysts for the
process, the corresponding carbonate obtained
either from natural sources or by precipitation 50'
reactions is preferably heated for variable pe- '
riods of time at temperatures in the neighborhood
of 800° C. (1472° F.) which insures the decompo
sition of most of the carbonate to oxide. ,The
conditions of time and temperature employed in 55
1 2,122,787
calcining any particular carbonate mineral will
to‘ 750° C. (752-1382" F.) The most commonly
used temperatures are around 500° C. (900° F. to
1000" F.). The catalyst tube may be heated ex
teriorly if desired to maintain the proper re
action temperature. The pressure employed may
be atmospheric or slightly superatmospheric of
the order of from 50 to 100 pounds per square
inch, though any large amount of pressure has a
depend, to a large extent, upon its physical and,
to a smaller extent, upon its chemical composi
tion. -Magnesite may contain at times several per
cent of ferrous oxide in isomorphous mixture with
magnesium oxide and since it occurs in nature
in a harder and more compact variety‘ than the
precipitated carbonate, it may require for both
reasons different conditions of time‘ and’ tem . tendency to depress the dehydrogenation reac
10 perature to reduce substantially all of‘ it to the tions disproportionately to .‘the increase in capac 10
desired oxide.
ity of the plant. The time during which the
The mineral oxide of magnesium may some
gases are exposed to dehydrogenating conditions
times be employed (this oxide being known as in the presence of the preferred catalyst is com
periclase) whenever the same is readily available paratively short, always below 20 seconds .and
and its physical properties as well as its content
of impurities permits. The mineral oxide occurs
frequently as low as from 4-8 seconds.
The exit gases from the tube or chamber may
in granular form or in de?nite cubic or 00
tahedral crystals and may contain in many cases
be passed through selective absorbents to com
bine with or absorb the ole?n or ole?n mixture
produced or the ole?ns may be selectively poly- ~»
besides relativelyinert siliceous'gangue materials
20 small amounts of iron and manganese replacing
- a portion of the magnesium.
The deposition of the promoting oxide may be
effected in a number of ways, any one of which
is comprised within the scope of the invention.
25. Thus, for example, lead chromate may be de
posited upon magnesium oxide by stirring the
magnesite in an aqueous solution of potassium
chromate or dichromate and thereafter impreg
nating in-a solution of lead acetate. For the fur
30 ther addition of salts it may su?ice to heat the
?ltered and washed particles containing chro
mate with other salt solutions such as, for ex
ample. a fairly concentrated solution of zinc sul
merized by suitable catalysts, caused to allwlate 20
other hydrocarbons such as aromatics or treated
directly with chemical reagents to produce de
sirable and commercially valuable derivatives'
After the ole?ns have been removed the residual
. gases may be recycled for further dehydrogenat
ing treatment with or without removal of hy-v
Members of the present group of catalysts are
selective in removing two hydrogen atoms from
a'paraf?n molecule to produce the corresponding 30
ole?n without furthering to any great degree
undesirable side reactions, and because of this
show an unusually long period of activity in '
fate, during- which step some of the dissolved ' service as will be shown in later examples. When,
however, their- activity begins to diminish it is 35
35 salt is occluded, after which the magnesite par
ticles are again filtered and washed. The oxide
containing the desired amounts of promoting- sub
readily regenerated by the simple expedient of
stance is then dried at a moderate temperature
to produce the ?nal catalyst.
moderately elevated temperature, usually within
In lieu of the foregoing procedure the incor
poration of the necessary promoters may be ef
_ 'fected by successive additions of relatively con
oxidizing with air or other oxidizing gas at a
~the range employed in the dehydrogenating re
This oxidation effectively" removes
traces of carbon deposits which contaminate the
surface of the particles and decrease their e?i
- actions.
centrated solutions of the required promoting vciency. It is characteristic of the present types
salts to ‘solid magnesium oxide until \a paste of - of catalysts that they may be repeatedly regen
uniform consistency is obtained, after which erated without loss of porosity or catalyzing ef
the water is evaporated to leave the salts de
posited upon the magnesium oxide. Thus the ' The results of numerous typical runs could be
process of addition comprises only well known ‘introduced to indicate the’ general applicability
procedures in the chemical art and may be varied of the present types‘of catalysts in dehydrogenat
50 to suit the needs of any particular combination ing para?ins, but the following examples are 50
. which has proven valuable in catalytic reform
sufliciently characteristic, though the scope of
ing operations.
the invention is not limited‘to correspond with
In regard to the relative proportionsof mag
the numerical data. nesium oxide and promoting materials it may be
55 stated in general that the latter are generally
Example I
less than 10% by weight of the total composites.v
The preparation of the catalyst was as follows:
The effect upon the catalytic activity of the mag . 50 parts by weight of magnesite burned one hour
nesium oxide caused by varying the percentage
. of any given compound or mixture of compounds
60 deposited thereon is not a matter for exact cal
culation but more one for determination by ex
. at 800° C. (1472° F.) and screened to‘ 8-10 mesh
was treated with 100 parts of a 1% solution of
chromic acid.
The magnesium oxide. impreg 60
periment. Frequently good increases in catalytic
effectiveness are obtainable by the deposition of
nated with the chromic acid was then dried and
thereafter treated with 100 parts of a solution
as low as 1 or 2% of a promoting salt upon the
65 surface and in the pores of the oxide, though the
general average is about 5%.
containing 1% of cobaltous nitrate, 1% of lead‘
In practicing the dehydrogenation of para?inic
gases according to the present process a solid
‘composite catalyst prepared according‘ to the
70 foregoing alternative methods is used as a ?ller
in a reaction tube or chamber in the form of
particles of graded size or small pellets and the
gas to be dehydrogenated is passed through the
catalyst am.‘ being heated to the proper tem
acetate and 1% of zinc acetate at 25° C. (77° F.) 65
for one half hour. The impregnated catalyst
was then dried without further washing. Iso
butane was passed through a treating tower con
taining the pellets of magnesite as filler at at
mospheric pressure‘ and temperatures of about 70.
600° C., (111_2° F.) with a space velocity of from
50 to 70 per hour.
The following table shows the nature of the
results obtained by means of gas analyses takenw
75 perature, usually within the range of from 400 - at indicated times from the start of the run.
Cmnpositionof dehydrooenated oases . '
Time alter‘start hours ....... -; ........ --
so ‘ 15o
i-Butylene. pew’ent -------------------- __ m m m
’ v25o
tigggggmpz?gggtitm-n; """"""" " 15,48 183 1488
ggl?exi butylenes and propylene, percent. .
Ethylene percent ------ u
Y ‘me’ WP“ ------------ --- ------ --
Para?in'skmainly '?mpli?éi'i?ic'eh
Para?lns (mainly i-butane), percent___._ 35.0
37. 1
Hydrogen, percent ____ __. .............. .. 31.0
Hyémgm'peimnt """"" "_' """"" "
3' 1
There was substantially no change in the cat
alytic activity oi! the catalyst used over a period 10
of 6 days of continuous operation.
From the above data it will ‘be seen that the
correspondsclosely to the cal
v10 dehydrogenation
culated equilibrium mixture at 600° 0., (1112‘’ F.)
which should'contain approximately 33% hy-.
drogen, 33% butane and 33% butylenes. ‘Sub
stantially 50% of the original isobutane was'con-'
The fforegoing speci?cation and'examples are
su?ieient to show that the invention has intrinsic
value when practiced in the ‘art, but neither sec
tion is to be construed as imposinglimitations 15
verted into- ole?ns and hydrogen.
Composition of dehydrogenated gases
It is to be further observed that the catalytic upon the scope of the invention, as both are given
activity was maintained substantially constant for illustrative purposes only.
I claim as my invention:
for the period of a run of approximately 10 days.
1. A process for converting normally gaseous
. Example II
para?‘lns into ole?ns which comprises dehydro
The catalyst used" in this case consisted of genating'the same in the presence of magnesium
granulated magnesium oxide supporting lead oxide admixed with ‘minor proportions of a chro
mate and a metal salt of an oxygen-containing
chromate and ferric sulfate. To make the cat
alyst, 75iparts by weight of ' a previously prepared acid selected from the group consisting of sul
phuric, nitric and acetic acids.
25 material containing lead chromate was added to
150 parts of a 1% ‘ferric sulfate solution, in which - 2. A process for converting normally gaseo
"J’it' was stirred for about 1/2 hour at 50° C. The 5' para?ins into olefins which comprises dehydro
catalyst particles were then ?ltered from the genating the same ‘in the presence of magnesium
solution and dried at 300° C. (572° F.) .
. oxide admixed with minor proportions of a ‘chro
mateand a metal sulphate.
Using smalllpellets of the above oxide mix
3. A process for converting normally gaseous -
ture n'-butane was passed through a treating
para?lns into ole?ns which comprises dehydro
. tower containing the pellets as ?ller at atmosY-Z
pheric pressure and temperatures of about 600°‘ - genating the same in the presence of magnesium
C.. (1112°'>F.) with a space velocity oi’ from 45 oxide admixed with minor proportions of a chro
_-mate and a metal'nitrate.
35 ‘to 55 per hmir.
4. A process for converting normally gaseous
The following table shows the nature of the
results obtained by means of gas analyses taken 'para?ins into ole?ns which comprises dehydro
genating the same in the presence of magnesium
at indicated times from the start of the run.
oxide admixed with minor proportions of a chro
Composition of 'dehudrogenated gases
mate-and a metal acetate.
5. A process for converting normally gaseous
Time after start, hours _________________ -_
n Butane, percent- _-.
Propylene, percent
l8. 6
12. 3
l8. 3
ll. 4
17. 5
9. 8
l6. 0
_- 9. 3
parathns into ole?ns which comprises dehydro
genating the same in the presence of magnesium :7
ity was maintained substantially constant for a
oxide admixed with minor proportions of lead
chromate and zinc sulphate.
6. A‘ catalyst suitable for use in the dehydro
genation of hydrocarbons comprising a major
proportion of magnesium oxide admixed with
period of a run which was in this case 5 days.
Example; III >
group consisting‘oi sulphuric, nitric and‘ acetic
Eth ene, perccn ._
2. 3
Para?lns (mainly n utane), Deree
2. 4 p 4. 7
2. 2
41. 0
42. 9
43. 7
50. 1
Hydrogen, percent _____________________ __ 25.8
It is again observable mat the catalytic activ
‘A catalyst was prepared whichcontained mag
minor- proportions of a chromate and a metal salt
oi’ an oxygen-containing acid selected from the 50
. .7. A ‘catalyst suitable .Igr use in the dehydro
nesium chromate‘ and zinc sulfate supported on
magnesium oxide by_ the ~following method. 45 > genation of hydrocarbons comprising a major
parts by weight of magnesium nitrate, an- equal
weight of magnesium chromate arid-10 parts by
weight of zinc sulfate were separately dissolved
in small amounts of water, the solutions mixed
and the composite evaporated to dryness. The
60 dry‘powder was heated at- 250° 'C. v(482“ F.) for
_ several hours and ?nally at 500° C. (932° F.) for .
one hour.. The material was then-ground and
- sized to conserve particles‘ of from 6-10 mesh di
proportion of magnesium oxide admixed with
minor proportions oi’ a‘chromate. and a metal
- ‘m
8. A catalyst suitable tor use in the dehydro
genation ‘of hydrocarbons comprising a major
proportion of~magnesium oxide admixed. with
minor proportions of a chromate and a metal ni
9. A catalyst suitable for use in the dehydro
genation 0'! hydrocarbons comprising a major
Using small pellets of the above oxide mixture _, v‘proportion of magnesium oxide admixed with 66
“ made‘by moistening and compressing and later
drying as in the previous examples, propane was
minor, proportions of a chromate and a metal }
acetate. ‘ "
10. A process for converting normally gaseo
, passed through a treating tower containing the
para?ins into olefins which comprises dehydro
pellets as ?ller atmospheric pressure and tem
peratures of about 600° C., (1112.“ 1".) .with a genating the same in the presence of a'cat‘alytic to
mixture of a major proportion of magnesium
space velocity oifrom 40 to .45 per hour.
The following table shows‘ the nature of the. ' oxide and a minor proportio o
11. A process for converting normally gaseous .
results obtained by means of gas analyses taken
I ' ‘at the same indicated times ‘from the start of
the run.
para?‘ins into ole?ns which comprises dehydro
f-genating the same in the presence of magnesium
oxide admixed wlthggless than 10% by weight of
lead chromate.
12:. A process for dehydrogenating hydrocar
' bons whichdcomprises subjecting the hydrocar
bons under dehydrogenating'conditions to theiac
tion of a magnesium oxide catalyst containing
:14. A piocess tor dehydrogenating hydgocar
hens which comprises subjecting the hydgocav
bcns to dehydrogenating conditions in the pres- '
eiice of a magnesium oxide catalyst, said catalyst
furthercontainlng a relatively small amount of
a metallic oxygen-containing salt selected from
lead chromate in relatively; small but su?lcient
the group consisting of the sulfates, nitrates and
‘ amount to promoteithe catalytic activity of the
acetates of zinc, copper and aluminum.
, 15. The process as de?ned in claim 13 further
magnesium oxide.
13. A process tot-1 dehydrogenating hydrocar
bons which comprises subjecting the hydrocar
bons to delaydijogenating conditions in the pres
ence of a magnesium oxide catalyst containing
characterized in that said catalyst also contains
é'relatively small amount of a metallic oxygen
cbntaining salt selected from theigroup consist
in; of the sulfates, nitrates and acetates of zinc,
a éhromate in relatively small but su?lcient -' copper and aluminum. "
amount to promote’ the catalytic aétivtty of the
l5 7
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