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Патент USA US2409374

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Patented Oct. 15, 1946
2,409,372
qUNlTED STATES PATENT OFFICE
REMOVAL OF ORGANIC FLUORINE
Maryan I’. Matuszak, Bartlesville, Okla, assignor
to Phillips Petroleum Company, a corporation
of Delaware
Application January 3.1944,
‘ No Drawing‘.
Serial No. 516,852
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10 Claims. (01. 196-411
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or otherwise. The other method involves treat
ment with a solid porous. contact material under
conditions binding the ?uorine so that the treated
hydrocarbon material is not only freed from a
embodiment it relates to the removal from hydro
carbon materials of ?uorine-containing organic 01 substantial part or all of the organically com
bined ?uorine but is also recovered without being
compounds which are present in relatively minor
contaminated with free hydrogen ?uoride. The
amounts. In a more speci?c embodiment my in
latter process is described in the copending appli
vention relates to the removal of at least a major
cation of Frederick E, Frey, Serial Number
portion of organically bound ?uorine from hydro
398,361, ?led June 16, 1941, now U. S. Patent
carbon materials containing organically bound
2,347,945, issued May 2, 1944. Among the con
?uorine in an amountnot greater than about 2
tact materials which may be used in such a proc~
per cent by weight, and often in an amount not
ess are those catalytically active for hydrogena-.
greater than about 0.1 to about 0.5 per cent by
This invention relates to the treatment of or
ganic materials to remove organic ?uorine-con
taining compounds therefrom. In one general
weight. The invention is particularly applicable
tion and dehydrogenation reactions, preferably
to such ?uorine removal as carried out with the 15 the oxides of various metals, such as the oxides
of metals chosen from the group consisting of
aid of naturally occurring minerals containing
aluminum, titanium, zirconium, hafnium, tho
silica as an impurity.
In the manufacture of hydrocarbons by proc
esses in which ?uorine-containing catalysts are
used, small proportions of organic ?uorine-con
taining lay-products are often formed. Processes
to which my invention may be generally applied
involve the alkylation of relatively low-boiling
hydrocarbons with ole?ns, alcohols, ethers, alkyl
halides, and the like, to produce higher-boiling
hydrocarbons in the presence of catalysts com
prising one or more such ?uorine compounds as
hydro?uoric acid, boron tri?uoride, antimony tri
rium, vanadium, chromium, moIy-bdenumtung
sen, uranium, manganese, iron, cobalt, nickel,
30 or the like, alone or in admixture, synthetically
produced or in naturally occurring forms such
as ores. Due primarily to their low cost and avail
ability, the naturally occurring ores are ordinarily
- used, and bauxite has been found to be particu
larly advantageous. Other naturally occurring
oxides such as limonite, manganite, baddeleyite,
brookite, brucite, diaspore, dysanalite, .gibbsite,
goethite, heusmannite, huebnerite, ilmenite, lep
?uoride, complexes of these with other materials
idocrite,,rutilefspinel', valentinite, etc., are also
such as are formed by boron tri?uoride and water, ‘
useful.__jr
various organic acids, alcohols, and acids of phos
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Unfortunately, natural contact materials of this
type contain up to as, much as 20 per cent by
weight Or vmore of siliceous material, most gener;
phorus. My invention may also be applied to
processes wherein such low-boiling hydrocarbons
are .isomerized in the presence of such catalysts.
The exact nature and composition of the organic
containing by-products which are formed and
acid believed to be formed by decomposition of
which are present as impurities in the desired
the organic ?uorinecompounds before such'hy
product has not been de?nitely established, al
though they are believed to be predominantly
alkyl and/or aryl ?uorides, but it is known that
they are not completely removed by washing the
products with alkali solutions, and that they tend
.to decompose at elevated temperatures such as
those employed in fractional distillation of the
products, thereby forming hydro?uoric acid which
is corrosive, especially in the presence of moisture.
drogen ?uoride becomes bound by the porous con
tact material. At anyrate, the formation of sili
con tetra?uoride occurs. This silicon tetrafluo
ride is highly objectionable because it contami
nates the hydrocarbon material, and because con
tact of it with moisture produces hydro?uoric
’ same time deposits gelatinous silicic acid which
accumulates , until the equipment is plugged.
In gases they may thus cause corrosion of han
Moreoventhe loss of ?uorine, in the form of sili
'dling equipment; in liquid motor fuel hydrocar
con tetra?uoride, is economically undesirable. ‘
bons they are undesirable for reasons that are
An object of this invention is to effect removal
of organically combined ?uorine from hydrocar
obvious.
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‘
Two general methods of removing-such organic
combined ?uorine are available.
One involves a
decomposition of the same under‘conditions liber
ating free hydrogen ?uoride, which is subsequent
ly removed from the hydrocarbons by distillation
ally silica, as an impurity. In'actual practice,
such silica apparently reacts with hydro?uoric
acid, Whichis exceedingly corrosive, and at the
bon'materials containing the same. _
'
Anotherobject is to eifect substantially com
plete removal of ?uorine from hydrocarbon ?uids
containing organic ?uorine compounds‘ as im
purities.
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2,409,372
4
3
monia thus recovered may be reused in the proc
Another object is to remove organic ?uorine
ess of the present invention.
from hydrocarbon materials that have been pre
In carrying out a treatment in accordance with
pared by a process in which a ?uorine-containing
my invention, the hydrocarbon material, contain
catalyst is used.
ing a small added proportion of ammonia, is
Another object of the invention is to avoid the
passed in the liquid or vapor phase, preferably
formation of silicon tetrafluoride in processes
in the liquid phase, through the contact mass,
wherein fluorineeconta-ining material is contacted
which is preferably bauxite, at a space velocity
with bauxite or other naturally occurring metal
of approximately 1 to 10 volumes of liquid per
oxide.
Further objects and advantages of my inven 10" volume of contact mass per hour and at a tem
perature-in the. range between about 100 and
tion will be apparent, to one skilled: inthearth
350° F. The pressure on the hydrocarbon ma
from the accompanying disclosure and discussion.
According to this invention,v in preferred-‘em
bodiment, a small proportion of ammonia, usu
terial, although not critical, is preferably be
tween about*15‘~ and 500 p. s. i. (pounds per square
inch), and is“ chosen to give vapor phase, mixed
ally less than 1 per cent by weight, and prefer
ably not more than approximately the. stoichie-J phase, or liquid phase operation as desired.‘
In_order to illustrate certain features of my
ometric equivalent of the ?uorine, such aszior
example 0.001 to 0.01 per cent by weight, is added. ' invention,4the following examples are offered. It
tact‘ material of‘ the’ nature described. Hydroe
fluoric acid present‘ in theihydrocarbon material
will of course be understood that the data given
are only exemplary in nature, and hence are not
to be. so1 construed as to unduly limit the inven
tion'.
or formed from the organic- ?uorine is" believed
to react with the’ ammonia‘ to form ammonium
In an exploratory'experiment, 03 gram of am
moniawas‘ mixed with 48.5‘ grams of n-butane
to the hydrocarbon material before contacting '
with the silicon-containing bauxite or other con- _
fluoride and/or ammonium acid ?uoride, where :5 containing 0.069‘ percent by~weight of silicon
tetra?uoride- After-the mixture had stood over
byj;it is prevented‘ from forming silicon» tetra
night',.the: butane‘ contained’ only 0.011 per cent
?uorid'e: Furthermore, any silicon tetra?uoride
by-weightof’sili-con tetra?uoride; indicating that
which maybe fbrmedisoconverted to" ammonium
84' per‘ cent‘ of the silicon tetra?uori'cl'e had been
?iiosiiicate‘," which‘ is relatively‘ less volatile; so‘
thafthe" hydrocarbon" material remains free : converted to" compounds of- lower volatility by- re
action: with the ammonia.
from this objectionable compound‘. The‘ ammo
In another exploratory‘ experiment, a‘ stream
nium salts. are retained by the contact‘ mate'
of n-butane containing'0.038 per cent by weight
rial'. The‘ addition‘ of ammonia: to. the‘ hydro
of? ammonia waspassed through spent bauxite
carb'on-st'ream has'the-pra‘ctical advantages that
pretreatment of'the bauxite is" unnecessary and -'-‘-'I fromthe bauxite treater of a commercial hydro
?uoric. acid alkylation plant‘ at a space velocity
that" the ammonia can‘ be added in' controlled
of 1.4 liquid volumes per volume of catalyst per
proportion in‘ accordance with need as‘ shown by
hour and at a temperature of'180°' F; After am
analysis‘ of‘ the effluent hydrocarbon material.
monia amounting to 3.4 percent by‘ weight of the
Any ammonia in' the hydrocarbon stream‘ inex
cess of‘ that‘ required for‘ reaction with'hydro 4:1) used bauxite had been adsorbed, a stream of'n
butane containing’ 0.0025 per cent by weight of
?uoricacid' and/or silicon tetrafluoride; appears
silicon'tetrafiuoride was passedv through the am
to‘ be adsorbed by the bauxite and/or‘ the. de
monia-containing bauxite at’ a- space velocity of
posited ammonium salt' or salts, so. that“ the
1.8lto 2.3 volumes‘ of 'liquid pervolume of contact
diluent hydrocarbon stream is' ammonia-free.
When the bauxite‘ has become spent; the passage 45 mass“ per hour. Substantially complete removal
of' hydrocarbon materials is interrupted; and‘the
of‘ the silicon tetra?uoride. occurred.
bauxite is revivi?ed" or" replaced.
Ingran illustrative speci?c example, a debutan
It will‘ be appreciated that natural‘ ores’ con
izer overhead e?luent- from the hydro?uoric‘ acid
alkylation of isobutane with butenes is mixed
taining relatively high proportions of silica. are
more readily available and much cheaper. than 50 with 0.005 per cent‘ by weight of ammonia, and
the mixture is! passed over bauxite; The rate of
those- having‘. an unusually“ low-v silica: content.
Such advantages of high-silica ores are even more
?ow of’_ the hydrocarbon is from 2 to 5 volumes
pronounced when_ comparedv with synthetically
of-hydrocarbon per volumeof' catalyst per hour;
the-temperatureis'maintained at 150 to 200° F.'.;
produced materials. My' invention“ may be vap- '
the‘ pressure is sufficient to maintain the hydro
pli'edeto treatment with materiaisv of' lower high
carbon in the liquid phase. Substantially com
silica-content to advantage, and the'choice of
particular" contact" material will be largely a
plete removal of the organic ?uorine oc.curs;.and
matter ‘of’ economic‘ consideration.
the e?luent hydrocarbon material is free from
When'the'spent contact‘mass'isi to be revivi?ed‘,
silicon tetra?uoride. When spent, the contact
it‘is-heated‘ to-an elevated temperature at which
ammonia and‘ ammonium‘ salts are‘ volatilized'.
The vol'atilizationmay be“ aided‘ by' a flowing. at
mosphere of‘ an" inert carrier gas.
Usually,
volatili'zat'i'onv of ‘all the ammonia and ammonium
salts need not. be practiced. During the. revivi
?cation some. silica may. be removed as silica tet
ra?uoride. and/or ammonium.?uosilicate;. in. fact,
insome instances, after revivi?cationthebauxite
mass is heated in a stream of gas, such as natural
gas or butane, to remove ammonia and ammoni
um' compounds; which are collected and used for
any ‘suitable purpose. The revivi?ed contact mass
is suitable for re-use. Any ammonia obtained by
the revivi?cationstep. isrecycl'ed. to the process.
It..will,readily, be, appreciatedthat. while cer
tain-speci?c aspects. of the. invention have been
described .in- considerable; detail, the. invention is
or.~other catalyst: may contain: so little: silica that 70 not to be so construed as to be unduly limited
subsequent use of. itrmay bemadeein‘theordinary
thereby, and’ various modi?cations. and‘ embodi
manner: without‘ use. of ' ammonia. The gases: and
ments; may be practiced, by one skilled'inv the
fumes; eifluent from‘ the revivi?cation. may‘ be
art; by following. the teachings of the. present
passed tov a. recovery’ stepv for: recovery._of am
disclosure. without departing from the spirit
monia and/or other desired compounda.
thereof‘ or from the scopeof'the- claims.
2,409,372
5
I claim:
6
,
5. The process of ‘claim 3, wherein said nat—
urally-occurring solid metal oxide contact ma—
_
1. The process of removing organic ?uorine
from hydrocarbon materials containing the same
terial is bauxite.
_
which comprises treating such hydrocarbon mae
6. The process of claim 3, wherein said nat
terials with a solid contact material comprising
urally-occurring solid metal oxide contact ma
a metal oxide catalytically active for hydrogena
terial is an oxide of an iron-group metal.
tion and dehydrogenation reactions and contain
'7. The process of claim 3, wherein said nat
ing silica as an impurity, said treating being
urally-occurring solid metal oxide contact ma
conducted in the presence of added ammonia uné
terial is iron oxide.
der conditions producing a hydrocarbon ef?uent 10
8. The process of claim 3, wherein, when said
of substantially reduced ?uorine content and
contact material becomes incapable of removing
substantially free from silicon compounds.
_
?uorine to a desired extent, said contact ma
2. The process of removing organic ?uorine
terial is heated in a stream of inert gas to an
from hydrocarbon materials containing the same,
elevated temperature adequate to effect the vola'
which comprises treating such hydrocarbon ma 15 tilization of at least a portion of the ammonium
terials with a naturally-occurring solid metal ox
compounds therefrom, and is then reused for said
ide contact material active for removal of or- .
ganically combined ?uorine from hydrocarbon
materials and containing a minor amount of silica
?uorine removal.
‘
9. In a process for the removal of organically
combined ?uorine from a hydrocarbon material
as an impurity, said treating being conducted in 20 containing the same, wherein such a material
the presence of ammonia under conditions pro
is contacted with bauxite containing siliceous
ducing a hydrocarbon eiiluent of substantially
impurities under conditions such that extensive
reduced ?uorine content and substantially free
chemicalv changes in said hydrocarbon material
from silicon compounds.
itself are not e?ected and such that the hydro
3. A process for treating a hydrocarbon ma 25 carbon effluent from said contacting is substan
terial to remove organically combined ?uorine
tially free of such organically combined ?uorine
therefrom, which comprises subjecting a hydro
but normally contains volatile compounds of sili
carbon material, containing a minor quantity of
con and ?uorine, the improvement which com
organically combined ?uorine and also contain
prises admixing with such hydrocarbon material
ing ammonia in an amount substantially stoi 30 undergoing said contaoting a minor quantity of
chiometrically equivalent to the ?uorine content '
ammonia at least stoichiometrically equivalent to
thereof, to the action of a naturally-occurring
the ?uorine content thereof.
solid metal oxide contact material active for re—
10. The process of claim 9, wherein said hy
moval of organically combined ?uorine from hy
drocarbon material contains not over about 2
drocarbon materials and containing a minor 35 per cent by weight of ?uorine, is contacted in the
amount of silica as impurity, under conditions
liquid phase with bauxite at temperatures be
such that extensive chemical changes in said hy- _
tween about 100 and about 350° F. at ?ow rates
drocarbon material itself are not effected and
between about 1 and about 10 volumes per vol
such that the total effluent from. said treatment
ume bauxite per hour, and in which a hydrocar
is substantially free from ?uorine in any form 40 bon e?luent from said contacting is'obtained sub
and from ammonia and ammonium compounds.
stantially free from silicon and from ?uorine.
4. The process of claim 3, wherein said nat
urally-occurring solid metal oxide contact ma—
MARYAN P. MATUSZAK.
terial comprises an alumina.
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