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2,408,785
‘ Patented Oct. 8, 1946
UNITED
STATES . PATENT . OFFICE ~ ‘
2,408,785
METHOD OF PRODUCTION OF ANHYDROUS
MONOFLUOROPHOSPHORIC ACID
Willy Lange, Cincinnati, Ohio, assignor, by direct
,and mesne assignments, to Ozark Chemical
Company, Tulsa, Okla, a corporationof Dela
ware
No Drawing. Application June 28, 1944,
Serial No. 542,603
.18 Claims. ‘(01. 23-139)
1
,
.
In an application for United States Letters
.
2
‘
A further object is to provide a method of pro
ducing the said acid either alone or in conjunction
Patent, Serial No. 478,838, ?led March 11, 1943 by
with anhydrous di?uorophosphoric acid (HIPOzFz)
Ralph Livingston and me, jointly, anhydrous
which, after separation from the mono?uoro
mono?uorophosphoric acid (HzPOaF) and a
method of producing it from anhydrous hydro 5 phosphoric acid, forms a valuble by-product.
A still further object is the provision of a
?uoric acid and water-free metaphosphoric acid
method of the character aforesaid which is capa
are described and claimed, but the production of
ble of performance in such manner that none of
metaphosphoric acid exactly corresponding to the
the di?uorophosphoric acid, substantially equal
formula H290: and free from its‘ dehydration
products for use in that method is accomplished 10 quantities of both ‘acids or, between these two
extremes, any desired percentage of di?uorophos
only with a certain amount of difficulty. Thus a
method for the production of mono?uorophos
phoric acid not requiring the use of the'somewhat
' phoric acid with relation to the mono?uorophos
phoric acid may be produced.
, Other objects, advantages and novel features,
, di?lcultly preparable metaphosphoric acid oilers
advantages over that disclosed in the said appli 15 steps and operations comprehended by or inci
dent to the invention are hereinafter more par
cation.
Moreover anhydrous di?uorophosphoric acid > ticularly pointed out or will be apparent from
~ (HPOzFa) would be of distinct commercial value
the following description.
This application is a continuationsin-part of I
if available to industry, but while a dilute aqueous
solution of this acid has been known for some' 20 my applications for United States Letters Patent,
Serial Nos. 503,420 and 503,421, filed September
time the solution cannot be concentrated with
22, 1943, in which, respectively, I described and
out complete hydrolysis of the acid. The anhy
claimed a method of preparing substantially equal
drous form of this acid obtained as a lay-product
parts of mono?uorophosphoric acid and di?uoro
in the high temperature reaction between cal
phosphoric acid through the reaction of phos
cium ?uoride and phosphorus pentcxide has also
phorus pentcxide with anhydrous hydro?uoric
been described in literature in recent years but
acid and subsequent distillation of the product ‘
the quantities of the acid obtainable in this way
resulting therefrom, and a method of preparing
are so small'that the process is of no interest as
mono?uorophosphoric acid by a generally corre
a possible commercial source of anhydrous di?u
orophosphoric acid.
sponding reaction of phosphorus pentcxide and
and mono-, di- and hex‘a?uorophosphoric (HPFc)
acids is obtained, the solution also containing
unreacted- hydro?uoric acid. But when'an at
tempt is made to concentrate this solution the
?uorophosphoric acids decompose with the re
aqueous hydro?uoric acid of about 69% concen
tration without production of an appreciable
amount of the di?uorophosphoric acid.
The present invention therefore comprehends
production either of mono?uorophosphoric acid
free or substantially free of di?uorophosphoric
acid or of mono?uorophosphoric acid in conjunc
tion with di?uorophosphoric acid in any desired
ratio up to substantially equal quantities of each
able concentration.
orophosphoric acids in a predetermined ratio
Earlier in the literature it has been, pointed
out that in reacting a 40% aqueous hydro?uoric
acid solution and phosphorus pentcxide, the aque
ous solution of a mixture of orthophosphoric acid .
40 by reaction of phosphorus pentoxide with hydro
sult that it likewise is of no industrial value.
?uoric acid of from about 69%-100% HF con- »
It is therefore a primary object of the present
centration, so that by suitable selection of the
invention to provide a method adapted for use
degree of concentration and amount of the hy
in a commercial way to produce anhydrous mono
dro?uoric acid, the method may be operated to
?uorophosphoric acid (HzPOaF) through the use
supply either - the mono?uorophosphoric acid
of phosphorus pentcxide (P205) , a readily obtain
alone or the mono?uorophosphoric and the di?u-.
able material, and hydro?uoric acid (HF) of suit
2,408,786
3
with consequent avoidance of production of an
excess of di?uorophosphoric acid in order to meet
\commercial demand for the mono?uorophos
phoric acid.
More speci?cally, I have discovered that the
reaction product obtained at low temperatures in
the violent reaction of phosphorus pentoxide with
hydro?uoric acid of between about 69% and 100%
inclusive HF concentration and in a predeter
mined ratio is a liquid in which all three ?uoro 10
phosphoric acids (namely, mono-, di- and hexa
?uorophosphoric acids) and a ?uorine-free phos
phoric acid are present as can be shown by
analytical methods described in the literature,
but this liquid as such cannot be used for com
mercial purposes so far as I am ‘aware. However,
if it be subjected to heat under conditions such
that none of the gaseous reaction products are
allowed to escape, a succession of complicated
intermediate reactions takes place, not presently 20
known in detail, the end-product of which has a
simple composition and is of de?nite commercial
interest, said end-product being in accordance
with the percentage concentration and relative
quantity of the hydro?uoric acid employed either 25
substantially pure mono?uorophosphorio acid or
a mixture of the mono?uorophosphoric and di?u
orophosphoric acids which may be readily sep
arated by distillation, preferably under vacuum,
the difluorophosphoric acid passing oiT as the 30
distillate and the mono?uorophosphorlc acid re
maining as the ‘distillation residue, the yield of
crude di?uorophosphoric acid approaching the
theoretical value.
Then if an analytically pure
4
resulting parts by weight of acid or acids which
in accordance with the invention are obtained :A
(‘onccnlra
tion of hy-
Value of
drofluoric
X in
?g‘éggt
p ‘H '
tifl'glsesr
‘
Parts by ‘Wight
or-hydmmmric
‘ liglightqogeplg?g
by weight of
phosphorus
Thfgfstigalgifiltlllstm
l
y
LL
_
Mono?uoro- n‘ftlllzgfo'
phosphoric
gho?c
pcntoxide
acid
acid
140. 84
140. 77
138. 57
136. 37
134. 17
131. 96
129. 74
127. 52
125. 29
123. 07
120. 76
118. 60
116. 35
114. 11
111. 85
109. 59
107. 32
105. 06
102. 78
100. 50
98. 22
95. 93
93. 64
91. 34
89. 03
86. 73
84. 41
82. 10
79. 77
77. 44
75. 11
72. 76
70. 42
O. 00
0. 08
68. 97
69. 00
0. 00
0. 001074
40. 84
40. 85
70. 00
71. 00
72. 00
73. 00
74. 00
75. 00
76. 00
77. 00
78. 00
79. 00
80. 00
81. 00
82. 00
83. 00
84. U0
85. 00
86. 00
87. 00
0. 03226
0. 06350
0 09483
0. 1262
0. 1577
0. 1892
0. 2208
0. 2524
0. 2852
0. 3159
0. 3478
0. 3797
0. 4118
0. 4438
0. 4760
0. 5082
0. 5405
0. 5728
40. 89
40. 93
40. 98
41. 02
41. 07
41. 11
41. 16
41. 20
41. 25
41. 29
41. 34
41. 38
41. 43
41. 47
41. 52
41. 56
41. 61
41. 65
88. 00
89. 00
90. 00
91. 00
92. 00
93. 00
94. 00
95. 00
96. 00
97. 00
98. 00
99. 00
100. 00
O. 6053
0. 6378
0. 6703
0. 7030
0. 7357
0. 7685
0. 8013
0. 8342
0. 8673
0. 9003
0. 9335
0. 9667
1. 0000
41. 70
41. 74
41. 79
41. 84
41. 88
41. 93
41. 97
42.02
42. 06
42. 11
42. 16
42. 20
42. 25
2. 32
4. 56
6. 81
9. 06
ll. 33
13. 59
15. 87
18. 13
20. 49
22. 69
24. 99
27. 27
29. 58
31. 88
34. 20
36. 50
38. 83
41. 15
43. 48
45. 81
48. 15
50. 50
52. 85
55. 2O
57. 56
59. 92
62. 30
64. 67
67. 05
69. 44
71. 83
It will be apparent from this table that when
material is desired the crude di?uorophosphoric 35 operating with hydro?uoric acid of 68.97% con
acid may be re-distilled under vacuum; the resid
centration no di?uorophosphoric acid is produced;
ual mono?uorophosphoric- acid of the ?rst distil
that when operating with hydro?uoric acid of
lation is of a technical grade and cannot be puri
substantially 100% concentration approximately
?ed by further distillation.
equal quantities of mono?uorophosphoric and di
The reaction between the phosphorus pent 40 ?uorophosphoric acids are produced and that
oxide and hydro?uoric acid of about 69% to 100%
between these two extremes progressively greater .
inclusive HF concentration to which reference
amounts of the di?uorophosphoric acid are pro
has been made proceeds in accordance with the
duced as the concentration of the hydro?uoric
general equation
acid increases.
45
The temperature at which the reaction is per
formed mayvary from very low ones to those
in which X has any value in the range from 0 to l
inclusive, and in the practice of the invention _
care should be taken that during the reaction
the phosphorus pentoxide, hydrogen ?uoride and
water, if any, always meet in the ratio of 1 mole
P2O5:(2+X) moles HF:(1—X) mole H2O in
which X has any value between 0 and 1 inclu
sive.
By bearing this condition in mind one
exceeding the boiling point of hydro?uoric acid of
100% concentration but at temperatures exceed
ing the boiling point of low boiling reaction prod
ucts, the reaction should be carried out in a closed
system, with or without pressure, in order to avoid
losses of hydro?uoric acid and of gaseous reaction
products, the presence of which are necessary
to secure an end-product consisting essentially
of mono?uorophosphoric acid or of mono?uoro
phosphoric and di?uorophosphoric acids.
For attainment of optimum results and prod
ucts of essential purity the proportions of ingre
tration between about 69% and 100% inclusive
dients employed when operating with hydro
which should be used with a. certain quantity of 60 ?uoric acid of any given HF concentration with
phosphorus pentoxide in order to obtain the best
in the ranges speci?ed must be carefully followed
skilled in the art can readily calculate the quan
itty of hydro?uoric acid of a given HF concen
results, as Well as the necessary concentration
in accordance with the foregoing table, as de
and quantity of the hydro?uoric acid required if
partures therefrom may result in production of
it be desired to produce both mono?uorophos
impure di?uorophosphoric acid distillates and/or
phoric and di?uorophosphoric acids in a desired 65 ?uorine-free phosphoric acid instead of distilla
ratio. 1
tion residues consisting only of mono?uorophos
However, to minimize the necessity for such
phoric acid, and it is of utmost importance that
calculations and to facilitate the practice of my
none of the products incident to the reaction be
invention, I have set out in the following table 70 tween the phosphorus pentoxide and hydro?uoric
the parts by weight of hydro?uoric acid of various
acid be permitted to escape from the reaction ves
HF concentrations between about 69% and 100%
sel. To this end the reaction may be carried out
inclusive which should be used with 100 parts
in a closed vesselof suitable type, or a vessel hav
by weight of phosphorus pentoxide. the value of
ing a re?ux condenser associated therewith
X in the said equation in terms of moles and the 75 whereby all gases and vapors developed during
2,408,786
5
6
the reaction are returned by condensation or, in
fact, by any means suitable for attainment of
the desired end.
'
In the practice of the invention the reaction of
the phosphorus pentoxide and the hydro?uoric
acid may be e?ected in various ways. Thus the
.
150° C. only slight pressure being developed dur
ing this operation. The resulting reaction prod
uct is anhydrous mono?uorophosphoric acid
which exhibits all analytical data and identifying
characteristics described in said application, Be
rial No. 478,838. It cannot be puri?ed by dis
phosphorus pentoxide may be added in small por
tions, applying agitation, to liquid hydro?uoric
tillation.
-
Example 2.—142 parts (by weight of phosphorus
pentoxide are placed in a closed, jacketed, stain
acid maintained at such low temperature that
the reaction products, gaseous at room tempera 10 less steel mixer having two constantly rotating
curved blades, and'oil is circulated through the
ture, remain dissolved in the liquid reaction prod
jacket. After the mixerhas been evacuated aque
uct at ordinary pressure. Or, if preferred, hydro
, ?uoric acid may be passed into a closed, evacuat
ous hydro?uoric acid of about 69% HF is run into
the mixer, later applying pressure, and by cooling
ed, rotating cylindrical and suitably cooled con
tainer holding the phosphorus pentoxide so that 15 the circulating oil and ‘regulating the rate ‘of in
troduction'of the acid a temperature of about 180°
hydrogen ?uoride and low boiling reaction prod
C. is maintained in the mixer. After 58 parts
ucts are condensed, or the hydro?uoric and may
by weight of the acid have been introduced the
be passed into a closed, evacuated container hold
reaction product is allowed to slowly cool down
in: the phosphorus pentoxide, applying pressure,
or the phosphorus pentoxide with air as the car 20 to room temperature during a period of approxi
mately 3 hours. The ?nal product again is an
rier gas may be blown into a stream of evaporated
hydrous mono?uorophosphoric acid.
hydro?uoric acid in such manner that the phos
,Since in these examples hydro?uoric acid or a
phorus pentoxide and hydrogen ?uoride always
concentration of about 69% HF is employed, the
meet in a ratio of 1 mol P205: (2+1!) moles
HF:(1-x) mole H:O,.if any, where x has any 25 value of x in the general equation is 0 and it is
thus simpli?ed to PaOs+2HF+HaO=2KzPOzE no
value in the range from 0 to 1 inclusive and all
di?uorophosphoric acid being produced.
reaction products are conserved.
At this point it may be observed that an aque
If a reaction temperature of lower than about
ous hydro?uoric acid of approximately 69% 81"
150° C. has been utilized, it is generally necessary
to keep the reaction product in a closed container 30 concentration contains the acid and water in a
ratio of 2 moles HF:1 mole H20, thus conforming
at an elevated temperature for a time sui’?cient
to the general equation when X equals 0.
to enable the above mentioned intermediate re
The following are illustrative of the practice
actions to come to completion, the rate of these
of the method where a more concentrated aqueous
reactions depending upon the temperature. The
‘
time and temperature of this treatment may vary 35 hydro?uoric ‘acid is used:
Ezanwle 3.--58.5 parts by weight of aqueous hy
although generally a temperature of irom about
dro?uoric acid of 77.43% HF are placed in a plati
90° C. to 150° C. and a time of from 2 to 12 hours
is required. It will be understood, however, that
the time and temperature just mentioned are by
num bottle and cooled with a mixture or solidcar- '
tion since other times and temperatures may be
tions under agitation so that the temperature of
bon dioxide and alcohol and 142 parts by weight
way of example only and not by way of limita 40 of phosphorus pentoxide are added in small por
the liquid does'not rise substantially. The phos
phorus pentoxide reacts vigorously with the aque
it the reaction of the phosphorus pentoxide with
ous hydro?uoric acid and dissolves quickly, and
the‘ hydro?uoric acid has taken place at tempera
ture above about 150° C. usually no after treat-v 4.5 after all the phosphorus pentoxide has been added
to the acid a clear liquid is obtained. The bottle
ment as just described is necessary since the
is then closed and heated for 10 hours at 100° C.
intermediate reactions may have already taken
only slight pressure being developed during this
place to greater or lesser extent.
employed‘with equal facility and, further, that
operation. The resulting reaction product is a It will be appreciated that the excess of water
in hydro?uoric acids of less than about 69% HF is 50 mixture of mono?uorophosphoric acid and di?uo
rophosphoric acid and is subjected to distillation
inimical to success of the method and attainment
at a pressure of 50 mm. of mercury to separate the
of the desired ends since when such acids are
acids, the temperature of the batch being slowly
used the mono?uorophosphoric acid produced is
raised to 150° C. but not higher. The vapors of
associated with ?uorine-free phosphoric acid
' di?uorophosphoric acid evolved during the distil
which cannot be separated from it.
lation are condensed by passing through a con
The following are illustrative of di?erent ways
denser cooled with brine of -20° C. and a yield
of practising the method of the invention in ac
of 176.2 parts by weight of mono?uorophosphoric
cordance with the general equation “
acid'is obtained and 24.2 parts of crude di?uoro
60 phosphoric acid. To further purify it, the di?uo
rophosphoric acid may be re-distiiled at a pres
sure of 200 mm. of mercury at which pressure it
in which'X has any value in the range from 0 to 1
inclusive‘:
'
boils at about 70° C. It will be noted that in the
reaction the components are used in the ratio of
Example 1.—58 parts by weight of aqueous
hydro?uoric acid of about 69% HF are placed in 65 i mole PzO5:(2+X) moles HF:(1-X) mole H2O.
Example 4.—59.0 parts by weight of aqueous
a platinum bottle and cooled with a mixture of
hydro?uoric acid of 84.95% HF are combined with
solid carbon dioxide and alcohol and 142 parts
142 parts by weight of phosphorus pentoxide in
by weight of phosphorus pentoxide are added in
small portions under agitation so that the tem
the manner described in Example 3 and the re
perature of the liquid does not rise substantially.
The phosphorus pentoxide reacts vigorously with
the aqueous hydro?uoric acid'and dissolves quick
ly and after all the phosphorus pentoxide has been
added to the acid avclear liquid is obtained.‘ The
bottle is then closed and heated for ten hours at 75
action product subjected to like treatment and
subsequent distillation to separate the di?uoro
phosphoric acid from the mono?uorophosphoric
acid._ A yield of 150.9 parts by weight of the
latter and 50.5 parts of the former is obtained
and it will'be noted that the components are 8119-4
2,408,785
plied in the same ratio as in Example 3 but with
pressure. After 60 parts by weight of the ?uoride
X accorded a dl?erent value.
have been introduced, the mixer inlet valve is
,
Example 5.-59.5‘ parts by weight of aqueous
closed and the mixer warmed up slowly to a
hydro?uoric acid of. 91.78% HF are combined
?nal temperature of 90° C. and maintained there
with 142 parts by weight of phosphorus pentoxide CI for 5 hours. The reaction product after distil
and the resultant product again treated as in
lation in the manner described in Example 6
Example 3. Components are thus supplied in
affords a yield of 96 parts by weight of crude di
the same ratio as in Examples 3 and 4 though
?uorophosphoric acid and a distillation residue
again with a suitably different value for X, but
of (:04 parts by weight of mono?uorophosphoric
because of the higher concentration of the hy 10 aei .
dro?uoric acid a yield of 128.3 parts by weight
Example 8.—'142 parts by weight of phosphorus
of mono?uorophosphoric acid and 73.9 parts of
pentoxide are placed in a mixer similar to that
di?uorophosphoric acid is obtained after the dis
described in Example 7 and oil is circulated
tillation step.
through its jacket. After the mixer has been
In the three last examples the value of X in 15 evacuated anhydrous hydrogen ?uoride is passed
the general equation is intermediate between 0
into it applying pressure. By suitable cooling of
and 1, having the lowest value in Eample 3 and
the circulating oil and regulation of the rate of
progressively higher values in the others.
introduction of the hydrogen ?uoride into the
The following are illustrative of the practice
mixer, a temperature of about-150° C. is main
of the method where hydro?uoric acid of a con 20 tained in the latter. After 60 parts by weight
centration of 100% HF is utilized, i. e., the an
of the ?uoride have been introduced, the mixer
hydrous form of the acid, and as under these
inlet valve is closed and the reaction product al
conditions the value of X in the general equa
lowed to slowly cool down to room temperature
tion is 1, it is correspondingly simpli?ed to
‘for a period of approximately three hours. By
25 like distillation of this product, a yield of 91 parts
by weight of di?uorophosphoric acid and 109
and in each instance a yield approximating the
parts of mono?uorophosphoric acid is obtained.
theoretical yield of mono?uorophosphoric and di
All the foregoing examples numbered 1 to 8
?uorophosphoric acids respectively as set forth
inclusive are given by way of illustration only
in the foregoing table is obtained.
30 and not in any restrictive or limiting sense since
Example 6.—60 parts by weight of anhydrous
it will be understood from the foregoing descrip
hydrogen ?uoride are placed in a platinum bot
tion of the invention that so long as phosphorus
tle and cooled to the temperature of a mixture
pentoxide and the proper quantity of hydro?u
of solid carbon dioxide and alcohol. 142 parts
oric acid of suitable HF concentration are mixed
by weight of phosphorus pentoxide arethen add 35 in the ratio of 1 mole P205: (2+X) moles
ed in small portions under agitation so that the
HE’: (1-X) mole H20 where X has any value in
temperature of the liquid does not rise appre
the range from 0 to 1 inclusive, with after treat
ciably. It will be-noted that in the reaction the
ment by heating the reaction product in a closed
components are used in the ratio of 1 mole
container or its equivalent if the reaction has
P205113 moles HF. The phosphorus pentoxide re 40 not gone to completion according to the equation
acts vigorously with the hydrogen ?uoride and
dissolves quickly and after all of it has been add
ed to the acid a clear liquid is obtained. The bot
tle is then closed and heated for 8 hours at 85°
in which X has any value in the range from 0
C., only slight pressure being developed during
to 1 inclusive, many other ways may be em
this operation. The resulting reaction product is
a mixture of di?uorophosphoric and mono?uoro
phosphoric acids and is subjected to distillation
ployed for combining and subsequently treating
. the initially supplied components in order to con
at a pressure of 50 mm. of mercury to separate
the former from the latter, the temperature of .
the batch being slowly raised to 150° C. but not
higher. The vapors of di?uorophosphoric acid
evolved during the distillation are condensed by
passing through a condenser cooled with a brine
of -20° C. and a yield of 97 parts by weight of
crude di?uorophosphoric acid is obtained and
103 parts of crude mono?uorophosphoric acid.
To further purify it the di?uorophosphoric acid '
may be re-distilled as in Example 3. This puri
?ed product when analyzed by analytical meth 60
ods established in the literature is found to con
tain P 30.6%; F 37.0% as against the calculated
values respectively of P 30.4% and F 37.2%. The
mono?uorophosphoric acid is obtained as a dis
tillation residue and is found to contain when
likewise suitably analyzed P 30.7% F 20.1% as
against the calculated values respectively of P
31.7% andF 19.0%.
Example 7.—l42 parts by weight of phosphorus
form to special requirements of the equipment
being utilized, the form in which the phosphorus‘
pentoxide is most readily available and the like.
The reaction vessels may be those customarily
utilized for similar or analogous operations and
thus may be of the usual mixer or rotating drum
types, while the distillation apparatus may be of
any desired construction suitable for the purpose.
The equipment may be made from stainless steel
or other corrosion resistant material or may be
plated therewith and, according to the conditions
of the reaction, ordinary or pressure vessels may
be used. The practice of the invention therefore
does not require specially constructed apparatus
and as substantially pure phosphorus pentoxide
and hydro?uoric acid may be obtained without
di?iculty in the open market the invention readily
lends itself to commercial usage.
It will now be apparent that practice of the
method may be readily adjusted from time to
time to conform to market demand for the acids
or for other reasons without change in the equip
70 ment employed. Thus, for example, if during a
less steel mixer having two constantly rotating
certain period the said demand approximates 7
curved blades and cooled with a brine of -20°
tons of the mono?uorophosphoric acid to 3 tons
pentoxide are placed in a, closed jacketed stain
C. circulating through the jacket. The mixer is
then evacuated and anhydrous hydrogen ?uoride
of the di?uorophosphoric acid, the method may
be operated to produce both acids in approxi
slowly passed into it, in the latest stage applying 75 mately that ratio, or should demand for the di
8,408,785“
0
. be operated to produce the mono?uorophosphoric
acid alone, a feature of the invention which is
United States:
?uorophosphoric acid, the steps or mixing phos
oi’ these acids. Thus my invention for the ?rst
time, as far as, I am‘aware. makes possible the
/
production of anhydrous mono?uorophosphoric
available materials in a convenient and commer
cially ‘practical way.
-
10'
Concerning some of the properties of ‘these
acids, it may be mentioned that anhydrous mono
?uorophosphoric acid HzPOaF exhibits to a de
cided degree some of thechemical properties of
concentrated sulfuric acid‘ without showing any
oxidizing action and anhydrous di?uorophos
phoric acid HPOaFz, resembles to some extent -
anhydrous perchloric acid without‘any oxidizing
’
1. In a method of producing anhydrous mono
obviously of, great importance to manufacturers
acid, as well as anhydrous
horicacid
suitable for industrial purposes. from readily
.
and desire‘to protect by letters Patent of the
?uorophosphoric acid" become negligible it may
phorus pentoxide and hydro?uoric acid oi any
HF concentration between about 69% and 100%
inclusive according to the equation
in which x has any value in the range from 0 to 1
inclusive, and maintaining the mixture in the
presence of heat and under conditions prevent;
'ing the escape of any products of the reaction
until the latter goes to completion according to
said equation.
‘
_
.
2. In a method of producing anhydrous mono
?uorophosphoric acid, the steps of mixing phos
phorus pentoxide and hydro?uoric acid or any
concentration between about 69% and 100%
or explosive properties. In addition to having a 20 HF
inclusive
according to the equation
number of properties of a non-oxidising “pseudo
sulfuric” acid HzPOsF and a non-explosive, non
oxidizing "pseudo-perchloric” acid HPOzFa, ‘both
acids are derivatives of hydrogen ?uorideas well
in which X has any value in the range from 0 to 1
as of orthophosphoric acid, and they combine in 25 inclusive, and heating while preventing escape
a convenient form the reactivities of both an
of the reaction products until the reaction has
hydrous orthophosphoric acid and anhydrous
gone to completion according to said equation.
hydrogen ?uoride for a number of reactions.
' 3. In a method of producing anhydrous mono
The salts of both mono?uorophosphoric and
?uorophosphoric acid, the steps of mixing phos
diiluorophosphoric acids have been described in 30 phorus pentoxide and hydro?uoric acid of any
the literature. They may be produced now on a
HF concentration from about 69% to 100% in
commercial scale by passing calculated quantities
clusive in the ratio of 1 mole P2Os:(2+x) moles
of the anhydrous acids in a thin stream into
HF:(1—X) mole H2O where X has any value in
aqueous solutions of alkali bases or aqueous sus
the range from 0 to 1 inclusive, and then heating
pensions of non-alkali bases undergoing stirring 35 the product in a closed vessel at a temperature
and kept at a low temperature, and then by
not exceeding about 150‘ C'. until the reaction
evaporating the water in good vacuo at a low
has gone to completion according to the equation
temperature to avoid hydrolysis. Or dry amines,
like anhydrous ammonia, methylamine, aniline,
pyridine, are reacted in the theoretically required 40
quantities with the strongly cooled acids. or
in which X represents any number between 0 and
special interest are the aniline salts, which may
1 inclusive.
.
be transformed into the dlazonium compounds
4. The method of producing anhydrous mono
which, in turn, .when heated in the absence or
?uorophosphoric acid which includes the steps
water, will form the corresponding aryl ?uoro 45 of mixing phosphorus pentoxide and a hydro?u
phosphates with loss of their nitrogen.
oric acid of concentration exceeding 69% H1“
The anhydrous ?uorophosphoric acids may be
substantially according to the equation
used as catalysts for polymerization, condensa
tion and alkylation reactions, especially for com
bining such compounds as isoalkanes an'd ole?nes 50
or lsoole?nes.
Esters may be prepared by re
acting ole?nic or acetylenic compounds with the
anhydrous acids in the presence of catalysts, or
by reacting alcohols or ethers with the anhydrous
acids. 01 special interest are the esters of mono
?uorophosphoric acid. Their similarity with the
corresponding sulfuric acid derivatives is far
reaching. The long-chain monoalkyl-(and iso
alkyl) mono?uorophosphoric acid salts,_such as
in which X has any value in the range from 0 to 1
inclusive, maintaining the mixture in a closed
container at a temperature su?icient to cause
the reaction to go to completion according to
55 said equation and thereby form a resultant prod
uct containing mono?uorophosphoric and di
?uorophosphoric acids, and then separating the
di?uorophosphoric acid in vapor form from the
mono?uorophosphoric acid by distillation.
sodium lauryl mdno?uorophosphate, are surface 60 5. The method of producing anhydrous mono
?uorophosphoric acid which includes the steps
active agents. Monoethyl-mono?uorophosphoric
of mixing phosphorus pentoxide and a hydro?u
acid, obtained e. gQby reacting the anhydrous acid
oric acid of a concentration of from 69% to 100%
with ethylene, forms diethyl mono?uorophos
phate in a reaction corresponding to that of 65 inclusive HF in the ratio of 1 mole‘ P20s2(2-|-X)
moles HF: (1-X) mole H2O in which X has any
value from 0 up to and including 1, maintaining
forms diethyl sulfate.
the ingredients in a closed vessel until comple
Due to their non-oxidizing nature, both said
monoethyl sulfuric acid which, when heated,
tion of the reaction among them substantially
?uorophosphoric acids may be used as anhydrous
acids in the non-oxidizing refining of oils and the 70 according to the equation
like, while other uses in addition to those just
suggested may be readily devised and other
compounds may be prepared from them by those
in which X has any value in the range from 0 to 1
skilled in the art.
‘Having thus described my invention, I claim 75 inclusive to thereby form a resultant product
2,408,786
11
12
containing mono?uorophosphoric and di?uoro
12. That step in a method of producing anhy
drous mono?uorophosphoric acid which com
phosphoric acids, and then separatingsaid acids
by distillation.
prises mixing phosphorus pentoxide andan aque
6. The method of producing anhydrous mono
?uorophosphoric acid which comprises combining
ous hydro?uoric acid of about 69% HP in a man
ner to prevent loss or reaction components or re
phosphorus pentoxide and hydro?uoric acid ‘of
action products.
HF concentration exceeding 69% substantially
according to the equation
-
13. The method or producing anhydrous mono
?uorophosphoric acid which comprises mixing
phosphorus pentoxide and an aqueous hydro
10 ?uoric acid of about 69% HF in the ratio of 1
mole Pzm:2 moles HF:1 mole H20, and then
maintaining the mixture in a closed vessel vuntil
the reaction has gone to completion according to
in which X has any value in the range from 0 to 1
inclusive, maintaining the reaction products in
a closed vessel at a temperature and for a time
su?icient to cause the reaction to go to comple
the equation P:Os+2HI'+H20=2I-I:POaF.
tion product in a closed vessel at a temperature
and for a time su?icient to cause the reaction to
?uorophosphoric
14. The method of producing anhydrous mono
tion according to said equation, and then sepa
?uorophrosphoric acid which comprises mixing
rating the mono?uorophosphoric and di?uoro
phosphorus pentoxide and an aqueous hydro
phosphoric acids in the resultant product by dis
?uoric acid of about 69% HF in the ratio of 1
tillation.
mole -P2O5:2 moles HFzl mole H2O,.and then
7. The method of producing anhydrous mono 20 heating the product in a closed vessel at a tem
?uorophosphoric acid which comprises mixing
perature not exceeding about 150° C. until the
phosphorus pentoxide and hydro?uoric acid of
reaction has gone to completion according to the
about 69% HF in the ratio of 1 mole P205Z2 moles
equation P205+2HF+H20=2H2PO3F.
HF:1 mole H20, and then maintaining the reac
15. The method of producing anhydrous di
P2O5+2HF+H2O=2H2PO3R
?uorophosphoric acid, the steps of mixing» phos
mono?uorophosphoric .
taining the resultant product in a closed vessel
until the reaction has gone to completion sub
8. In a method of producing anhydrous mono
phorus pentoxide and hydro?uoric acid of any
I-IF' concentration from about 69% to 100% in
clusive in the ratio of 1 mole P205: (2+X) moles
HF: (l-X) mole H2O in which X has any value
in the range from 0 to 1 inclusive, and then main
taining the reaction products in a closed vessel
and
acids ‘which comprises mixing phosphorus pent
oxide and anhydrous hydro?uoric acid and again
go to completion according to the equation
30
at a temperature and for a time sufficient to cause _
the reaction to go to completion according to the
stantially according to the equation
16. The ‘method. of producing anhydrous di
?uorophosphoric and mono?uorophosphoric acids
which comprises mixing phosphorus pentoxide
and anhydrous hydro?uoric acid, maintaining the
resultant mixture in a closed vessel until the re
action has gone to completion, substantially ac
equation
cording to the equation
>
40
and then separating the two acids in the result
ant product by distillation.
17. The method of producing anhydrous di
?uorophosphoric acid, the steps of mixing phos A v
phorus pentoxide and hydro?uoric acid in the -" ?uorophosphoric and mono?uorophosphoric acids
which comprises mixing phosphorus pentoxide
ratio of 1 mole P2O5Z(2+X) moles HF:(1—X)
and anhydrous hydro?uoric acid, maintaining
mole H2O in which X has any value in the range
in which X represents any value in said range.
9. In a method oi’ producing anhydrous, mono
the resultant mixture in a closed vessel to there
from 0 to 1 inclusive, and maintaining the reac
tion products in a closed vessel to prevent loss 50 by prevent the escape of reaction products until
the reaction has gone to completion substantially
thereof until the reaction has gone to completion
according to the equation
according to the equation
then distilling the resultant product to separate
the di?uorophosphoric ‘acid, in vapor form from
in which X represents any value in said range.
10. The method of producing anhydrous mono
the residual mono?uorophosphoric acid, and
condensing the vapor.
?uorophosphoric acid in conjunction with anhy
drous di?uorophosphoric acid which comprises
mixing phosphorus pentoxide and anhydrous hy
18. The method of simultaneously producing
anhydrous di?uorophosphoric and mono?uoro
phosphoric acids which includes the steps of mix
ing phosphorus pentoxide and anhydrous hydro
dro?uoric acid substantially in the ratio of 1
mole P205:3 moles HF, and then maintaining the
reaction products in a closed vessel at a tempera
ture and for a time su?icient to cause the reac
tion to go to completion according to the equa
tion P2O5+3HF=H2PO3F+HPO2F2.
65
?uoric acid in the ratio of l mole:3 moles, pre
venting the escape of reaction products from the
mixture until the reaction has gone to completion
substantially according to the equation
11. The method of producing anhydrous mono
?uorophosphoric acid which comprises mixing
phosphorus pentoxide and‘ an aqueous hydro
?uon‘c acid of about 69%‘HF and maintaining
the mixture in a closed vessel until‘the reaction
has gone to completion according to the equa
tion P205+2HF+H20=2H2P03F.
and then separating the di?uorophosphoric acid
in vapor form from the residual mono?uorophos
phoric acid by distillation. ~
WILLY LANGE.
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