3,689,216

United States Patent Office Patented Sept. 5, 1972

2
low yield. Such processes require considerable expendi
3,689,216 tures, both in terms of operating expense and initial capital
PRODUCTION OF HYDROGEN FLUORIDE FROM investment. Two-step processes for hydrogen fluoride
FLUOSLCIC ACED recovery from fluosilicic acid are disclosed in U.S.P.. Nos.
Russel A. Brown, Idaho Falls, Idaho, assignor to Allied 3,218,125 through 3,218,129, wherein silicon tetrafluoride
Chemical Corporation, New York, N.Y. and hydrogen fluoride are separated from a moderately
No Drawing. Filed Apr. 26, 1971, Ser. No. 137,618 concentrated sulfuric acid medium. This process has two
Int, C. C01b 7/22, 7/00 disadvantages-a large volume of concentrated sulfuric
U.S. C. 423-483 5 Clais
acid is required per unit of fluosilicic acid and both steps
O of the process must be carried out at relatively high tem
ABSTRACT OF THE DISCLOSURE peratures. For these reasons, the prior are processes for
A process for producing gaseous anhydrous hydrogen recovering hydrogen fluoride from the waste gases result
fluoride from fluosilicic-containing solutions by forming ing from the acidulation of phosphate rock and the con
an alkali metal fluosilicate and reacting said fluosilicate
centration of the phosphoric acid obtained therefrom, have
5 not been economically attractive.
with excess HSO at temperatures between 20 and 100 SUMMARY OF THE INVENTION
C. to produce gaseous silicon tetrafluoride and a fluoride
containing by-product and heating said by-product to a By-product fluosilicic acid, such as would be obtained
temperature between 80 to 300° C. to obtain the hydro from the acidulation or concentration step of a wet process
gen fluoride product. 20 phosphoric acid manufacturing unit or from a phosphate
fertilizer manufacturing operation is treated to recover
its fluorine values as anhydrous hydrogen fluoride. By
BACKGROUND OF THE INVENTION product fluosilicic acid from these sources would normally
This invention relates to a process for the recovery of be an aqueous 15-30% solution. In addition, silicon
hydrogen fluoride and more particularly to a process for 25 tetrafluoride which is produced in the present invention,
recovering hydrogen fluoride from the waste gases pro as will be described later, is hydrolyzed to produce addi
duced in the acidulation of phosphate rock. tional fluosilicic acid. In the present process the fluosilicic
As is well known, chemically combined fluorine is usual acid-containing solution is reacted with an inorganic alkali
ly present in substantially all of the mineral phosphates metal salt. Preferably, the alkali metal is either sodium
or the "phosphate rock” of commerce. Generally, such 30 or potassium with potassium being especially preferred.
phosphate rock contains as much as 3-4% by weight of While the salt may be derived from any of the inorganic
fluorine. When this phosphate rock is acidulated as, for mineral acids, preferably an alkali metal bisulfate or
example, with sulfuric or phosphoric acid, and subse sulfate is employed because sulfuric acid is produced as
quently, when the phosphoric acid is concentrated as in a by-product and can be used in the acidulation of the
the production of phosphate fertilizers or wet-process 35 phosphate rock. While reference herein below is made
phosphoric acid, a considerable portion of the fluorine to potassium bisulfate and sulfate, it is intended to cover
value is released from the system as gaseous silicon tetra other inorganic alkali metal salts.
fluoride. Because of the noxious nature of this gas, it must In addition to the alkali metal salt originally added,
be handled so as to avoid pollution of the atmosphere. there is also charged into the reaction vessel the entire
Accordingly, it is customary to pass the gases which 40 heel of potassium bisulfate or sulfate and sulfuric acid
result from the acidulation of phosphate rock through from the hydrogen fluoride generator, described here
water absorption towers or venturi scrubbers, to absorb inbelow, which represents the last step of the process.
the silicon tetrafluoride and yield a water solution of Sufficient make-up potassium bisulfate or sulfate should
fluosilicic acid. As a result of this hydrolysis, insoluble be added to the batch either in solid form or in solution
silica is formed which is then separated, and the re 45 to provide a slight excess of potassium ion over the
maining solution of fluosilicic acid is either marketed as stoichiometric quantity, sufficient to react with the fluo
such or used in the manufacture of various fluosilicates silicic acid solution to form a precipitate of fluosilicate
which have industrial applications. While there is a limited as the potassium salt. One way in which this may be
market for the fluosilicic acid or for the fluosilicates accomplished is by determining the fluosilicic acid still
derived therefrom, the market price of such compounds is 50 present in an aliquot portion by conventional means
not sufficiently high to make their production very at (after precipitation of the greater portion as potassium
tractive. It is, therefore, advantageous to be able to re fluosilicate by the potassium ions already present), then
cover the fluorine values in the silicon tetrafluoride pro adding about a 0 to 10% excess of potassium sulfate or
duced in such processes in a form which commands a potassium bisulfate over the stoichiometric quantity. The
higher market price as, for example, hydrogen fluoride. 55 temperature range for the fluosilicate precipitation is not
In the past, numerous processes have been proposed critical, but to minimize losses the precipitation should be
for the recovery of the fluorine values as hydrogen fluor carried out preferably within the range of 20° to 80° C.
ide, but generally such processes require operation at The agitated slurry is now filtered and the filtrate which
excessively high temperatures or under severe conditions. consists of approximately 5 to 40% sulfuric acid, can be
Some employ an excessive. number of processing steps 60 concentrated or returned without further treatment to the
or consume uneconomic quantities of raw materials. Some wet process phosphoric acid manufacturing facility or to
of the proposed processes comprise a sequence of re the phosphate fertilizer manufacturing facility for the
actions, some of which produce undesirable by-products dilution of the H2SO4 used in the digestion of phosphate
and a contaminated product hydrogen fluoride, often in rock.
 3,689,216
3 4.
Preferably, the filter cake of potassium fluosilicate is gen fluoride contains less than 0.5% of water and less
given a water wash, and then transferred to a dryer main than 1% of silicon tetrafluoride.
tained at a temperature of about 120° C. where the wa In the preferred embodiment of the present invention,
ter content is reduced preferably to less than 1%. The the residual mixture of the alkali metal (potassium) bi
dry potassium fluosilicate is next charged into a reaction sulfate and sulfuric acid remaining after the evolution of
zone, preferably equipped with agitation means, which is the hydrogen fluoride in the last processing step, is re
also vented to a silicon tetrafluoride hydrolyzer. In this cycled to the precipitation vessel to provide the major
reaction zone, about 1.5 to 6 times, preferably between portion of the potassium ions required for the precipita
2 and 4 times, the stoichiometric quantity of concentrated tion of the potassium fluosilicate. As previously men
sulfuric acid is added to the alkali metal fluosilicate to O tioned, only a small additional amount of make-up po
produce silicon tetrafluoride (SiF), which is driven off tassium sulfate or bisulfate is required.
leaving a residual by-product of potassium bifluoride, po The present invention also provides for the utilization
tassium bisulfate and sulfuric acid. The reaction is car of the evolved silicon tetrafluoride so as to eventually re
ried out at temperatures between about 20 and 100° C., cover its fluorine values as hydrogen fluoride. This is ac
preferably within the range of about 25 to 60° C. The complished by passing the silicon tetrafluoride gas into
silicon tetrafluoride is liberated over a relatively short water, or preferably into a 5 to 15% solution of fluo
period of time without substantial loss of hydrogen fluo silicic acid, wherein it is hydrolyzed to produce more
ride. Actually, the reaction proceeds rapidly and com fluosilicic acid with the precipitation of silica. The use of
pletely at a temperature of about 25 C. It has been found diluted fluosilic acid to hydrolyze the tetrafluoride has
that substantially all of the silicon tetrafluoride is rapidly 20 been found to provide a more easily filterable silica. The
evolved from the reaction vessel without the loss of hy silica is removed, preferably during the hydrolysis, by cir
drogen fluoride at temperatures below about 100° C. The culating the solution through continuous separating means
amount of hydrogen fluoride lost during the silicon tet such as a continuous filter, since otherwise the slurry
rafluoride evolution depends upon the amount of excess could become too thick for effective handling. The fluo
Sulfuric acid used, the reaction temperature and the con 25 silicic acid solution is thus brought to a concentration of
tact time in the reactor. Although contact times of as between about 15 and 30%, preferably to about 20%
long as 10 minutes may be used, generally, about 4 to H2SiF6. Preferably, it is then divided into two portions,
8 minutes is sufficient. Loss of hydrogen fluoride ap one being diluted to between 5 to 15% to serve as the
proaches 10% at the longer reaction times, at higher tem hydrolyzing medium for further additions of silicon tet
peratures and/or when a smaller amount of excess sul 30 rafluoride, whereas the second portion is combined with
furic acid is employed. When the process is carried out in the fluosilicic acid process feed for conversion to potas
the preferred ranges of time, temperature and sulfuric sium fluosilicate. The hydrolysis may be carried out with
acid concentration, the loss of hydrogen fluoride with in the range of 10 to 100° C., preferably between 20 and
the silicon tetrafluoride is generally less than about 5%. 70° C.
Accordingly, a short contact time for the reaction be Example 1
tween the sulfuric acid and the potassium fluosilicate is
especially desirable, as well as adequate means for re 240 parts of by-product 20% aqueous fluosilicic acid
moving the evolved silicon tetrafluoride gas from the re solution containing 48 parts of HSiF6 are combined in a
actor. It has also been found especially desirable to con fluorocarbon-lined vessel with 480 parts of recycled 20%
duct this reaction as well as the subsequent hydrogen fluo 40 fluosilicic acid containing 96 parts HSiF6. The fluosilicic
ride removal step, described hereinbelow, under sub acid solution is reacted with a 1:1 mixture of potassium
stantially anhydrous conditions. Since water may be in sulfate and essentially 100% sulfuric acid, comprising 174
troduced into the mixture from the precipitated alkali parts of KSO and 174 parts of sulfuric acid. The tem
metal fluosilicate and/or from the sulfuric acid, it can perature in the reaction vessel is maintained at 40° C.
be appreciated that the desired anhydrous conditions de 45 The precipitate of potassium fluosilicate which forms is
pend upon the sulfuric acid concentration as well as upon filtered (to recover 850 parts of 32% HSO4), and then
the degree to which the drying step of the alkali metal washed with 250 parts of water, to remove the last of the
fluosilicate has been carried. Accordingly, the water con sulfuric acid and other soluble impurities. The potassium
tent in the reaction mixture should be less than about fluosilicate is then dried at 120° C. until its water content
10% by weight, based on the acid present, but it is pref 50 is less than 1%. The concentration of the dilute sulfuric
erably kept to less than about 5% by weight. acid may be used to supplement that employed in the
After evolution of substantially all of the silicon tetra digestion of phosphate rock in wet-process phosphoric
fluoride, the remaining fluoride-containing by-product acid manufacture, or in the manufacture of phosphates
comprises an alkali metal bisulfate an alkali metal bi and phosphate fertilizers. The dried fluosilicate salt (220
fluoride and sulfuric acid. This mixture is heated to, and parts) is next reacted with 196 parts of 100% sulfuric acid
maintained at a relatively high temperature until essen in a fluorocarbon lined agitated vessel for 6 minutes at
tially all of the hydrogen fluoride, substantially free of a temperature maintained at about 50° C. Substantially
silicon tetrafluoride, is evolved as an anhydrous gas. In all of the thoretical silicon tetrafluoride (104 parts), and
this hydrogen fluoride generation step, the completeness a small amount (less than 10% of the theoretical), of the
of the hydrogen fluoride removal and the rate of evolu 60 hydrogen fluoride, are evolved. These gases are removed
tion depends upon temperature, retention time in the re from the vessel and recycled in a manner to be explained
actor and the amount of sulfuric acid present. Although later. The vented vessel containing the remaining fluoride
a contact time as long as about 2 hours may be used, it mixture (312 parts) comprising 43% potassium bisul
is preferred that the contact time be less than about 1 fate, 25% potassium bifluoride and 32% sulfuric acid
hour. The reaction temperatures may vary from about 65 (100%) is heated to 180° C. with agitation and main
80 C. to about 300° C. At temperatures above about tained at this temperature for about 60 minutes, during
300° C. sulfur trioxide begins to evolve. which time substantially all of the remaining hydrogen
fluoride of the mixture is evolved. The 36 parts of hydro
PREFERRED EMBODIMENT OF THE gen fluoride obtained contain less than 0.5% of water and
INVENTION essentially no silicon tetrafluoride. The recovered hydro
gen fluoride constitutes a yield of about 90% of theory.
An operating temperature of about 100 to 200 C. is 245 parts of potassium bisulfate (about 90% of theory)
preferred because of the corrosion problems that would remaining in the vented vessel after the hydrogen fluoride
develop at the higher temperatures. Under the conditions is evolved, is recycled for use in the succeeding run as the
within the preferred ranges specified, the evolved hydro potassium fluosilicate precipitant.
 3,689,216
5 6
The silicon tetrafluoride evolved from the reaction be tion step of the previous batch (Example 2) comprising
tween the dry KSiF6 and H2SO4 in the manner previously 245 parts of anhydrous KHSO4 and 88 parts of 100%
explained, is slowly sparged into a fluorocarbon-lined ves HSO 17 parts of make-up potassium sulfate are added,
sel (at a point near the bottom), containing 864 parts and the temperature maintained with agitation at 40 C.
of 11.1% fluosilicic acid maintained at 30° C. The slurry The precipitate of potassium fluorsilicate is filtered (to
is constantly circulated, by being removed from the bot thus recover 850 parts of 32% H2SO4), washed with 250
tom of the vessel and returned to the top, by employing a parts of water and dried in the kiln at 120° C. until the
slurry pump. A portion of the slurry is constantly drawn water content is less than 1%. The dry potassium fluo
from the system to a continuous filter wherein the silica silicate is next contacted with 392 parts of 100% sulfuric
cake is continuously removed and the filtrate is returned O acid in a fluorocarbon-lined agitated and vented vessel
to combine with the circulating slurry. This simultaneous for 8 minutes at a temperature maintained at 30° C. The
addition of SiF, circulation of the slurry, and removal of gases evolved at this point represent substantially the
precipitated SiO, is continued until the concentration of theoretical quantity of the hydrogen fluoride. These gases
the HSiF reaches 20%. About 20 parts of silica are are slowly bubbled through the 864 parts of 11.1% fluo
produced by the hydrolysis and removed by the continu silicic acid solution while the temperature is maintained
ous filter, leaving 960 parts of a 20% fluosilicic acid Solti at 30° C. The resulting 20 parts of silica produced during
tion. One half of this amount, namely 480 parts, are held the hydrolysis is separated by filtration, according to the
for recycle and the remaining 480 parts are diluted with continuous procedure described in Example 1, yielding
384 parts of water to again provide 864 parts of 11.1% 960 parts of clear 20% fluosilicic acid. One half of this
fluosilicic acid. This is held for use in the hydrolysis 20 quantity, or 480 parts, is recycled to the succeeding batch
step of the succeeding run, to convert the silicon tetra wherein it will be combined with a by-product 20% fluo
fluoride to additional fluosilicic acid. silicic acid which comprises the starting material. The
Example 2 other half, or 480 parts, is diluted with 384 parts of Water
480 parts of 20% fluosilicic acid recycled from Exam
to again provide 864 parts of 11.1% fluosilicic acid which
ple 1 are combined with 240 parts of 20% by-product
25 will be used in hydrolyzing the silicon tetrafluoride from
the following run. The by-product mixture remaining as a
fluosilicic acid to provide a combined 720 parts of 20% heel in the vented vessel after the evolution of the SiFa
fluosilicic acid containing 144 parts H2SiF6. This charge is totals 508 parts, comprising 27% KHSO4, 15% KHFa
passed into a fluorocarbon-lined agitated vessel and treated and 58% HSO4. This mixture is next brought to a ten
with 245 parts of anhydrous potassium bisulfate recycled 30 perature of 180° C., while applying a vacuum of 26 of
from the previous batch, 17 parts of make-up potassium mercury to the system. This temperature is maintained
sulfate and 86 parts of make-up 100% sulfuric acid. The for 10 minutes, during which time substantially all of the
temperature is maintained at 40° C. The precipitate of remaining hydrogen fluoride, amounting to 36 parts or
potassium fluosilicate is filtered (to thus recover 850 parts 90% of theory, is evolved. The use of reduced pressure
of 32% sulfuric acid as by-product), washed with Water does not measurably improve the yield, and as a result
and dried at 120° C. until its water content is less than of its application, much lower temperatures are required
1%. The dried potassium fluosilicate (220 parts) is next to condense the anhydrous HF product. The HF product
contacted with 294 parts of 100% sulfuric acid in a fluo removed contains less than 0.5% of water and essentially
rocarbon-lined agitated and vented vessel for 10 minutes no silicon tetrafluoride. The potassium bisulfate and sul
at a temperature maintained at 40° C. The gases evolved 40 furic acid mixture remaining in the vented vessel after
at this point represent substantially all of the theoretical removal of the hydrogen fluoride, which amounts to about
silicon tetrafluoride (104 parts) and a small amount, less 422 parts, or 90% of theory, is recycled to the first oper
than 10% of the theoretical, of hydrogen fluoride. These ation where it is held as the precipitant for the succeeding
gases are passed into the 864 parts of 11.1% fluosilicic batch of fluosilicic acid.
acid which was prepared during the previous run. 20 parts
of silica were filtered off, according to the continuous fil Example 4
tering procedure of Example 1, and discarded, leaving a 240 parts of by-product 20% fluosilicic acid containing
clear filtrate of 960 parts of 20% fluosilicic acid. One half
of this, 480 parts, is held for recycle to the Succeeding 48 parts HSiF6 are combined with 480 parts of 20% fluo
batch. The second portion of 480 parts is diluted with silicic acid containing 96 parts of HSiF6, which was re
384 parts of water to provide 864 parts of an 11.1% fluo cycled from the previous batch. This mixture comprising
silicic acid solution for the hydrolysis of silicon tetra 720 parts of 20% H2SiF6 is charged into a fluorocarbon
fluoride in the succeeding batch. The residual mixture lined agitated vessel. Here, the fluosilicic solution contain
remaining in the vented vessel after separation of the ing a total of 144 parts of HSiF6 is treated with the heel
silicon tetrafluoride totals 410 parts comprising 33% po from the HF generation step of the previous batch (Ex
tassium bisulfate, 19% potassium bifluoride and 4.8% 55 ample 3) comprising 245 parts of anhydrous KHSO4 and
sulfuric acid. Heat is next applied to the vented vessel 177 parts of 100% HSO4. 17 parts of potassium sulfate
bringing the temperature to 120° C., at which temperature are added as make-up. The batch is agitated and main
the mixture is maintained with agitation for 120 minutes. tained at 40° C. The precipitate of potassium fluosilicate
During this period, substantially all of the remaining po is filtered (to thus recover 939 parts of 38.7% HSO4),
tassium bifluoride is converted to hydrogen fluoride which 60 washed with about 250 parts of water and dried at 120°
is evolved. The removed hydrogen fluoride, which C. in a kiln until its water content is less than 1%. The
amounts to about 36 parts, represents a yield of about dried potassium fluosilicate is then contacted with 490
90%. It contains less than 0.5% of water and essentially parts of 100% sulfuric in a fluorocarbon-lined vented
no silicon tetrafluoride. 333 parts of potassium bisulfate vessel for 10 minutes at a temperature maintained at 30
and sulfuric acid remaining in the vented vessel after re C. The gases evolved at this point represent substantially
moval of the hydrogen fluoride (about 90% of theory) all of the theoretical silicon tetrafluoride and a small
are recycled for use as the potassium fluosilicate precipi amount, less than 10% of the theoretical, of hydrogen
tant in the succeeding batch. fluoride. These gases are hydrolyzed by being bubbled
Example 3 through the 864 parts of 11.1% fluosilicic acid which were
70 recycled from the previous batch. 20 parts of silica are
240 parts of by-product 20% fluosilicic acid containing precipitated, filtered, and discarded, using the method of
48 parts of the acid are combined with the 480 parts of continuous filtration described in Example 1. The filtrate.
20% fluosilicic acid recycled from the previous batch in a now consists of 960 parts of 20% fluosilicic acid which
fluorocarbon-lined agitated vessel. Here, the fluosilicic may be used to supplement the feed of 20% by-product
acid solution is treated with the heel from the HF genera 75 fiuosilicic acid in future batches. The vented vessel con
 3,689,216
7 3
taining the remaining residual by-product, totals about tion, as it is realized that changes therewithin are possible,
606 parts, and comprises essentially 22.5% KHSO4, 12.8% and it is further intended that each element recited in the
KHF and 64.7% H2SO4. This mixture is next heated to following claims is to be understood as referring to all
180 C. while bubbling a small amount of dry air (about equivalent elements for accomplishing substantially the
2 parts) through the mixture over a period of 10 minutes. Same results in substantially the same or equivalent man
The temperature and gas flow is maintained throughout ner, it being intended to cover the invention broadly in
this interval during which time substantially all of the Whatever form its principle may be utilized.
remaining hydrogen fluoride is evolved. About 510 parts What is claimed is:
comprising about 245 parts of potassium bisulfate and i. A process for producing gaseous anhydrous hydro
the balance as 100% sulfuric acid (about 90% of theory), O gen fluoride from an aqueous fluosilicic acid-containing
remain as heel in the vessel. This may be held for use as Solution, which comprises the steps of:
the precpitant in future batches in which potassium fluo (a) reacting said solution with a water-soluble in
silicate is to be precipitated from a fluosilicic acid solu organic alkali metal salt of sulfuric acid to form an
tion. About 36 parts of hydrogen fluoride containing less alkali metal fluosilicate and sulfuric acid;
than 0.5% moisture is obtained by condensation from the (b) separating said alkali metal fluosilicate from the
air stream as product, representing a yield of about 90% Sulfuric acid in an essentially anhydrous state;
of theory. The use of the dry air did not contribute (c) heating said fluosilicate at a temperature within the
measurably to the yield of hydrogen fluoride obtained, range of about 20 to 100° C. with about 1.5 to 6
and as a result of its use, extremely low temperatures were times the stoichiometric quantity of sulfuric acid,
required to condense the anhydrous HF product. 20 having a concentration of at least 90%, whereby
These examples demonstrate the fact that an anhydrous silicon tetrafluoride is evolved, leaving a fluoride
hydrogen fluoride is obtainable from by-product fluosilicic containing by-product comprising an alkali metal bi
acid in a process wherein potassium sulfate, sulfuric acid sulfate, an alkali metal bifluoride, and sulfuric acid;
and silicon tetrafluoride are recycled, so that in addition (d) heating said fluoride-containing by-product at a
to the raw material by-product fluosilicic acid, the only temperature between about 100 and 300° C. for a
auxiliary chemicals required are 10% sulfuric acid and a sufficient time to evolve substantially silicon tetra
Small amount of make-up potassium sulfate or bisulfate. fluoride-free hydrogen fluoride, whereby a residual
Furthermore, dilute Sulfuric acid is obtained as by-prod mixture of alkali metal bisulfate and sulfuric acid
luct, the strength of which depends on the quantity of sul remains.
furic acid chosen for the reaction with potassium fluo 30 2. The process of claim 1 wherein the alkali metal salt
silicate. The Sulfuric acid may be returned to the wet is selected from the group consisting of sodium and
process phosphoric acid plant for the acidulation of phos potassium.
phate rock. 3. The process of claim 1 wherein the alkali metal salt
This process provides an economic means of recovering is a potassium salt.
fluorine values which would otherwise present a pollution 4. The process of claim 1 wherein the alkali metal salt
problem to the phosphoric acid plant or the phosphate of sulfuric acid is selected from the group consisting of
fertilizer plant wherein they are produced. The alkali sulfate and bisulfate.
metal fluosilicate which is precipitated is preferably the 5. The process of claim 1 wherein the alkali metal
potassium salt. The sodium ion can also be used as the fluosilicate separated from the sulfuric acid is dried to a
precipitant but the solubility of sodium fluosilicate is con 40 moisture content of less than about 1.0%.
siderably higher in water and sulfuric acid than is the 6. The process of claim 1 wherein the silicon tetra
potassium salt. The energy requirement for the reaction fluoride evolved is hydrolyzed in an aqueous solution to
between Sodium fluosilicate and concentrated sulfuric acid form a fluosilicic acid solution and silica, separating the
is also appreciably higher than that between potassium precipitated silica, and treating the fluosilicic acid solution
fluosilicate and concentrated sulfuric; hence, the stated with the water-soluble inorganic alkali metal salt of
preference for the use of the potassium ion. In this pre Sulfuric acid to form the alkali metal fluosilicate.
cipitation step, it is unimportant whether the precipitant 7. The process of claim 1 in which the residual mixture
is added to the fluosilicic acid or the fluosilicic acid is of alkali metal bisulfate and sulfuric acid remaining after
added to the potassium sulfate or potassium bisulfate the evolution of the hydrogen fluoride, is recycled to
precipitant. The concentrated sulfuric acid added to the 50 react with the fluosilicic acid-containing solution.
essentially dry alkali metal fluosilicate should preferably 8. The process of claim 1 in which the sulfuric acid,
be present in a large excess (100% to 300%) to provide produced simultaneously with the alkali metal fluosilicate,
a liquid medium for the reaction. If the stoichiometric is used to treat phosphate rock to produce phosphoric acid
quantity is used, only a very narrow temperature range and gaseous SiF4 and preparing an aqueous fluosilicic
(20-40 C.) can be tolerated. Above this range, a con 55 acid-containing solution by passing the gaseous SiFi by
siderable amount of hydrogen fluoride is generated. When product into an aqueous solution.
an excess of sulfuric acid is present, broader temperature 9. The process of claim wherein the alkali metal of
ranges can be used such as 20 to 100° C., because the said fluoride-containing by-product comprises potassium.
hydrogen fluoride formed is retained by the excess acid. 10. The process of claim 1 wherein the alkali metal of
On the other hand, too large an excess of sulfuric is im 60 said residual mixture of alkali metal bisulfate comprises
practical because the recovery of hydrogen fluoride from potassium.
it, in the final reaction step, is difficult. 11. The process of claim 1 wherein the sulfuric acid
When an excess of sulfuric acid is used with the essen used throughout the process is essentially 100% sulfuric
tially dry alkali metal fluosilicate, the residual alkali metal acid.
bisulfate and sulfuric acid is substantially in a molten 65 12. The process of claim 6 wherein the aqueous solu
state. In recycling this residue, said residue may be added tion in which the silicon tetrafluoride is hydrolyzed is a
either in the molten or solid form to the fluosilicic acid dilute solution of fluosilicic acid.
solution. 13. The process of claim 12 wherein the aqueous fluo
The use of an applied partial vacuum, or of sweep silicic acid in which the silicon tetrafluoride is hydrolyzed
gases in the HF generation step is not recommended, as 70 has an initial concentration of between 5 and 15%
much lower temperatures are then required to condense HSiF6.
the anhydrous hydrogen fluoride product. 14. The process of claim 13 wherein the silicon tetra
While there have been described herein various em fluoride hydrolysis is continued until the strength of the
bodiments of the invention, the methods described are fluosilicic acid reaches a concentration of between 15 and
not to be understood as limiting the scope of the inven 5 30%.
 3,689,216
9 O
15. The process of claim 13 wherein the precipitated 3,256,061 6/1966 Tufts et al. -------- 23-205 X
silica formed during the hydrolysis is continuously re- 3,257,167 6/1966 Mohr et al. ---------- 23-153
moved from the slurry by circulating the slurry through FOREIGN PATENTS
separating means. 5 226,491 11/1925 Great Britain.
References Cited w
UNITED STATES PATENTS EDWARD STERN, Primary Examiner
1,247,165 11/1917 Stahl ---------------- 23-88 U.S. Cli, X.R.
33: A3; Exi.; E 10 423–332, 520, 320, 23-182 R, 182 V, 341
,354,1 i---------- --- o