United States Patent 0 "ice 3,167,391

Patented Jan. 26, 1965

r,

1 2
plied by steam coils or the like. As gaseous hydrogen
3,167,391 ?uoride is driven off, the absorber liquid lowerd in con
PURIFICATION OF ANHYDRGUS centration of HP is continually cycled back to absorb
HYDROGEN FLUORKDE more crude HF.
Carl F. Swinehart, University Heights, Ohio, assignor to It is common to include a certain percentage of sulfuric
The Harshaw Chemical Company, Cleveland, Ohio, a acid in the absorbing liquid for reducing the corrosiveness
corporation of Ulrio of aqueous hydrogen ?uoride and also to control hydrogen
No Drawing. Filed July 18, 1963, Ser. No. 296,12ii
8 Ciaims. (Cl. 23-153) ?uoride~water azeotrope. Sulfur trioxide (S03) additions
balanced with water additions conveniently control the
This invention relates to the preparation of anhydrous concentrations of the sulfuric acid.
hydrogen ?uoride and more Speci?cally to the prepara The hydrogen ?uoride coming from the reboiler is then
tion of high purity anhydrous hydrogen ?uoride. The scrubbed with liquidhydrogen ?uoride in one or more
invention further relates to the preparation of electronic stages to remove residual water vapor and mist from the
grade hydro?uoric acid. absorber liquid. As the gaseous hydrogen ?uoride is be
The distillation of aqueous hydrogen ?uoride to prepare ing scrubbed, it gradually associates to form di-, tri- and
a pure product is well known but little has been done to tetramolecules of hydrogen ?uoride (e.g., H2132, H3F3 and
upgrade commercially acceptable anhydrous hydrogen H4F4). The scrubbed gas after condensation is then passed
?uoride to a product of extreme purity. Within the last on to a stripper for substantial removal of any low boil
few years the demand for anhydrous hydrogen ?uoride of ing impurities present.
very high purity has increased tremendously, especially 20 The resulting product from this commonly used process,
with the advent of the exploitation of nuclear energy. while being perfectly acceptable as commercial grade, fails
Exemplary of such use is the preparation of uranium, to meet the rigid speci?cations of purity necessary for use
zirconium and beryllium ?uorides which are of primary in atomic energy. Moreover, the product is not uniformly
importance in the harnessing of nuclear energy, especial produced. Sometimes the product contains trace amounts
ly in the production of very pure uranium oxide for re 25 of phosphoric acid. Other times the product contains
actors. only'trace amounts of sulfuric acid or sulfurous acid.
The reaction vessels employed for the preparation of Sometimes silicon and boron are present in intolerable
these compounds are usually composed of nickel or amounts.
Inconel (nickel alloy). Because hydrogen ?uoride is It has now been discovered that the above-described
commonly prepared commercially from the mineral ?uor 30 process for preparing hydrogen ?uoride from a reaction
spar, sulfur impurities such as sulfur dioxide (S02) and which produces phosphorus and/ or sulfur impurities such
sulfur trioxide (S03) and phosphorus impurities such as as from the reaction of ?uorspar with sulfuric acid can be
P205 (which reacts with HBO and HF) are generated in modi?ed to uniformly prepare high purity anhydrous or
minor amounts with hydrogen ?uoride and are uniformly electronic grade hydrogen ?uoride by continually adding
present in commercial grade hydrogen ?uoride. The Water to the hydrogen ?uoride scrubbing liquid in minor
nickel or Inconel containers which are used as reaction controlled amounts. _
vessels for the preparation of uranium, zirconium and While the reasons for the surprising upgrading are not
beryllium ?uorides are rapidly corroded interstitially at de?nitely known, a possible explanation is as follows.
the high reaction temperature if there is any combined The hydrogen ?uoride which is distilled from an aque
or free sulfur in the hydrogen ?uoride and it is therefore ous acid solution containing high boiling impurities es
expedient that this element (sulfur) particularly be re pecially those comprising hexavalent sulfur and pentava
moved. In order ot reduce the rate of corrosion of the lent phosphorus are easily dehydrated when the residual
reaction vessels employed in the process of producing the water vapor is removed by scrubbing the distilled hydro
?uorides for use in atomic energy, the US. Government gen ?uoride gas with liquid anhydrous hydrogen ?uoride.
has set up speci?cations requiring that the sulfur content If these compounds are not prevented from being dehy
of high purity anhydrous hydrogen ?uoride be at a mini drated, they form compounds which are more volatile
mum and the water concentrations be maintained below than the hydrogen ?uoride, escape through the scrubbing
.04 percent by weight. stages and go on to a stripping operation. If the water
Such high purity anhydrous hydrogen ?uoride may be 50 content in the reboiler liquid drops below about 10 per
produced by passing a commercial grade hydrogen ?uoride cent, P2O5 in the hydrated form (H3PO4) dehydrates and
gas over argentic ?uoride which removes water and sulfur reacts with the hydrogen ?uoride to form the “low boiler,”
‘impurities (see for example US. Patent No. 2,526,585) phosphoryl ?uoride (P0133); and if the sulfuric acid mists
or by electrolyzing potassium hydrogen ?uoride to remove during the distillation, it is partially or completely dehy
water and subsequently fusing the product and distilling 55 drated in the scrubbing to form (S03) and/ or a sulfuryl
highly pure hydrogen ?uoride therefrom (see J. H. Simon, ?uoride. Further to being additional impurities, sulfur
Fluorine Chemistry, Academic Fress Inc. Publishers, New trioxide, sulfuryl ?uoride, and phosphoryl ?uoride react
York, 1950, p. 227). However, these procedures are too with water generated by sulfur dioxide after scrubbing but
expensive to be used as a practical procedure for the pro prior to or during the stripping of the hydrogen ?uoride
duction of high purity anhydrous hydrogen ?uoride and 60 gas. If there are signi?cant amounts of these impurities
much effort has been made to ?nd a relatively low cost present when water is generated, they combine with water
commercially feasible process. to form sulfuric acid and phosphoric acid respectively
The common and commercially feasible method of pre which, when formed at this point in the process, cannot
paring hydro?uoric acid is carried out by treating ?uorspar be removed.
with concentrated sulfuric acid in a retort which is heated The impurities, particularly hexavalent sulfur com
65 pounds and pentavalent phosphorus compounds, become
to temperatures of 150° C. to 300° C.
As the hydrogen fluoride gas along with the above men ionized in the scrubbing liquid and having very low vapor
tioned impurities is generated, it is continually absorbed pressure are cycled back to the reboiler or absorber liquid
by the absorbing liquid which contains a very large per and are consequently prevented from passing further into
centage of hydrogen ?uoride compared to that wln'ch can the system with the sulfur dioxide-containing’ hydrogen
be absorbed in the residence time of the liquid through an 70 ?uoride.
absorbing zone. Conventionally the absorber liquid is For the HF system conventional distillation procedures
channeled to a reboiler (distilling pot) where heat is ap operated without control of the water content are limited
 in their. ability to give an overall removal of phosphate, , C072, HZS, etc. can then bev stripped down to a low con
sulfate, etc. since the high boiling impurities escaping centration range without limiting complications.
with the hydrogen ?uoride become dehydrated to form Q Also, the'fugacity of the high boiler impurities in ion
compoundsmany of whichare more volatile or lower form is so, small that without’che‘mical conversion to low
boiling than thehydrogen ?uoride. ‘Sulfur dioxide (S02) fboilers only'one. or two*theoretical plates can reduce
which is‘a low boiler ‘and isalways‘present in the distilled their concentrationjin the" product far more e?ectively
hydrogen ?uoride in small or trace amounts, by reacting than a very large number of plates in ‘expelling the low
with thermetal walls of the‘reactor and/or hydrogen’ boiler dehydrating products, evenif. there was not some
?uoride gas, generates smallamount-s of. water in the reversal by'the chemical reactions with-traces ofv water
I product after it has been dehydrated substantially. 1 " 10 set free from. dehydrationiof S02 or reactions of it with
Not only is the generated water- undesirable as a con the metal'containers; Though all the compounds referred
taminant as such butit reacts with various low ‘boiling to here are well known, the" conversions and the way in
impurities POF3', S03 and the like which'result from " which they limit the puri?cation by‘ distillation have not
dehydration of high boiling impurities as H3PO4, H2804 ' previously been "recognizeddespite the fact that many
and thelike. ' > . ' ' " a V'millions of pounds of HF have been processed. Not only
In addition to phosphorus and sulfurimpurities, silicon, V ‘is the control of, the water content an important feature
and boron‘are likely to be present in combined form as ’ inthe process, but the product from it can be of far better
impurities in the generated gaseous hydrogen ?uoride. quality thanfrom other known processes. ‘' The range of
These impurities are arbitrarily either classi?ed as high " ratios in which water, holds or suppressesthe vaporiza-'
boiling impurities or as low boiling impurities using the 20. tion of sulfate, phosphate, and certain other impurities
boiling point of HF,~19.4° C., aslia division for the classi- ; is less than'500 partsrby weight of HF to 1 part of H20.
?cation. Possible impurities which maybe present in HF to'water ratios of the distilled hydrogen ?uoride gas
the crude hydrogen ?uoride gas'include some‘ or all of muchbelow 19:1 are not of ‘interest in the production
the following: . ‘of I. anhydrous hydrogen: ?uoride. unless the sulfuric‘ acid
, ’ r ‘

' exceeds 30 percent. , ' ’

The major contaminant removed by the process of this

> High Boiling ' Low Boiling '. ' '_invention is phosphorus in the vform of PO;3 ion and
' POF3. .Substantially all phosphate .ion will remain in,
HzSO4 _________ __; _____ __ d340° 0. S02 _____ __ —10°O. ‘ the absorbing liquid (acid inv HF system which is not be
H3190; ........... -_‘."_____ (1213. POF3.___- .—?r9.5 sub 30 ing treated‘ forv removal ,of impurities other than air)
' - ' . llmes. ' '

where over'10' percent H2O is'present. ,‘POF3, however,

HzPOaF _______________ __
BF3‘0.32HF-2.29HiO_____
>185 vac.
170 azeotrope.
'
_ ,
cannot be removed and is retained in the associator gas
HSO3F _ _ . _ _ _ _ _ __ _ 162.5. 28 _____ -_ ~59.6. (gas in the HFsystem which is being treated for-removal
HPOiFa ____ __
HzO-0.55HF_'_' _________ __
_- ___ 111. '
112 azeotrope.
" CO2 ____ __'_
H01--.
~78 sublimes.
— . v
of highboilin'g impurities) when less than 0.2 percent
‘ SiF4 ' ~95 sublunes. H2O is present in the scrubbing. liquid. The term ‘t‘scrub
(CHQQS ................ __ 37.3. BFg- —101. v
‘ Air_. —190.
~, bing liquid” as used herein de?nes liquids containing cer
Hi ______ -. —253. " tain- critical amounts of water which are contacted with
associatorgas in order'to purify the gas. The ‘reactions
taking place Within the systemare asv follows:
The impurities designated bothrHigh and Low Boiling t 40
are carried off ‘with the HF gas produced in a'varying, . - Po4—3-'|-'3H,F+'->H,Po4+3HF
7 H3PO4+HF—>H2PO3F+HZO
degree of contaminatiomdepending on the amounts of ' '5.
impurities present in sulfuric acid and the extent of reac
tion with the apparatus.’ >_R‘emoval of POPS from HP associator gas is effected by
‘No positive evidence for-So‘zFz’is foundjin the gases‘ I contacting the impureI-IF gas with scrubbing liquids con
usually generated, but its formation under abnormal ~ j taining water in quantities greater than 0.2 percent, the
conditions is not out of the question. Even so, small reaction probably being as follows:
amounts of, hexavalent sulfur generally appear in the
product, indicating volatilization as 'HSO3F, 805502132, ' POF3+2H2O+>VH2PO3FV+2HF '
or SOF4. None of the phosphorus compounds have been 50 H2PO3F isa high boiling ionizable impurity and will thus
found to have a lower valence thanq-i-S. t be removed from the 'HF-gas.
The process of the present invention is advantageously ' Control vof the water contentin the plates will suppress
carried out bycontactingthe impure HF gas with a series ' the phosphorus, that, heretoforeQwas present as a vola
of liquid scrubbing media containing controlled amounts tile compound,» so that they' are retained in the liquid
of water. The process starts with vapor wherein the‘I-pIF 5 phase as ionized ?uopho‘sphates and can be easily removed
to water‘ ratio is from 19:1 toiessentially anhydrous HF from the system. 1At the lo-wwater-contents which would
and contacting .it'ra plurality _of vtimes with a scrubbing I naturally prevailin the colu'mmphosphoric acid or ?uo-v
liquid containing “from "1 part hi9,’ to _1 part in 500' of phosphoric acid are convertedjto} the gaseous POF3; thus,
water (.10 percent to 0.2' percent water by weight).7 The ; any that/leaves the reb‘oile'rv goes on to contaminate the ‘1
non-aqueous, portion, of the} scrubbing‘ liquid’?v includes’ co product. Re?ux tends to dry the column, defeating rather.
those impurities which are present within an HF‘ genera thaniaiding'phosphat'e removal. .With wateradded‘to the
tion system. "Though the’ scrubbing’ liquids will bepre- v column, POP-'3 'for'mation‘is suppressed. Borates and
dominantly HF, they, in use,’ accumulate as much as two " sulfates behave in like. manner. 7
percent each of H2804 and H3PO4, 50 vp.p.mJB, and %] Substantially all of the phosphate leaves the retort, as
SiF4, and still function well.‘ The ratioof quantities of‘ 65 POI-l3, passing to'reboiler or absorber liquid acid where
scrubbing liquid to HF associator gas employed is de-. "I it accumulates. ,As long as at least. 10 percent to 18
pendent on variables such‘ as thetype of‘ equipment and percent H2O, depending onthe impurities, is present in
operating temperatures. The optimum ratios,’ however, the absorber or reboiler liquidgthe H3PO4'remains behind;
for any particular system are determinable by ‘a skilled but if the water content is lowered, such as, forexample
operator. ' Water concentration maintained, at the afore 70 by sulfurtrioxiyde (S03) coming over tothe reboiler,
mentioned ratios willprevent volatilization of phosphate ' POF3 again is formed, this time in vhigher concentrations
and yield a ‘gas that, when condensed, contains, as high which, though it may go onto tail, also puts troublesome
boiling impurities less than 1 p.p.m. PDQ-3,1 p.p.m. traces in’v the product. Regulating the water‘conc'entra- I
804-2, 1 p.p.'m.,boron,y-andj.012 percent H2O. tion in the absorber'o'r reboiler, liquid so that it is main
The low boiling group of impurities, SO27, SiF4, IjICl, tained, at a'concentration of at least about 10 percent
 3,167,391
5 . 6
and preferably at least about 18 percent is considered to may not be reduced su?iciently but the other impurities
be the preferred form or mode of the present invention. will be held back. As long as there is no more than
It is to be understood by those skilled in the art that 5 percent by weight water in the scrubbed product, it is
the water content should not exceed concentrations which considered to be outside of the range of water concen
would produce an azeotrope with the hydrogen ?uoride trations where the hydrogen ?uoride is referred to as aque
and/or the sulfuric acid present in the absorber liquid. ous hydrogen ?uoride. It is within the scope of the
In the preferred form of this invention, substantially no present invention to prepare such products wherein they
P0133 passes into the associator gas stages so all of the have reduced amounts of phosphorus and sulfur even
phosphate leaving the retort remains in or is returned though they have excessive water (up to 5 percent).
to the absorber liquid and does not reach the product. 10 Moreover, it is within the scope of the present inven
The HF productiproducedby the process of this in tion to add a further scrubbing step using anhydrous liq
vention may be controlled within limits such that there uid hydrogen ?uoride to reduce as far as possible the
is less than 1 p.p.m. of boron present, less than 1 p.p.m. water content in the hydrogen ?uoride gas. Once the
phosphorus expressed as phosphate present, less than 1 phosphorus and sulfur impurities have been removed by
p.p.m. hexavalent sulfur expressed as sulfate present, less 15 the initial scrubbing, the water content in the product can
than 20 p.p.m. of sulfur dioxide and less than 0.1 percent be reduced below 0.02 percent by the additional scrub
water. bing.
The following description of the ?ow sheet which will Use of all types of liquid gas contacting devices is con
clarify various embodiments of the invention is given for sidered as being within the scope of this invention. Liq
purposes of illustration and is not to be considered as limit 20 uid-gas contacting devices which have been found to be
ing the spirit and scope of the invention. especially suitable for purposes of this invention are
scrubbers, packed columns and bubble cap columns.
Example This application is a continuation-in—part of applica
HF gas (containing above mentioned impurities) from tion Serial No. 140,847, ?led September 26, 1961, and
retorts reacting ?uorspar and sulfuric acid is absorbed 25 now abandoned. ' ‘

in the absorber unit by a mixture of H2804 (56.4%), It is to be understood that the present invention in
H2O (25.6%) and HF (18%) which ?ows countercur cludes all of‘the embodiments thereof falling within the
rent to the gas. The resulting liquor then ?ows to the scope of the appended claims and is not to be limited by
reboiler where essentially anhydrous HF gas (plus vola the speci?c embodiments set forth above.
tile impurities-S02, SiF4, POF3, S03, etc.) is released 30 What is claimed is:
by heat and passed through a two-plate fractionating 1. In a process for the puri?cation of anhydrous hy
tower. The ?rst plate liquid concentration is maintained drogen ?uoride from the reaction between sulfuric acid
at 96.5% HF and 3.5% H20 by the addition of water and ?uorspar comprising e?ecting said reaction to pro
directly to the plate. The HF gas containing 0.07 H2O duce free gaseous hydrogen fluoride, absorbing said hy
in equilibrium with the liquid on Plate No. 1, then passes 35 drogen ?uoride gas in an aqueous acid solution, heating
to Plate No. 2 where the concentration is maintained at said solution containing the absorbed hydrogen ?uoride
99.65% HF and 0.35% E20 by the further addition of gas to distill said gaseous hydrogen ?uoride containing
water to this plate. HF gas containing 0.01% H2O or impurities comprising water vapor, pentavalent phospho
less in equilibrium with the liquid on Plate No. 2 then rus compounds and hexavalent sulfur compounds and
?ows from the tower at 20° C. to a condenser where the 40 contacting said hydrogen ?uoride gas with a scrubbing
resulting liquid then ?ows to storage for further puri?ca liquid consisting essentially of liquid hydrogen ?uoride,
tion. The concentration of H20 on the plates is deter the improvement comprising continually adding liquid
mined by conductivity readings on a cell positioned in water to said scrubbing liquid to maintain the water con
the liquid of each plate. centration between 1 part by weight water to 9 parts by
Liquid feed of essentially anhydrous HF is introduced weight hydrogen ?uoride and 1 part by weight water to
on Plate No. 2 from the condenser and is of the same 500 parts by weight hydrogen ?uoride whereby to retain
composition as the liuqid that ?ows to storage prior to said phosphorus and said sulfur in said scrubbing liquid
entering the stripping apparatus for S02 and Sin removal. and to reduce the phosphorus content and the sulfur con
At this point the liquid will test less than 1 ppm. PO.{-3, tent of said gaseous hydrogen ?uoride and to recover
1 p.p.m. S04v2, 1 p.p.m. B, and .01 percent H20. After substantially pure anhydrous hydrogen ?uoride.
stripping, the water content may rise to .02 percent but 2. The process of claim 1 wherein said acid solution
the S02 and Sin can easily be reduced to under 10 p.p.m. comprises at least 10 percent by weight water.
each and HCl to less than 1 p.p.m. without change in 3. The process of claim 1 wherein said acid solution
the P044’, S052 and B contents. comprises sulfuric acid and at least about 18 percent by
Reboiler liquid which has been depleted of dissolved weight water.
HP is circulated back to the absorber tower after passing 4. The process of claim 1 wherein said scrubbing liq
through a heat exchanger to cool to the required tempera uid comprises from about .35 percent by weight water
ture. Any increase of water content in the reboiler liquid to about 3 .5 percent by weight water.
is converted to sulfuric acid by the addition of S03 to the5. The process of claim 1 wherein said gas is con
stream ?owing back to the absorber tower. The volume 60 tacted with a second scrubbing liquid comprising from
of this liquor is kept constant by continuous removal of about 0.2 percent to about 0.35 percent by weight water
a portion which also removes phosphorus which has been and is passed through a stripper to recover anhydrous
retained in the liquid phase. hydrogen ?uoride.
It should be understood that water content can be con 6. In a process for puri?cation of anhydrous HF in
trolled by appropriate use of that water which is already 65 order to reduce the concentration of sulfur and phosphorus
within the HF generation system as well as by addition impurities present only in trace amounts, comprising the
from an external source of water. Water content in the steps of: (a) absorbing a high purity vapor phase hydrogen
associator apparatus is conveniently measured and regu ?uoride into a liquid phase mixture of H2804, H20 and
lated by conductivity cells. The conductivity cells can HF, phosphoric acid and traces of other impurities, (b)
be used to regulate the reflux or feed back of scrubbing 70 H2O being present to the extent of at least 10 percent to
liquid, thereby controlling the Water ratio, or they may 18 percent, based on the weight of said liquid phase (0)
be used to determine the injection of water from an ex and phosphoric acid being present but not above 2 percent
ternal source. in said liquid phase, the balance being substantially all
If excessive amounts of water are added to the scrubbing HF and H2804 (d) heating said liquid phase to drive off
liquid, the water content of the distilled hydrogen ?uoride 75 a second vapor phase containing hydrogen ?uoride and
 31167591
' 8
water in concentration ratio from. 19 to 1 to essentially ' ' ' ride, Vabsonbing-said hydrogen?uoride-gas in'anr aqueous
anhydrous, (e) passing said second vapor phase in con acid ‘solution, heating said {solution . containing the ab
tact with a scrubbing liquid comp'rising'liquid water and ' sorbed hydrogen ?uoride gas ‘to distill‘ said gaseous hydro
hydrogen ‘?uoride wherein said’ liquid waterris added H Q g'erij-?uoridecontainin'g impurities "com-prising water va
continually to maintain the water to hydrogen ?uoride ,por', penta'val‘ent phosphorus'compounds and hexavalent
concentration ratio of ~1 t0'9 to 1 to 500, and (f) recov~~ - ' sulfur compounds 'and contactingv said-hydrogen ?uoride
ering from’ the resulting material a more highly puri?ed gas with a scrubbing liquid consisting lessentiallyrof liquid
anhydrous hydrogen ?uoride wherebys'aid sulfur and‘ hydrogen ?uoride, the improvement cOm'prising-continw.
phosphorus impurities are retained in said 'scrubbingrrliq- a’ ally adding liquid water to said scrubbing liquid to main
uid; ” ' 10 tain theiwater concentration between l'part by weight
p 7. ha process for the puri?cation ,of, anhydrous)’ hy- ’ ' water to _9 :parts ' by weight‘ hydrogen'l?uoride vand 1 part
'drogen ?uoride gas from hydrogen ?uoride gas having a ' by weight water to, 500 parts by weightjhydrogen ?uoride
hydrogen ?uoride to Water concentrationof from 19 (to 1 : V whereby to tretaiin ‘said; phosphorus and‘ said sulfur in
to essentially anhydrous an’dcontaining pentavalent phos-‘ said scrubbing liquid and to reducerthe phosphorus con
phorus impurities comprising passing said gas'through at tent and the, sulfur content of‘ said gaseous hydrogen
‘least one scrubbing stage wherein said gas is scrubbed v . ?uoride and 'to'recoverzsubstan'tially pure-anhydroushy
with liquid anhydrous hydrogen ?uoride, the improvement drogen ?uoride. ' > v
water to retain said phosphorus, impuritiesin saiduscrub
bing liquid fat-least at one of said’ stages (to?maintainthe v I <_ 2 References
UNITED STATES
Cited by the
PATENTS
Examiner
water concentration between 1 part by weight water to9 20. .
parts by Weight‘ hydrogen ?uoridevand 1 part byrweightr
water to retain said phosphorus impurities in'said scrub
bing liquid and to 500 parts by weight hydrogen‘ ?uoride.
whereby to reduce the phosphorus content‘ of said. gas
and_to recover‘ substantially-pure anhydroust’hydroge'n; ; , g f ‘FOREIGN-PATENTS, ,
8. In a process for the puri?cation of hydrogen ?uoride / 289,333 “7/29 >Great'Britain," 1 ' r v
which comprises generating free gaseousthydr'ogen ?uo MAURICE ‘A, 'BVRINDISI‘, Primary ‘Examiner.
 UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No. 3, 167 ,391 January 26, 1965
Carl F. Swinehart

It is hereby certified that error appears in the above numbered pat

ent requiring correction and that the said Letters Patent should read as
corrected below.

Column 2, line 2, for "lowerd" read —— lowered ——; column

5, line 47, for "liuqid" read —— liquid ——; column 7, lines
11 to 26, claim 7 should appear as shown below instead of as
in the patent:
7. In a process for the purification of
anhydrous hydrogen fluoride gas from hydrogen
fluoride gas having a hydrogen fluoride to water
concentration of from 19 to l to essentially
anhydrous and containing pentavalent phosphorus
impurities comprising passing said gas through at
least one scrubbing stage wherein said gas is
scrubbed with liquid anhydrous hydrogen fluoride
the improvement comprising continually adding
liquid water to said scrubbing liquid at least at
one of said stages to maintain the water concen
tration between 1 part by weight water to 9 parts
by weight hydrogen fluoride and 1 part by weight
water to 500 parts by weight hydrogen fluoride
whereby to retain said phosphorus‘ impurities in said
scrubbing liquid and to reduce the phosphorus
Content‘o‘f said'gas and to recover substantially
pure anhydrous hydrogen fluoride.
Signed and sealed this 13th day of July 1965,

(SEAL),
Attes't:
‘ ERNEST W. SWIDER EDWARD J. BRENNER
Attesting Officer Commissioner of Patents