Feb. 24, 1948.

2,436,432

--F. yl.. HUNTER

METHOD FOR MAKING HYDROCHLORIC ACID
Filed Feb. 26, 1943

lli.;
36

[f6

4X

if

lul-lul.'
F/E. 1
INVENTOR
BY

ATTORNEY

2,436s432

Patented Feb. 24, 1948

UNITED ,STATES PATENT n(lFl-"-ICE

2,436,432
METHODY FOR MAKING 'HYDROCHLORIC
ACID

Frederick L. Hunter,y Lake B'liiil", vIll., assigjnornto

Eansteel .Metallurgical yCorporation, North Chif
cago, Ill., Ya corporation of 'New `York

Applicationl February 26, I1943, Serial-No. @4717 219

4rl5 Claims. (Cl. V23m-,154.)

1
This invention relates toea fmethod Afor treat
ing gases with liquids or for treating liquids-'with
gases and ,to apparatus Vfor .practising `theirneth

The solution of Vhydrochloric :acid :gas in water

is dependent upon the following conditions:
(ai) .The temperature n-fithe gas and the liquid;

(b.) The concentrationyof the gas in the gases

to ibe scrubbed and 4theeconoentration .of .the acid
liquid yto be produced;
ent invention :ma-y best :be rdescrbed by reference
-(c) Thetime -of con-tact, between .the gas and
to vits application >to various :common Iand well
the liquid, the average-,distance between the gas
known examples fof :suc-h treatments.
eous particles and the liquid particles, the thick
The Vpresen-t v-in-veri-.tion-is 'based :upon . the :dis
covery that rexothermiccreactions between gases 10 ness of ythe yliquid flayerfandits movement internal
and asa whole.
'
and liquids may be ca-rriedyout withggreat `-facil-ity
In Lthe vpracticeof the .invention lthese factors
by Ypassing _the reacting ~-substances downwardly
are msome of them >-more and somebf `thorn much
in .concurrent flow. .Advantageously the liquid
less important thanr in .the practice `of .prior :art
is passed down a vthermally >:conductive wall
while the heat :of reaction l.isremovecl by passing 15 methods. >In generaL-howeven so far-las `has been
observed,'these are the principal .factors involved
a suitable heat exchange medium .up.the-foplaiosite
and .they -are allimportant .to some .degree in
side-of the wall,
determining the success of any system.
Where .the -gas contains y.unreacting compo
In the foregoing lparagrapl'ls .and in the re
nents, it is gener-ally desired to remove wthe gas
from 'contactar-ith the> liquid before iall the-react 20 mainder-of .the speciflication,l reference is 4made to
the lsolubility 4vof Ahydrochloric acidgas in water.
ing component has .beenconsumed The residual
Itis the _commonlyaccepted view-that no chemi
body of gas may .then be passed incountercurrent
cal reaction takesplace when vthe :gas is >con-.
manner through a scrubbing towerand the inert
tacted `with water. Some observations lead Vto
portion vented from the top of 'the tower. Ad
vantageously, .the scrubbing .liquid may be the 25 the Lbelief .that ,perhaps lthere `is .areaction ltaking
place, 4but becauseof the .uncertainty .which still
reacting liquid and the partially >.reacted liquid
exists .it is simpler tofadopt the conventionally
withdrawn from the.scrfulibing towermay-beused
held view without, .however,.,express limitation in
as Vthe initial materialin .the .principal reaction.
any wayby Aeither view.
According to e, modification, also applicable
Three `general methods .suggest themselves forl
where the gas contains .an inert component, .after 30
bringing about intimate contactl between ,gasand
removal of thegasirom theeontact zone, a small
absorbing liquid:
_
quant-ity of :rich gas is passed -countercurrent to
(a) Spraying the liquid into the gas;
the reacted liquid to render the .reaction more
"(b) Bubbling `.the .gas .through .the liquid;
complete. :It is advantageous in such .case to
=(c) -Contact Lbetween liquid .and gas byadis
35
locate :the two .reaction zones so-that the `same
tributionof .the-liquid .over relatively .large sur
gas dischargel may be employed for --bottiquanti
faces.
ties of gas.
l
A
>
The first :method mentioned ,above has not
According to Aa _further ;mo.clicatio_n, l_the raw
been found preadily .practical .or -eicient in the
gas zmay be 'delivered to the @reaction y.zone at
spaced gpoints 4along the down iowing, lm so 40 case of lhydrochloric .acid because :of the high
heat of solutionaand the-dililculty lthat has been
that the reaction may take place more even-ly.
encountered in 'removing-the .heat generated. `By
This invention has been found :especially
this rstmethod-theproduction ,of-.acid of other
adapted-for themanufacture of hydrochlorciacld
than .flovvr strength has not ,beentknown The
from hydrogenfchlor-ideand Water.
.The solution roi hydrochloric acid -gas -ln Water 45 second method, while in theory being satisfactory
from the standpoint .otproducing acid of good
is one which is .highly exothermc and the `solu
strength and thesuccessiul `removalof heat, also
bility oi the gasfis inversely,proportional tofthe

od. The treatment ,of gases with ~liquids `or lof

liquids with gases is quite common, and themes

temperature. Asanexample-of this, it ispos

sible Aat `a '-temperatu'reof0 >C. to dissolve .over

500 volumes .ci V,tlfielgas in 1 :volume .of water,

while :at a :temperature oi `-160"_(3`.. less than 350
volumes foi'gas canrbe dissolvedin lvolume of
water and at a :temperaturefoif-l-l C, on'ygabout
160 volumes. may' be :retained .by f1 volume Qi
water.

'

liasproved 4to-beimpractical because of :the highly

corrosive :nature -of the gas -to .be handled vand
so the AVhighypressureencountered. Thus, there is
left only thethirdmethod, or the` direct _exposure
of the liquid to ther-:easter fthe satisfactory pro
duction of high-.strengthhydrochloricacid. This
method of direct exposure of the liquid to thegas

5.5 ,and absorption `through ...an interface lends itself

2,436,432

especially to situations wherever the proportion

at the instant'it is generated and at the exact

locality of its generation;

of liquid in the body to the interface is kept

small.
At the present time two general methods are
used for bringing about this intimate contact be
tween the soluble gas and the absorbing liquid.
One of these methods employs glass, stoneware

(b) Spreading out the liquid in a thin lm so

that the heat at the gas interface can be removed
as rapidly as that from the solid interface;
(c) Intimate contact of the gas and the ab

sorbing liquid;

or fused silica Vessels (tourills or S-bends) so de

(d) Cooling of the acid produced to a tem

signed that a relatively large surface of liquid

perature below the boiling point for the particu

lar concentration;

is exposed to the gas. These vessels are also def Ym

signed for cooling. The second method uses the
(e) Continuous and automatic regulation of
vertical tower with a suitable packing material i Athe flow of water to the absorber chamber and
over which the absorbing liquid is passed, thus A of the cooling water to maintain constant condi
exposing extremely large surfaces of absorbing . tions in the absorber which always respond to
liquid to the gas. This latter method is used
the rate of introduction of hydrogen chloride;
extensively where gas concentrations are low.
(f) A source of weak hydrochloric acid in
The tourill type of pant is satisfactory for the
quantityV suilicient tov provide all of the water

production of the higher strengths of acid, and

. required to take up the hydrogen chloride, the

the design of the apparatus is such as to allow

presence of a small amount of hydrogen chloride

satisfactory cooling and surface exposure of the 20 7n solution in the make water greatly facili

absorbing liquid to the gases. There is, however,

the objection that this plant requires a consider
able oor space and necessitates many connec
tions to maintain a circulation of both liquid and
gas. Another diiculty commonly encounteredrin
this tvp@ of plant is the necessity for maintaining
a rather large volume of acid in order to balance
the differences in concentration of acid produced
from time to time. In most plants either the
flow of gas or the percentage of hydrogen chlo
ride in the gas is constantly fluctuating and on

tating the v'absorption-'of additional hydrogen

chloride;

it

'

is withdrawn at the bottom. In cold weather

little cooling vis attempted, since the Yplant is
usually given free access to open air in order to
provideV adequate ventilation in the event of

break-down. In, warmer weather cooling is ac

complished by allowing water to shower down
_ _

_'

be set forth as the description proceeds. There

is provided tantalum apparatus taking advantage
of these unique properties, which apparatus en-ables the avoidance of many> of the difficulties
heretofore attendant upon the manufacture of
strong hydrochloric acid.
In connection with the provision of said appa

the top of the unit. while the gas is introduced

at or near the bottom l'flowing countercurrent to (o
the water supply( Finished acid is withdrawn at
the bottom. It has also been proposed to operate
a plantof this type by introducing the gas near
the top of the unit so that it flows in the same _
direction as the water. In such case also the acid 45

produced.

columbium and alloys of these two metals are"

According to the usual method of operation of

this plant, _the supply of water is introduced at

over the apparatus,

further contact with raw gas as rapidly as it is

uniquely suited'fo'r the construction of apparatus

for the manufacture of hydrochloric acid. A
io number of these unusually desirable qualities will

matic _regulation has not _been found readily

applicable. _It is an object of this invention to
afford a method which >is'readily susceptible of
'

It has been found that the metals tantalum,

this account careful regulation is'required. Auto

automatic regulation.

(y) Removal of the cooled strong acid from

The tower- hasbeen used extensively for the

ratus, it hasbeen'discover'ed that it 'functions

most >satisfactorily when operated contrary to

many of the accepted practices known to the art,

and to theend of taking best advantage of theI

properties of'this new -material of construction,
there has been devised a new method of treating
acid gases.

_ It is the more -commonly accepted practice in-the art to operate absorbers on the countercur
rent now principle, supplying the water or weak
acid to the upper part of the apparatus and the
gasto the -lower part of the apparatus, withdraw
ing the finished acid at the base of the apparatus.
When a high gas velocity is encountered, there isA
considerable disturbance of the liquid flow be
cause of the tendency of the gas to blow the liquid `
olf the cooling surface. When the weak acid and
raw gas are flowed concurrently, it has been
found that there is much less tendency for the

absorption ofhydrochloric acid gas, particularly

where the concentration of hydrogen chloride in
the gas is not high, but from this it is difllcult to>

produce acids of the higher strengths, as __it is not

nlm to be disturbed by high gas velocities.

practical to construct absorption -towers with

'_ In accordance with the present invention` the
suiiicient cooling to keepthe tower temperature _ absorption is effected by passing the absorbing

down to a point where high strength acid is pro 60 liquid downwardly on a thermally Vconductive wall
duced. i So far as is known, all'tower plants op-`
concurfre'rit` with the hydrogen chloride containing
eraterin a _countercurrent manner, that is, the
gas. The heat of reaction-is removed by passing

water is supplied at _the top and withdrawn as

acid at the bottom and the gas is"introduced near
the bottom.

'

'

a suitable heat exchange medium up the opposite'

65

The new absorber possesses particular merit, in

that it eliminates external cooling and recircula-

tion, thereby making it possible to produce high

strength acid continuously, provided cooling>

side of the wall'.__ In those instances where the'

gas containsunreactive constituents, it is gener
ally desired to remove the gas from contact with
the liquid beforeall of the hydrogen chloride has
been absorbed.- The residual gas may then be
passed through a scrubbing tower countercurrent

water of the necessary Ytemperature is available.

to the ilow'of water, and the liquid drawn" from

The conditions which are favorable to continu

ous absorption of hydrochloric acid gas and rap
idly increasing the strength -of solution are as

the scrubbingtowerfmay be used-advantageously

follows;

'

(a) Removal of the heat of reaction or solution 75

as the initial'absorbin'gliduid in the principal

absorption' or reaction. The inert constituents
of the ga's are vented from the top of the tower.l

In accordance with a, modification, also ap-l

plicablefwherethehydrogenchloridegascontains
mertrsconstituents, after- removal ofthe gas. from

the contact. zone, aqua-ntity-.of gasarichin hydro

gen .. chloride
passed v.countercurrent through
the . reacted . liquid. to .render the reaction more
complete. "Itis . advantageous .in vsuch case to: 1o
catethe two zreactionnzones. yso that the vsame .gas

dischargefmay be employed. for both ,A quantities .of

gas.

temperature-in .-theabsorbing section -or column;

whichi--nal'temperature is dependent upon the
optimum temperatures of vabsorption for the
character'ifor. :gas employed. The inlet tothe
jacketv isv .provided with an automatic valve 4S

which 4is controlled by `thermo~regulator il inthe

outlet line in order-to maintain the outgoingvacid
at -the appropriate .anddesircd temperature. The
cooled acid isfthen withdrawn to storage or for

vAccording Ato aurther modification, the . raw 10 useat 48; It has :been found desirable where there

hydrogen .chloride l.containing gas may. be deliv

ered tothe reaction zone'at spaced `'points .along
the down flowing -film; of absorbing liquidl vso `that
the reaction may takefplacer more evenly.
This invention can. .be more fully appreciated
and illustratedfby referenceto the accompanying

drawings; wherein there is illustrated' Vdiagram

maticallyapparatus which. forms two embodi
ments of the invention.`
Fig. 1 is. a. partially schematic, partially sec
tional elevati'on of. one vvembodiment,of the appara

tus of :this invention.

Fig.2~?is a partiallyschematic, partially sec
tional elevation-oi?v another embodiment ofthe ap..
paratus ofi this. invention.
Referring to Fig. l, .hydrogen .chloride enter
ing through inlet lil passes through upper bon
net 1.6 down; the absorber column walll it. The
wall letifis-.in thex?orm of.. a Agenerally;vertical. tube

are .appreciable .quantities of inert dilo-.ent gas .to

halt the absorption operation while there is yet
hydrogen: chloride available. Since the distribu-v
tion of hydrogen >chloride betweenl gas and liquid
tendstoreach an equilibrium near the end .of the
travel of the gas `down the column, .itis obvious
that to remove all of the hydrogen chloride from
the gas in a reasonable-sized apparatus it would
befnecessary to maintain the finished acid at a

relatively lovv concentration.

Furthermore, in

order to -cooi the linished acid and maintain it

cool, it is -des'iralbleto maintain it out of contact
with hot .hydrogen .chloride gas or vapor which
tends to heat up the acid. Accordingly, at about
the pointV where-'the acid passes from the absorp
tion chamber to the `temperature conditioningl
chamber,I the unabsorbed gas passes through vent
luf-in. the gas separator tube 38 which is located

conoentricallyA within the temperature condition~

and is. advantageously -'formed from relatively-thin 30 ing chamber.
The gas passes through tuber and tailing gas
tantalum, columbium or alloys predominating, in

liquididistributor ring.24. at the top of column M..

line-64 tolgas scrubbing tower 5d. Here the gases

meet 4"the down-ilow-ing make water sup-ply from
56 which scrubs out the last traces of hydrogen
chloride to form weak hydrochloric acid, the ab
sorbing medi-um. The unabsorbed gases are re

The .arrangement .of these parts vis such .as to

moved by way of line ed in any suitable manner;

one. or bothmetals. Weak- hydrochloric acid :is

delivered 4to the .upper bonnet Vby wayA of inlet i8,
collecting ln pool 28. Thence it Apasses under gas
trap and water baffle Z2 .and over the notched 35

The `iiow of make water may be regulated by

Valve 5G which is responsive to the speoi?ic gravity
controller 62 in the finished acid line d3. As the
40
thesdewallof .column I4. Serrations of V-shape
speciiic vgravity oi the finished acid varies from
have the additional advantage of accommodating.
the concentration which has been predetermined,
a .considerable Variationin the volume of. flow with
more or less make water is adnited to the
desired. exibility vof operation. Cooling water is
tower 5t to bring the concentration back in line
suppliedto the jacket 26 by inlet lines and mani
fold 28 and controlled directly by cooling water 45 with the predetermined value. Line ed also Vhas
the function of accommodating any instantaneous
distributing valves 32. The water escapes to the
surge in the absorber proper, enabling thea`o~Y
drain at 30.
sorber to lbe designed for continuous operation at
Temperatures from amoderate high of about
a sustained level without unnecessary capacity
180 F. down to 40 Il. andfbelow are favorable lto
which would be required only in the event of an
the initial vsteps of theabsorption of hydrogen
occasional surge.
i
chloriclein` theweak acid, but as the concentra
The grooves or beads tit rolled into the thin
tion increases the temperature lmust be reducedl
tantaluin wall hl. of the absorber column tend to
to keep the solution from boilingl and decompos
assist
promo-ting oven .distribution over the
ing. >The flow-of cooling water, therefore, is pre-t
erably- regulated 'by the nal temperature ofthe 55 entire wall area, as well as providing additional
rigidity for supporting thewall. Even distribu
cooling water'as it emerges from the jacket. 'This
tion may .be further improved by thoroughly
regulation is effected by thermo-regulator 3f-1l
cleaning the surface of the tantalum, particular
which controls the action of valve 36 in line 2%.
care beingl exercised to remove grease and oil
An increase in the amount Yof hydrogen chloride
introduced results >in .an increase in the outlet 60 films. Valves 5t are provided to drain the Vapl
paratus when notvin use.
l
temperature of the .cooling water. >The thermo~
.Several niodications which have been found
regulator Si and valve 3E are so connectedlthat-lan
desirablev in certain insta ces are shownv in Fig.'v
increase in lthe Aoutlet temperature >causes valve
2. According-.to th' modification, the` gas en-y
36 to-fbe opened, thereby-increasing ~the ow -of
water. The object .of- valves 32 Els toY distribute 65 ters the gas distrib .tor tube i2 located wit-hin
'ion tube it. The
the `admission oi` cooling >waterto the jacket so
hydrogen chloride passes tn ough the distribu
thatv zones of rapid absorption, which `tend .to
tor .tube
by. .means of a series of holes i3 and
vary somewhat with the amount of `inertgas .prese

promote quiescence of the -pool and to provide

for the -formation of a plurality of streams `dov/.n

ent in the inta-ke gas, may be- maintained ata

is therebypermitted- to come in Contact with a

suitably low temperature. In general .it has. been 70 falling :film of liquid on the inner surface of the.
absorption tube ill. By modi-.tying the size and
found that it is desirable to introduce most ot
area of vthe holes
it is possible to seiectively.
the .water through the-lowestofithese valves.
control the ratel of bsorption n1ong the wall of
The lower'part ofthe column is providedfWi-th
the tubedilt, .as
1 red. It
preferred to con-`
an" independent :cooling jacket -4'51 to reduce the
struct the distributor .tubein two or more sec-1
temperaturenf 'etheziinished acidv 'from the final

2,436,432

tions, the upper section I2 being made of thin

tantalum which, because of its great strength,
occupies comparatively little space. As the gas
passes out through the upper holes in the dis
tributor tube and is reduced in volume, it is

8
with other metals, tantalum, besides being'prac'
tically non-corrodible, is one of the stronger
puremetals, having approximately the same me
chanical properties as mild steel. Columbium

and tantalum-columbium alloys also possess

these same desirable properties and it is, there
fore, to be understood that wherever the use of
tantalum is suggested it is meant to imply that
thereof. After the gas has passed down a fair f
these equivalent metals may be substituted.
portion of the column, a separator plug I5 is 10
As examples of the results which may be
inserted in the distributor tube in order to force
achieved by the practice of the invention when
all of the gas out into intimate contact with the
employed in the manufacture of hydrochloric
failing lm of liquid. The gas and water then
acid, the following conditions are typical:
pass through an equilibrium section I'I of the
Hot gases containing about 90% hydrochloric
absorption tube, in which section the gas and 15 acid are supplied to the absorber at a tempera
liquid tend to reach equilibrium conditions. In
ture of from 90 to 120 F., the gases being sup
the construction shown in Fig. 2 holes @0' pro
plied at the rate of from about 200 pounds to
vided in the lower section of the distributor I2
about 350 pounds per hour to a column 4 inches
permit the unabsorbed gas to pass out through
in diameter and 6 feet long. Cooling water en
tube 38 into the tailing as line 64.
ters at about 75 F. and may be removed at a
Another modification shown in Fig. 2 may be 20 temperature not less than 140 F. Very satisfac
employed to increase the concentration of the
tory results are obtained by operating the'. out-.i
acid when the concentration of hydrogen chlo~
let between 165 and 170 F. The finished acid,
ride inthe gas supplied at I0 is low. A rela
depending upon the requirements, is withdrawn
tively small amount of gas rich in hydrogen
at
concentrations of 12 to 24 B. The supply
25
chloride is supplied to the line 6I. Line 4I by
of make water is varied according to the
branches 42 supplies this gas to a number of
strength of acid required.
'
inlets in tube 38 to a low point in the absorption
Where it is desired to produce very strong acid
tube below tailing gas outlets 0'. The high
in the apparatus described in the previous exam- concentration of hydrogen chloride in the gas
at this point tends to throw the equilibrium over 30 ple, the cooling water is used as cold as may be
obtained, or, if it is available, cold brine is used
so that the acid produced is of considerably
at temperatures of about 20 to 40 F. The cool
greater concentration. The unabsorbed portion
ing liquid outlet temperature is maintained as
of the rich gas travels upward along the liquid
nlm and out through the tailing gas vents 40'. 35 low as is economical. The concentration of the
finished acid is relatively high, only a few per
This slightly increases the proportion of hydro
cent below the equilibrium percentage corre
gen chloride in the tailing gas, but since the
spending to the cooling liquid temperature. If
amount of rich gas supplied to line 4I is rela
the column is operated below -atmospheric tem
tively small, not exceeding 30% of the total `eas
supplied, the amount of hydrogen chloride in 40 perature, it will be necessary to store the acid
under super-atmospheric pressure to prevent de
the tailing gas will not exceed that portion which
composition.
.
is necessary to supply weak acid to inlet I8. In
This type of operation may be employed to
Fig. 2 the cooling medium inlets, corresponding
increase the capacity of the column to take care
to those of Fig. 1 supplied by the manifold 28,
are indicated by the numeral 28 and the con 45 of temporary increase in the supply of gas or
demand for finished acid. The tantalum wall is
duits, corresponding to those shown in Fig. 1
capable of transmitting such a relatively large
as provided with valves 6 and 4T, are designat
amount of heat that it is necessary only- vto con
ed in Fig. 2 by the numerals 46 and 4l' respec
satisfactory to increase the space occupied by
the distributor tube by using a less expensive
non-metallic material for the lower portion

tively.

duct it away in order to accommodate an in

When the system is producing acid of a con 50 creased now of gas. The finished acid may be
diluted with water in order to avoid the necessity
centration lower than 20.5 B., the tower can be
for. storage under elevated pressure.
~
permitted to boil Without fear of losing an ex
cess of hydrochloric acid vapor through the
When the invention is operated according to
vent, the reason being that the concentration of
the foregoing disclosure, such modication being
the tower acid is below that of a constant-boil 55 permissible as would be obvious to one skilled
ing mixture. At temperatures up to 105 C.
in the art, several important advantages will re
water is evolved upon boiling instead of acid.
sult therefrom. One of the major advantages
Attempts to produce stronger acid under the
which proceeds from the use of the method and
same conditions will result in the loss of acid
apparatus of my invention is the substantial re
through the exhaust gas.
`
60 duction in the size of the equipment necessary
Tantalum is peculiarly suitable as a material
to handle a given through-put of hydrochloric
of construction ' in acid-manufacturing appa

acidgas.

'

ratus._ Its resistance to corrosive agents, partic

ularly hydrochloric acid, at relatively low tem

A further advantage is the freedom from oper-ating shutdowns, which results from the use of
peratures is so great that it may be said to have 65 a lighter and lessfragile material of construction.
substantially infinite life. Contrasted with ce
Even if the saving in the cost of replacing ceramic
ramic materials, such as glass or fused silica,.it
material were wholly neglected, the use of the
has- the high heat transfer qualities character
new absorber would still be justied for the rea
istic of the metals. Heat transfer rates involv
sonthat costly and annoying shut-downs, due
ing liquid hydrochloric acid on one side of the 70 to breakage of ceramic equipment, are done away

metal range from 800 to 1,600 B. t. u. per sq. it.

per degree F. per hour, values twice as great as
that being not uncommon. Throughout its use

with.

Another prime advantage is the flexibility of

operation coupled with ease of control, which
ful life it maintains these values without loss
enables the production of finished acid direct
due to oxidation or film-formation. Compared 75 from the apparatus-having such a constant qual

'andenes
ity thatv it may bie: marketed without kfurther
treatment;

>

The method and apparatus, as described here

inbefore, may >also be employed in carrying out

other reactions between liquids andfgases.

Sulfurousacid may be manufactured in a man
ner similar to that describedfor the manufac
ture of hydrochloric acid'. Water or dil-utesul

furous lacid maybe employed as the absorbing

liquid, which is passed downwardly ona thermally
conductive Wall. ASulfur dioxide or gas containing
sulfur dioxide is passed concurrent with thewa
ter. The rheat of reaction is removed by passing
a suitable heat exchange medium up 'the Voppo
site side of the Wall. The method and apparatus
employed in this reaction may be identical tofthe
one described for the'manufacture of hydro
chloric acid.
In a similar manner it is 4possible to react car

bon dioxide with rwater to forml carbonio acid.

Ammonium hydroxide may be prepared in a
like manner by passing water and gaseousam'

be continuously vhalogenated: in accordance vwith

the present invention. Specific applications of
the. present invention to hydrocarbons of pe
troleum origin include the halogenation ofkero
sone, gasoline and naphtha in apparatus such as
described' herein. The liquid is passed down the
thermally conductive wall and the halogenating
'agent-is passed concurrent with the liquid'. Gase
>cus. chlorine, bromineor hydrogen bromide may
'be employed in this halogenation process.
This- inventionis-not limited tothe treatment
of liquid. hydrocarbons, but it may also be em
ployed in reacting gaseous hydrocarbons with
liquid reactants. The gaseous hydrocarbon may
be ahydrocarbon which exists as a gas at ordinary
temperatures such as ethane lor propane, or it

`may be a relatively low boiling hydrocarbon

'which exists in a liquid state at ordinary tem
peratures such as pentane or hexane. SuchV gase
ous> hydrocarbons' or vaporized hydrocarbons may
bereacted with various reactants, such as fuming
sulfuric acid or chlorosulfonic acid. The liquid

reactant is passedv downwardly on the thermally

lconductive Wall and the gaseous reactant is

It is obvious that in the manufacture of these
and other materials, in accordancefwith the pres-- 25 passed concurrent with the liquid.
The invention may also be employed for other
ent invention, the optimum temperatures along
reactions involving organic materials. The re
the thermally conductive wall may vary 'from
action between alcohols andr` gaseous hydrogen
those employed in the manufacture 'of hydro
"chloride, hydrogen` bromide and hydrogen fluoride
ehlor'ic acid. The various temperaturesfwill be
is'alsoreadily effected bythe use of the present
dependent upon the product being manufactured.
invention. Any of the alcohols which react With
The present method is alsovsatisfactory for the
the-gaseousk agents are satislactory, such as the
preparation of aqueous solution ofvsalts; 'An
monia in concurrent flow.

aqueous or other solution containing one of the

'prim-ary aliphaticalcohols, for example, methyl,

reactants is passed/downV the thermally conduc

--etliyL butyl, iso-butyl alcohols and the like. In a

tive wall concurrent with a gas containing a re :35 similairfmanner >ketones, forl example, di--methyl
ketone, methyl ethyl ketone, di-ethyl kenne,
actant, in the same manner as described in the

preparation of the acids. The present invention,

for example is satisfactory for the preparation of
ammonium chloride. Hydrochloric acid solution
is passed down the wall in concurrent flow with
gaseous ammonia.

As analternative, an am

methyl-.lpropfyl ketone and the like, may be re

Yacted-Withitlie gaseous agen-ts. It is to be under

stood- that other valcohols and ketones may be
>treated in accordance with this invention and
that the 'foregoingV specific compounds are set

monium hydroxide solution maybe passed down

forthfmerely by way yCif-example,

wardly on the wall. land hydrogen chloride .passed

concurrent with the ammonium hydroxide solu

In lthose instances where the liquid reactant or

the product of the reaction is volatilized atv the
temperature 'of reaction or due to the heat of

tion.

Other salts may be prepared in a similar-man

ner. For example, an yalkaline solution, suchV as

ammonium, calcium, sodium or potassium hy

dro-xide solutions, may be passed downwardly on

reaction, vthe method may be-practised by reacting

the materials and maintaining 'the product under
suitable pressure.

Although the apparatus has been described and

the wall and carbon dioxide, hydrogenchloride 60 illustrated to show the use of tantalum, colum
biumor alloys-predominatin-gin tantalum, colum
or sulfur` dioxide gas, or'a -gas containing carbon
bium or both, lasconstituting the thermally con
dioxide, hydrogen chloride or sulfur dioxide may
ducti've` wall, it` will be apparent that other 'ma
be passed in concurrent flow Ywith _the alkaline
terials of construction-may be employed where
solution. In such methodsthe optimum tem
peratures will also vary from 4those specifically 55 such ' other . material withstands -the corrosive ac
tion of the particularvreactants and of the prod
set forth illustrating. the manufacture' ofhydro
uctsof the reaction; v'TheA thermally conductive
chloric acid, and the particular' temperatures will
-vvallzshould beras thin as practical so thatthere
be governed by the reactants` and other condi
may'- bey a rapid" transferV of heat between 'the
tions of the reaction.
liquids on `opposite sides of thewall.
The present method is also satisfactory in ef
fecting various reactions involving the use of or

This application is a continuation in part of

illustrative of the invention as applied to the

my copending application, Serial No. 235,354,

filed October 17, 1938, now abandoned, entitled

field of organic chemistry, is the halogenation of

Method and apparatus for treating gases, which

ganic materials. The simplest of such reactions,

aliphatic hydrocarbons. The hydrocarbon in liq 85 application is a continuation in part of my prior

application, Serial No. 174,603, filed November 15,
uid state is passed downwardly on the thermally
1937, now abandoned, entitled Method and ap
conductive wall. The gaseous reactant is passed
paratus for treating gases. For so much of the
concurrent with the hydrocarbon. vIn certain
instances it may be necessary to supply heat so
subject matter herein disclosed, which is also
that the particular hydrocarbon enters the ap 70 disclosed in either of my said applications, I claim
priority of said applications.
paratus in a liquid state.
It is to be understood that this invention is not
Various hydrocarbon materials may be treated
in accordance with this invention, and it has been
limited to the preferred embodiments of the
found that hydrocarbons of petroleum orig'n,
method and apparatus or to the specic details set
which are liquid at ordinary temperatures, may 75 forth herein. The foregoing description is in->

'2,436,432

11

12

tended merelyto' illustrate the invention, and

4. In the art of conducting an exothermic re

action between a gas and a liquid wherein the
gas is admixed with non-reacting gas, the im
movement of passing the gas and liquid in ex
tended concurrent ow while removing heat of
reaction by out-of-contact heat exchange, re
moving the gaseous admixture of reacting and
non-reacting gas from the locus of reaction be
fore completion of the reaction, passing a smaller
quantity of gas relatively richer in the reacting
component in countercurrent relation to the ow

various modications will suggest themselves to

those skilled in the art and may be made without
departing from the spirit and scope of my inven
tion. For example, it is obvious that this method

and apparatus is applicable to reactions which

require external heat to maintain the reacted
material in liquid state. The heat of reaction may
be insucient to insure temperatures at which the
reaction products exist in a liquid state, and in
such instances a heating liquid or medium may

Vbe substituted for the usualcooling liquid.

of reacting liquid and continuing the cooling of

the liquid beyond the point of initial contact be
1. In the, art of producing hydrochloric acid
tween the liquid and the rich gas.
from hydrogen chloride and water, the improve
5. In the art oi producing hydrochloric acid
ment which includes the steps of passing a minor
from water and gas which contains hydrogen
`proportion of hydrogen chloride in countercur
chloride, the improvement which includes the
rent contact now with water to produce dilute
steps of flowing a thin iilm of relatively dilute
hydrochloric acid, passing the major proportion
hydrochloric acid down a generally Vertical, ther
of hydrogen chloride in concurrent contact flow 20 mally conductive tube. passing the gas contain
with said dilute acid while cooling with counter
ing hydrogen chloride down the tube in intimate
current out-of-contact new of heat exchange
-contact with said lm, passing a stream of cool
medium and collecting a strong hydrochloric acid
ing fluid up and around said tube to maintain the
at a point remote from the point of initial con
temperature of said iilm below thedecomposing
current contact.
Y
temperature of the concentration of hydrochloric
2. In the art of producing hydrochloric acid 25 acid prevailing at each point on said tube, col
from hydrogen chloride and water, the improve
lecting and removing the hydrochloric acid at the
ment which includes the steps of passing hy
bottom of said tube, passing the gas unabsorbed
drogen chloride and connate gases in concurrent
in concurrent now in countercurrent flow with
contact iiow with dilute hydrochloric acid, cool 80 water to form dilute hydrochloric acid and utiliz
ing with countercurrent cut-of-contact flow of
ing the dilute hydrochloric acid as the absorption
cooling water, collecting a strong hydrochloric
acid in the concurrent absorption.
I claim:

acid at a point remote from the point of initial

concurrent Contact, collecting the connate gases

with minor amounts of entrained hydrogen chlo
ride, passing the collected gases in countercur
rent contact with Water to scrub the hydrogen
chloride from the connate gases thereby produc

FREDERICK L. HUNTER.

REFERENCES CITED
The following references are of record in the

le of this patent:
UNITED STATES PATENTS
Number
Name
Date

ing dilute hydrochloric acid, removing the

scrubbed gases and> utilizing the dilute hydro
chloric acid in the concurrent absorption.
3. In the art of producing hydrochloric acid

from hydrogen chloride, the improvement which

includes the steps of ,owing a thin lm of dilute
hydrochloric acid down a generally vertical tube 45
of relatively thin-walled tantalum, passing a gas

consisting principally of hydrogen chloride down

2,221,787

Downs ___..___..__-_ Nov. 19, 1940

1,969,381
1,563,732
1,141,266
1,654,181

>Mullen ___________ __ Aug. 7,

Egleson __________ _.. Dec. 1,
Raschig __________ .__ June 1,
Mann '_ _________ _'_.. Dec. 27,

1934
1925
1915

1927

1,398,224
Frederikson --.______ Nov. 29, 1921
the tube in intimate contact with said nlm, pass
OTHER REFERENCES
ing a stream of cooling water up and around
said tube to maintain thetemperature of said 50
Lunge, Sulphuric Acid and Alkali, vol. 2, part
film below 180 F. and above 140 F. at the top of
1,19page 37. Pub. by Sweeney & Jackson, London
said tube and below the decomposing point of the
( 09) .
concentration of hydrochloric acid prevailing at
Cumming, Hydrochloric Acid and Salt Cake,
each point on said tube, collecting and removing
.page 241. Published by D. Van Nostrand Co.,

the hydrochloric acid produced, collecting the 55

unabsorbed gases, scrubbing the same by pass

Mellor, Inorganic and Theoretical Chemistry,

ing them upwardly against a downwardly fiowing

stream of water and utilizing the dilute hydro

vol. 9, pages 849, 891. Pub. by Longmans, Green

and Ce., London (1929) .

chloric acid thus formed to provide an absorption

medium in the principal absorption operation.

NewYork (1923).

60