United States Patent [19] [11] 3,944,401

Diirr et al. [45] Mar. 16, 1976

[54] PROCESS FOR THE REMOVAL OF 3,524,801 8/1970 Parsi ................................. .. 204/104
GASEOUS IMPURITIES FROM THE 322833;
, ,
1;; D I
orr et a . ............................ ..
55/73
FOR THE 3,788,043 1/1974 D‘tirr et al. .......................... .. 55/237

PRODUCTION OF SULFURIC ACID FOREIGN PATENTS OR APPLICATIONS

[75] Inventors: Karl-Heinz Dtirr, Mainz; Hugo 670,966 1939 I Germany .......................... .. 423/242
Grimm, Frankfurt am Main; Ulrich 1,234,912 1967 Germany .......................... .. 423/242
Sander, Friedrichsdorf; Robert
Peichl, Kelheim; Michael Tacke, Primary Examiner-John Adee
Offenbach, all Of Germany Attorney, Agent, or Firm—Karl F. Ross; Herbert
[73] Assignees: Metallgesellschaft Aktiengesellschaft, Dubno
Frankfurt am Main; Sud-Chemie
AG, MLll'llCh, both of Germany [57] ABSTRACT
[22] Filed: May 6’ 1974 Sulfur compounds oxidizable to form sulfuric acid and
[21] Appl. No.: 467,387 organic compounds oxidizable to CO2 and H20 are re
, ‘moved from an exhaust gas of a contact-process plant
. . . . . for producing sulfuric acid by treating the exhaust gas
[30] Foreign Apphcanon Pnonty Data with a scrubbing solution consisting of dilute sulfuric
May 8, Germany .......................... .. acid and peroxydisulfuric acid‘ The peroxydisulfuric
acid is produced electrolytically from fresh dilute sul—
[52] US. Cl.2 ....................... .. 55/73; 55/94; 423/522 furic acid and the resulting electrolyte is continuously
Int. Cl.f ...................................... .. B01D 47/14 introduced into the scrubbing acid cycle_ The exhaust
[ 1 Field 0 earch """" " 204/ 103’ 104; 55/73’ 94; gas is treated in a vertical venturi with uniflow, i.e. co
261/1 17, 116; 423/242, 533, 522 directional ?ow of the gas and the scrubbing solution,
_ and the gas is then passed through a horizontal venturi
[56] UNlTE§f;;ences cllated
ATES ATENTS
and subsequently upwardly through a packing layer.
3,523,880 8/1970 Parsi ................................. .. 204/104 21 Claims’ 1‘ D'awmg F‘gure

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l Aug!
US. Patent March 16, 1976 3,944,401
 1-1 .2
jointly with¢another~, as‘decribedin application Ser. No.
PROCESS FOR THE REMOVAL OF GASEOUS 308,849, thatwastegases can be economically treated
IMPURITIES FROM THE EXHAUST GASES OF A 'with a dilute sulfuric‘acidicontaining peroxydisulfuric
- CONTACT-PROCESS PLANT FOR THE acid in such mannerthat sulfur trioxide results. A criti
PRODUCTION OF SULFURIC ACID 5 cal feature I“ of the system described in ‘the last-men
tioned application is that the peroxydisulfuric acid level
. "cRos's-RE'F'ERENoE‘To. RELATED APPLICATION in the treating solution is replenished by the electrolysis
The present Application is related to the commonly ofjfresh dilute sulfuric acid (electrolysis-cell acid) with
assigned copending application Ser. No. 308,849 ?led the peroxydisulfuric acid .solution thus produced being
Nov. 22, 1972 and entitled METHOD OF REMOVING 10 mixed with dilute sulfuric acid to form the gas-treating
GASEOUS IMPURITIES F ROM WASTE GASES now liquor. The peroxydisulfuric acid which decomposes
abandoned. The latter application relates to subject upon treatment of the gas, the sulfuric acid formed by
matter disclosed and claimed in copending application absorption of the sulfur trioxide in the dilute sulfur acid
Ser. No. 74,629 ?led Sept-23, l970‘now abandoned, and the dilute sulfuric acid serving as the treatment
commonly assigned copending application Ser. No. ‘ vehicle and absorber can thus be drawn off without
188,127 ?led Oct. 12, .1971, and commonly assigned recycling to the electrolysis cell. - . ~ I ,
copending application Ser. No. 188,128 ?led Oct. 12, Best results were obtained using this system with gas
1971, now US. Pat. Nos. 3,780,499 and 3,788,043 streams containing sulfur-dioxide and those with the
respectively, all dealing with absorption systems and exhaust‘ gases of combustion installations such as fur
gases containing sulfur oxides and naming one or more naces, metal or roasting plants and, sulfuric acid plants.
of the present joint ‘inventors. ' ' I The system of application Ser. No. 308,849 may be
used, in addition, to remove sulfur-containing impuri
FIELDOF THE‘ INVENTION ties other than sulfur dioxide froman exhaust gas. It has
The present invention relates to a process for the been found that inorganic sulfur compounds containing
.removal of sulfur compounds oxidizable to form sulfu 25 sulfur in an oxidation state in whichit can be oxidized
ric_ acid and organic compounds oxidizable to form'CO2 to elemental sulfur and/or ‘to sulfur dioxide can be
and H20 from the exhaust gases produced by contact removed with that system: For example, inorganic sul
process plants for making sulfuric acid. I‘ 8 ?des and hydrogen sul?de can be treated with the perf
oxydisulfuric acid solution and oxidized to elemental
BACKGROUND OF THE INVENTION 30 sulfur and eventually sulfur trioxide. 7.
‘ As pointed (min application Ser. No. 308,849, sul The peroxydisulfuric acid concentration was prefera
fur-‘eontaining. gases and particulates are a major prob vbly between .200 and 300v grams of peroxydisulfuric
lem 'in modern societies because they ‘are released into acid per liter in the ,cell acid, most advantageously
the atmosphere from many sources and‘ are highly toxic between 240 and 260 grams per liter. At these concen
'to the population, to vegetation and’ to metal, stone and 35 trations a high yield orv efficiency. was obtained _-and
other structures. _ practically no water was introduced into the system so
In the combustion 'of fuel oil ‘and coal, for example, that local overheating and thermal degradation of the
elemental sulfur and sulfur oxides maybe released into peroxydisulfuric acid was avoided. '
the-atmosphere. ' " ' - ' i ,The dilute sulfuric acid had a concentration of 25 to
From ' chemical plants,‘ organic “sulfur, compounds, 40 60% by weight, this concentration ‘giving the efficient
hydrogen-sulfide and sulfur oxides may be released into washing and absorption characteristics. Sulfur trioxide,
the-atmosphere. > ' > . > . _ 1 ' ‘ - present in the exhaust gas, and/or‘sulfuric acid mist
In sulfuric acid plants, the waste gases following the (which- is generally present when the exhaust gas is
?nal absorption may contain toxic or dangerous quanti derived‘from a sulfuric acid plant) can be removed
ties of residual sulfur dioxide and sulfur trioxide. 45 simultaneously‘ in spite of the fact that these compo
In the roasting of metal and othergmetallurgical ‘pro nents are not oxidized. The exhaust gas may contain
cesses, the release of elemental sulfur, and sulfur com organic co'mpoundswhich are oxidized by the peroxy
pounds, especially sulfur oxides, has long been a prob disulfuric acid system to carbon dioxide and water
lem. ' v‘ . 1‘ "1 vapor. _ ,1 . I a I‘

Consequently, considerable effort has been made to 50 _ The gas was treatedwith the, liquid phase in uniflow
obtain an efficient, low-cost system for removing sulfur by passing the gas phase and the .liquid phase jointly
compoundsfrom waste gasesand capable of minimiz through the constriction of a venturi absorber. As de
ing the release. of such gases into the atmosphere. scribed in.applications Ser. Nos. 74,629, 188,127 and
A large number of processes have been suggested for 188,128. and in our. earlier. individual and joint efforts,
this purpose as described, fonéxample, in .the literature 55 for reasons which are'not fully understood the intimate
references cited in application _Ser. No. 308,849..These contact produced by forcing the liquid phase jointly
processes includewashing the gas withsodium carbon through a construction and thereafter permitting the
ate solution followed by. crystallization of sodium vsul¢ mixture of the two phases to expand past the constric
?te, washing the gas with a magnesia slurry followed by tion yieldsa far moreeffective interaction of the two
crystallization and recovery of the magnesia as well as phases than can be obtained with theoretically equiva
concentrated sulfur dioxide, washing the gas with gase lent washing towersin. which the, gas and liquid have
ous potassium sul?te which is then recovered by strip similar contact times and interflow velocity. The gas,
ping from the precipitated, pyrosul?te. More complex after the treatment with and separation from dilute
and extensive systems may’also be mentioned here, sulfuric acid, was conductedthrough a droplet separa
although they have been more or less lfullygdescribed in 6.5 tor designed to avoid ,entraining of acid droplets along
the aforementioned copending applicationsjas repre with the gas. The droplet separator was a packed bed
senting the state of thearL'Suf?ce ‘it ‘to ‘say that it has traversed by the gas‘ and from aniimpingement, collec
been discovered by some of the present applicants tor and interaction surfaceskwhlich not only prevent
 3,944,401
4
passage of the acid droplets through the layer but also was composed of a porous material such as sintered
bring about an intimate contact of the gas phase with glass or porcelain. The gas permeability, gas-?ow ve
the acid in the form of a liquid ?lm of the latter or locity and volume were so dimensioned that little or no
so-called after-absorption and after-reaction. sulfuric acid solution passed through the plate. Best
Where the gas is passed upwardly through a ?lter bed results were obtained when the after-absorber and aft
of this type, the lowermost layer consisted of a porous er-separator beds of packing were provided upon the
packing bed with particles of a particle size of 5 to 20 perfoated plate or upon respective prerforated plates in
millimeters, preferably 9 to 15 millimeters. In this layer cascade.
precipitation and removal of entrained acid droplets The parts of the apparatus which came into contact
occurs. The packing bodies are coated with a liquid with the acid solution were constituted from or were
?lm in which the aforementioned after-absorption coated with acid resistance, preferably polyvinil chlo
takes place. When this liquid ?lm tends to become ride. ‘
thicker, the sulfuric acid droplets fall from the layer.
The rising gas stream and the pore size maintain a thin OBJECTS OF THE INVENTION
liquid layer above the packing mass. 15
It is the principal object of the present invention to
The after-absorption is preferably effected in a layer provide an improved method of removing gaseous im
having a height of 50 to 200 millimeters, preferably 80 purities from the waste gases of a contact-process plate
to 120 millimeters, this bed height having been found for producing sulfuric acid.
to provide after-absorption with a minimum of in Another object of the invention is to extend the prin
creased ?ow resistance. The gas velocity furing after 20 ciples originally set forth in application Ser. No.
absorption was 1 to 2.5 meters per second, preferably 308,849.
1.3 to 1.7 meters per second.
After traversing the after-absorption layer of a thick SUMMARY OF THE INVENTION
ness of 50 to 200 millimeters and composed of porous According to the invention, this object is accom
packing bodies with a particle size of 5 to 20 millime 25 plished in that the exhaust gas is treated in a vertical
ters at a gas velocity of l to 2.5 meters per second, the venturi tube with cocurrent injected circulating scrub
gas passed through a layer of acid-resistance nonporous bing acid from the sump of the venturi tube, at least
packing bodies with a particle size of 20 to 50 millime part of the injected scrubbing acid being separated and
ters in an after-absorption stage, the latter overlying the
after-absorption bed. 30 collected in the sump of the venturi tube.
The gas is conducted into a substantially horizontal
The after-separation bed not only loads the after
absorption bed to prevent migration of the packing venturi tube disposed between the sump and the outlet
bodies but also provides impingement-type liquid-sepa opening of the vertical venturi tube and opening into a
ration surfaces together with narrower and random tower, the gas being treated in the horizontal venturi
channels in which residual droplets of acid may be 35 tube with cocurrent injected circulating scrubbing acid
separated from the gas phase. The after-separation bed from the sump of the tower.
has a thickness of 50 to I50 millimeters, preferably 80 The injected scrubbing acid is separated and is col
to 120 millimeters, a range which has been found to be lected in the sump of the tower; the gas rising in the
effective for efficient separation of the residual liquid tower, which contains a packing layer, is treated with
from the gas phase without materially increasing the 40 countercurrent circulating scrubbing acid coming from
?ow resistance. the sump of the tower and injected above the packing
It was found to be desirable to treat the gas (contain layer, and with the added acid electrolyte which con
ing sulfur compounds and other compounds oxidizable tains peroxydisulfuric acid, and the acids fed into the
by peroxydisulfuric acid to sulfur dioxide, carbon diox tower are separated and are collected to the sump of
ide and water vapor) with a dilute sulfuric acid contain 45 the tower.
ing the peroxydisulfuric acid in a venturi-type appara Preferably a large part of the circulating scrubbing
tus in uni?ow, i.e. a system in which the gas and liquid acid injected into the vertical venturi tube is separated
phases ?ow in the same direction. The venturi absorber and is collected in the sump of this venturi tube since
was provided ahead of the venturi constriction and even the scrubbing acid which has been entrained into
expansion chamber with a liquid-collecting chamber 50 the inlet of the substantially horizontal venturi tube as
and means for diverting the gas stream from its axial far as the throat thereof is recycled.
flow direction as it emerges from the venturi chamber. The separation and recycling of the scrubbing acid
The gas stream was diverted by an angle of 90° or more, which has been entrained to the narrowest part or
thereby causing droplets of high kinetic energy to pass throat of the substantially horizontal venturi tube from
through the bodies of liquid in the bath disposed ahead 55 the vertical venturi tube may be accomplished by
of the venturi outlet. The venturi absorber was prefera downwardly inclining the gas outlet conduit from the
bly oriented vertically so that its outlet was directed vertical venturi tube, or by the provision of baffles in
downwardly into this bath and the expansion chamber the gas outlet conduit and by the provision of drain
was provided with lateral outlets above the bath so that openings in the lower portion of the gas outlet conduit
the main body of gas is ?rst directed downward toward 60 or in the inlet portion of the substantially horizontal
the bath and is then diverted upwardly and laterally to venturi tube. These drain openings are connected by
shed larger droplets and high-energy particles. conduits to the sump of the vertical venturi tube.
The acid collected in the sump was in part recircu As a result of these measures, which may be used
lated to the venturi. It was also advantageous to pass individually or in combination, a major portion of the
the gas phase into contact with the peroxydisulfuric 65 scrubbing acid entrained from the vertical venturi tube
acid/dilute sulfuric acid liquid phase by forcing the gas is separated and conducted into the sump of that ven
upwardly through a gas-permeable plate upon which turi tube so that the scrubbing acid cycles can be sepa
the acid layer was provided. The gas—permeable plate rated to a high degree.
 Advantageously, a large part of the circulating scrub active oxygen so that there is initially a high content of
bing acid injected into the vertical venturi tube is sepa active oxygen in all absorption stages.
rated and is collected in the sump of the venturi tube The intermediate storage is continued until a hydro
because a packing layer is provided below the outlet lysis of 30 — 90% has been effected. That degree of
opening of the venturi tube and above the inlet opening hydrolysis gives good results in operation.
of the substantially horizontal venturi tube. This pack The stationary steady-state concentration of the
ing layer has a‘ thickness of about 10—20 centimeter. scrubbing acid in the sump of the tower most desirably
The high turbulence produced in that layer also pro amounts to 30 — 50% by weight, preferably 38 - 45% by
motes the separation of the scrubbing acid, which is weight, sulfuric and a molar concentration of active
then collected in the sump of the vertical venturi tube. oxygen 0.4-1.26 moles, preferably 0.6—l.0 moles per
Scrubbing acid can be transferred from the sump of liter. High degrees of oxidation are obtained with these
the tower via an over?ow into the sump of the vertical concentrations.
venturi tube in a quantity which corresponds to the The stationary steady-state concentration of the
added electrolyte acid containing peroxydisulfuric acid scrubbing acid in the sump of the vertical venturi tube
and to the sulfuric acid formed as an oxidation product 5 is advantageously 25 — 40% by weight sulfuric acid,
in the substantially horizontal venturi tube. In this sim preferably 28 - 32% by weight, and the active oxygen
ple way, a constant level is maintained in the tower has a concentration of 0.06—0.3 moles per liter, prefer~
sump and the entire system is operated in countercur ably 0.1 —- 0.15 moles per liter. A relatively high water
rent of liquid and gas flow so that the active oxygen is ' vapor partial pressure in the gas phase and high degrees
optimally utilized. Besides, a steady-state concentra 20 of oxidation are obtained with these concentrations.
tion of active oxygen in the sump of the vertical venturi The residence time of the scrubbing acid which con
tube is maintained constant. tains the residual peroxydisulfuric acid in the sump of
The steady-state sulfuric acid concentration of the the tower and in the sump of the vertical venturi tube is
scrubbing acid in the sump of the vertical venturi tube adjusted so that 20 — 90% of the residual peroxydisulfu
is 'held constant by an addition of water. As a result, the 25 ric acid are hydrolyzed in each sump. The further hy
evaporative loss of water is compensated and the heat drolysis of B28208 to I-I2SO5 and H2804 improves the
of the resulting mixture is utilized for a hydrolysis of the degree of oxidation. Besides, the volumes of the sumps
residual peroxydisulfuric acid in the sump of the verti can be dimensioned such that the higher S02 content of
cal venturi tube. the exhaust gases produced during the starting period
The level of the sump in the vertical venturi tube is of the contact process plant can be absorbed because
held constant by a withdrawal of scrubbing acid, which an adequate supply of active oxygen is available.
contains the oxidation product, from the sump. In that The included angle at the outlet of the vertical ven
case, the product is withdrawn from the system at a turi tube and of the substantially horizontal venturi
point where the content of residual active oxygen is tube is 10° — 20°, preferably 14° — 17°. As a result, the
lowest. 35 total gas pressure loss in the venturi tube is minimized
Different concentrations of sulfuric acid are main and, in addition to the venturi effect proper, a turbu
tained in the cycles of the circulating scrubbing acid, lence is created to provide for an optimum gas-liquid
the highest concentrations of sulfuric acid and active interface allowing an optimum degree of oxidation.
oxygen being provided in the acid which is sprayed into The gas is passed through the entire system with an
the tower, a lower concentration being provided in the 40 average retention time of 2 - 4 seconds. This retention
acid which is injected into the substantially horizontal time allows a high degree of oxidation while keeping
venturi tube, and the lowest concentration being pro the dimensions of the equipment at a minimum.
vided in the acid which is injected into the vertical The withdrawn scrubbing acid which contains the
venturi tube. This results in an optimum oxidation of oxidation product is supplied to the ?nal absorber of
SO2 and/or of other oxidizable gas components and an the contact process plant. In this way, the residual
optimum utilization of the active oxygen supplied to active oxygen withdrawn from the system is utilized for
the system. an oxidation in the ?nal absorber of the contact process
The electrolyte acid which emerges from the electro plant and the content of oxidizable compounds in the
lytic unit and contains peroxydisulfuric acid consists of exhaust gases is reduced before they enter the system.
sulfuric acid which has a concentration of 30 — 50% by 50 The quantity of peracids depends on the oxidation
weight H2804, preferably 35 — 40% by weight H2804, equivalent of the exhaust gas components to be oxi
and contains 180 — 350 grams, preferably 200 - 300 dized and on the desired degree of oxidation and the
grams, peroxydisulfuric acid per liter. These concentra desired purity of the exhaust gases.
tions give very good results in operation. The packing layer in the tower has suitably a thick
Advantageously, the acid electrolyte which contains 55 ness of 40-80 centimeters. This results in a high degree
peroxydisulfuric acid is held in intermediate storage to of oxidation and in a relatively low gas pressure loss.
increase the hydrolysis of the peroxydisulfuric acid. The outlet opening of the tower is preceded by a wire
The increased hydrolysis of H28208 to I-I2SO5 and mesh ?lter which provides for a good separation of
H2504 results in a higher rate of oxidation of the gas entrained liquid in conjunction with a low pressure loss.
components in the succeeding scrubber. Besides, the 60 The entire system can be made to a large extent from
intermediate storage provides for a supply from which plastic or synthetic-resin material.
acid electrolyte which contains activeoxygen can be
withdrawn immediately at a suitable rate in case of
BRIEF DESCRIPTION OF THE DRAWING
?uctuations of the gas rate. Besides, the high S02 con The above and other objects, features and advan
tent of the exhaust gas from a sulfuric acid contact 65 tages of the present invention will become more readily
process plant when being started up, may be absorbed apparent from the following description, reference
in that the entire system is ?lled from the supply tank being made to the accompanying drawing in which the
with electrolyte acid containing a high concentration of sole FIGURE is a ?ow diagram illustrating the inven
 3,944,4Ul
7
tion. conduit 12 to the nozzle 33. The circulating scrubbing
acid and acid electrolyte supplied into the tower trickle
SPECIFIC DESCRIPTION through the packing layer 28 into the sump 27.
A mixing vessel 3 is supplied with sulfuric acid The gas outlet 34 is preceded by a wire mesh ?lter
through conduit 1 and with diluent water through con 35, in which residual acid is separated from the gas and
duit 2. The dilute sulfuric acid is used as electrolyte drips onto the packing layer 28. The puri?ed gas 36 is
acid and is supplied through conduit 4 into the cathode discharged into the atmosphere. Scrubbing acid from
space 5 of the electrolytic unit. The acid electrolyte the sump 27 is transferred over the over?ow 37 into the
?ows through conduit 6 over ?lter 7 for an intermedi sump 17. The scrubbing acid ?ows over at a rate which
ate puri?cation and through conduit 8 into the anode 0 corresponds to the rate at which electrolyte acid con
space 9 of the electrolytic unit. The electrolyte acid taining active oxygen is supplied to the tower plus the
which contains peroxydisulfuric acid ?ows through rate at which sulfuric acid is produced by oxidation in
conduit 10 into a supply container 11 for an intermedi the tower 26 and the venturi tube 22. Water is supplied
ate storage to increase the degree of hydrolysis. Scrub through conduit 38 into the sump 17 of the venturi tube
bing acid which contains active oxygen is supplied 5 14. The rate is controlled so that a steady-state concen
through conduit 12 into the scrubbing acid cycle at the tration of sulfuric acid in the sump 17 remains con
required rate. stant. Scrubbing acid which contains the oxidation
The exhaust gas 13 from the ?nal absorber of the product is withdrawn through conduit 39. The rate is
contact process plant for producing sulfuric acid is fed controlled so that the level in the sump 17 remains
into the head of the vertical venturi tube 14. Through constant. The withdrawn acid is supplied to the ?nal
the nozzle 15, circulating scrubbing acid is injected into absorber of the contact process plant where the resid
the head of the venturi tube 14 and is mixed with the ual active oxygen is utilized for oxidation.
exhaust gas. A packing layer 16 is disposed below the The advantages afforded by the invention reside
outlet opening of the venturi tube 14. In this layer 16,mainly in that a conversion of 95% and more of S02,
the gas and scrubbing acid are further mixed and the 25 depending on the rate at which active oxygen is added,
injected scrubbing acid is separated. may be obtained so that the puri?ed gas contains less
A large part of the injected scrubbing acid is col than 50 ppm S02, and that the 70-90% of the sulfuric
lected in the sump 17 of the venturi tube 14. The circu acid mist contained in the exhaust gas are absorbed.
lating scrubbing acid which contains active oxygen is This extreme puri?cation of the exhaust gas is accom
pumped from the sump 17 through conduit 18, pump plished with a small dimensioning of equipment and
19 and conduit 20 to the nozzle 15. The gas leaves the with a relatively high economy and results in a true
venturi tube 14 and enters the inlet pipe 21 of the increase of the total production of the sulfuric acid
substantially horizontal venturi tube 22. plant. Only electric energie is consumed as an operat
The inlet pipe 21 is downwardly inclined, and drain ing supply; all other components are supplied from and
openings 23 are installed in the lower part of the inlet 35 returned to the cycle of the contact process plant for
pipe 21 and of the inlet portion of the venturi tube 22 producing sulfuric acid. The water which is supplied is
and are connected to the sump 17 by return conduits used to adjust the concentration in the acid cycles of
24. As a result, a large part of the scrubbing acid en the contact process plant. The residual active oxygen
trained from the venturi tube 14 into the venturi tube contained in the product which is withdrawn, is utilized
22 is separated and flows into the sump 17. Through in the ?nal absorber so that virtually no active oxygen
the nozzle 25, circulating scrubbing acid is injected into is lost. The pressure loss is low. ‘
the venturi tube 22 and mixed with the gas. The mix Because the cooling water for the electrolytic unit is
ture of gas and scrubbing acid enters the tower 26. only slightly heated, it may be used in the contact pro
A large part of the scrubbing acid which has been cess plant, e.g. in the coolers for the acid cycles. In the
injected into the venturi tube 22 is separated already in 45 puri?cation of exhaust gases that have been used for
the lower part of the tower 26 and enters the sump 27. reconcentration of acid, organic components and ni
The gas rises through the packing layer 28. trous gases are oxidized in addition to the sulfur com
Circulating scrubbing acid which contains active pounds.
oxygen is pumped from the sump 27 through conduit The compact and simple installation requires only a
29, pump 30 and conduit 31 to the nozzle 25 and 50 small space and may be made to a large extent from
through conduit 32 to the nozzle 33 in the upper part of plastic material. It may well be integrated in contact
the tower 26. Electrolyte acid which contains active process plants.
oxygen is also supplied from the container 11 through

Examples:
The Position Nos. 1 II III IV
correspond to the drawing
P05. 13 gas volume m“/h (STP) 10 000 I0 000 10 000 I0 000
SOz-content ppm $02 550 600 850 l 050
gas temperature DC 76 75 76 76
Pos. 36 sOz-content ppm SO, 51 47 98 I05
gas temperature °C 32 34 35 35
gas retention time 3 3 3 3
in system
sec
Pos. [2 composition of
the peroxidsulfuric
acid
a) active oxygen
calculated as
H2520Z gH2S2OK/liter 220 220 220 220
 I _ v \ I -continued

Examples: _ 3. _, _ K - , ~ ' r

The Position Nos. I a l ' ll lll , lV

correspond to the drawing ‘ "

b) H2SO4-content , % H280, 4l , 45 ' 45 j ,45'

‘c) degree of hyd'ro- " "a ' ' '1 " '
lysis H,SO,,/ - , - ,
14,520,, % 10 “70 70 70
Pos. 27 stationary stead-state '
composition of scrubbing :
acid I I ,. . ,

a) molar concentra- mol/liter 0.62 0,50 0.40 0.40

tion of active oxygen ‘
b) H2SO.-concentra¢
tion %H,s‘o, ‘ 42 43 45 45 >
c) degree of hydro- ' '
lysis HZSO5/ ~‘
H2520, % 40 ' 40 40 ' 40
P05.‘ 17 ‘ stationary steady
~ -. , state composition
of scrubbing acid
a) molar concentration
~, of active oxygen mol/liter 0.12 0.08 0.06 0.06
1 b) H2SO4-conce‘ntra- % H2804 31 , 32 32 32
tion' ‘ i

c) degree of'hydro- '

lysis H2805!
nzszoE % 30 30 30 30
Pos. 14 included angle 11 ll ll 11
‘ at the venturi '
P05. 22 included angle l5 l5 l5 15
at the venturi

> . v the acid collected at the base of said tower being

We claim: ' i I exclusively ,fed in a ?rst part to said tower above
1. In a method of removing sulfur compounds oxidiz- > 30 said packing layer, a second part to said horizontal
able to form sulfuric acid and organic compounds oxi- venturi tube and in a third part to the sump of said
dizable to form carbon dioxide and water from an ex- vertical venturi tube; and
haust gas of a contact-process plant for the production maintaining the scrubbing acid level in the base of
of sulfuric acid, whereinz» said tower substantially constant by continuously
the exhaust gas is treated in a scrubbingcycle with a 35 transferring to said sump as said third part a quan
recirculated scrubbing acid consisting of a mixture tity of scrubbing acid equal to the quantity of
of dilute sulfuric acid and peroxydisulfuric acid, added peroxydisulfuric acid and sulfuric acid in
the peroxydisulfuric acid is produced by electrolyz- said tower and to the sulfuric acid formed as an
ing continuously dilute sulfuric acid, oxidation product therein.
the peroxydisulfuric acid is added to the scrubbing- 40 2. The improvement de?ned in claim 1 wherein a
acid cycle and the scrubbing acid takes up sulfuric large part of the scrubbing acid injected into said verti
acid formed as an oxidation product, and cal venturi tube is collected in said sump, the balance
the scrubbing acid is withdrawn from the cycle to being entrained with said gas to said horizontal venturi
remove the oxidation product, the improvement tube, said improvement further comprising the step of
which comprises the steps of: 45 trapping at least a portion of said balance of scrubbing
treating said gas in a vertical venturi tube and in acid in pockets along the inlet portion of said horizon
uni?ow with circulating scrubbing acid collected in tal venturi tube and returning the trapped scrubbing
a sump below said venturi tube; acid to said sump.
passing the gas into a substantially horizontal venturi 3. The improvement de?ned in claim 1, further com
tube between said vertical tube and said sump, said 50 prising the step of separating a substantial portion of
horizontal venturi tube opening into an upwardly the scrubbing acid injected into said vertical venturi
extending tower; tube from said gas upon emergence of said gas from
treating the gas in said horizontal venturi tube in said vertical venturi tube by passing said gas through a
uni?ow with circulating scrubbing acid collected at packing layer between said vertical venturi tube.
the base of said tower and separating scrubbing 55 4. The improvement de?ned in claim 1, further com
acid from the gas in said tower for collection at the prising the step of maintaining the scrubbing acid level
base thereof; in the base of said tower substantially constant by con
passing the gas together with entrained scrubbing tinuously transferring to said sump a quantity of scrub
acid through a packing layer and treating the gas in bing acid equal to the quantity of added peroxydisulfu
said packing layer with a countercurrent flow of 60 ric acid and sulfuric acid in said tower and to the sulfu
circulating scrubbing acid from the base of said ric acid formed as an oxidation product therein.
tower and introduced above said packing layer; 5. The improvement de?ned in claim 1, further com
introducing the peroxydisulfuric acid into the scrub prising the step of maintaining the sulfuric acid concen
bing acid cycle by injecting it into said tower above tration in said sump at a substantially constant steady
said layer; 65 state concentration by adding water to said scrubbing
said peroxy disulfuric acid being produced from fresh acid in said sump.
dilute sulfuric acid independently of the acid circu 6. The improvement de?ned in claim 5, further com
lated from the base of said tower; prising the step of maintaining the level of scrubbing
 3,744,4u1
11
acid in said sump constant by continuously withdraw
ing scrubbing acid therefrom.
7. The improvement defined in claim 1 wherein the
scrubbing acid in said tower and in said vertical venturi
tube have different concentrations of sulfuric acid, the
highest sulfuric acid concentration being provided in
the scrubbing acid above said layer in said tower, a
lower sulfuric acid concentration being provided for
the scrubbing acid in said horizontal venturi tube and
the lowest concentration of sulfuric acid being main
tained in the scrubbing acid injected into said vertical
venturi tube.
8. The improvement defined in claim 1 wherein the
peroxydisulfuric acid is introduced into said tower in a
solution having a concentration of 30 to 50% sulfuric
acid and 180 to 350 g/liter peroxydisulfuric acid.
9. The improvement defined in claim 8 wherein the
peroxydisulfuric acid is introduced into said tower in a
solution having a concentration of 35 to 40% sulfuric
acid and containing 200 to 300 g/liter of peroxydisulfu
ric acid.
10. The improvement de?ned in claim 8 wherein the
solution containing peroxydisulfuric acid is held in
intermediate storage following its production by elec
trolysis to increase the hydrolysis of peroxydisulfuric
acid.
11. The improvement de?ned in claim 10 wherein
the solution containing peroxydisulfuric acid is held in
intermediate storage prior to introduction into said
tower for a period sufficient to effect a degree of hydro 30 the gases pass through said tubes and said tower with an
lysis between 30 and 90% of the peroxydisulfuric acid.
12. The improvement de?ned in claim 11 wherein a
steady-state concentration of the scrubbing acid is
maintained in the base of said tower at 30 to 50% sulfu
ric acid and a molar concentration of active oxygen of 35 the production of sulfuric acid.
0.4 to 1.26 moles of active oxygen per liter.
13. The improvement de?ned in claim 12 wherein
the steady-state concentration of sulfuric acid in the
scrubbing acid at the bottom of said tower is 38 to 45%
and the molar concentration of active oxygen is sub
stantially 0.6 to 1.0 moles per liter.
14. The improvement de?ned in claim 12 wherein
the scrubbing acid in said sump has a steady-state sulfu
ric acid concentration of 25 to 40% and a molar con
centration of active oxygen of 0.06 to 0.3 moles per
liter.
15. The improvement de?ned in claim 14 wherein
the sulfuric acid concentration in said sump is 28 to
32% and the active oxygen concentration is 0.1 to 0.15
moles per liter.
16. The improvement de?ned in claim 14 wherein
the residence time of the scrubbing acid at the bottom
of said tower is selected to e?ect 20 to 90% hydrolysis
of the residual peroxysulfuric acid.
20 17. The improvement de?ned in claim 16 wherein
the residence time of the scrubbing acid in said sump is
selected to effect 20 to 90% hydrolysis of the residual
peroxydisulfuric acid therein.
18. The improvement de?ned in claim 17 wherein
25 said venturi tubes have outlets with included angles of
substantially 10° to 20°.
19. The improvement de?ned in claim 18 wherein
said included angles are between 14° and 17°, inclusive.
20. The improvement de?ned in claim 18 wherein
average residence time of 2 to 4 seconds.
21. The improvement de?ned in claim 20, further
comprising the step of feeding the withdrawn scrubbing
acid to a ?nal absorber of a contact-process plate for
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50
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60
65