US00783797OB2

(12) United States Patent (10) Patent No.: US 7,837,970 B2

Daum (45) Date of Patent: Nov. 23, 2010

(54) PROCESS AND PLANT FOR THE (56) References Cited

PRODUCTION OF SULPHURCACD U.S. PATENT DOCUMENTS
(75) Inventor: Karl-Heinz Daum, Mainz (DE) 2,180,727 A 1 1/1939 Carter ......................... 23, 175
2,655.431 A 10/1953 Allen et al. ................... 23,168
3,490,868 A 1/1970 Furkert ........................ 23,168
(73) Assignee: Outotec Oyj. Espoo (FI) 3,780,499 A 12/1973 Dorr et al. ..................... 55/32
(*) Notice: Subject to any disclaimer, the term of this (Continued)
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS
DE 1054431 4f1959
(21) Appl. No.: 11/816,693
(Continued)
(22) PCT Fled: Feb. 11, 2006
OTHER PUBLICATIONS
(86) PCT NO.: PCT/EP2006/OO1260 PCT International Search Report, International Application No.
PCT/EP2006/001260, mailed Nov. 28, 2006.
S371 (c)(1),
(2), (4) Date: Sep. 2, 2008 (Continued)
Primary Examiner Melvin C Mayes
(87) PCT Pub. No.: WO2O06/087150 Assistant Examiner Sheng Han
(74) Attorney, Agent, or Firm Leydig, Voit & Mayer, Ltd.
PCT Pub. Date: Aug. 24, 2006
(57) ABSTRACT
(65) Prior Publication Data
The invention relates to a process and plant for producing
US 2009/O269272 A1 Oct. 29, 2009 sulphuric acid by catalytic oxidation of SO to form SO in a
converter with at least one contact stage, the SO-containing
(30) Foreign Application Priority Data process gas, after it has passed through at least one contact
Feb. 21, 2005 (DE) ....................... 10 2005 O08109 stage, being withdrawn from the converter and fed to an
apparatus for recovering heat, in which steam is generated
(51) Int. C. from feedwater by means of the heat of the process gas, and
COIB 7/43 (2006.01) the process gas then being fed to an absorber, in which the
COIB 7/69 (2006.01)
SO is absorbed in sulphuric acid. To improve the utilization
of heat during the production of sulphuric acid, the feedwater
COIB 17/74 (2006.01) is fed to the heat recovery apparatus at a higher temperature
(52) U.S. Cl. ..................... 423/573.1; 423/522; 423/528 than the process gas fed to the absorber.
(58) Field of Classification Search ....................... None
See application file for complete search history. 18 Claims, 14 Drawing Sheets

Sulphur
re-roro
A. Sulphur furnaca
See

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- o intermedia absorber 17Oc
 US 7,837,970 B2
Page 2

U.S. PATENT DOCUMENTS DE 19522927 1, 1997

DE 19800 800 7, 1999
3,788,043 A 1/1974 Dorr et al. .................... 55/237 DE 102004.012293 9, 2005
3,875,294 A 4, 1975 Reh et al. ... ... 423,534 EP 0218411 4f1987
3,907,979 A 9/1975 Jenninges ................... 423,522 EP O 130967 B1 1, 1988
4,285,927 A 8, 1981 Hara et al. EP O181313 B1 1, 1988
4,368,183 A 1/1983 Dorr et al. .................. 423,522 GB 21 81 120 A 4f1987
4,576,813 A 3, 1986 McAlister et al. RU 2040465 C1 7, 1995
4,654,205 A 3, 1987 Cameron .................... 423,522 RU 21 19890 C1 10, 1998
4,670,242 A 6, 1987 McAlister et al. RU 22O1393 C1 3, 2003
4,996,038 A 2, 1991 McAlister et al. ........... 423,522 RU 2217383 C1 11/2003
5,538,707 A * 7/1996 McAlister ...... 423,522 SU 1583351 A1 8, 1990
5,593,652 A 1/1997 Peng ....... 423,522 SU 1782303 A3 12/1992
6,153,168 A * 1 1/2000 Seitz et al. ..... 423,522 WO WO 91.14651 10, 1991
6.279,514 B1 8/2001 Browder et al. ................ 122/7 WO WO 2004/O37719 5, 2004
6,500,402 B1* 12/2002 Winkler et al. .............. 423,522
OTHER PUBLICATIONS
FOREIGN PATENT DOCUMENTS
Elvers, B. Ullmann's Encyclopedia of Industrial Chemistry; vol A25,
DE 3O303 10, 1963 Sulfuric Acid and Sulfur Trioxide 655-668 1992.
DE 15 67716 7, 1970 Derwent Publications Ltd. An 2002-032802, XP002269015 & RU
DE 20 SO 58O 4f1972 2174945, Abstract Oct. 20, 2001.
DE 2223 131 5, 1972 Connock, L., “Systems for Enhanced Energy Recovery'. Sulphur,
DE 22 13 580 A1 3, 1975 Sulphuric Acid Technology, British Sulphur Publishing Co, London,
DE 28 20231 5, 1978 GB, No. 278, pp. 41-47 (Jan.-Feb. 2002) XP-001075186.
DE 30 OO 599 T 1980 U.S. Appl. No. 1 1/592.290, filed Aug. 23, 2007, Karl-Heinz Daumet
DE 29 45 021 5, 1981 al.
DE 33O3289 8, 1984 U.S. Appl. No. 1 1/579,435, filed Aug. 21, 2007, Karl-Heinz Daumet
al.
DE 691 05961 10, 1991
DE 383O365 C2 6, 1996 * cited by examiner
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 US 7,837,970 B2
1. 2
PROCESS AND PLANT FOR THE below 130-170° C. A further restriction results from the use of
PRODUCTION OF SULPHURIC ACID deaerated boiler feedwater (i.e. boiler feedwater from which
dissolved oxygen has been Substantially removed) in the
This application claims the benefit of International Appli steam generators (e.g. economizers), which is necessary in
cation No. PCT/EP2006/001260 filed on Feb. 11, 2006 under 5 order to avoid corrosion on the water side. The so-called
35 U.S.C. S371, entitled, “PROCESS AND PLANT FOR unpressurized (typically 0.1-0.3 bar, all pressures are given
THE PRODUCTION OF SULPHURICACID which claims relative to atmospheric pressure) thermal deaeration of the
benefit of German Patent Application No. 10 2005 008 109.6 feedwater which is generally used means that the temperature
filed on Feb. 21, 2005. of the feedwater is approximately 102-105°C. In thermody
10
FIELD OF THE INVENTION namic terms, therefore, significant, economically justifiable
gas cooling to below 130°C. would hardly be possible even
The invention relates to a process and a plant for the pro without taking into account dew point corrosion.
duction of sulphuric acid by catalytic oxidation of SO to During the Subsequent part of the conventional process for
form SO in a converter with at least one contact stage, the 15 producing Sulphuric acid, the gases are cooled further both
SO-containing process gas, after it has passed through at during the intermediate absorption and during the final
least one contact stage, being withdrawn from the converter absorption. This sensible energy, like the energy from the
and fed to an apparatus for heat recovery, in which steam is condensation of the SOs and the heat released through the
generated from feedwater by means of the heat of the process energy of formation of HSO from SO, and HO and the
gas, and the process gas then being fed to an absorberin which 20 dilution of the Sulphuric acid formed, is consequently at a low
the SO is absorbed in sulphuric acid. temperature level and is generally removed from the process
Sulphuric acid is usually produced by what is known as the indirectly by means of cooling water.
double absorption process, as described in Ullmann's Ency In the past, various processes have been developed for also
clopedia of Industrial Chemistry, 5" Edition, Volume A 25, obtaining some of this heat as low-pressure steam, and
pages 635 to 700. Sulphur dioxide (SO) obtained by com- 25 thereby overall increasing the economic viability of the plant,
bustion of Sulphur or as a waste gas from metallurgical plants cf. in this respect U.S. Pat. No. 4,576,813 held by Monsanto
is converted into Sulphur trioxide (SO) in a four-stage or (also EP 0181 313 B1) and the “HEROS' process developed
five-stage converter with the aid of a solid catalyst, for by Lurgi in accordance with DE 38 30 365 C2. Numerous
example comprising Vanadium pentoxide as active compo attempts have been made to improve these processes, but
nent. After the contact stages of the converter, the SO 30 these modifications have hitherto been of only limited use.
obtained is withdrawn and fed to an intermediate absorberor, Reference may be made to the Monsanto patent U.S. Pat. No.
after the last contact stage of the converter, to a final absorber, 4,670,242. (EPO 130967 B1) and the Outokumpu process in
in which the gas containing SO is passed in countercurrent to accordance with the as yet unpublished German patent appli
concentrated Sulphuric acid and absorbed therein. cation DE 10 2004 012 293.8. Depending on the process
Plants for producing Sulphuric acid from elemental Sulphur 35 engineering circuit and quality of the low-pressure steam
in economic terms “suffer from the fact that the costs of the
raw material Sulphur often significantly exceed the income (generally Saturated Steam at 6-10 bar), it is possible to
which can be realized from the product sulphuric acid. increase the overall efficiency from approx. 60% to up to
These plants can be operated economically only by maxi 80-85%. However, the use of these low-temperature heat
mizing/optimizing the generation of by-products, such as 40 recovery processes is restricted to situations in which there
high-pressure and low-pressure steam, and thereby generat are available consumers for low-pressure steam, which is of a
reduced quality. If this is not the case, the low-pressure steam
ing additional income. can of course also be fed to a turbo alternator, but on account
In the past, considerable efforts have been made to utilize of the low steam pressure this is generally not very economi
the heat released during the oxidation (combustion) of cal. Consequently, the majority of plants which are currently
elemental sulphur to form SO by means of atmospheric 45 in operation are not equipped with Such systems.
oxygen and the heat released during the catalytic oxidation of The remainder of the heat generated in the sulphuric acid
SO, to form SO, as completely as possible for the generation production, amounting to 15-20%, is generally dissipated to
of high-pressure steam. Various pieces of apparatus, for cooling water and thereby withdrawn from active use. A small
example evaporators, economizers (boiler feedwaterpreheat
ers) and steam Super heaters are in this case connected up in 50 amount of this heat, can additionally be recovered by fresh,
“cold' feedwater (typically 20-30° C. as return from for
a suitable way for the generation of steam, with process example condenser of a condensation turbine/alternator)
engineering boundary conditions being the main determining being indirectly heated with the “hot” sulphuric acid (typi
factors. For example, the predetermined reaction tempera cally 80-110° C.) before this feedwater then passes to the
tures for catalysis need to be complied with, and within cer
tain limits the desired steam quality (e.g. pressure and tem- 55 thermal deaeration. Preheating to above, for example, 85-90°
C. is not possible, since the atmospheric thermal deaeration
perature) also has to be taken into account. This steam can still requires a certain temperature increase of 10-20°C. in
then be converted into electrical energy in a known way by order for this deaeration to be operated efficiently and effec
means of a turbo alternator. If, for example, elemental Sulphur tively. Therefore, this additional degree of heat recovery is
is used as starting material, depending on the process and
steam quality produced (pressure and temperature), generally 60 also limited.
about 60% of the energy which was originally present in the SUMMARY OF THE INVENTION
Sulphur is utilized for Steam generation. The degree of energy
conversion for the generation of high-pressure steam is
restricted by the limited options for cooling the process gas It is an object of the present invention to further improve the
prior to the intermediate or final absorption. To prevent the 65 utilization of heat in the production of sulphuric acid.
temperature from dropping below the Sulphuric acid dew The invention substantially achieves this object by the fea
point, for example, the process gases should not be cooled to tures of Claims 1 and 19, with the temperature of the feed
 US 7,837,970 B2
3 4
water fed to the heat recovery apparatus for steam generation The preheating of the cold feedwater before it enters the
being higher than the temperature of the process gas which thermal deaeration according to the invention is carried out
enters the absorber. indirectly by means of waste heat from the absorption part
As a result, it is possible to increase the proportion of and/or the contact part of the Sulphuric acid plant.
higher-quality high-pressure steam which is generated and to 5 In a refinement of the invention, the thermal deaeration of
use heat which is conventionally utilized only for the genera the feedwater is operated at a pressure which is higher than
tion of low-pressure Steam for this purpose. At the same time, atmospheric pressure, preferably at 3-10 bar.
the amount of low-pressure steam can be kept approximately In another embodiment, the feedwater is deaerated under
constant, which ultimately leads to a lower heat loss (for atmospheric conditions and before it enters the heat recovery
example to cooling water). 10 apparatus is heated in a heat exchanger to a temperature above
With otherwise identical boundary conditions, in the pro the temperature of approximately 105° C. produced during
cess according to the invention the thermal deaeration of the the deaeration.
boiler feedwater is carried out for example at higher tempera In this case, the heating of the feedwater is carried out, for
ture or higher pressure. As a result, it is possible to pre-heat example, by means of low-pressure steam, imported waste
the “cold' feedwater by means of low-temperature heat to a 15 steam, medium-pressure Steam (at a pressure below the pres
much higher temperature of, for example, 165°C. (compared Sure of the high-pressure Steam generated in the plant) or
to conventionally 85°C.). This in turn ultimately allows a heated heat-transfer oil originating from outside the plant.
higher temperature of, for example, 175° C. of the boiler According to the invention, the economizers are arranged
feedwater passed into the plant for high-pressure Steam gen in Such a way that in thermodynamic terms it is possible to
eration. For the same total available heat quantity, it is as a transfer the excess heat out of the process, with the degree of
result possible to increase the quantity of high-pressure steam excess heat which is transferred being comparable to that of a
which is generated compared to the conventional process conventional plant involving the thermal feedwater deaera
with boiler feedwater which is at only approx. 105°C. tion being operated at atmospheric pressure.
As an alternative to pressure deaeration, it is of course also The gases which emerge from the heat recovery apparatus
possible for the deaerator to continue to be operated at atmo 25 are preferably at a temperature of approximately 170-350° C.
spheric pressure, but in this case downstream the boiler feed which is equal to or above (2171°C.) the conventional tem
pump the feedwater is to be heated to a higher inlet tempera peratures of 120-170° C., and the further cooling of these
ture (into the economizer) by means of heat exchangers using gases (and hence indirect heat recovery for high-pressure
the low-pressure steam. Naturally, the maximum temperature steam generation) can be utilized for the partial heating of for
in this context is slightly below the temperature which can be 30
example, combustion air, for the reheating of the gases from
achieved for the same low-pressure Steam pressure during the intermediate absorption and/or for the partial heating/
pressure deaeration. preheating of feedwater before it enters the thermal deaera
However, this gives rise to a thermodynamic obstacle, tion.
since boiler feedwater of, for example, 175° C. can no longer In particular low-pressure Steam, for example Saturated
be utilized to cool the process gases to 130-170° C. for 35
steam at a pressure of approximately 10 bar, is used for the
example in an economizer. Therefore, the invention also thermal deaeration.
relates to possible ways of indirectly getting round this It is also possible for demineralized water to be used as
obstacle and as a result still ensuring the above-described feedwater.
increased production of high-pressure steam. If, in a plant according to the invention, there is a device for
According to a preferred configuration of the invention, the 40
generating low-pressure steam, it is preferable for the low
temperature difference between feedwater and the process pressure steam to be at least partially fed to the deaerator. The
gas which enters the absorber is between 5° C. and 100° C. pressure of the low-pressure steam is in this case kept at a
preferably 20-50° C. level which is above the pressure of the device for thermal
According to the invention, the feedwater is fed to the deaeration.
high-pressure part of the heat recovery apparatus at a tem 45
According to a preferred configuration of the invention, the
perature of over 102° C., preferably 140-1900C., with the
process gas preferably being withdrawn from the converter at absorbers and a drying tower for drying air with the aid of
an intermediate contact stage, fed to an intermediate absorber Sulphuric acid are connected to a common pump system for
and then being fed back into the converter, and the process Supplying Sulphuric acid, as described in the Applicant's DE
10 2004 O12 293.8.
gas, after it has passed through the final contact stage of the 50
converter, being fed to a final absorber, with the gas inlet In this case, it is preferable for the heat recovery apparatus,
temperature at the intermediate absorber being approxi which is intended to cool the gas prior to the intermediate
mately 130-170° C. and at the final absorber being approxi absorption, to have a gas bypass.
mately 120-150° C. If a separate hot absorber is provided, this too has a gas
Before it enters the heat recovery apparatus, the feedwater 55 bypass according to the invention.
is thermally deaerated, preferably at a feed temperature of The invention is explained in more detail below on the
20-90° C., which then rises to, for example, 102-105° C. basis of exemplary embodiments and the drawing. All the
during the deaeration. features described and/or illustrated in the figures, either on
In a particularly preferred configuration of the invention, their own or in any desired combination, form the subject
the cold feedwater which has not been deaerated, by contrast, 60 matter of the invention, irrespective of the way in which they
is preheated to over 105° C. preferably to 130-190° C., and in are summarized in the claims or the way in which the claims
particular to approximately 165°C., before it enters the ther are referred back.
mal deaeration, in which case the maximum preheating tem
perature of the feedwater is preferably approximately 5 to 20° BRIEF DESCRIPTION OF THE DRAWING
C. below the steam saturation temperature for the pressure at 65
which the deaerator is operated, so that the function of ther FIG. 1 diagrammatically depicts a conventional double
mal deaeration is still retained. catalysis contact plant for the production of Sulphuric acid,
 US 7,837,970 B2
5 6
FIG. 2 shows the water or steam circuit of a plant as shown ate or final absorption is typically 160° C. at the water heater
in FIG. 1, and 140°C. at the heat exchanger CRE, which means there
FIG. 3 diagrammatically depicts a plant for producing fore that the heat quantity transferred to the high-pressure
Sulphuric acid by the process according to the invention, steam generators (WHB, 1, ECO2. SHE1, SHE2) within the
FIG. 4 shows a variant of the plant shown in FIG. 3, 5 contact system is identical to that of Example 1. The water
FIG. 5 shows a further modification to a plant according to heater mentioned in FIG. 3 in this case serves to preheat the
the invention, “cold' feedwater prior to the thermal deaeration, or alterna
FIG. 6 shows a variant on the plant shown in FIG. 4. tively to utilize the heat in other ways, for example heating of
FIG. 7 shows a variant on the plant shown in FIG. 5, imported water. Table 1 shows the respective gas composi
FIG. 8 shows a further modification to a plant according to 10 tions and flows for a Sulphuric acid plant with a capacity of
the invention, 3000 t/day. (The numbers given in line 1 of Tables 1 to 8 in
FIG.9 shows a drying and absorption plant for use with one each case relate to the points denoted by the corresponding
of the plants shown in FIG. 3 to 8, number in the associated figure).
FIG. 10 shows a modification to the plant shown in FIG.9, EXAMPLE 4
FIG. 11 shows the steam and water arrangement of the 15
high-pressure and low-pressure steam generation of the
plants shown in FIGS. 3 to 8 with a drying and absorption FIG. 4 shows a double catalysis contact plant in accordance
plant as shown in FIG. 9. with Example 3, except that, with otherwise identical param
FIG. 12 shows the steam and water arrangement of the eters, the water heater is replaced by a heat exchanger GHE
high-pressure and low-pressure steam generation of the 20 which is used to preheat Some of the air required in the plant.
plants shown in FIG.3 to 8 with a drying and absorption plant The arrangement then typically corresponds to the applica
as shown in FIG. 10, tion if for example, the Sulphur combustion is carried out
FIG. 13 shows the steam and water arrangement of the with SO concentrations (e.g. 17-18% by volume) which are
high-pressure and low-pressure steam generation of the above the concentration fed to the contact system (e.g. 11.8%
plants shown in FIG.3 to 8 with a drying and absorption plant 25 by volume), and therefore further air is required for dilution,
as shown in FIG. 9 with a modified form of operation, which is then preheated in the GHE as described above. The
FIG. 14 shows the steam and water arrangement of the SO-side gas outlet temperature is typically 173° C. at the
high-pressure and low-pressure steam generation of the GHE and 140° C. at the heat exchanger CRE, which means
plants shown in FIGS. 3 to 8 with a conventional drying and that the quantity of heat transferred to the high-pressure steam
absorption plant. 30 generators (WHB, ECO1, ECO2, SHE1, SHE2) within the
contact system is therefore approximately identical to the
DESCRIPTION OF THE PREFERRED quantity in accordance with Example 1. Table 2 shows the
EXEMPLARY EMBODIMENTS respective gas compositions and flows for a Sulphuric acid
plant with a capacity of 3000 t/day.
EXAMPLE1 35 EXAMPLE 5
FIG. 1 shows a conventional double catalysis contact plant, FIG. 5 shows a detailed illustration of a double catalysis
in which the economizers ECO1 and ECO2 are each arranged contact system, similar to Example 4, but with a total of 5
directly in the gas stream upstream of the final absorption and contact levels, a heat exchanger integrated in the converter
intermediate absorption, respectively. The gas outlet tem- 40 and quench cooling between the contact stages 4 and 5, with
perature is typically 140°C. at the outlet of ECO1 and 170° C. a wearing heat exchanger connected upstream of the outer
at the outlet of ECO2, with the two economizers being con CRE. The air preheater has the same function as the GHE in
nected either in series or in parallel on the water side, and the Example 4. The plant is equipped with corresponding
boiler feedwater fed to the plant being at a temperature of bypasses (indicated by dashed lines) to control the tempera
typically 105° C. 45 tures at the inlet into the respective catalyst beds. The gas
EXAMPLE 2
outlet temperatures to the intermediate and final absorption
are approximately identical to those in Example 4.
FIG. 2 shows the corresponding conventional water or EXAMPLE 6
steam circuit. The preheater shown in the feedwater inlet is in 50
this case fed on the shell side with hot sulphuric acid from the FIG. 6 shows a double catalysis contact system in accor
absorption part, with acid temperatures of 60-120° C. typi dance with Example 4, in which with otherwise identical
cally occurring and the feedwater being heated from typically parameters the heat exchanger (air preheater in Example 5) is
20-40°C. to approx. 85-90° C. used not to preheat dilution air but rather to partially reheat
55 the gases from the intermediate absorber (now CRE2). This
EXAMPLE 3 arrangement then typically corresponds to the application if
for example the sulphur combustion is operated with the same
FIG.3 shows a double catalysis contact plant, in which the or a slightly higher concentration (e.g. 11-13% by Volume) as
economizers ECO1 and ECO2 are arranged in such away that the gas which is fed to the contact system (e.g. 11.5% by
they can be fed either in series or in parallel with boiler 60 volume). In this case, the heat exchangers CRE1 and CRE2
feedwater at typically 175, and consequently the gas outlet are connected in parallel on the SO, gas side. The SO-side
temperatures at these apparatuses cannot be lower than this gas outlet temperature is typically 170° C. at CRE2 and 140°
temperature of the boiler feedwater, but rather are typically C. at heat exchanger CRE1, which means that the heat quan
200° C. and 334°C., respectively. The residual gas heat is in tity transferred to the high-pressure steam generators (WHB,
this case utilized to partially heat the gas from the intermedi- 65 ECO1, ECO2. SHE1, SHE2) within the contact system is
ate absorption in the CRE and/or to preheat or heat deminer therefore approximately identical to the quantity in accor
alized water. The gas temperature upstream of the intermedi dance with Example 2.
 US 7,837,970 B2
7 8
EXAMPLE 7 EXAMPLE 11

FIG. 7 shows an alternative embodiment of Example 5, in FIG. 11 shows the steam and water arrangement/circuit of
which the air which has been preheated in the air heater is the individual elements of the high-pressure and low-pressure
entirely passed into the combustion furnace for combustion of 5
steam generation as typically arranged when using the con
the Sulphur. In this case too, the gas outlet temperatures to the tact system in accordance with Examples 3-8 and in combi
intermediate and final absorption are approximately identical nation with the drying and absorption system in accordance
to Example 6. with Example 9. The starting point in this context is for the
EXAMPLE 8 10 deaerator to be operated at 9 bar. The demineralized water,
before it enters the deaerator, is preheated within the drying
FIG. 8 shows another embodiment of Example 5 with a and absorption system, in this case to 98°C. at the outlet of the
5-stage contact system and two heat exchangers located preheater 2. Table 6 shows the respective temperatures, con
within the converter for re-heating the gases following the centrations and flows for a Sulphuric acid plant with a capac
intermediate absorber, and in addition the steam Superheater 15 ity of 3000 t/day.
SHE2 integrated in the converter. The air which has been EXAMPLE 12
preheated in the air preheater is partially passed for Sulphur
combustion and partially utilized for further dilution of the
combustion gases. This example constitutes a typical FIG. 12 shows the steam and water arrangement/circuit of
embodiment of the present invention. Table 3 shows the the individual elements of the high-pressure and low-pressure
respective gas compositions and flows for a Sulphuric acid steam generation as typically arranged when using the con
plant with a capacity of 3000 t/day. tact system shown in Examples 3-8 and in combination with
the drying and absorption system in accordance with
25 Example 10. The starting point in this case is for the deaerator
EXAMPLE 9 to be operated at 9 bar. Within the drying and absorption
system and before it enters the deaerator, the demineralized
water is in this case preheated to 166° C. at the outlet of the
FIG. 9 shows the drying and absorption system belonging acid cooler 3. Table 7 shows the respective temperatures,
to the contact system of Examples 3-8, with a heat recovery 30 concentrations and flows for a Sulphuric acid plant with a
system "HEROS (from HEat RecCovery System) for the capacity of 3000 t/day.
generation of low-pressure steam being integrated. Accord EXAMPLE 13
ing to the process of the invention, all the acid circuits of the
towers, i.e. drying tower, intermediate absorber and final 35
absorber, are designed as a common circuit with the same acid FIG. 13 shows the steam and water arrangement/circuit of
concentration and the same acid feed temperature. Only the the individual elements of the high-pressure and low-pressure
HEROS absorber is equipped with its own acid circuit, with steam generation as typically arranged when using the con
the temperature level here being significantly higher than in tact system in accordance with Examples 3-8 and in combi
nation with the drying and absorption system in accordance
the abovementioned acid circuit, specifically so high that 40
with Example 9. The starting point is in this case for the
low-pressure steam at typically 6-10 bar can be produced deaerator to be operated atmospherically, i.e. at approx. 0.1
directly in the evaporator. Also, the gas bypass around the bar and equivalent approx. 105° C. and for the boiler feedwa
"HEROS' absorber inaccordance with patent application DE terfor high-pressure steam generation to be heated by means
10 2004.012293.8 is illustrated, which is hereby, in particular 45 of low-pressure steam in the steam heaterheat exchanger. The
to the extent illustrated, incorporated in the subject matter of boiler feedwater for the low-pressure steam generation is
the present application. Table 4 shows the temperatures, con preheated by means of hot acid in the preheater 2. No data
centrations and flows for a Sulphuric acid plant with a capac table is given, since the results are similar to those achieved in
ity of 3000 t/day. Example 11 or 12.
50
EXAMPLE 10 EXAMPLE 1.4

FIG. 10, like Example 9, shows the integration of the heat FIG. 14 shows the steam and water arrangement/circuit of
recovery by means of "HEROS', but in this case with an the individual elements of the high-pressure and low-pressure
arrangement which is applied in particular for large plants, 55 steam generation as typically arranged when using the con
i.e. with a capacity of over 3000 t/d, although it can in prin tact system in accordance with Examples 3-8 and in conjunc
ciple also be applied to smaller plants. All the absorbers and tion with a conventional drying and absorption system with
the drying tower are designed as integrated Venturi packed out additional low-pressure steam production HEROS, with
towers, the intention being to improve the gas distribution. In the feedwater temperature consequently being typically 85°
this case, the heat to be dissipated from the drying tower and 60 C. In this context, it has likewise been assumed that the
the two SO absorbers is also completely recovered. In this deaerator is operated atmospherically, i.e. at approximately
case, only a small proportion is still removed from the system 0.1 bar and equivalent approx. 102°C., and the boiler feed
by means of cooling water, i.e. only the cooling of the product water for high-pressure steam generation is heated by means
acid. The plant circuit according to this example can belong to of imported low-pressure steam in the preheater heat
any contact system as shown in Examples 3-8. Table 5 shows 65 exchanger. Table 8 shows the respective temperatures, con
the respective temperatures, concentrations and flows for a centrations and flows for a Sulphuric acid plant with a capac
sulphuric acid plant with a capacity of 3000 t/day. ity of 3000 t/day.
 US 7,837,970 B2
12
TABLE 3-continued
SO, %-vol. O O O O 18
SO %-vol. O O O O O
O %-vol. 20.9 20.9 20.9 20.9 2.57
N %-vol. 79.1 79.1 79.1 79.1 79.43
Temperature C. 135 115 1684 168.4 1684 543.3

Number 6 7 8 9 10 11

Sulphur kg/h
Gas m/h (s.t.p.) 236900 228,349 228,349 224 779 224 779 223 633
SO, %-vol. 11.8 4.9 4.9 1.87 1.87 0.79
SO %-vol. O 7.35 7.35 10.59 10.59 11.73
O2 %-vol. 8.89 5.46 5.46 3.96 3.96 3.44
N %-vol. 79.31 82.28 82.28 83.59 83.59 84.04
Temperature C. 420 622.9 440 525.5 430 463.1

Number 12 13 14 15 16 17

Sulphur kg/h
Gas m/h(s.t.p.) 223 633 223 633 197394 197394 180 186 17 208
SO, %-vol. 0.79 0.79 O.89 O.89 O.89 O.89
SO %-vol. 11.73 11.73 O O O O
O2 %-vol. 3.44 3.44 3.9 3.9 3.9 3.9
N %-vol. 84.04 84.04 95.21 95.21 95.21 95.21
Temperature C. 200 150 82 274 274 274

Number 18 19 2O 21 22 23

Sulphur kg/h
Gas m/h(s.t.p.) 197394 196532 196532 1965.15 1965.15 1965.15
SO, %-vol. O.89 O.04 O.04 O.O2 O.O2 O.O2
SO %-vol. O O.86 O.86 O.88 O.88 O.88
O2 %-vol. 3.9 3.47 3.47 3.46 3.46 3.46
N %-vol. 95.21 95.63 95.63 95.64 95.64 95.64
Temperature C. 415 442.4 410 410.6 309.7 135

TABLE 4
Number 1 2 3 4 5 6 7 9

Aci kg/h 217538 217103 435 217103 18512 198591, 1950SS 4436863
Concentration % H2SO 98.5
Temperature o C. 2O 2O 2O 85 85 98 95.7
Flow rate m/h 218 217.5 0.4 224 19.1 205 206.9 2S19.6

Number 10 11 12 14 15

Aci kg/h 1681863 2755OOO 2755OOO 1681863 1597232, 1419762

Concentration % H2SO 98.5 98.5 98.5 98.5 98.5 98.5
Temperature o C. 95.7 95.7 82 82 82 82
Flow rate m/h 955.1 1564.5 1552.4 947.7 900 800

Number 16 17 18 2O 21

Aci kg/h 1419762 16O2848 1459.270 14257OO 126904 126904

Concentration % HSO 98.5 98.58 98.81 98.09 98.5 98.5
Temperature o C. 82 90.8 110.4 85.9 95.7 40
Flow rate m/h 800 907.7 835.9 804.9 72.1 69.8

Number 22 23 24 25 26

Acid kg/h 2607052 75949 2683OOO 2683OOO 75949

Concentration % H2SO 98.5 98.5 98.5 98.5 98.5
Temperature o C. 185 185 18S 210.7 99
Flow rate m/h 1560 45.4 1605.4 1630.6 43.2

TABLE 5
Number 1 2 3 4 6 7 8

Acid kg/h 23.9994 23.9994 O 23.9994 23.9994 18948 221045 221045

Concentration % HSO
Temperature o C. 30 30 30 45.8 69.5 69.5 69.5 1661
Flow rate m/h 241.1 241.1 O 242.4 245.3 19.4 225.9 244.9
 US 7,837,970 B2

TABLE 5-continued
Number 9 10 11 12 13 14

Acid kg/h 177118O 1777115 2005040 177118O 233861 55069

Concentration % H2SO 96 95.68 96 96 96 96
Temperature o C. 67 71.8 72.9 72.9 72.9 72.9
Flow rate m/h 990 996 112S 993 131 31

Number 15 16 17 18 19 2O

Acid kg/h 294127 178792 2271 610 1922414 2271 610 227925
Concentration % HSO 98.5 96 98.5 98.57 98.5 98.5
Temperature o C. 90 72.9 82 89.4 89 85
Flow rate m/h 167 1OO 128O 1048 1285 128

Number 21 22 23 24 25 26

Acid kg/h 127007 2SO678O 30924O6 S85626 S85626 291499

Concentration % H2SO 98.5 98.5 98.5 98.5 98.5 98.5
Temperature o C. 40 185 204 185 90 90
Flow rate m/h 70 1SOO 1872 350 332 16S

TABLE 6
Number

Dimension 1 2 3 4 5 6 7

Flow rate kg/h 198 591 180 570 180 570 180 57O 178 782 178 782 178 782
Pressure bar abs. 10 71 69 67 66 64 62
Temperature C. 98 175.4 235 266 281.8 341 48O

Number

Dimension 8 9 10 11 12 13 14

Flow rate kg/h 1 788 56 927 56 363 38 S41 17 822 S 601 33 369
Pressure bar abs. 66 12 10 10 1O 10 10
Temperature C. 281.8 175.4 179.9 179.9 179.9 179.9 179.9

Number

Dimension 15 16 17 18 19 2O

Flow rate kg/h S S36430 1 358 S64 5515 4156

Pressure bar abs. 10 10 9 10 1 1
Temperature o C. 90 179.9 177.7 179.9 60 2O

TABLE 7
Number

Dimension 1 2 3 4 5 6 7

Flow rate kg/h 221 O4S 179 312 179 312 179 312 176 662 176 662 176 662
Pressure bar abs. 10 72 69 67 67 65 62
Temperature C. 166.1 175.4 238.3 265.7 282.8 338.6 48O

Number

Dimension 8 9 10 11 12 13 14

Flow rate kg/h 2 650 48 946 48 461 6 S79 41 864 2 393 4 847
Pressure bar abs. 67 12 10 10 1O 10 10
Temperature C. 282.8 175.4 179.9 179.9 179.9 179.9 179.9

Number

Dimension 15 16 17 18 19 2O

Flow rate kg/h 2 365644 2 OO6 485 7239 5233

Pressure bar abs. 10 10 9 10 1 1
Temperature o C. 90 179.9 177.7 179.9 60 2O
 US 7,837,970 B2

TABLE 8
Number

Dimension 1 2 3 4 5 6 7

Flow rate kg/h 1SO487 1793.12 179 312 179 312 179 312 176 662 176 662
Pressure bar abs. 2 72 71 69 67 67 65
Temperature C. 85 102 175.4 238.3 265.7 282.8 338.6

Number

Dimension 8 9 10 11 12 13 14

Flow rate kg/h 1766.62 2 6SO 28 82S114 28311 28311

Pressure bar abs. 62 67 12 12 12 12
Temperature C. 480 282.8 188 188 188 188

LIST OF REFERENCE NUMBERS 7. Process according to claim 5, wherein the feedwater is

preheated to over 105°C., preferably to 130-190° C., and in
CRE Cold Reheat Exchanger (Gas-Gas heat exchanger) particular to approximately 165°C., before it enters the ther
ECO Economizer (boiler feedwater preheater) mal deaeration.
GHE Gas Heat Exchanger (Gas-air heat exchanger) 8. Process according to claim 7, wherein the maximum
HRE. Hot Reheat Exchanger (Gas-gas heat exchanger) preheating temperature of the feedwater is approximately 5 to
WHB Waste Heat Boiler 20° C. below the steam saturation temperature of the pressure
SHE Superheater 25 at which the deaerator is operated.
9. Process according to claim 7, wherein the preheating of
LP Low Pressure the cold feedwater before it enters the thermal deaeration is
HP High Pressure carried out indirectly by means of waste heat from the absorp
The invention claimed is:
tion part and/or from the contact part of the Sulphuric acid
30
plant.
1. Process for producing Sulphuric acid from a process gas 10. Process according to claim 1, wherein the feedwater is
containing SO2 comprising, deaerated under atmospheric conditions, and before it enters
catalytically oxidizing SO in a converter with at least one the heat recovery apparatus is heated in a heat exchanger to a
contact stage to form SO-containing process gas; temperature above the temperature of approximately 105°C.
withdrawing from the converter and feeding to an appara which is caused during the deaeration.
tus for heat recovery, in which steam is generated from 35 11. Process according to claim 10, wherein the heating of
feedwater by means of the heat of the process gas, the the feedwaterprior to the thermal deaeration is carried out, for
SO containing process gas, after it has passed through example, by means of low-pressure steam, imported waste
the at least one contact stage; and then steam, medium-pressure steam (at a pressure lower than the
feeding the SOs containing process gas to an absorber in high-pressure steam generated in the plant) or heated heat
which the SO, is absorbed in sulphuric acid, 40 transfer oil originating from outside the plant.
wherein the temperature of the feedwater fed to the heat 12. Process according to claim 1, wherein-the gases which
recovery apparatus for steam generation is higher than emerge from the heat recovery apparatus are at a temperature
the temperature of the process gas which enters the of approximately 170-350° C.
absorber. 13. Process according to claim 12, wherein the gases which
2. Process according to claim 1, wherein the temperature 45 emerge from the heat recovery apparatus are utilized for the
difference between the feedwater and the process gas which partial heating of, for example, combustionair, for the reheat
enters the absorber is between 5° C. and 100° C., preferably ing of the gases from the intermediate absorption and/or for
20-50° C. the partial heating/preheating offeedwater before it enters the
3. The process as claimed in claim 1, wherein the feed thermal deaeration.
water is fed to the heat recovery apparatus at a temperature of 50
14. Process according to claim 1, wherein low-pressure
over 102°C., preferably 140-190° C. steam, for example Saturated Steam at a pressure of approxi
4. Process according to claim 1, wherein the process gas is mately 10 bar, is used for the thermal deaeration.
withdrawn from the converter at an intermediate contact 15. Process according to claim 1, wherein the absorbers
stage, is fed to an intermediate absorber and is then fed back and a drying towerfor drying air with the aid of sulphuric acid
in to the converter, and in that the process gas, after it has are operated with a common acid circuit at the same concen
55 tration.
passed through the final contact stage of the converter, is fed 16. Process according to claim 15, wherein the sulphuric
to a final absorber, with the gas inlet temperature at the inter acid plant is operated with a separate hot absorber, this hot
mediate absorber being approximately 130-170° C. and at the absorber being equipped with a gas bypass.
final absorber being approximately 120-150° C. 17. Process according to claim 1, wherein the heat recovery
5. Process according to claim 1, wherein the feedwater is 60 apparatus, which is intended to cool the gas prior to the
thermally deaerated, preferably at a feed temperature of intermediate absorption, has a gas bypass.
20-90° C., before it enters the heat recovery apparatus. 18. Process according to claim 1, wherein the feedwater
6. Process according to claim 5, wherein the thermal used is demineralized water.
deaeration of the feedwater is operated at a pressure higher
than atmospheric pressure, preferably at 3-10 bar. k k k k k