TEPZZ_85__7ZB_T

(19)

(11) EP 1 851 170 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C01B 17/76 (2006.01)
07.05.2014 Bulletin 2014/19
(86) International application number:
(21) Application number: 06706875.9 PCT/EP2006/001260

(22) Date of filing: 11.02.2006 (87) International publication number:

WO 2006/087150 (24.08.2006 Gazette 2006/34)

(54) PROCESS AND PLANT FOR THE PRODUCTION OF SULPHURIC ACID

VERFAHREN UND ANLAGE ZUR HERSTELLUNG VON SCHWEFELSÄURE
PROCEDE ET INSTALLATION DESTINES A LA PRODUCTION D’ACIDE SULFURIQUE

(84) Designated Contracting States: (74) Representative: Keil & Schaafhausen

DE ES FR IT Patent- und Rechtsanwälte
Friedrichstrasse 2-6
(30) Priority: 21.02.2005 DE 102005008109 60323 Frankfurt am Main (DE)

(43) Date of publication of application: (56) References cited:

07.11.2007 Bulletin 2007/45 WO-A-91/14651 DE-A1- 3 000 599
DE-A1- 19 522 927 US-A- 3 490 868
(73) Proprietor: Outotec Oyj US-A- 4 996 038 US-B1- 6 279 514
02230 Espoo (FI)

(72) Inventor: DAUM, Karl-Heinz

55124 Mainz (DE)
EP 1 851 170 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 851 170 B1

Description

Field of the invention

5 [0001] The invention relates to a process and a plant for the production of sulphuric acid by catalytic oxidation of SO2
to form SO3 in a converter with at least one contact stage, the SO3-containing process gas, after it has passed through
at least one contact stage, being withdrawn from the converter and fed to an apparatus for heat recovery, in which steam
is generated from feedwater by means of the heat of the process gas, and the process gas then being fed to an absorber
in which the SO3 is absorbed in sulphuric acid.
10 [0002] Sulphuric acid is usually produced by what is known as the double absorption process, as described in Ullmann’s
Encyclopaedia of Industrial Chemistry, 5th Edition, Volume A 25, pages 635 to 700. Sulphur dioxide (SO2) obtained by
combustion of sulphur or as a waste gas from metallurgical plants is converted into sulphur trioxide (SO3) in a four-stage
or five-stage converter with the aid of a solid catalyst, for example comprising vanadium pentoxide as active component.
After the contact stages of the converter, the SO3 obtained is withdrawn and fed to an intermediate absorber or, after
15 the last contact stage of the converter, to a final absorber, in which the gas containing SO3 is passed in countercurrent
to concentrated sulphuric acid and absorbed therein.
[0003] Plants for producing sulphuric acid from elemental sulphur in economic terms "suffer" from the fact that the
costs of the raw material sulphur often significantly exceed the income which can be realized from the product sulphuric
acid.
20 [0004] These plants can be operated economically only by maximizing/optimizing the generation of by-products, such
as high-pressure and low-pressure steam, and thereby generating additional income.
[0005] In the past, considerable efforts have been made to utilize the heat released during the oxidation (combustion)
of elemental sulphur to form SO 2 by means of atmospheric oxygen and the heat released during the catalytic oxidation
of SO2 to form SO3 as completely as possible for the generation of high-pressure steam. Various pieces of apparatus,
25 for example evaporators, economizers (boiler feedwater preheaters) and steam super heaters are in this case connected
up in a suitable way for the generation of steam, with process engineering boundary conditions being the main determining
factors. For example, the predetermined reaction temperatures for catalysis need to be complied with, and within certain
limits the desired steam quality (e.g. pressure and temperature) also has to be taken into account. This steam can then
be converted into electrical energy in a known way by means of a turbo alternator. If, for example, elemental sulphur is
30 used as starting material, depending on the process and steam quality produced (pressure and temperature), generally
about 60% of the energy which was originally present in the 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 prior to the intermediate or final absorption. To prevent the temperature from dropping below the sulphuric acid dew
point, for example, the process gases should not be cooled to below 130-170°C. A further restriction results from the
35 use of deaerated boiler feedwater (i.e. boiler feedwater from which dissolved oxygen has been substantially removed)
in the steam generators (e.g. economizers), which is necessary in order to avoid corrosion on the water side. The so-
called unpressurized (typically 0.1 - 0.3 bar, all pressures are given relative to atmospheric pressure) thermal deaeration
of the feedwater which is generally used means that the temperature of the feedwater is approximately 102-105°C. In
thermodynamic terms, therefore, significant, economically justifiable gas cooling to below 130°C would hardly be possible
40 even without taking into account dew point corrosion.
[0006] During the subsequent part of the conventional process for producing sulphuric acid, the gases are cooled
further both during the intermediate absorption and during the final absorption. This sensible energy, like the energy
from the condensation of the SO3 and the heat released through the energy of formation of H2SO4 from SO3 and H2O
and the dilution of the sulphuric acid formed, is consequently at a low temperature level and is generally removed from
45 the process indirectly by means of cooling water.
[0007] In the past, various processes have been developed for also obtaining some of this heat as low-pressure steam,
and thereby overall increasing the economic viability of the plant, cf. in this respect US patent 4,670,242 held by Monsanto
(also EP 0 181 313 B1) and the "HEROS" process developed by Lurgi in accordance with DE 38 30 365 C2. Numerous
attempts have been made to improve these processes, but these modifications have hitherto been of only limited use.
50 Reference may be made to the Monsanto patent US 4,576,813 (EP 0 130 967 B1) and the Outokumpu process in
accordance with the as yet unpublished German patent application DE 10 2004 012 293.8. Document DE 195 22 927
A1 discloses a process for the production of concentrated sulphuric acid by converting SO 2 to SO 3 in a multistage
converter in the presence of steam. From the final stage of the converter, the process gas is fed via a superheater and
heat exchangers to an absorber. In the superheater, the steam having the temperatures of 250 °C is heated by heat
55 exchange with the process gas exiting the last stage of the converter to a temperature of 300 °C. The process gas
leaving the superheater is cooled in heat exchanger and air preheater before entering the final absorber. Depending on
the process engineering circuit and quality of the low-pressure steam (generally saturated steam at 6-10 bar), it is
possible to increase the overall efficiency from approx. 60% to up to 80-85%. However, the use of these low-temperature

2
 EP 1 851 170 B1

heat recovery processes is restricted to situations in which there are available consumers for low-pressure steam, which
is of a reduced quality. If this is not the case, the low-pressure steam can of course also be fed to a turbo alternator, but
on account of the low steam pressure this is generally not very economical. Consequently, the majority of plants which
are currently in operation are not equipped with such systems.
5 [0008] The remainder of the heat generated in the sulphuric acid production, amounting to 15-20%, is generally
dissipated to cooling water and thereby withdrawn from active use. A small amount of this heat, can additionally be
recovered by fresh, "cold" feedwater (typically 20-30°C as return from for example condenser of a condensation tur-
bine/alternator) being indirectly heated with the "hot" sulphuric acid (typically 80-110°C) before this feedwater then
passes to the thermal deaeration. Preheating to above, for example, 85-90°C is not possible, since the atmospheric
10 thermal deaeration still requires a certain temperature increase of 10-20°C in order for this deaeration to be operated
efficiently and effectively. Therefore, this additional degree of heat recovery is also limited.

Summary of the invention

15 [0009] It is an object of the present invention to further improve the utilization of heat in the production of sulphuric acid.
[0010] The invention substantially achieves this object by the features of Claims 1 and 17, with the temperature of the
feedwater fed to the heat recovery apparatus for steam generation being higher than the temperature of the process
gas which enters the absorber. Before it enters the heat recovery apparatus, the feedwater is thermally deaerated,
preferably at a feed temperature of 20-90°C, which then rises to, for example, 102-105°C during the deaeration.
20 [0011] As a result, it is possible to increase the proportion of higher-quality high-pressure steam which is generated
and to use heat which is conventionally utilized only for the generation of low-pressure steam for this purpose. At the
same time, the amount of low-pressure steam can be kept approximately constant, which ultimately leads to a lower
heat loss (for example to cooling water).
[0012] With otherwise identical boundary conditions, in the process according to the invention the thermal deaeration
25 of the boiler feedwater is carried out for example at higher temperature or higher pressure. As a result, it is possible to
preheat the "cold" feedwater by means of low-temperature heat to a much higher temperature of, for example, 165°C
(compared to conventionally 85°C). This in turn ultimately allows a higher temperature of, for example, 175°C of the
boiler feedwater passed into the plant for high-pressure steam generation. For the same total available heat quantity, it
is as a result possible to increase the quantity of high-pressure steam which is generated compared to the conventional
30 process with boiler feedwater which is at only approx. 105°C.
[0013] As an alternative to pressure deaeration, it is of course also possible for the deaerator to continue to be operated
at atmospheric pressure, but in this case downstream the boiler feed pump the feedwater is to be heated to a higher
inlet temperature (into the economizer) by means of heat exchangers using the low-pressure steam. Naturally, the
maximum temperature in this context is slightly below the temperature which can be achieved for the same low-pressure
35 steam pressure during pressure deaeration.
[0014] However, this gives rise to a thermodynamic obstacle, since boiler feedwater of, for example, 175°C can no
longer be utilized to cool the process gases to 130-170°C for example in an economizer. Therefore, the invention also
relates to possible ways of indirectly getting round this obstacle and as a result still ensuring the above-described
increased production of high-pressure steam.
40 [0015] According to a preferred configuration of the invention, the temperature difference between feedwater and the
process gas which enters the absorber is between 5°C and 100°C, preferably 20-50°C.
[0016] According to the invention, the feedwater is fed to the high-pressure part of the heat recovery apparatus at a
temperature of over 102°C, preferably 140-190°C, with the process gas preferably being withdrawn from the converter
at an intermediate contact stage, fed to an intermediate absorber and then being fed back into the converter, and the
45 process gas, after it has passed through the final contact stage of the converter, being fed to a final absorber, with the
gas inlet temperature at the intermediate absorber being approximately 130-170°C and at the final absorber being
approximately 120-150°C.
[0017] In a particularly preferred configuration of the invention, the cold feedwater which has not been deaerated, by
contrast, is preheated to over 105°C preferably to 130-190°C, and in particular to approximately 165°C, before it enters
50 the thermal deaeration, in which case the maximum preheating temperature of the feedwater is preferably approximately
5 to 20°C below the steam saturation temperature for the pressure at which the deaerator is operated, so that the function
of thermal deaeration is still retained.
[0018] The preheating of the cold feedwater before it enters the thermal deaeration according to the invention is carried
out indirectly by means of waste heat from the absorption part and/or the contact part of the sulphuric acid plant.
55 [0019] In a refinement of the invention, the thermal deaeration of the feedwater is operated at a pressure which is
higher than atmospheric pressure, preferably at 3-10 bar.
[0020] In another embodiment, the feedwater is deaerated under atmospheric conditions and before it enters the heat
recovery apparatus is heated in a heat exchanger to a temperature above the temperature of approximately 105°C

3
 EP 1 851 170 B1

produced during the deaeration.

[0021] In this case, the heating of the feedwater is carried out, for example, by means of low-pressure steam, imported
waste steam, medium-pressure steam (at a pressure below the pressure of the high-pressure steam generated in the
plant) or heated heat-transfer oil originating from outside the plant.
5 [0022] According to the invention, the economizers are arranged in such a way that in thermodynamic terms it is
possible to transfer the excess heat out of the process, with the degree of excess heat which is transferred being
comparable to that of a conventional plant involving the thermal feedwater deaeration being operated at atmospheric
pressure.
[0023] The gases which emerge from the heat recovery apparatus are at a temperature of approximately 170-350°C,
10 which is equal to or above (≥ 171 °C) the conventional temperatures of 120-170°C, and the further cooling of these
gases (and hence indirect heat recovery for high-pressure steam generation) can be utilized for the partial heating of,
for example, combustion air, for the reheating of the gases from the intermediate absorption and/or for the partial
heating/preheating of feedwater before it enters the thermal deaeration.
[0024] In particular low-pressure steam, for example saturated steam at a pressure of approximately 10 bar, is used
15 for the thermal deaeration.
[0025] It is also possible for demineralized water to be used as feedwater.
[0026] If, in a plant according to the invention, there is a device for generating low-pressure steam, it is preferable for
the low-pressure steam to be at least partially fed to the deaerator. The pressure of the low-pressure steam is in this
case kept at a level which is above the pressure of the device for thermal deaeration.
20 [0027] According to a preferred configuration of the invention, the absorbers and a drying tower for drying air with the
aid of sulphuric acid are connected to a common pump system for supplying sulphuric acid, as described in the Applicant’s
DE 10 2004 012 293.8.
[0028] In this case, it is preferable for the heat recovery apparatus, which is intended to cool the gas prior to the
intermediate absorption, to have a gas bypass.
25 [0029] If a separate hot absorber is provided, this too has a gas bypass according to the invention.
[0030] The invention is explained in more detail below on the basis of exemplary embodiments and the drawing. All
the features described and/or illustrated in the figures, either on their own or in any desired combination, form the subject
matter of the invention, irrespective of the way in which they are summarized in the claims or the way in which the claims
are referred back.
30
Brief description of the drawing

[0031]

35 Fig. 1 diagrammatically depicts a conventional double catalysis contact plant for the production of sulphuric acid,

Fig. 2 shows the water or steam circuit of a plant as shown in Fig. 1,

Fig. 3 diagrammatically depicts a plant for producing sulphuric acid by the process according to the invention,
40
Fig. 4 shows a variant of the plant shown in Fig. 3,

Fig. 5 shows a further modification to a plant according to the invention,

45 Fig. 6 shows a variant on the plant shown in Fig. 4,

Fig. 7 shows a variant on the plant shown in Fig. 5,

Fig. 8 shows a further modification to a plant according to the invention,

50
Fig. 9 shows a drying and absorption plant for use with one of the plants shown in Fig. 3 to 8,

Fig. 10 shows a modification to the plant shown in Fig. 9,

55 Fig. 11 shows the steam and water arrangement of the high-pressure and low-pressure steam generation of the
plants shown in Figs. 3 to 8 with a drying and absorption plant as shown in Fig. 9,

Fig. 12 shows the steam and water arrangement of the high-pressure and low-pressure steam generation of the

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 EP 1 851 170 B1

plants shown in Fig. 3 to 8 with a drying and absorption plant as shown in Fig. 10,

Fig. 13 shows the steam and water arrangement of the high-pressure and low-pressure steam generation of the
plants shown in Fig. 3 to 8 with a drying and absorption plant as shown in Fig. 9 with a modified form of operation,
5
Fig. 14 shows the steam and water arrangement of the high-pressure and low-pressure steam generation of the
plants shown in Figs. 3 to 8 with a conventional drying and absorption plant.

Description of exemplary embodiments

10
[0032] Comparative example 1: Fig. 1 shows a conventional double catalysis contact plant, in which the economizers
ECO1 and ECO2 are each arranged directly in the gas stream upstream of the final absorption and intermediate ab-
sorption, respectively. The gas outlet temperature is typically 140°C at the outlet of ECO1 and 170°C at the outlet of
ECO2, with the two economizers being connected either in series or in parallel on the water side, and the boiler feedwater
15 fed to the plant being at a temperature of typically 105°C.
[0033] Comparative example 2: Fig. 2 shows the corresponding conventional water or steam circuit. The preheater
shown in the feedwater inlet is in this case fed on the shell side with hot sulphuric acid from the absorption part, with
acid temperatures of 60-120°C typically occurring and the feedwater being heated from typically 20-40°C to approx.
85-90°C.
20 [0034] Example 3: Fig. 3 shows a double catalysis contact plant, in which the economizers ECO1 and ECO2 are
arranged in such a way that they can be fed either in series or in parallel with boiler feedwater at typically 175°, and
consequently the gas outlet temperatures at these apparatuses cannot be lower than this temperature of the boiler
feedwater, but rather are typically 200°C and 334°C, respectively. The residual gas heat is in this case utilized to partially
heat the gas from the intermediate absorption in the CRE and/or to preheat or heat demineralized water. The gas
25 temperature upstream of the intermediate or final absorption is typically 160°C at the water heater and 140°C at the
heat exchanger CRE, which means therefore that the heat quantity transferred to the high-pressure steam generators
(WHB, 1, ECO2, SHE1, SHE2) within the contact system is identical to that of Example 1, The water heater mentioned
in Fig. 3 in this case serves to preheat the "cold" feedwater prior to the thermal deaeration, or alternatively to utilize the
heat in other ways, for example heating of imported water. Table 1 shows the respective gas compositions and flows
30 for a sulphuric acid plant with a capacity of 3000 t/day. (The numbers given in line 1 of Tables 1 to 8 in each case relate
to the points denoted by the corresponding number in the associated figure).
[0035] Example 4: Fig. 4 shows a double catalysis contact plant in accordance with Example 3, except that, with
otherwise identical parameters, the water heater is replaced by a heat exchanger GHE which is used to preheat some
of the air required in the plant. The arrangement then typically corresponds to the application if, for example, the sulphur
35 combustion is carried out with SO2 concentrations (e.g. 17-18% by volume) which are above the concentration fed to
the contact system (e.g. 11.8% by volume), and therefore further air is required for dilution, which is then preheated in
the GHE as described above. The SO3-side gas outlet temperature is typically 173°C at the GHE and 140°C at the heat
exchanger CRE, which means that the quantity of heat transferred to the high-pressure steam generators (WHB, ECO1,
ECO2, SHE1, SHE2) within the contact system is therefore approximately identical to the quantity in accordance with
40 Example 1. Table 2 shows the respective gas compositions and flows for a sulphuric acid plant with a capacity of 3000
t/day.
[0036] Example 5: Fig. 5 shows a detailed illustration of a double catalysis contact system, similar to Example 4, but
with a total of 5 contact levels, a heat exchanger integrated in the converter and quench cooling between the contact
stages 4 and 5, with a wearing heat exchanger connected upstream of the outer CRE. The air preheater has the same
45 function as the GHE in Example 4. The plant is equipped with corresponding bypasses (indicated by dashed lines) to
control the temperatures at the inlet into the respective catalyst beds. The gas outlet temperatures to the intermediate
and final absorption are approximately identical to those in Example 4.
[0037] Example 6: Fig. 6 shows a double catalysis contact system in accordance with Example 4, in which with
otherwise identical parameters the heat exchanger (air preheater in Example 5) is used not to preheat dilution air but
50 rather to partially reheat the gases from the intermediate absorber (now CRE2). This arrangement then typically corre-
sponds to the application if for example the sulphur combustion is operated with the same or a slightly higher concentration
(e.g. 11-13% by volume) as the gas which is fed to the contact system (e.g. 11.5% by volume). In this case, the heat
exchangers CRE1 and CRE2 are connected in parallel on the SO2 gas side. The SO3-side gas outlet temperature is
typically 170°C at CRE2 and 140°C at heat exchanger CRE1, which means that the heat quantity transferred to the
55 high-pressure steam generators (WHB, ECO1, ECO2, SHE1, SHE2) within the contact system is therefore approximately
identical to the quantity in accordance with Example 2.
[0038] Example 7: Fig. 7 shows an alternative embodiment of Example 5, in which the air which has been preheated
in the air heater is entirely passed into the combustion furnace for combustion of the sulphur. In this case too, the gas

5
 EP 1 851 170 B1

outlet temperatures to the intermediate and final absorption are approximately identical to Example 6.
[0039] Example 8: Fig. 8 shows another embodiment of Example 5 with a 5-stage contact system and two heat
exchangers located within the converter for reheating the gases following the intermediate absorber, and in addition the
steam super heater SHE2 integrated in the converter. The air which has been preheated in the air preheater is partially
5 passed for sulphur combustion and partially utilized for further dilution of the combustion gases. This example constitutes
a typical embodiment of the present invention. Table 3 shows the respective gas compositions and flows for a sulphuric
acid plant with a capacity of 3000 t/day.
[0040] Example 9: Fig. 9 shows the drying and absorption system belonging to the contact system of Examples 3-8,
with a heat recovery system "HEROS" (from HEat Recovery System) for the generation of low-pressure steam being
10 integrated. According to the process of the invention, all the acid circuits of the towers, i.e. drying tower, intermediate
absorber and final absorber, are designed as a common circuit with the same acid concentration and the same acid
feed temperature. Only the HEROS absorber is equipped with its own acid circuit, with the temperature level here being
significantly higher than in the abovementioned acid circuit, specifically so high that low-pressure steam at typically 6-10
bar can be produced directly in the evaporator. Also, the gas bypass around the "HEROS" absorber in accordance with
15 patent application DE 10 2004 012 293.8 is illustrated. Table 4 shows the temperatures, concentrations and flows for a
sulphuric acid plant with a capacity of 3000 t/day.
[0041] Example 10: Fig. 10, like Example 9, shows the integration of the heat recovery by means of "HEROS", but in
this case with an arrangement which is applied in particular for large plants, i.e. with a capacity of over 3000 t/d, although
it can in principle also be applied to smaller plants. All the absorbers and the drying tower are designed as integrated
20 venturi packed towers, the intention being to improve the gas distribution. In this case, the heat to be dissipated from
the drying tower and the two SO 3 absorbers is also completely recovered. In this case, only a small proportion is still
removed from the system by means of cooling water, i.e. only the cooling of the product acid. The plant circuit according
to this example can belong to any contact system as shown in Examples 3-8. Table 5 shows the respective temperatures,
concentrations and flows for a sulphuric acid plant with a capacity of 3000 t/day.
25 [0042] Example 11: Fig. 11 shows the steam and water arrangement/circuit of the individual elements of the high-
pressure and low-pressure steam generation as typically arranged when using the contact system in accordance with
Examples 3-8 and in combination with the drying and absorption system in accordance with Example 9. The starting
point in this context is for the deaerator to be operated at 9 bar. The demineralized water, before it enters the deaerator,
is preheated within the drying and absorption system, in this case to 98°C at the outlet of the preheater 2. Table 6 shows
30 the respective temperatures, concentrations and flows for a sulphuric acid plant with a capacity of 3000 t/day.
[0043] Example 12: Fig. 12 shows the steam and water arrangement/circuit of the individual elements of the high-
pressure and low-pressure steam generation as typically arranged when using the contact system shown in Examples
3-8 and in combination with the drying and absorption system in accordance with Example 10. The starting point in this
case is for the deaerator to be operated at 9 bar. Within the drying and absorption system and before it enters the
35 deaerator, , the demineralized water is in this case preheated to 166°C at the outlet of the acid cooler 3. Table 7 shows
the respective temperatures, concentrations and flows for a sulphuric acid plant with a capacity of 3000 t/day.
[0044] Example 13: Fig. 13 shows the steam and water arrangement/circuit of the individual elements of the high-
pressure and low-pressure steam generation as typically arranged when using the contact system in accordance with
Examples 3-8 and in combination with the drying and absorption system in accordance with Example 9. The starting
40 point is in this case for the deaerator to be operated atmospherically, i.e. at approx. 0.1 bar and equivalent approx. 105°C
and for the boiler feedwater for high-pressure steam generation to be heated by means of low-pressure steam in the
steam heater heat exchanger. The boiler feedwater for the low-pressure steam generation is preheated by means of
hot acid in the preheater 2. No data table is given, since the results are similar to those achieved in Example 11 or 12.
[0045] Example 14: Fig. 14 shows the steam and water arrangement/circuit of the individual elements of the high-
45 pressure and low-pressure steam generation as typically arranged when using the contact system in accordance with
Examples 3-8 and in conjunction with a conventional drying and absorption system without additional low-pressure
steam production HEROS, with the feedwater temperature consequently being typically 85°C. In this context, it has
likewise been assumed that the deaerator is operated atmospherically, i.e. at approximately 0.1 bar and equivalent
approx. 102°C, and the boiler feedwater for high-pressure steam generation is heated by means of imported low-pressure
50 steam in the preheater heat exchanger. Table 8 shows the respective temperatures, concentrations and flows for a
sulphuric acid plant with a capacity of 3000 t/day.

Table 1
Numbers 4-6 not given
55 Number 0 1 2 3 7 8
Sulphur kg/h 40948 - - - - -
Gas m3/h(s.t.p.) - 237546 237546 236 905 236 905 228 415

6
 EP 1 851 170 B1

(continued)
Numbers 4-6 not given
Number 0 1 2 3 7 8
5 SO2 %-vol. - 0 0 11.8 11.8 4.95
SO3 %-vol. - 0 0 0 0 7.3
O2 %-vol. - 20.9 20.9 8.89 8.89 5.49
N2 %-vol. - 79.1 79.1 79.31 79.31 82.26
Temperature °C 135 95 95 1 141.30 420 620.8
10
Enthalpy kcal/Nm3 - 29.74 29.74 418.97 142.98 225.15
Number 9 10 11 12 13 14
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 228 415 224 764 224 764 223.453 223453 223.453
15 SO2 %-vol. 4.95 1.85 1.85 0.71 0.71 0.71
SO3 %-vol. 7.3 10.6 10.6 11.82 11.82 11.82
O2 %-vol. 5.49 3.95 3.95 3.38 3.38 3.38
N2 %-vol. 82.26 83.6 83.6 84.09 84.09 84.09
Temperature °C 435 522.3 430 461.6 200 160
20
Enthalpy kcal/Nm3 154.06 190.27 154.74 167.85 70.02 55.65
Number 15 16 17 18 19 20
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 197 046 197 046 197 046 196 266 196 266 196266
25 SO2 %-vol. 0.8 0.8 0.8 0.028 0.028 0.028
SO3 %-vol. 0 0 0 0.78 0.78 0.78
O2 %-vol. 3.84 3.84 3.84 3,455 3,455 3,455
N2 %-vol. 95.36 95.36 95.36 79,314 95,737 95,737
Temperature °C 90 286 410 434.8 334.4 140
30 Enthalpy kcal/Nm3 28.22 90.52 131.06 139.86 106.66 44.12

Table 2
Number 0 1 2 3 4 5
35
Sulphur kg/h 40948 - - - - -
Gas M3/h(s.t.p.) - 235555 165081 164440 164 440 70474
SO2 %-vol. - 0 0 17 17 0
SO3 %-vol. - 0 0 0 0 0
40 O2 %-vol. - 20.9 20.9 3.59 3.59 20.9
N2 %-vol. - 79.1 79.1 79.41 79.41 79.1
Temperature °C 135 95 95 1521.80 506.2 95
Enthalpy kcal/Nm3 - 28.74 29.74 590.5 178.74 29.74
Number 6 7 8 9 10 11
45
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 70474 234914 226476 226476 222825 222825
SO2 %-vol. 0 11.9 5.04 5.04 1.91 1.91
SO3 %-vol. 0 0 7.31 7.31 10.65 10.65
50 O2 %-vol. 20.9 8.78 5.38 5.38 3.82 3.82
N2 %-vol. 79.1 79.32 82.27 82.27 83.62 83.62
Temperature °C 190 420 621.1 435 523 430
Enthalpy kcal/Nm3 59.76 143.05 225.42 154.15 190.88 154.65
Number 12 13 14 15 18 17
55
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 221492 221.492 221492 195 142 195142 195142
SO2 %-vol. 0.74 0.74 0.74 0.84 0.84 0.84

7
 EP 1 851 170 B1

(continued)
Number 12 13 14 15 18 17
SO3 %-vol. 11.9 11.9 11.9 0 0 0
5 O2 %-vol. 3.24 3.24 3.24 3.68 3.68 3.68
N2 %-vol. 84.12 84.12 84.12 95.48 95.48 95.48
Temperature °C 462.4 200 173.5 90 279.7 405
Enthalpy kcal/Nm3 168.3 70.07 60.52 28.23 88.51 129.42
Number 18 19 20
10
Sulphur kg/h - - -
Gas m3/h(s.t.p.) 194 332 194 332 194.332
SO2 %-vol. 0.027 0.027 0.027
SO3 %-vol. 0.818 0.818 0.818
15 O2 %-vol. 3.275 3.275 3.275
N2 %-vol. 79.316 95.879 95.879
Temperature °C 431 328.2 140
Enthalpy kcal/NM3 138.65 104.66 44.13

20

Table 3
Number 0 1 2 3 4 5
Sulphur kg/h 40948 - - - - -
25
Gas m3/h(s.t.p.) - 237541 237541 155 942 81 599 155 301
SO2 %-vol. - 0 0 0 0 18
SO3 %-vol. - 0 0 0 0 0
O2 %-vol. - 20.9 20.9 20.9 20.9 2.57
N2 %-vol. - 79.1 79.1 79.1 79.1 79.43
30 Temperature °C 135 115 168.4 168.4 168.4 543.3
Number 6 7 8 9 10 11
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 236900 228349 228349 224779 224779 223633
SO2 %-vol. 11.8 4.9 4.9 1.87 1.87 0.79
35
SO3 %-vol. 0 7.35 7.35 10.59 10.59 11.73
O2 %-vol. 8.89 5.46 5.46 3.96 3.96 3.44
N2 %-vol. 79.31 82.28 82.28 83.59 83.59 84.04
Temperature °C 420 622.9 440 525.5 430 463.1
40 Number 12 13 14 15 16 17
Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 223633 223633 197 394 197 394 180 186 17 208
SO2 %-vol. 0.79 0.79 0.89 0.89 0.89 0.89
SO3 %-vol. 11.73 11.73 0 0 0 0
45
O2 %-vol. 3.44 3.44 3.9 3.9 3.9 3.9
N2 %-vol. 84.04 84.04 95.21 95.21 95.21 95.21
Temperature °C 200 150 82 274 274 274
Number 18 19 20 21 22 23
50 Sulphur kg/h - - - - - -
Gas m3/h(s.t.p.) 197 394 196532 196532 196515 196515 196515
SO2 %-vol. 0.89 0.04 0.04 0.02 0.02 0.02
SO3 %-vol. 0 0.86 0.86 0.88 0.88 0.88
O2 %-vol. 3.9 3.47 3.47 3.46 3.46 3.46
55
N2 %-vol. 95.21 95.63 95.63 95.64 95.64 95.64
Temperature °C 415 442.4 410 410.6 309.7 135

8
 EP 1 851 170 B1

Table 4
Number 1 2 3 4 5 6
Acid kg/h 217538 217103 435 217103 18512 198591
5
Concentration %H2SO 4 - - - - - -
Temperature °C 20 20 20 85 85 85
Flow rate m3/h 218 217.5 0.4 224 19.1 205
Number 7 9 10 11 12 13
10 Acid kg/h 195055 4436863 1681863 2755000 2755000 1681863
Concentration %H2SO 4 - 98.5 98.5 98.5 98.5 98.5
Temperature °C 98 95.7 95.7 95.7 82 82
Flow rate m3/h 206.9 2519.6 955.1 1564.5 1552.4 947.7
Number 14 15 16 17 18 19
15 Acid kg/h 1597232 1419762 1419762 1602848 1459270 1425700
Concentration %H2SO 4 98.5 98.5 98.5 98.58 98.81 98.09
Temperature °C 82 82 82 90.8 110.4 85.9
Flow rate m3/h 900 800 800 907.7 835.9 804.9
20
Number 20 21 22 23 24 25
Acid kg/h 126904 126904 2607052 75949 2683000 2683000
Concentration %H2SO 4 98.5 98.5 98.5 98.5 98.5 98.5
Temperature °C 95.7 40 185 185 185 210.7
Flow rate m3/h 72.1 69.8 1560 45.4 1605.4 1630.6
25 Number 26
Acid kg/h 75949
Concentration %H2SO 4 98.5
Temperature °C 99
Flow rate m3/h 43.2
30

Table 5
Number 1 2 3 4 5 6
35 Acid kg/h 239994 239994 0 239994 239994 18948
Concentration %H2SO4 - - - - - -
Temperature °C 30 30 30 45.8 69.5 69.5
Flow rate m 3/h 241.1 241.1 0 242.4 245.3 19.4
40
Number 7 8 9 10 11 12
Acid kg/h 221045 221045 1771180 1777115 2005040 1771180
Concentration %H2SO4 - - 96 95.68 96 96
Temperature °C 69.5 166.1 67 71.8 72.9 72.9
Flow rate m 3/h 225.9 244.9 990 996 1125 993
45 Number 13 14 15 16 17 18
Acid kg/h 233861 55069 294127 178792 2271610 1922414
Concentration %H2SO4 96 96 98.5 96 98.5 98.57
Temperature °C 72.9 72.9 90 72.9 82 89.4
Flow rate m 3/h 131 31 167 100 1280 1048
50
Number 19 20 21 22 23 24
Acid kg/h 2271610 227925 127007 2506780 3092406 585626
Concentration %H2SO4 98.5 98.5 98.5 98.5 98.5 98.5
Temperature °C 89 85 40 185 204 185
55 Flow rate m 3/h 1285 128 70 1500 1872 350
Number 25 26
Acid kg/h 585626 291499

9
 EP 1 851 170 B1

(continued)
Number 25 26
Concentration %H2SO4 98.5 98.5
5 Temperature °C 90 90
Flow rate m 3/h 332 165

Table 6
10
Number Dimension 1 2 3 4 5 6
Flow rate kg/h 198 591 180 570 180 570 180 570 178 782 178 782
Pressure bar abs. 10 71 69 67 66 64
Temperature °C 98 175.4 235 266 281.8 341
15 Number Dimension 7 8 9 10 11 12
Flow rate kg/h 178 782 1 788 56 927 56 363 38 541 17 822
Pressure bar abs. 62 66 12 10 10 10
Temperature °C 480 281.8 175.4 179.9 179.9 179.9
Number Dimension 13 14 15 16 17 18
20 Flow rate kg/h 5 601 33369 5536 430 1 358 564
Pressure bar abs. 10 10 10 10 9 10
Temperature °C 179.9 179.9 90 179.9 177.7 179.9
Number Dimension 19 20
25
Flow rate kg/h 5 515 4 156
Pressure bar abs. 1 1
Temperature °C 60 20

30
Table 7
Number Dimension 1 2 3 4 5 6
Flow rate kg/h 221 045 179 312 179 312 179 312 176662 176662
Pressure barbs. 10 72 69 67 67 65
35 Temperature °C 166.1 175.4 238.3 265.7 282.8 338.6
Number Dimension 7 8 9 10 11 12
Flow rate kg/h 176662 2650 48946 48461 6579 41 864
Pressure bar abs. 62 67 12 10 10 10
Temperature °C 480 282.8 175.4 179.9 179.9 179.9
40 Number Dimension 13 14 15 16 17 18
Flow rate kg/h 2 393 4 847 2 365 644 2 006 485
Pressure bar abs. 10 10 10 10 9 10
Temperature °C 179.9 179.9 90 179.9 177.7 179.9
45
Number Dimension 19 20
Flow rate kg/h 7 239 5 233
Pressure bar abs. 1 1
Temperature °C 60 20

50

Table 8
Number Dimension 1 2 3 4 5 6
Flow rate kg/h 150487 179 312 179 312 179 312 179312 176662
55 Pressure bar abs. 2 72 71 69 67 67
Temperature °C 85 102 175.4 238.3 265.7 282.8

10
 EP 1 851 170 B1

(continued)
Number Dimension 7 8 9 10 11 12
Flow rate kg/h 176662 176662 2650 28 825 114 28 311
5 Pressure bar abs. 65 62 67 12 12 12
Temperature °C 338.6 480 282.8 188 188 188
Number Dimension 13 14
Flow rate kg/h 28 311
Pressure bar abs. 12
10
Temperature °C 188

List of reference numbers:

15 [0046]

CRE Cold Reheat Exchanger (Gas-Gas heat exchanger)

ECO Economizer (boiler feedwater preheater)
GHE Gas Heat Exchanger (Gas-air heat exchanger)
20 HRE Hot Reheat Exchanger (Gas-gas heat exchanger)
WHB Waste Heat Boiler
SHE Superheater

LP Low Pressure
25 HP High Pressure

Claims

30 1. Process for producing sulphuric acid from process gas containing SO2
in which the SO2 is catalytically oxidized in a converter with at least one contact stage to form SO3,
in which the SO 3-containing process gas, after it has passed through at least one contact stage, is withdrawn from
the converter and fed to an apparatus for heat recovery, in which steam is generated from feedwater by means of
the heat of the process gas, and
35 in which the process gas is fed to an absorber, in which the SO3 is absorbed in sulphuric acid,
characterized in that the temperature of the feedwater fed to the heat recovery apparatus for steam generation is
higher than the temperature of the process gas which enters the absorber and the feedwater is thermally deaerated,
preferably at a feed temperature of 20-90°C, before it enters the heat recovery apparatus, and that the gases which
emerge from the heat recovery apparatus are at a temperature of approximately 170-350°C.
40
2. Process according to Claim 1, characterized in that the temperature difference between the feedwater and the
process gas which enters the absorber is between 5°C and 100°C, preferably 20-50°C.

3. The process as claimed in Claim 1 or 2, characterized in that the feedwater is fed to the heat recovery apparatus
45 at a temperature of over 102°C, preferably 140-190°C.

4. Process according to one of the preceding claims, characterized in that the process gas is withdrawn from the
converter at an intermediate contact stage, is fed to an intermediate absorber and is then fed back in to the converter,
and in that the process gas, after it has passed through the final contact stage of the converter, is fed to a final
50 absorber, with the gas inlet temperature at the intermediate absorber being approximately 130-170°C and at the
final absorber being approximately 120-150°C.

5. Process according to one of the preceding claims, characterized in that the thermal deaeration of the feedwater
is operated at a pressure higher than atmospheric pressure, preferably at 3-10 bar.
55
6. Process according to one of the preceding claims, characterized in that the feedwater is preheated to over 105°C,
preferably to 130-190°C, and in particular to approximately 165°C, before it enters the thermal deaeration.

11
 EP 1 851 170 B1

7. Process according to Claim 6, characterized in that the maximum preheating temperature of the feedwater is
approximately 5 to 20°C below the steam saturation temperature of the pressure at which the deaerator is operated.

8. Process according to Claim 6 or 7, characterized in that the preheating of the cold feedwater before it enters the
5 thermal deaeration is carried out indirectly by means of waste heat from the absorption part and/or from the contact
part of the sulphuric acid plant.

9. Process according to one of the preceding claims, characterized in that the feedwater is deaerated under atmos-
pheric conditions, and before it enters the heat recovery apparatus is heated in a heat exchanger to a temperature
10 above the temperature of approximately 105°C which is caused during the deaeration.

10. Process according to Claim 9, characterized in that the heating of the feedwater prior to the thermal deaeration is
carried out, for example, by means of low-pressure steam, imported waste steam, medium-pressure steam (at a
pressure lower than the high-pressure steam generated in the plant) or heated heat-transfer oil originating from
15 outside the plant.

11. Process according to Claim 10, characterized in that the gases which emerge from the heat recovery apparatus
are utilized for the partial heating of, for example, combustion air, for the reheating of the gases from the intermediate
absorption and/or for the partial heating/preheating of feedwater before it enters the thermal deaeration.
20
12. Process according to one of the preceding claims, characterized in that low-pressure steam, for example saturated
steam at a pressure of approximately 10 bar, is used for the thermal deaeration.

13. Process according to one of the preceding claims, characterized in that the absorbers and a drying tower for drying
25 air with the aid of sulphuric acid are operated with a common acid circuit at the same concentration.

14. Process according to Claim 13, characterized in that the sulphuric acid plant is operated with a separate hot
absorber, this hot absorber being equipped with a gas bypass.

30 15. Process according to one of the preceding claims, characterized in that the heat recovery apparatus, which is
intended to cool the gas prior to the intermediate absorption, has a gas bypass.

16. Process according to one of the preceding claims, characterized in that the feedwater used is demineralized water.

35 17. Plant for producing sulphuric acid, in particular by a process according to one of the preceding claims, having
a converter for the catalytic oxidation of SO2 to form SO 3 with at least one contact stage,
at least one absorber, to which SO3-containing process gas is fed following a contact stage of the converter in order
for the SO 3 to be absorbed in sulphuric acid,
a heat recovery apparatus, in which the process gas releases some of its heat to feedwater in order to generate
40 steam, and
a deaerator for deaeration of the feedwater before it is introduced into the heat recovery apparatus,
characterized by a heat exchanger for heating the feedwater which is fed to the heat recovery apparatus to a higher
temperature than the process gas fed to the absorber.

45 18. Plant according to Claim 17, characterized by an intermediate absorber, to which the SO3-containing process gas
is fed following an intermediate contact stage of the converter, and a final absorber, to which the SO 3-containing
process gas is fed after the last contact stage of the converter.

19. Plant according to Claim 17 or 18, characterized in that there is a device for generating low-pressure steam, and
50 in that at least some of the low-pressure steam is fed to the deaerator.

20. Plant according to Claim 17 or 19, characterized in that the heat recovery apparatus, which is intended to cool the
gas prior to the intermediate absorption, has a gas bypass.

55 21. Plant according to one of Claims 17 to 20, characterized by a separate hot absorber, this hot absorber being
equipped with a gas bypass.

22. Plant according to one of Claims 17 to 21, characterized in that the absorbers and a drying tower for drying air

12
 EP 1 851 170 B1

with the aid of sulphuric acid are connected to a common pump system for supplying sulphuric acid.

Patentansprüche
5
1. Verfahren zur Herstellung von Schwefelsäure aus SO2 enthaltendem Prozessgas,
wobei das SO2 in einem Konverter mit mindestens einer Kontaktstufe katalytisch zu SO3 oxidiert wird,
wobei das SO3-haltige Prozessgas nach Durchlaufen wenigstens einer Kontaktstufe aus dem Konverter abgezogen
und einer Vorrichtung zur Wärmerückgewinnung zugeführt wird, in welcher mittels der Wärme des Prozessgases
10 aus Speisewasser Dampf erzeugt wird, und
wobei das Prozessgas einem Absorber zugeführt wird, in welchem das SO3 in Schwefelsäure absorbiert wird,
dadurch gekennzeichnet, dass die Temperatur des der Wärmerückgewinnungsvorrichtung zur Dampferzeugung
zugeführten Speisewassers höher ist als die Temperatur des in den Absorber eintretenden Prozessgases und das
Speisewasser vor dem Eintritt in die Wärmerückgewinnungsvorrichtung thermisch entgast wird, vorzugsweise bei
15 einer Zuführungstemperatur von 20-90°C, und dass die aus der Wärmerückgewinnungsvorrichtung austretenden
Gase eine Temperatur von etwa 170-350°C aufweisen.

2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die Temperaturdifferenz zwischen dem Speisewasser
und dem in den Absorber eintretenden Prozessgas zwischen 5°C und 100°C beträgt, vorzugsweise 20-50°C.
20
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Speisewasser der Wärmerückgewin-
nungsvorrichtung mit einer Temperatur von über 102°C, vorzugsweise 140-190°C, zugeführt wird.

4. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Prozessgas an einer
25 Zwischenkontaktstufe aus dem Konverter abgezogen, einem Zwischenabsorber zugeführt und dann wieder in den
Konverter zurückgeführt wird, und dass das Prozessgas nach Durchlaufen der letzten Kontaktstufe des Konverters
einem Endabsorber zugeführt wird, wobei die Gaseintrittstemperatur am Zwischenabsorber etwa 130-170°C und
am Endabsorber etwa 120-150°C beträgt.

30 5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die thermische Entgasung
des Speisewassers bei höherem als atmosphärischem Druck betrieben wird, vorzugsweise bei 3-10 bar.

6. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Speisewasser vor
Eintritt in die thermische Entgasung auf über 105°C, vorzugsweise auf 130-190°C, und insbesondere auf etwa
35 165°C vorgewärmt wird.

7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass die maximale Vorwärmtemperatur des Speisewassers
etwa 5 bis 20°C unterhalb der Dampf-Sättigungstemperatur des Druckes liegt, mit dem der Entgaser betrieben wird.

40 8. Verfahren nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass die Vorwärmung des kalten Speisewassers
vor Eintritt in die thermische Entgasung indirekt mittels Abwärme aus dem Absorptionsteil und/oder aus dem Kon-
taktteil der Schwefelsäureanlage erfolgt.

9. Verfahren nach einem der einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Speise-
45 wasser unter atmosphärischen Bedingungen entgast wird und vor Eintritt in die Wärmerückgewinnungsvorrichtung
in einem Wärmetauscher auf eine Temperatur über der bei der Entgasung entstehenden Temperatur von etwa
105°C aufgewärmt wird.

10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass das Aufwärmen des Speisewassers vor der thermi-
50 schen Entgasung bspw. mittels Niederdruckdampf, importiertem Abdampf, Mitteldruckdampf (unterhalb des Druckes
des in der Anlage erzeugten Hochdruckdampfes) oder von außerhalb der Anlage stammendem erhitzten Thermoöl
erfolgt.

11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die aus der Wärmerückgewinnungsvorrichtung aus-
55 tretenden Gase zur teilweisen Aufheizung von z.B. Verdünnungsluft, zur Wiederaufheizung der Gase aus der Zwi-
schenabsorption und/oder zur teilweisen Aufheizung/Vorwärmung von Speisewasser vor Eintritt in die thermische
Entgasung genutzt werden.

13
 EP 1 851 170 B1

12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass zur thermischen Entga-
sung Niederdruckdampf, bspw. Sattdampf mit einem Druck von etwa 10 bar, verwandt wird.

13. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Absorber und ein
5 Trockenturm zur Trocknung von Luft mit Hilfe von Schwefelsäure mit einem gemeinsamen Säurekreislauf gleicher
Konzentration betrieben werden.

14. Verfahren nach Anspruch 13, dadurch gekennzeichnet, dass die Schwefelsäure-Anlage mit separatem Heißab-
sorber betrieben wird, wobei dieser Heißabsorber mit einem gasseitigen Bypass ausgestattet ist.
10
15. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Wärmerückgewin-
nungsvorrichtung, die zur Abkühlung des Gases vor der Zwischenabsorption vorgesehen ist, einen gasseitigen
Bypass aufweist.

15 16. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass als Speisewasser demi-
neralisiertes Wasser verwendet wird.

17. Anlage zur Herstellung von Schwefelsäure, insbesondere nach einem Verfahren gemäß einem der vorhergehenden
Ansprüche, mit
20 einem Konverter zur katalytischen Oxidation von SO2 in SO3 mit mindestens einer Kontaktstufe,
wenigstens einem Absorber, dem SO3-haltiges Prozessgas nach einer Kontaktstufe des Konverters zur Absorption
des SO3 in Schwefelsäure zugeführt wird,
einer Wärmerückgewinnungsvorrichtung, in welcher das Prozessgas einen Teil seiner Wärme zur Dampferzeugung
an Speisewasser abgibt, und
25 einem Entgaser zur Entgasung des Speisewassers vor Einführung in die Wärmerückgewinnungsvorrichtung,
gekennzeichnet durch einen Wärmetauscher zum Aufheizen des der Wärmerückgewinnungsvorrichtung zuge-
führten Speisewassers auf eine höhere Temperatur als das dem Absorber zugeführte Prozessgas.

18. Anlage nach Anspruch 17, gekennzeichnet durch einen Zwischenabsorber, dem das SO3-haltige Prozessgas
30 nach einer Zwischenkontaktstufe des Konverters zugeführt wird, und einen Endabsorber, dem das SO3-haltige
Prozessgas nach der letzten Kontaktstufe des Konverters zugeführt wird.

19. Anlage nach Anspruch 17 oder 18, dadurch gekennzeichnet, dass eine Einrichtung zur Erzeugung von Nieder-
druckdampf vorgesehen ist und dass der Niederdruckdampf wenigstens teilweise dem Entgaser zugeführt wird.
35
20. Anlage nach Anspruch 17 oder 19, dadurch gekennzeichnet, dass die Wärmerückgewinnungsvorrichtung, die
zur Abkühlung des Gases vor der Zwischenabsorption vorgesehen ist, einen gasseitigen Bypass aufweist.

21. Anlage nach einem der Ansprüche 17 bis 20, gekennzeichnet durch einen separaten Heißabsorber, wobei dieser
40 Heißabsorber mit einem gasseitigen Bypass ausgestattet ist.

22. Anlage nach einem der Ansprüche 17 bis 21, dadurch gekennzeichnet, dass die Absorber und ein Trockenturm
zur Trocknung von Luft mit Hilfe von Schwefelsäure mit einer gemeinsamen Pumpvorlage zur Schwefelsäurever-
sorgung verbunden sind.
45

Revendications

1. Procédé de production d’acide sulfurique à partir d’un gaz de transformation contenant du SO2
50 dans lequel le SO2 subit une oxydation catalytique dans un convertisseur avec au moins une étape de contact pour
former du SO3,
dans lequel le gaz de transformation contenant du SO3, une fois qu’il a subi au moins une étape de contact, est
éliminé du convertisseur et envoyé dans un appareil de récupération de la chaleur, dans lequel de la vapeur est
générée par l’eau d’alimentation au moyen de la chaleur du gaz de transformation, et
55 dans lequel le gaz de transformation est envoyé dans un absorbeur, dans lequel le SO 3 est absorbé dans l’acide
sulfurique,
caractérisé en ce que la température de l’eau d’alimentation envoyée dans l’appareil de récupération de la chaleur
pour la génération de vapeur est supérieure à la température du gaz de transformation qui entre dans l’absorbeur

14
 EP 1 851 170 B1

et l’eau d’alimentation est thermiquement dégazée, de préférence à une température d’alimentation de 20 °C à 90

°C, avant son entrée dans l’appareil de récupération de la chaleur, et en ce que les gaz qui sortent de l’appareil de
récupération de la chaleur sont à une température d’environ 170 °C à 350 °C.

5 2. Procédé selon la revendication 1, caractérisé en ce que la différence de température entre l’eau d’alimentation et
le gaz de transformation qui entre dans l’absorbeur est comprise entre 5 °C et 100 °C, de préférence entre 20 °C
et 50 °C.

3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l’eau d’alimentation est envoyée dans l’appareil de
10 récupération de la chaleur à une température supérieure à 102 °C, de préférence comprise entre 140 °C et 190 °C.

4. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que le gaz de transformation
est éliminé du convertisseur à une étape de contact intermédiaire, est envoyé dans un absorbeur intermédiaire puis
est renvoyé dans le convertisseur, et en ce que le gaz de transformation, une fois qu’il a subi l’étape de contact
15 final du convertisseur, est envoyé dans un absorbeur final, la température d’entrée du gaz au niveau de l’absorbeur
intermédiaire étant d’environ 130 °C à 170 °C et au niveau de l’absorbeur final d’environ 120 °C à 150 °C.

5. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que le dégazage thermique
de l’eau d’alimentation est effectué à une pression supérieure à la pression atmosphérique, de préférence entre 3
20 bar et 10 bar.

6. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’eau d’alimentation est
préchauffée à plus de 105 °C, de préférence entre 130 °C et 190 °C, et en particulier à environ 165 °C, avant son
entrée dans le dégazeur thermique.
25
7. Procédé selon la revendication 6, caractérisé en ce que la température de préchauffage maximale de l’eau d’ali-
mentation est environ 5 °C à 20 °C au-dessous de la température de saturation de la vapeur de la pression à laquelle
le dégazeur est utilisé.

30 8. Procédé selon la revendication 6 ou 7, caractérisé en ce que le préchauffage de l’eau d’alimentation froide avant
son entrée dans le dégazeur thermique est effectué de manière indirecte à l’aide de la chaleur résiduelle provenant
de la partie d’absorption et/ou de la partie de contact de l’installation d’acide sulfurique.

9. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’eau d’alimentation est
35 dégazée dans des conditions atmosphériques et, avant son entrée dans l’appareil de récupération de chaleur, est
chauffée dans un échangeur thermique à une température supérieure à la température d’environ 105 °C qui est
atteinte pendant le dégazage.

10. Procédé selon la revendication 9, caractérisé en ce que le chauffage de l’eau d’alimentation avant le dégazage
40 thermique est effectué, par exemple, à l’aide de vapeur basse pression, de vapeur résiduelle importée, de vapeur
moyenne pression (à une pression inférieure à la vapeur haute pression générée dans l’installation) ou d’huile
caloporteuse chauffée provenant de l’extérieur de l’installation.

11. Procédé selon la revendication 10, caractérisé en ce que les gaz qui sortent de l’appareil de récupération de
45 chaleur sont utilisés pour le chauffage partiel, par exemple, de l’air de combustion, pour le réchauffage des gaz
issus de l’absorption intermédiaire et/ou pour le chauffage/préchauffage partiel de l’eau d’alimentation avant son
entrée dans le dégazeur thermique.

12. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que la vapeur basse pression,
50 par exemple la vapeur saturée à une pression d’environ 10 bar, est utilisée pour le dégazage thermique.

13. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que les absorbeurs et une
tour de séchage destinée à sécher l’air à l’aide d’acide sulfurique sont utilisés avec un circuit d’acide commun à la
même concentration.
55
14. Procédé selon la revendication 13, caractérisé en ce que l’installation d’acide sulfurique est utilisée avec un
absorbeur chaud séparé, cet absorbeur chaud étant équipé d’une dérivation des gaz.

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15. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’appareil de récupération
de chaleur, qui est destiné à refroidir le gaz avant l’absorption intermédiaire, possède une dérivation des gaz.

16. Procédé selon l’une quelconque des revendications précédentes, caractérisé en ce que l’eau d’alimentation utilisée
5 est de l’eau déminéralisée.

17. Installation de production d’acide sulfurique, en particulier par un procédé selon l’une des revendications précéden-
tes, ayant
un convertisseur pour l’oxydation catalytique du SO2 pour former du SO3 avec au moins une étape de contact,
10 au moins un absorbeur, dans lequel le gaz de transformation contenant du SO3 est envoyé après une étape de
contact du convertisseur pour que le SO3 soit absorbé dans l’acide sulfurique,
un appareil de récupération de chaleur, dans lequel le gaz de transformation libère une partie de sa chaleur dans
l’eau d’alimentation pour générer de la vapeur,
et
15 un dégazeur pour dégazer l’eau d’alimentation avant son introduction dans l’appareil de récupération de chaleur,
caractérisée par un échangeur thermique pour chauffer l’eau d’alimentation qui est envoyée dans l’appareil de
récupération de chaleur à une température supérieure au gaz de transformation envoyé dans l’absorbeur.

18. Installation selon la revendication 17, caractérisée par un absorbeur intermédiaire, dans lequel le gaz de transfor-
20 mation contenant du SO3 est envoyé après une étape de contact intermédiaire du convertisseur, et un absorbeur
final, dans lequel le gaz de transformation contenant du SO3 est envoyé après l’étape de contact final du conver-
tisseur.

19. Installation selon la revendication 17 ou 18, caractérisée en ce qu’elle comprend un dispositif de génération de
25 vapeur basse pression et en ce qu’au moins une partie de la vapeur basse pression est envoyée dans le dégazeur.

20. Installation selon la revendication 17 ou 19, caractérisée en ce que l’appareil de récupération de chaleur, qui est
destiné à refroidir le gaz avant l’absorption intermédiaire, possède une dérivation des gaz.

30 21. Installation selon l’une des revendications 17 à 20, caractérisée par un absorbeur chaud séparé, cet absorbeur
chaud étant équipé d’une dérivation des gaz.

22. Installation selon l’une des revendications 17 à 21, caractérisée en ce que les absorbeurs et une tour de séchage
destinée à sécher l’air à l’aide d’acide sulfurique sont raccordés à un système de pompe commun pour fournir de
35 l’acide sulfurique.

40

45

50

55

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21
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22
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23
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24
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25
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26
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27
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28
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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• US 4670242 A [0007] • EP 0130967 B1 [0007]

• EP 0181313 B1 [0007] • DE 102004012293 [0007] [0027] [0040]
• DE 3830365 C2 [0007] • DE 19522927 A1 [0007]
• US 4576813 A [0007]

Non-patent literature cited in the description

• Ullmann’s Encyclopaedia of Industrial Chemistry. vol.

25, 635-700 [0002]

31