(19)

*EP003904279A1*
(11) EP 3 904 279 A1
(12) EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43) Date of publication: (51) Int Cl.:

03.11.2021 Bulletin 2021/44 C01B 17/80 (2006.01) C01B 17/79 (2006.01)
C01B 17/76 (2006.01) B01D 53/48 (2006.01)
(21) Application number: 19906226.6
(86) International application number:
(22) Date of filing: 21.11.2019 PCT/CN2019/119983

(87) International publication number:

WO 2020/134751 (02.07.2020 Gazette 2020/27)

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • HUANG, Rui
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Shanghai 200235 (CN)
PL PT RO RS SE SI SK SM TR • WANG, Dan
Designated Extension States: Shanghai 201502 (CN)
BA ME • ZHANG, Huayong
Designated Validation States: Shanghai 201502 (CN)
KH MA MD TN • ZHANG, Yuan
Shanghai 201502 (CN)
(30) Priority: 26.12.2018 CN 201811600891 • QI, Junling
26.12.2018 CN 201822211197 U Shanghai 201502 (CN)

(71) Applicants: (74) Representative: Maiwald Patent- und

• Keyon Process Co., Ltd Rechtsanwaltsgesellschaft mbH
Shanghai 201502 (CN) Elisenhof
• Huang, Rui Elisenstraße 3
Shanghai 200235 (CN) 80335 München (DE)

(54) PROCESS SYSTEM AND PROCESS METHOD FOR CONVERSION OF SULFUR-CONTAINING

FLUE GAS TO SULFURIC ACID

(57) Disclosed is a process system and a process catalytic oxidation of SO2 in the acid process gas; a sul-
for converting the sulfur-containing flue gas into the sul- furic acid steam condenser for condensing SO3 gener-
furic acid. The process system comprises: a flue gas pre- ated by the combined reactor into sulfuric acid; the cold
heater, which for preheating the sulfur-containing flue end of the sulfuric acid steam condenser is further con-
gas to 15~30°Cabove its dew point, and the flue gas pre- nected with the flue gas preheater for providing hot air
heater has a glass tube as a heat exchange tube; a flue to the flue gas preheater. The device of the present in-
gas fan for boosting the pressure of the preheated acid vention can resist the fluctuation of SO2 concentration in
process gas and transporting one part of which to a com- the feed gas, and can realize considerable economic
bustion furnace, and the other part of which to a process benefits and rational utilization of energy.
gas steam heater; the combustion furnace and the proc-
ess gas steam heater are connected in parallel with a
combined reactor, which is used for generating SO3 by
EP 3 904 279 A1

Printed by Jouve, 75001 PARIS (FR) (Cont. next page)

EP 3 904 279 A1

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 1 EP 3 904 279 A1 2

Description device are simple, while the investment and the operation
cost of device are low.
[0001] The present application claims priority of China [0006] The present invention provides a process sys-
patent application No. 201811600891.9, filed on Decem- tem for converting sulfur-containing flue gas into sulfuric
ber 26, 2018 and the China patent application No. 5 acid. The process system comprise:
201822211197.X filed on December 26, 2018, the con- [0007] a flue gas preheater for preheating the sulfur-
tents of which are incorparated herein by their entireties. containing flue gas to 15~30°C above its dew point,
wherein the flue gas preheater has a glass tube as a heat
Technical Field exchange tube;
10 [0008] a flue gas fan for boosting the pressure of the
[0002] The present invention relates to the technical preheated acid process gas from the flue gas preheater,
field of smelting sulfur-containing flue gas treatment, in and transporting one part of which to a combustion fur-
particular to a process system and process for converting nace, and the other part of which to a process gas steam
sulfur-containing flue gas into sulfuric acid. heater, wherein the combustion furnace and the process
15 gas steam heater are used for heating the preheated acid
Background Arts process gas to catalytic oxidation temperature of SO 2;
[0009] the combustion furnace and the process gas
[0003] SO2 is one of the main pollutants in the atmos- steam heater are connected in parallel with a combined
phere, which is an important indicator of whether the at- reactor, which is used for generating SO3 by catalytic
mosphere is polluted. Sulfur dioxide is a serious health 20 oxidation of SO 2 in the acid process gas;
hazard and a major source of acid rain, which damage [0010] a sulfuric acid steam condenser for condensing
the ecological environment. There are various sources SO3 generated by the combined reactor into sulfuric acid;
of SO 2 feed gas, most of which come from the combustion the cold end of the sulfuric acid steam condenser is fur-
of sulfur-containing fuels. The front-end processing of ther connected with the flue gas preheater for providing
desulfurization is the desulfurization of sulfur-containing 25 hot air to the flue gas preheater.
fuels, and the back-end processing is the desulfurization [0011] The process system of the present invention is
of sulfur-containing flue gas. At present, smelting sulfur- further described below:
containing flue gas can not meet the existing relevant [0012] In the embodiments of the present invention,
standards for emission. the low concentration of smelting sulfur-containing flue
[0004] The common desulfurization techniques for 30 gas is heated by setting a flue gas preheater. The low
smelting sulfur-containing flue gas comprises wet meth- concentration of smelting sulfur-containing flue gas after
od, dry method and semi-dry method. Dry and semi-dry the front end cooling, dedusting, cooling and purification
desulfurization have slow reaction speed, low desulfuri- is generally entrained with dilute sulfuric acid with strong
zation efficiency, difficulty in device maintenance, and corrosive. The dew point is generally around 120~150°C,
more restrictions on use. Dry method and semi-dry meth- 35 in order to avoid the corrosion of subsequent device and
od also have disadvantages such as complex process, reduce the investment of subsequent devices, and the
low energy utilization rate, complex operation, large land flue gas preheater is set to preheat acidic process gas
occupation and the production of a small amount of waste to 15~30°C above the dew point.
acid. At present, a method of the molten salt heat transfer [0013] In the embodiments of the present invention,
is used for the smelting flue gas treatment in foreign wet 40 the heat exchanger tube of the flue gas preheater is made
acid process. However, molten salt is a hazardous waste, of glass tube, which can effectively avoid corroding the
which is very corrosive to device. At the same time, the device by acid gas.
foreign technology further has the defects of high energy [0014] In the embodiments of the present invention,
consumption and high cost. the flue gas preheater uses hot air from the cold end of
45 the sulfuric acid steam as the heat source, which im-
Content of the present invention proves the heat utilization rate and reduces the energy
consumption of the device.
[0005] The technical problem to be solved by the [0015] In the embodiments of the present invention, a
present invention is to overcome the defects of the prior flue gas fan is arranged behind the flue gas preheater.
art, such as high energy consumption and large equip- 50 The acid process gas preheated by the flue gas preheater
ment corrosion in the device for treating a low concen- is 15~30°C above the dew point. Therefore, the corrosion
tration of smelting sulfur-containing flue gas, and to pro- of the acid process gas has been minimized, and the flue
vide a production system and production process for con- gas fan can be effectively protected from the corrosion
verting sulfur-containing flue gas into sulfuric acid. The of the acid process gas and ensure its long period of
process of the present invention can resist the fluctuation 55 operation.
of SO2 concentration in the feed gas, and can achieve [0016] In the embodiments of the present invention,
considerable economic benefits and rational utilization the pressure of the acid process gas is boosted to adopt
of energy of the device. Moreover, the process and the the shunt measure, and the fuel gas and its by-product

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 3 EP 3 904 279 A1 4

steam are respectively used to heat the acid process gas the acid process gas leaving the first bed of the combined
to the optimal reaction temperature of the SO2 catalyst. reactor is relatively increased. The acid process gas from
When the acid process gas has a low concentration of the outlet of the first bed of the combined reactor enters
SO2, the heat of the system reaction cannot satisfy the into the shell side of the interstage steam superheater
autothermal equilibrium, then the flow to the combustion 5 for cooling and heat recovery.
furnace will be a little more. This allows heat to be ob- [0021] Preferably, the process system further compris-
tained by burning the external fuel gas. When the acid es a steam drum, wherein the steam drum and the waste
process gas has a high concentration of SO2, the heat heat recycler are connected to form a first waste heat
of the system reaction can satisfy the autothermal equi- collection circuit, the steam drum and the process gas
librium, then the flow to the combustion furnace will be a 10 cooler are connected to form a second waste heat col-
little less. This ensures that no matter how the SO2 con- lection circuit, and the steam drum is further connected
centration in the acid process gas fluctuates, the temper- to the interstage steam superheater, so that the saturated
ature of the acid process gas entering the catalyst reach- steam from the steam drum enters the cold end of the
es the optimal reaction temperature. After the acid proc- interstage steam superheater to recover heat generated
ess gas is shunted, the flow rate into the combustion 15 by acid process gas reaction.
furnace is reduced, so the size of the combustion furnace [0022] The acid process gas is cooled by the interstage
is reduced and the investment can be saved. When the steam superheater to recover the heat and then enters
sulfur concentration of the feed gas is relatively low, the the second bed inlet of the combined reactor. SO2 in the
fuel gas will be added to maintain the thermal equilibrium acid process gas is further converted. After the reaction
of the system. When the sulfur concentration of which is 20 in the second bed of the combined reactor, the acid proc-
relatively high, less fuel gas is required. ess gas enters into the process gas cooler for cooling.
[0017] In the embodiments of the present invention, a The cold end of the process gas cooler uses a circulating
combustion furnace is specially arranged. The acid proc- boiler feed water from the steam drum. The circulating
ess gas, fuel gas and hot air enter the combustion furnace boiler feed water and the acid process gas exchange
together and burn to 900∼1200°C, which can not only 25 heat and then vaporizes and returns to the steam drum
provide enough heat under the low concentration of SO2 for flash evaporation to generate 5.0~5.8MPag medium
in the acid process gas, but further can be used as a pressure saturated steam.
start-up heating furnace. [0023] The acid process gas passing through the proc-
[0018] Preferably, the combustion furnace is further ess gas cooler is sent to the sulfuric acid steam condens-
provided with a waste heat recycler for converting the 30 er for condensation into acid. In this process, gaseous
heat of the high-temperature flue gas in the combustion SO3 is combined with water to form sulfuric acid and con-
furnace into saturated steam. The waste heat recycler densed to form 93-98% concentrated sulfuric acid.
uses a shell and tube heat exchanger, with all the heat [0024] Preferably, the sulfuric acid steam condenser
exchange tubes submerged in the boiler feed water gen- comprises a shell, wherein the shell is equipped with an
erating 5.0~5.8MPag medium pressure saturated steam 35 exhaust discharge port at the top and a liquid outlet at
outside the heat exchange tubes. the bottom. A plurality of glass tubes for circulating cool-
[0019] On this basis, preferably, the combined reactor ing medium are arranged in the shell along the long axis
is provided with a first bed, an interstage steam super- direction, and all the glass tube span between two side
heater, a second bed and a process gas cooler from top wall of the shell. One end of the glass tube located up-
to bottom, and the waste heat recycler and the process 40 stream of the cooling medium is head end, the other end
gas steam heater are connected with the first bed after located downstream of the cooling medium end is tail
being paralleled connected. The outlet of the interstage end, and adjacent glass tubes are connected end to end
steam superheater is further connected with the hot end between the upstream and downstream of the cooling
of the process gas steam heater, and the superheated medium so as to form at least one unidirectional flow
steam is used for a heating process of the acid process 45 channel of the cooling medium. The unidirectional flow
gas. The superheated steam after the heating of the in- channel of the cooling medium formed by the glass tube
terstage steam superheater is divided into two streams: can withstand high temperature and strong corrosion,
one stream is sent out of the boundary as the final steam thus ensuring the fluidity of the cooling medium and the
product; the other stream is sent to the process gas steam safety of the heat exchanger in long term use. The glass
heater as a heat source to heat up the acid process gas, 50 tubes may be made of borosilicate glass tubes, quartz
which condenses itself into saturated condensed water glass or other high temperature resistant and strong cor-
and is sent out of the boundary area. rosive resistant glass.
[0020] The process is described as follows: the acid [0025] Preferably, the upper part of the sulfuric acid
process gas from the waste heat recycler and the process steam condenser is further connected with the combus-
gas steam heater are mixed and enter the first bed inlet 55 tion furnace through a fan for providing hot air for the
of the combined reactor, and the SO2 is converted to SO3 combustion furnace.
under the catalysis of the catalyst. This reaction process [0026] Preferably, a top exhaust outlet of the sulfuric
is a strong exothermic reaction, so the temperature of acid steam condenser is further connected with an acid

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mist eliminator and an advance exhaust treatment sys- achieve a better equilibrium conversion rate.
tem in turn (e.g., an exhaust scrubbing tower, which is [0033] In the present invention, the process gas after
provided with an external circulation loop formed by a catalytic oxidation reaction is sent into the sulfuric acid
circulating cooler and a circulating pump). The un- steam condenser for condensation, the obtained product
condensed acid process gas containing a small amount 5 is cooled to a temperature greater than or equal to10°C
of SO2 and a small amount of sulfuric acid is sent to the above the dew point of H2SO4, then further cooled to
acid mist eliminator, and the exhaust after removing tiny 60°C~120°C, and obtained H2SO4 product is collected.
droplets by the acid mist eliminator enters the advanced The cooled gas can be directly exhausted after coales-
exhaust treatment system. A variety of mature wet flue cence and separation; preferably the further cooling has
gas desulfurization processes can be used in the ad- 10 a temperature of 105°C~120°C. After catalytic oxidation
vanced exhaust treatment system, such as ammonia reaction, the process gas is cooled to a temperature high-
desulfurization, calcium desulfurization, double alkali er than 10°C above the dew point of H2SO4 by the con-
desulfurization and other new forms of desulfurization. ventional heat exchanger in the art, and the cold process
All the desulfurization methods of the advanced exhaust gas or medium or low pressure saturated steam can fur-
treatment system can make the final exhaust meet the 15 ther be used as a cooling medium to produce highpres-
emission standards. sure saturated steam or superheated steam, which can
[0027] The present invention further provides a proc- further be used to reduce energy consumption. Wherein,
ess for converting the sulfur-containing flue gas into sul- the medium and low pressure saturated steam has a
furic acid, which is carried out in the process system. The pressure of 0.5 MpaG - 7.8 MpaG.
process comprises the following steps: preheating, pres- 20 [0034] In the present invention, the obtained H2SO4
suring and heating the sulfur-containing flue gas, per- has a concentration of 93%~98%, which can be further
forming catalytic oxidation to obtain SO3, and then con- adjusted to a constant concentration of an industrial-
densing; wherein, the sulfur-containing flue gas has a grade concentrated sulfuric acid according to specific
concentration of SO2 higher than 0.1mol%, and the cat- needs for convenient use, and the percentage is a mass
alytic oxidation has a temperature of above 390°C. 25 percentage.
[0028] In the present invention, the feed gas is the low [0035] On the basis of the common sense in the art,
concentration of smelting sulfur-containing flue gas the above preferred conditions can be arbitrarily com-
(hereinafter further referred to as acid process gas) ob- bined to obtain the preferred examples of the present
tained after the front end cooling and dedusting, temper- invention.
ature reduction and purification. In a preferred embodi- 30 [0036] The reagents and raw materials used in the
ment of this application, the sulfur-containing flue gas present invention are commercially available.
consists of 2%SO2, 15.5%O2, 3.6%CO2, 77.5%N2 and [0037] The positive and progressive effect of the
1.4%H2O, and the percentage is a molar percentage. present invention is as follows: based on the technology
[0029] In the present invention, the sulfur-containing of wet acid method, the present invention provides a proc-
flue gas that enters the flus gas preheater has a dew 35 ess system for converting SO2 from the smelting sulfur-
point of 120~150°C. After passing through the flue gas containing flue gas, which cannot meet the relevant
preheater, the sulfur-containing flue gas is preheated to standard for emission, into H2SO4 to solve the problems
15~30°C above the dew point, preferably 140~170°C. that the low concentration of smelting sulfur-containing
[0030] In the present invention, preferably, the pres- flue gas cannot be treated or cannot meet the relevant
sure of the acid process gas preheated by the flue gas 40 standard of emission; at the same time, it further solves
preheater is boosted to 115~125kPa by the flue gas fan. the problems of high energy consumption and large
[0031] In the present invention, a combustion reaction equipment corrosion of the device for treating low con-
of the acid process gas, fuel gas and hot air is carried centration of smelting sulfur-containing flue gas. It has
out in the combustion furnace, where the acid process advantages of high desulfurization efficiency, fast reac-
gas is heated by ignition to 900~1200°C. The hot air used 45 tion speed, simple process flow, low energy consump-
herein may come from the sulfuric acid steam condenser. tion, no secondary pollution, and producing high grade
[0032] In the present invention, in the combined reac- medium pressure steam as a by-product which can
tor, the process gas containing SO 2 must be heated to achieve certain economic benefits. It will be a widely used
above 390°C before being introduced into the catalytic desulfurization technology.
bed in order to achieve a more complete conversion re- 50 [0038] The present invention utilizes the heat generat-
action of SO2 to SO 3, preferably the acid process gas ed by the reaction of SO2 conversion of the system itself
entering the combined reactor has a temperature of to achieve the autothermal equilibrium. It realizes the ef-
390~430°C. The catalyst used for the oxidation catalytic fective use of energy and saves the investment of the
reaction occurring in the catalyst bed is a vanadium cat- device. At the same time, by burning combustible gas
alyst such as V2O5. The conversion rate of SO2 can reach 55 according to specific requirements, it can not only provide
above 99% by the two-bed catalytic reaction. The order steam for other device, but also stabilize the SO2 con-
of catalytic reaction is preferably 2, but it can be adjusted version reaction.
according to the actual needs. Multiple catalyst beds can

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Brief description of the drawings Example 1

[0039] [0042] The flue gas consists of 2%SO2, 15.5%O2,

3.6%CO2, 77.5%N2 and 1.4%H2O, and the percentage
Fig.1 is a flowchart of the process system for con- 5 is a molar percentage.
verting sulfur-containing flue gas into sulfuric acid in [0043] As shown in Figure 1, the active components
Example 1 of the catalyst for converting SO2 into SO3 is mostly V2O5.
The sulfur-containing flue gas needs to reach a certain
Fig. 2 is a flowchart of the process system for con- reaction temperature before entering the catalyst. The
verting sulfur-containing flue gas into sulfuric acid in 10 flue gas in the front section is preheated, and the heat of
comparative Example 1. the flue gas preheating first comes from the heat gener-
ated by the condensation of sulfuric acid, and the heat
[0040] In Fig. 1 and Fig. 2, marks are illustrated as generated by the waste pot and the heat released from
follows: each reaction bed can be used subsequently. See draw-
15 ing for the detailed process.
flue gas preheater 1 [0044] After front end cooling and dedusting, temper-
ature reduction and purification, the low concentration of
flue gas fan 201 smelting sulfur-containing flue gas (hereinafter referred
to acid process gas) enters the cold end inlet of the flue
fan 202 20 gas preheater 1, an the acid process gas is preheated
to 165°C. The hot end of the flue gas preheater 1 is the
combustion furnace 3 hot air from the cold end outlet of the sulfuric acid steam
condenser 6. The acid process gas preheated by the flue
waste heat recycler 301 gas preheater 1 is then boosted to 118kPa by the flue
25 gas fan 201.
process gas steam heater 4 [0045] The acid process gas with boosted pressure is
divided into two streams using a split flow, and then en-
combined reactor 5 ters the combustion furnace 3 and the process gas steam
heater 4 respectively for heating. One stream of the acid
the first bed 501 30 process gas, the fuel gas and the hot air enter the com-
bustion furnace 3 for combustion and heating to 1050°C,
interstage steam superheater 502 then enter into the pipe side of the waste heat recycler
301 for cooling and heat recovery. The waste heat recy-
the second bed 503 cler 301 uses a shell and tube heat exchanger, and all
35 the heat exchange pipes are immersed in boiler feed wa-
process gas cooler 504 ter. 5.6 MPag medium pressure saturated steam is gen-
erated outside the heat exchange tube; the other stream
sulfuric acid steam condenser 6 of the acid process gas enters the process gas steam
heater 4 for heating. The hot end of the process gas
acid mist eliminator 7 40 steam heater 4 uses superheated steam from the outlet
of the interstage steam superheater 502 of the combined
exhaust scrubbing tower 8 reactor 5 to heat the acid process gas. The acid process
gas heated by the waste heat recycler 301 and by the
circulating cooler 801 process gas steam heater 4 are mixed and sent to the
45 inlet of the first bed 501 of the combined reactor 5 after
circulating pump 802 reaching the best reaction temperature of 420°C.
[0046] The acid process gas mixed from the waste heat
steam drum 9 recycler 301 and the process gas steam heater 4 enters
the inlet of the first bed 501 of the combined reactor 5.
Detailed description of the preferred embodiment 50 Under the action of catalyst, SO2 is converted into SO3.
This reaction process is a strong exothermic reaction, so
[0041] The present invention is further illustrated by the temperature of the acid process is increased after
the following examples, but the scope of the present in- leaving the first bed 501 of the combined reactor 5. The
vention is not limited therein. The experimental methods acid process gas from the outlet of the first bed 501 of
for which specific conditions are not indicated in the fol- 55 the combined reactor 5 enters the shell side of the inter-
lowing examples shall be selected in accordance with stage steam superheater 502 for cooling and heat recov-
the conventional methods and conditions or the commod- ery. The saturated steam from the medium pressure
ity specifications. steam drum 9 enters the cold end of the interstage steam

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 9 EP 3 904 279 A1 10

superheater 502 to recover the heat generated by the 3.3%CO2, 78.07%N2, 1.2%H2O, and other 0.31%, and
acid process gas reaction. The superheated steam after the percentage is a molar percentage.
the heating of the interstage steam superheater 502 is [0052] As shown in Figure 2, the active components
divided into two streams: one stream of steam is sent out of the catalyst for converting SO2 into SO3 is mostly V2O5.
of the boundary area as the final steam product; The 5 The sulfur-containing flue gas needs to reach a certain
other stream of steam is sent to the process gas steam reaction temperature before entering the catalyst. The
heater 4 as a heat source to heat up the acid process process gas in the front section is heated by burning fuel
gas, which condenses itself into saturated and conden- gas and hot air, and the heat of combustion can further
sate water and is sent out of the boundary area. be recovered by the waste heat recycler 301. See draw-
[0047] The acid process gas cooled by the interstage 10 ing for the detailed process.
steam superheater 502 to recover heat enters the inlet [0053] After front end cooling and dedusting, temper-
of the second bed 503 of the combined reactor 5. SO2 ature reduction and purification, and concentration, the
in the acid process gas is further converted. After reaction low concentration of smelting sulfur-containing flue gas
in the second bed 503 of the combined reactor 5, the (hereinafter referred to acid process gas) and the hot air
acid process gas enters the process gas cooler 504 for 15 and the fuel gas from the combustion fan 202 enter the
cooling. The cold end of the process gas cooler 504 uses combustion furnace 3 for combustion with a combustion
the circulating boiler feed water from the steam drum 9. temperature of 1025°C, and then enter the pipe side of
The circulating boiler feed water exchanges heat with the the waste heat recycler 301 for cooling and heat recovery.
acid process gas, then vaporizes and returns to steam The waste heat recycler 301 uses a shell and tube heat
drum 9 for flash evaporation to produce 5.6MPag medi- 20 exchanger, and all the heat exchange pipes are infiltrated
um pressure saturated steam. into boiler feed water. 5.6 MPag of medium pressure sat-
[0048] The acid process gas from the process gas urated steam is generated outside the heat exchange
cooler 504 is sent to the sulfuric acid steam condenser tube. The acid process gas is sent to the inlet of the first
6 for condensing into acid, and the product is cooled to bed 501 of the combined reactor 5 when the acid process
10 ° C above the dew point of H2SO4, and then further 25 temperature after heat recovery by the waste heat recy-
cooled to 110 ° C. H2SO4 products are collected, and the cler 301 reached the optimal reaction temperature of 423
gas obtained after cooling is coalesced and separated, °C.
and then directly exhausted. In this process, the gaseous [0054] The acid process gas from the waste heat re-
SO3 is combined with water to form sulfuric acid and con- cycler 301 enters the inlet of the first bed 501 of the com-
densed to form 98% concentrated sulfuric acid. The up- 30 bined reactor 5, and under the action of catalyst, SO2 is
per part of the sulfuric acid steam condenser 6 is further converted into SO3. This reaction process is a strong
connected with the combustion furnace 3 through a fan exothermic reaction, so the temperature of the acid proc-
202 for supplying hot air for the combustion furnace 3. ess gas is increased after leaving the first bed 501 of the
[0049] The uncondensed acid process gas containing combined reactor 5. The acid process gas from the outlet
a small amount of SO 2 and a small amount of sulfuric 35 of the first bed 501 of the combined reactor 5 enters the
acid is sent to the acid mist eliminator, and the exhaust shell side of the interstage steam superheater 502 for
after removing tiny droplets by the acid mist eliminator cooling and heat recovery. The saturated steam from the
enters the advanced exhaust treatment system (e.g, an medium pressure steam drum 9 enters the cold end of
exhaust scrubbing tower 8, in which an external circula- the interstage steam superheater 502 to recover the heat
tion loop formed by a circulating cooler 801 and a circu- 40 generated by the acid process gas reaction. The super-
lating pump 802 is arranged). The advanced exhaust gas heated steam heated by the interstage steam superheat-
treatment system can adopt a variety of mature wet flue er 502 is sent out of the boundary area as a steam prod-
gas desulfurization processes, such as ammonia desul- uct.
furization, calcium desulfurization, double alkali desul- [0055] The acid process gas cooled by the interstage
furization and other new forms of desulfurization. 45 steam superheater 502 to recover heat enters the inlet
[0050] The heat exchange network in this example is of the second bed 503 of the combined reactor 5. SO2
relatively complex, but self-heat balance can be com- in the acid process gas is further converted. After reaction
pletely realized, with less fuel gas consumption. The acid in the second bed 503 of the combined reactor 5, the
process gas adopts a shunt measure, and the fuel gas acid process gas enters the process gas cooler 504 for
and its own by-product steam are respectively used to 50 cooling. The cold end of the process gas cooler 504 uses
heat the acid process gas to the optimal reaction tem- the circulating boiler feed water from the steam drum 9.
perature of the SO2 catalyst, which can resist the fluctu- The circulating boiler feed water exchanges heat with the
ation of the sulfur-containing flue gas SO2, and stabilize acid process gas, then vaporizes and returns to the steam
the operation of the device. drum 9 for flash evaporation to produce 5.6MPag of me-
55 dium pressure saturated steam.
Comparative example 1 [0056] The acid process gas from the process gas
cooler 504 is sent to the sulfuric acid steam condenser
[0051] The flue gas consists of 1%SO2, 16.12%O2, 6 for condensing to acid. In this process, the gaseous

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 11 EP 3 904 279 A1 12

SO3 is combined with water to form sulfuric acid and con- SO3 generated by the combined reactor into sul-
densed to form 98% concentrated sulfuric acid. furic acid; the cold end of the sulfuric acid steam
[0057] The uncondensed acid process gas containing condenser is further connected with the flue gas
a small amount of SO 2 and a small amount of sulfuric preheater for providing hot air to the flue gas
acid is sent to the acid mist eliminator, and the exhaust 5 preheater.
after removing tiny droplets by the acid mist eliminator
enters the advanced exhaust treatment system (e.g., an 2. The process system according to claim 1, wherein,
exhaust scrubbing tower 8, in which an external loop the combustion furnace is further provided with a
formed by a circulating cooler 801 and a circulating pump waste heat recycler for converting the heat of high-
802 is arranged). The advanced exhaust gas treatment 10 temperature flue gas in the combustion furnace into
system can adopt a variety of mature wet flue gas des- saturated steam.
ulfurization processes, such as ammonia desulfurization,
calcium desulfurization, double alkali desulfurization and 3. The process system according to claim 2, wherein,
other new forms of desulfurization. the combined reactor is provided with a first bed, an
[0058] The heat exchange network in the comparative 15 interstage steam superheater, a second bed and a
example is simple, but it will consume more fuel gas to process gas cooler from top to bottom, and the waste
supplement heat, and correspondingly, the combustion heat recycler and the process gas steam heater are
furnace 3 and the waste heat recycler 301 are larger in connected with the first bed after being paralleled
size. connected; the outlet of the interstage steam super-
[0059] According to the above analysis, the low con- 20 heater is further connected with the hot end of the
centration of smelting sulfur-containing flue gas and flue process gas steam heater, and superheated steam
gas containing SO 2 in various chemical devices are pu- is used for a heating process of the acid process gas.
rified and then enter the described process system and
device to solve the problem that current low concentra- 4. The process system according to claim 3, wherein,
tion of flue gas anti-fluctuation has poor ability and cannot 25 the process system further comprises a steam drum,
meet the existing relevant standards for emission of and the steam drum and the waste heat recycler are
SO2-containing flue gas, and simultaneously produce connected to form a first waste heat collection circuit,
sulfuric acid products and high grade superheated the steam drum and the process gas cooler are con-
steam. The present invention not only solves the prob- nected to form a second waste heat collection circuit,
lems in environmental protection, but also produces cer- 30 and the steam drum is further connected to the in-
tain economic benefits. terstage steam superheater, so that the saturated
steam from the steam drum enters the cold end of
the interstage steam superheater to recover heat
Claims generated by acid process gas reaction.
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1. A process system for converting sulfur-containing 5. The process system according to claim 1, wherein,
flue gas into sulfuric acid, wherein, the process sys- the upper part of the sulfuric acid steam condenser
tem comprises: is further connected with the combustion furnace
through a fan for providing hot air for the combustion
a flue gas preheater for preheating the sulfur- 40 furnace.
containing flue gas to 15~30°Cabove its dew
point, wherein the flue gas preheater has a glass 6. The process system according to claim 1, wherein,
tube as a heat exchange tube; a top exhaust outlet of the sulfuric acid steam con-
a flue gas fan for boosting the pressure of the denser is further connected with an acid mist elimi-
preheated acid process gas from the flue gas 45 nator and an advance exhaust treatment system in
preheater, and transporting one part of which to turn.
a combustion furnace, and the other part of
which to a process gas steam heater, wherein 7. A process for converting sulfur-containing flue gas
the combustion furnace and the process gas into sulfuric acid, wherein, the process is carried out
steam heater are used for heating the preheated 50 in the process system as defined in any one of claims
acid process gas to catalytic oxidation temper- 1 to 6, and comprising the following steps: preheat-
ature of SO2; ing, pressuring and heating, and then subjecting the
the combustion furnace and the process gas sulfur-containing flue gas to catalytic oxidation to ob-
steam heater are connected in parallel with a tain SO3, and then condensing; wherein the sulfur-
combined reactor, which is used for generating 55 containing flue gas has a concentration of SO2 high-
SO3 by catalytic oxidation of SO2 in the acid er than or equal to 0.1mol%, and the catalytic oxida-
process gas; tion has a temperature of above 390°C.
a sulfuric acid steam condenser for condensing

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 13 EP 3 904 279 A1 14

8. The process according to claim 7, wherein, the sul-

fur-containing flue gas consisting of: 2%SO2,
15.5%O2, 3.6%CO2, 77.5%N2, 1.4%H2O, and the
percentage is a molar percentage;
5
the sulfur-containing flue gas that enters the flue
gas preheater has a dew point of 120~150°C;
after passing through the flue gas preheater,
preheating the sulfur-containing flue gas to
15~30°C above the dew point, preferably to 10
140~170°C;
boosting the pressure of the acid process gas
preheated by the flue gas preheater to
115~125kPa by the flue gas fan;
carrying out a combustion reaction of the acid 15
process gas, fuel gas and hot air in the combus-
tion furnace, where the acid process gas is heat-
ed by ignition to 900~1200°C.

9. The process according to claim 7, wherein, the acid 20

process gas that enters the combined reactor has a
temperature of 390~430°C; the catalytic oxidation
has a reaction order of 2;
sending the process gas after catalytic oxidation re-
action into the sulfuric acid steam condenser for con- 25
densation, cooling obtained product to 10°C above
the dew point of H2SO 4, then further cooling to
60°C∼120°C, and collecting obtained H2SO4, coa-
lescing and separating, and directly exhausting
cooled gas; preferably the further cooling has a tem- 30
perature of 105 °C~120°C.

10. The process according to claim 7, wherein, the ob-

tained H2SO4 has a concentration of 93%~98%, and
the percentage is a mass percentage. 35

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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

• CN 201811600891 [0001] • CN 201822211197X [0001]

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