CN111071996A - Method for preparing sulfuric acid - Google Patents
Method for preparing sulfuric acid Download PDFInfo
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- CN111071996A CN111071996A CN201911413284.6A CN201911413284A CN111071996A CN 111071996 A CN111071996 A CN 111071996A CN 201911413284 A CN201911413284 A CN 201911413284A CN 111071996 A CN111071996 A CN 111071996A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 269
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 371
- 239000007789 gas Substances 0.000 claims abstract description 291
- 238000010521 absorption reaction Methods 0.000 claims abstract description 260
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 167
- 239000002918 waste heat Substances 0.000 claims abstract description 41
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 133
- 238000001035 drying Methods 0.000 claims description 120
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 50
- 239000011593 sulfur Substances 0.000 claims description 50
- 229910052717 sulfur Inorganic materials 0.000 claims description 45
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 34
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 26
- 238000007599 discharging Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/775—Liquid phase contacting processes or wet catalysis processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/78—Preparation by contact processes characterised by the catalyst used
- C01B17/79—Preparation by contact processes characterised by the catalyst used containing vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
- C01B17/76—Preparation by contact processes
- C01B17/80—Apparatus
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The invention relates to the technical field of inorganic chemical manufacturing, in particular to a method for manufacturing sulfuric acid, which comprises the steps of furnace gas generation, impurity removal and conversion, absorption to form acid, sulfuric acid circulation and cooling, waste heat recovery and tail gas emission, and combines the advantages of dry method, wet method and semi-dry method acid manufacturing process technologies, so that various sulfuric acid products such as fuming sulfuric acid, reagent sulfuric acid and the like can be prepared, and no low-concentration dilute acid byproduct is generated; the sulfuric acid manufacturing method has the advantages of short process flow, low tail gas concentration, low production energy consumption, high waste heat recovery efficiency, small equipment quantity, low investment cost, large-scale device, easy realization and realization of automatic control.
Description
Technical Field
The invention relates to the technical field of inorganic chemical manufacturing, in particular to a method for manufacturing sulfuric acid.
Background
At present, GB/T534-2014 industrial sulfuric acid is executed according to the quality standard of domestic industrial sulfuric acid, a contact sulfuric acid preparation process is adopted in all production, and an industrial production device for preparing acid by a contact method mainly comprises three manufacturing processes of a dry method, a wet method and a semi-dry method according to the difference of moisture contents of raw materials and furnace gas.
The 'dry method' acid making technology is mature and reliable, is the mainstream sulfuric acid manufacturing technology at present, and the raw material of the technology comprises sulfurPyrite, smelting flue gas, acidic gas containing hydrogen sulfide, waste sulfuric acid and the like. The "dry method" acid-making process is that the SO-containing gas produced by incineration in the previous working section is used2After high-temperature level heat recovery, the furnace gas is subjected to wet purification, cooling and demisting, and is dried by a concentrated sulfuric acid drying tower and then enters a converter to generate SO3Furnace gas containing SO3The furnace gas enters an absorption tower to be absorbed into acid. The acid making process equipment has low requirement and can produce fuming sulfuric acid, but has long process flow and large heat energy loss, 5 to 10 percent of dilute sulfuric acid can be produced, and the environmental pressure is increased when the dilute sulfuric acid is discharged.
The wet process for preparing acid mainly uses the acid gas containing hydrogen sulfide as raw material, and the sulfur-containing material and hydrogen sulfide in the raw material are combusted in incinerator to produce SO2While producing water, the dust content of raw materials required by the acid production process by the wet method is extremely low, and the process generally comprises the step of burning the raw materials to produce SO2After the high-temperature level heat recovery of the furnace gas mixed with water, wet furnace gas directly enters a converter to convert SO2Conversion to SO3Gaseous water and SO3The mixed furnace gas enters a condenser to be condensed into liquid sulfuric acid. The process has short flow, high heat energy utilization rate and no dilute acid, but has high equipment requirement, high energy consumption and partial heat energy loss, and in addition, the concentration of the finished product sulfuric acid of the wet process is only 98 percent, fuming sulfuric acid can not be produced, and the process can not produce liquid SO in a downstream industrial chain3And the production of downstream products with higher added value, such as high-purity electronic-grade sulfuric acid, by the absorption method constitute limitations.
The semi-dry process for preparing acid mainly uses the acid gas containing hydrogen sulfide and waste sulfuric acid as raw materials, when it is burnt, a certain proportion of sulfur is infiltrated and burnt or a certain quantity of SO is added in the furnace gas before it is fed into converter2Gas to maintain water balance. The process has long process flow, can not realize automatic control, and can not produce reagent sulfuric acid and fuming sulfuric acid, thereby failing to obtain industrial application.
Disclosure of Invention
The invention aims to provide a preparation method of sulfuric acid, which combines the advantages of the acid preparation process technologies of a dry method, a wet method and a semi-dry method to prepare industrial sulfuric acid and reagent sulfuric acid with different concentrations.
In order to achieve the purpose, the invention adopts the following technical scheme:
provided is a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove part of moisture, and then is mixed with acid gas containing hydrogen sulfide and liquid sulfur and is sent into an incinerator to be combusted to generate SO2Mixed furnace gas of water and gas;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler for cooling, and then removing NO in the mixed furnace gas through a denitration reactorxThen the mixture enters a conversion device for furnace gas conversion to obtain the product containing SO3And water gas shift converter gas;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to be in reverse contact with the sulfuric acid entering from the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and the high-temperature concentrated sulfuric acid is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; one part of furnace gas sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid entering from the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The back furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid is discharged to a fuming circulating groove from the bottom of the fuming acid absorption tower; furnace gas sent out from the upper part of the fuming acid absorption tower is mixed with another part of furnace gas sent out from the upper part of the high-temperature absorption tower, enters the bottom of the reagent acid absorption tower and is in countercurrent contact with the reagent sulfuric acid entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid is discharged to a reagent circulating groove from the bottom of the reagent acid absorption tower; the tail gas is discharged to the tail absorption tower from the bottom of the drying acid concentration tower, and the drying acid is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying acid concentration tower;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; one part of the dry acid sent to the drying circulation tank is sent to the high-temperature circulation tank through a dry acid pump, the other part of the dry acid is sent to the upper part of the drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan and enters the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent to the upper part of the dry acid concentration tower through the concentrated acid pump and is discharged to the dry acid pump side of the drying circulation tank from the bottom of the drying concentration tower after being contacted with dry tail gas from a reagent acid absorption tower and enters the lower part of the dry acid concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: the desalted water is conveyed to a pure water heater through a desalted water pump and then enters a deaerator for deoxidation and heating, then part of sulfuric acid heat energy is recovered through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, then the high-temperature sulfuric acid heat energy is recovered through a boiler feed water pump to a feed water heater, then the high-temperature sulfuric acid heat energy is conveyed to a boiler, and superheated steam is discharged after passing through a low-temperature superheater and a high-;
step six, tail gas emission: and D, sending the tail gas obtained in the step three to a tail absorption tower for treatment, demisting by an electric demister, and then discharging by a tail gas chimney.
In the technical scheme, in the first step, air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove part of moisture, and then is mixed with hydrogen sulfide-containing acid gas with the pressure of 0.05-0.06 MPa and liquid sulfur atomized by a high-pressure pump of 0.8-0.9 MPa and a sulfur gun to be combusted in an incinerator to generate sulfur-containing gas2Mixed furnace gas with water vapor at 1000-1200 deg.c and SO in the mixed furnace gas2Concentration of 6% -10%, NOxThe content is less than or equal to 600mg/Nm3。
In the technical scheme, in the second step, the mixed furnace gas obtained in the first step is sent to a boiler to be cooled to 400-410 ℃, and then NO in the mixed furnace gas is removed through a denitration reactorxThe denitration efficiency is 90-95 percent, the denitration efficiency is then fed into a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 550-560 ℃, the temperature of the furnace gas is reduced to 415-425 ℃ after passing through a high-temperature superheater and then fed into a second section of the converter, the temperature of an outlet of the second section of the converter is 470-480 ℃, the temperature of the furnace gas is reduced to 390-400 ℃ after passing through a low-temperature superheater and then fed into the third section of the converter, the temperature of an outlet of the third section of the converter is 405-415 ℃, the temperature of the3And water-gas conversion furnace gas, the conversion rate is 99-99.9%.
In the above technical scheme, in the third step, the SO-containing product obtained in the second step3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with sulfuric acid with the concentration of 98.8-99.2 percent at the temperature of 175-185 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99-99.4% is discharged from the bottom of the high-temperature absorption tower to a high-temperature circulating tank; one part of furnace gas with the temperature of 185-195 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 55-65 ℃ and the concentration of 104-105 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and the concentration is 106.5% ~ up to107.5 percent of fuming sulfuric acid is discharged from the bottom of the fuming acid absorption tower to a fuming circulation tank; furnace gas with the temperature of 65-75 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 185-195 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 60-70 ℃ and the concentration of 98-98.2 percent, which enters the upper part of the reagent acid absorption tower, SO as to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 98.8 to 99 percent is discharged from the bottom of the reagent acid absorption tower to a reagent circulating tank; and feeding the dried tail gas with the temperature of 65-75 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a drying acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 45-55 ℃ and the concentration of 75-76% sent into the upper part of the drying acid concentration tower to absorb the water of the dried tail gas, then feeding the tail gas out from the upper part of the drying acid concentration tower to a tail absorption tower, and discharging the dried acid with the concentration of 79-80% from the bottom of the drying acid concentration tower to the side of a drying acid pump of a drying circulation tank.
In the fifth technical scheme, in the fifth step, desalted water is pumped into a pure water heater through a desalted water pump, then enters a deaerator to be deoxidized and heated to 102-105 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, is pumped into a feed water heater to recycle high-temperature sulfuric acid heat energy through a feed water pump of a boiler with the pressure of 4.8MPa, and is then sent to a waste heat boiler, wherein one part of boiler water is sent to a water pipe boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam pocket, is heated to 410-430 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a one-section outlet of the converter, the.
In the sixth step, hydrogen peroxide with the concentration of 6-8% is added into the tail absorption tower to treat the tail gas.
Specifically, the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 10-90%, the content of S in the liquid sulfur is 99.3-99.9%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1: 0-9 by mass ratio of sulfur contained in each of the liquid sulfur and the hydrogen sulfide-containing acid gas.
Specifically, urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter.
The invention has the beneficial effects that:
the invention provides a method for preparing sulfuric acid, comprising several steps of furnace gas generation, impurity removal and conversion, absorption into acid, sulfuric acid circulation and cooling, waste heat recovery and tail gas emission, wherein the method for preparing sulfuric acid combines the advantages of the acid preparation process technologies of dry method, wet method and semi-dry method, can prepare various sulfuric acid products such as fuming sulfuric acid, reagent sulfuric acid and the like, and does not generate low-concentration dilute acid byproducts; the sulfuric acid manufacturing method has the advantages of short process flow, low tail gas concentration, low production energy consumption, high waste heat recovery efficiency, small equipment quantity, low investment cost, large-scale device, easy realization and realization of automatic control.
Drawings
FIG. 1 is a flow chart of a sulfuric acid production process according to a method for producing sulfuric acid according to the present invention.
FIG. 2 is a flow chart of the sulfuric acid circulation and cooling process of a method for producing sulfuric acid according to the present invention.
FIG. 3 is a process flow diagram of the waste heat recovery process of a sulfuric acid manufacturing method of the present invention.
FIG. 4 is a process flow diagram of a conversion apparatus of a method of producing sulfuric acid according to the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1.
As shown in fig. 1 to 3, there is provided a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters the air filter and is pressurized by the main fanThen the sulfur-containing sulfur is fed into a drying tower to remove partial water, and then the sulfur-containing acid gas with the pressure of 0.06MPa and the liquid sulfur which is mechanically atomized by a high-pressure pump of 0.8MPa and a sulfur gun are fed into an incinerator to be mixed and combusted to generate SO-containing sulfur2Mixed furnace gas with water vapor and temperature of 1100 ℃, SO in the mixed furnace gas2Concentration of 8% NOxThe content is 600mg/Nm3；
Wherein the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 80%, the content of S in the liquid sulfur is 99.5%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1:1.5 of the mass ratio of sulfur contained in each;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler to be cooled to 400 ℃, and then removing NO in the mixed furnace gas through a denitration reactorxThe denitration efficiency is 93 percent, the denitration efficiency enters a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 550 ℃, the temperature of the furnace gas is reduced to 420 ℃ after passing through a high-temperature superheater, the furnace gas enters a second section of the converter, the temperature of an outlet of the second section of the converter is 475 ℃, the temperature of the furnace gas is reduced to 390 ℃ after passing through a low-temperature superheater, the furnace gas enters a third section of the converter, the temperature of an outlet of the third section of the converter is 410 ℃, the temperature of3And water-gas conversion furnace gas, the conversion rate is 99.5%;
urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with the sulfuric acid with the concentration of 99.0 percent at 180 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99.2 percent is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; part of furnace gas with the temperature of 190 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 60 ℃ and the concentration of 104 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and the concentration of the rear furnace gas is 107 percentThe fuming sulfuric acid is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; furnace gas with the temperature of 70 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 190 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 65 ℃ and the concentration of 98 percent entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 99 percent is discharged to a reagent circulating tank from the bottom of the reagent acid absorption tower; feeding the dry tail gas with the temperature of 70 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a dry acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 50 ℃ and the concentration of 75% which is fed into the upper part of the dry acid concentration tower to absorb the moisture of the dry tail gas, then feeding the tail gas out from the upper part of the dry acid concentration tower into a tail absorption tower, and discharging the dry acid with the concentration of 80% from the bottom of the dry acid concentration tower to the side of a dry acid pump of a dry circulation tank;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater A, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater B and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater C and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; the drying acid sent to the drying circulation tank is sent out by a drying acid pump to enter the upper part of a drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan entering the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent out by a concentrated acid pump to enter the upper part of the drying acid concentration tower, is contacted with dry tail gas from a reagent acid absorption tower entering the lower part of the drying acid concentration tower and is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: desalted water is pumped to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 105 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, and is pumped to a water feed heater to recycle high-temperature sulfuric acid heat energy through a boiler water feed pump with the pressure of 4.8MPa, and then is sent to a boiler, wherein one part of boiler water is sent to a water tube boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam drum, is heated to 420 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, has the;
step six, tail gas emission: and D, delivering the tail gas obtained in the step three to a tail absorption tower, adding 8% hydrogen peroxide into the tail absorption tower to treat the tail gas, and then demisting by an electric demister and discharging by a tail gas chimney.
Example 2.
As shown in fig. 1 to 3, there is provided a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove partial moisture, and then is mixed with hydrogen sulfide-containing acid gas with the pressure of 0.06MPa and liquid sulfur which is mechanically atomized by a high-pressure pump and a sulfur gun with the pressure of 0.8MPa and is sent into an incinerator to be combusted to generate SO-containing sulfur2Mixed furnace gas with water vapor and temperature of 1000 ℃, SO in the mixed furnace gas2Concentration of 6% NOxThe content is 500mg/Nm3；
Wherein the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 75 percent, the content of S in the liquid sulfur is 99.3 percent, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1:2 of the mass ratio of sulfur respectively;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler to be cooled to 400 ℃, and then removing NO in the mixed furnace gas through a denitration reactorxThe denitration efficiency is 90 percent, the denitration efficiency enters a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 530 ℃, the temperature of the furnace gas is reduced to 420 ℃ after passing through a high-temperature superheater, the furnace gas enters a second section of the converter, the temperature of an outlet of the second section of the converter is 455 ℃, the temperature of the furnace gas is reduced to 390 ℃ after passing through a low-temperature superheater, the furnace gas enters a third section of the converter, the temperature of an outlet of the third section of the converter is 410 ℃, the temperature of3And water-gas conversion furnace gas, the conversion rate is 99.0%;
urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with the sulfuric acid with the concentration of 99 percent at 180 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99.2 percent is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; part of furnace gas with the temperature of 190 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 60 ℃ and the concentration of 104 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid with the concentration of 107 percent is discharged from the bottom of the fuming acid absorption tower to a fuming circulating groove; furnace gas with the temperature of 70 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 190 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 65 ℃ and the concentration of 98 percent entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 99 percent is discharged to a reagent circulating tank from the bottom of the reagent acid absorption tower; the upper part of the reagent acid absorption tower is sent outThe tail gas with the temperature of 70 ℃ enters the bottom of a drying acid concentration tower, and is in countercurrent contact with concentrated acid with the temperature of 50 ℃ and the concentration of 75% entering the upper part of the drying acid concentration tower to absorb the water of the tail gas, the tail gas is sent out to a tail absorption tower at the upper part of the drying acid concentration tower, and the dried acid with the concentration of 80% is discharged to the side of a drying acid pump of a drying circulation tank from the bottom of the drying acid concentration tower;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater A, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater B and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater C and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; the drying acid sent to the drying circulation tank is sent out by a drying acid pump to enter the upper part of a drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan entering the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent out by a concentrated acid pump to enter the upper part of the drying acid concentration tower, is contacted with dry tail gas from a reagent acid absorption tower entering the lower part of the drying acid concentration tower and is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: desalted water is pumped to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 103 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, and is pumped to a water feed heater to recycle high-temperature sulfuric acid heat energy through a boiler water feed pump with the pressure of 4.8MPa, and is then sent to a boiler, wherein one part of boiler water is sent to a water tube boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam drum, is heated to 420 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, has the;
step six, tail gas emission: and D, delivering the tail gas obtained in the step three to a tail absorption tower, adding 6% hydrogen peroxide into the tail absorption tower to treat the tail gas, and then demisting by an electric demister and discharging by a tail gas chimney.
Example 3.
As shown in fig. 1 to 3, there is provided a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove partial moisture, and then is mixed with hydrogen sulfide-containing acid gas with the pressure of 0.06MPa and liquid sulfur which is mechanically atomized by a high-pressure pump and a sulfur gun with the pressure of 0.8MPa and is sent into an incinerator to be combusted to generate SO-containing sulfur2Mixed furnace gas with water vapor at 1200 ℃ and SO in the mixed furnace gas2Concentration of 10% NOxThe content is 600mg/Nm3；
Wherein the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 85%, the content of S in the liquid sulfur is 99.7%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1:1 by mass ratio of sulfur respectively;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler to be cooled to 400 ℃, and then removing NO in the mixed furnace gas through a denitration reactorxThe denitration efficiency is 93 percent, the denitration efficiency enters a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 530 ℃, the temperature of the furnace gas is reduced to 420 ℃ after passing through a high-temperature superheater, the furnace gas enters a second section of the converter, the temperature of an outlet of the second section of the converter is 465 ℃, the temperature of the furnace gas is reduced to 390 ℃ after passing through a low-temperature superheater, the furnace gas enters a third section of the converter, and theThe temperature of the opening is 410 ℃, the temperature is reduced to 250 ℃ after passing through a water tube boiler, and SO is obtained3And water-gas conversion furnace gas, the conversion rate is 99.9%;
urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with the sulfuric acid with the concentration of 99 percent at 180 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99.2 percent is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; part of furnace gas with the temperature of 190 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 60 ℃ and the concentration of 104 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid with the concentration of 107 percent is discharged from the bottom of the fuming acid absorption tower to a fuming circulating groove; furnace gas with the temperature of 70 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 190 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 65 ℃ and the concentration of 98 percent entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 99 percent is discharged to a reagent circulating tank from the bottom of the reagent acid absorption tower; feeding the dry tail gas with the temperature of 70 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a dry acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 50 ℃ and the concentration of 75% which is fed into the upper part of the dry acid concentration tower to absorb the moisture of the dry tail gas, then feeding the tail gas out from the upper part of the dry acid concentration tower into a tail absorption tower, and discharging the dry acid with the concentration of 80% from the bottom of the dry acid concentration tower to the side of a dry acid pump of a dry circulation tank;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater A, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater B and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater C and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; the drying acid sent to the drying circulation tank is sent out by a drying acid pump to enter the upper part of a drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan entering the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent out by a concentrated acid pump to enter the upper part of the drying acid concentration tower, is contacted with dry tail gas from a reagent acid absorption tower entering the lower part of the drying acid concentration tower and is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: desalted water is pumped to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 105 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, and is pumped to a water feed heater to recycle high-temperature sulfuric acid heat energy through a boiler water feed pump with the pressure of 4.8MPa, and then is sent to a boiler, wherein one part of boiler water is sent to a water tube boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam drum, is heated to 420 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, has the;
step six, tail gas emission: and D, delivering the tail gas obtained in the step three to a tail absorption tower, adding hydrogen peroxide with the concentration of 7% into the tail absorption tower to treat the tail gas, and then demisting through an electric demister and discharging through a tail gas chimney.
Example 4.
As shown in fig. 1 to 3, there is provided a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove partial moisture, and then is mixed with hydrogen sulfide-containing acid gas with the pressure of 0.06MPa and liquid sulfur which is mechanically atomized by a high-pressure pump and a sulfur gun with the pressure of 0.8MPa and is sent into an incinerator to be combusted to generate SO-containing sulfur2Mixed furnace gas with water vapor at 1050 ℃ and SO in the mixed furnace gas2Concentration of 7% NOxThe content is 550mg/Nm3；
Wherein the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 77%, the content of S in the liquid sulfur is 99.4%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1:1.7 in terms of the mass ratio of sulfur respectively;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler to be cooled to 400 ℃, and then removing NO in the mixed furnace gas through a denitration reactorxThe denitration efficiency is 91 percent, the denitration efficiency enters a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 540 ℃, the temperature of the furnace gas is reduced to 420 ℃ after passing through a high-temperature superheater, the furnace gas enters a second section of the converter, the temperature of an outlet of the second section of the converter is 455 ℃, the temperature of the furnace gas is reduced to 390 ℃ after passing through a low-temperature superheater, the furnace gas enters a third section of the converter, the temperature of an outlet of the third section of the converter is 410 ℃, the temperature of3And water-gas conversion furnace gas, the conversion rate is 99.3%;
urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The steam-mixed converter gas is sent to the bottom of the high-temperature absorption tower andsulfuric acid with the concentration of 99 percent at 180 ℃ entering the upper part of the high-temperature absorption tower reversely contacts and absorbs the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99.2 percent is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; part of furnace gas with the temperature of 190 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 60 ℃ and the concentration of 104 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid with the concentration of 107 percent is discharged from the bottom of the fuming acid absorption tower to a fuming circulating groove; furnace gas with the temperature of 70 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 190 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 65 ℃ and the concentration of 98 percent entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 99 percent is discharged to a reagent circulating tank from the bottom of the reagent acid absorption tower; feeding the dry tail gas with the temperature of 70 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a dry acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 50 ℃ and the concentration of 75% which is fed into the upper part of the dry acid concentration tower to absorb the moisture of the dry tail gas, then feeding the tail gas out from the upper part of the dry acid concentration tower into a tail absorption tower, and discharging the dry acid with the concentration of 80% from the bottom of the dry acid concentration tower to the side of a dry acid pump of a dry circulation tank;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater A, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater B and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater C and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; the drying acid sent to the drying circulation tank is sent out by a drying acid pump to enter the upper part of a drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan entering the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent out by a concentrated acid pump to enter the upper part of the drying acid concentration tower, is contacted with dry tail gas from a reagent acid absorption tower entering the lower part of the drying acid concentration tower and is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: desalted water is pumped to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 105 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, and is pumped to a water feed heater to recycle high-temperature sulfuric acid heat energy through a boiler water feed pump with the pressure of 4.8MPa, and then is sent to a boiler, wherein one part of boiler water is sent to a water tube boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam drum, is heated to 420 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, has the;
step six, tail gas emission: and D, delivering the tail gas obtained in the step three to a tail absorption tower, adding hydrogen peroxide with the concentration of 7% into the tail absorption tower to treat the tail gas, and then demisting through an electric demister and discharging through a tail gas chimney.
Example 5.
As shown in fig. 1 to 3, there is provided a method for producing sulfuric acid, comprising the steps of:
step one, furnace gas generation: air enters the air filter and then passes through the main filterPressurizing by a fan, then entering a drying tower to remove partial water, and then feeding the dried product and hydrogen sulfide-containing acid gas with the pressure of 0.07MPa and liquid sulfur which is mechanically atomized by a high-pressure pump of 0.9MPa and a sulfur gun into an incinerator for mixed combustion to generate SO-containing sulfur2Mixed furnace gas with water vapor at 1150 ℃ and SO in the mixed furnace gas2Concentration 9% NOxThe content is 600mg/Nm3；
Wherein the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 83%, the content of S in the liquid sulfur is 99.6%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1:1.3 of the mass ratio of sulfur respectively;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler to be cooled to 400 ℃, and then removing NO in the mixed furnace gas through a denitration reactorxThe denitration efficiency is 93 percent, the denitration efficiency enters a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 530 ℃, the temperature of the furnace gas is reduced to 420 ℃ after passing through a high-temperature superheater, the furnace gas enters a second section of the converter, the temperature of an outlet of the second section of the converter is 455 ℃, the temperature of the furnace gas is reduced to 390 ℃ after passing through a low-temperature superheater, the furnace gas enters a third section of the converter, the temperature of an outlet of the third section of the converter is 410 ℃, the temperature of3And water-gas conversion furnace gas, the conversion rate is 99%;
urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with the sulfuric acid with the concentration of 99 percent at 180 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99.2 percent is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; part of furnace gas with the temperature of 190 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid with the temperature of 60 ℃ and the concentration of 104 percent entering the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The rear furnace gas is sent out from the upper part of the fuming acid absorption tower, and the concentration of the rear furnace gas isDischarging 107% fuming sulfuric acid from the bottom of the fuming acid absorption tower to a fuming circulation tank; furnace gas with the temperature of 70 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 190 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 65 ℃ and the concentration of 98 percent entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 99 percent is discharged to a reagent circulating tank from the bottom of the reagent acid absorption tower; feeding the dry tail gas with the temperature of 70 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a dry acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 50 ℃ and the concentration of 75% which is fed into the upper part of the dry acid concentration tower to absorb the moisture of the dry tail gas, then feeding the tail gas out from the upper part of the dry acid concentration tower into a tail absorption tower, and discharging the dry acid with the concentration of 80% from the bottom of the dry acid concentration tower to the side of a dry acid pump of a dry circulation tank;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater A, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank; the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater B and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower; the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater C and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower; the drying acid sent to the drying circulation tank is sent out by a drying acid pump to enter the upper part of a drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan entering the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent out by a concentrated acid pump to enter the upper part of the drying acid concentration tower, is contacted with dry tail gas from a reagent acid absorption tower entering the lower part of the drying acid concentration tower and is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying concentration tower; the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: desalted water is pumped to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 105 ℃, then is recycled to part of sulfuric acid heat energy through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, and is pumped to a water feed heater to recycle high-temperature sulfuric acid heat energy through a boiler water feed pump with the pressure of 4.8MPa, and then is sent to a boiler, wherein one part of boiler water is sent to a water tube boiler at a three-section outlet of a converter to recycle heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam drum, is heated to 420 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, has the;
step six, tail gas emission: and D, delivering the tail gas obtained in the step three to a tail absorption tower, adding 8% hydrogen peroxide into the tail absorption tower to treat the tail gas, and then demisting by an electric demister and discharging by a tail gas chimney.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for producing sulfuric acid, characterized by comprising: the method comprises the following steps:
step one, furnace gas generation: air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove part of water, and then is sent into an incinerator with acid gas containing hydrogen sulfide and liquid sulfurMixed combustion to produce SO-containing2Mixed furnace gas of water and gas;
step two, impurity removal and transformation: sending the mixed furnace gas obtained in the step one into a boiler for cooling, and then removing NO in the mixed furnace gas through a denitration reactorxThen the mixture enters a conversion device for furnace gas conversion to obtain the product containing SO3And water gas shift converter gas;
step three, absorbing into acid: the SO contained in the product obtained in the step two3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to be in reverse contact with the sulfuric acid entering from the upper part of the high-temperature absorption tower to absorb the water and part of SO3The rear furnace gas is sent out from the upper part of the high-temperature absorption tower, and the high-temperature concentrated sulfuric acid is discharged from the bottom of the high-temperature absorption tower to the high-temperature circulating tank;
one part of furnace gas sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is in countercurrent contact with fuming sulfuric acid entering from the upper part of the fuming acid absorption tower to absorb part of SO of the furnace gas3The back furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid is discharged to a fuming circulating groove from the bottom of the fuming acid absorption tower;
furnace gas sent out from the upper part of the fuming acid absorption tower is mixed with another part of furnace gas sent out from the upper part of the high-temperature absorption tower, enters the bottom of the reagent acid absorption tower and is in countercurrent contact with the reagent sulfuric acid entering the upper part of the reagent acid absorption tower to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid is discharged to a reagent circulating groove from the bottom of the reagent acid absorption tower;
the tail gas is discharged to the tail absorption tower from the bottom of the drying acid concentration tower, and the drying acid is discharged to the drying acid pump side of the drying circulation tank from the bottom of the drying acid concentration tower;
step four, sulfuric acid circulation and cooling: sending high-temperature concentrated sulfuric acid sent to the high-temperature circulating tank out by a high-temperature acid pump, cooling by a feed water heater and a pure water heater, sending to the upper part of a high-temperature absorption tower, contacting with reformer gas entering from the bottom of the high-temperature absorption tower, and then discharging from the bottom of the high-temperature absorption tower to the high-temperature circulating tank;
the fuming sulfuric acid sent to the fuming circulating tank is sent out by a fuming acid pump, is cooled by a pure water heater and a fuming acid cooler, is sent to the upper part of a fuming acid absorption tower, is contacted with furnace gas from a high-temperature absorption tower entering from the bottom of the fuming acid absorption tower, and is discharged to the fuming circulating tank from the bottom of the fuming acid absorption tower;
the reagent sulfuric acid sent to the reagent circulating tank is sent out by a reagent acid pump, is cooled by a pure water heater and a reagent acid cooler, is sent to the upper part of a reagent acid absorption tower, is contacted with furnace gas entering from the bottom of the reagent acid absorption tower and coming from a high-temperature absorption tower and a fuming acid absorption tower, and is discharged to the reagent circulating tank from the bottom of the reagent acid absorption tower;
one part of the dry acid sent to the drying circulation tank is sent to the high-temperature circulation tank through a dry acid pump, the other part of the dry acid is sent to the upper part of the drying tower, is discharged to the concentrated acid pump side of the drying circulation tank from the bottom of the drying tower after being contacted with air from a main fan and enters the lower part of the drying tower, and the concentrated acid at the concentrated acid pump side of the drying circulation tank is sent to the upper part of the dry acid concentration tower through the concentrated acid pump and is discharged to the dry acid pump side of the drying circulation tank from the bottom of the drying concentration tower after being contacted with dry tail gas from a reagent acid absorption tower and enters the lower part of the dry acid concentration tower;
the redundant high-temperature concentrated sulfuric acid, fuming sulfuric acid and reagent sulfuric acid discharged to the high-temperature circulating tank, the fuming circulating tank and the reagent circulating tank are respectively conveyed to respective reservoir areas for storage and use through a high-temperature acid pump bypass, a fuming acid pump bypass and a reagent acid pump bypass;
step five, waste heat recovery: the desalted water is conveyed to a pure water heater through a desalted water pump and then enters a deaerator for deoxidation and heating, then part of sulfuric acid heat energy is recovered through a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer, then the high-temperature sulfuric acid heat energy is recovered through a boiler feed water pump to a feed water heater, then the high-temperature sulfuric acid heat energy is conveyed to a boiler, and superheated steam is discharged after passing through a low-temperature superheater and a high-;
step six, tail gas emission: and D, sending the tail gas obtained in the step three to a tail absorption tower for treatment, demisting by an electric demister, and then discharging by a tail gas chimney.
2. The method of claim 1A process for producing sulfuric acid, characterized by comprising: in the first step, air enters an air filter, is pressurized by a main fan, then enters a drying tower to remove part of moisture, and then is sent into an incinerator to be mixed and combusted with hydrogen sulfide-containing acid gas with the pressure of 0.05-0.06 MPa and liquid sulfur which is mechanically atomized by a high-pressure pump and a sulfur gun with the pressure of 0.8-0.9 MPa to generate sulfur-containing gas2Mixed furnace gas with water vapor at 1000-1200 deg.c and SO in the mixed furnace gas2Concentration of 6% -10%, NOxThe content is less than or equal to 600mg/Nm3。
3. The method for producing sulfuric acid according to claim 1, wherein: in the second step, the mixed furnace gas obtained in the first step is sent into a boiler to be cooled to 400-410 ℃, and then NO in the mixed furnace gas is removed through a denitration reactorxThe denitration efficiency is 90-95 percent, the denitration efficiency is then fed into a first section of the converter, the temperature of furnace gas discharged from the first section of the converter is 550-560 ℃, the temperature of the furnace gas is reduced to 415-425 ℃ after passing through a high-temperature superheater and then fed into a second section of the converter, the temperature of an outlet of the second section of the converter is 470-480 ℃, the temperature of the furnace gas is reduced to 390-400 ℃ after passing through a low-temperature superheater and then fed into the third section of the converter, the temperature of an outlet of the third section of the converter is 405-415 ℃, the temperature of the3And water-gas conversion furnace gas, the conversion rate is 99-99.9%.
4. The method for producing sulfuric acid according to claim 1, wherein: in the third step, the SO-containing product obtained in the second step3The converter gas with water vapor is sent to the bottom of the high-temperature absorption tower to reversely contact with sulfuric acid with the concentration of 98.8-99.2 percent at the temperature of 175-185 ℃ entering the upper part of the high-temperature absorption tower to absorb the water and part of SO3The furnace gas is sent out from the upper part of the high-temperature absorption tower, and high-temperature concentrated sulfuric acid with the concentration of 99-99.4% is discharged from the bottom of the high-temperature absorption tower to a high-temperature circulating tank;
one part of furnace gas with the temperature of 185-195 ℃ sent out from the upper part of the high-temperature absorption tower enters the bottom of the fuming acid absorption tower and is concentrated with the temperature of 55-65 ℃ entering from the upper part of the fuming acid absorption towerThe fuming sulfuric acid with the degree of 104 to 105 percent contacts and absorbs part of SO of the fuming sulfuric acid in a counter-current way3The back furnace gas is sent out from the upper part of the fuming acid absorption tower, and fuming sulfuric acid with the concentration of 106.5 to 107.5 percent is discharged from the bottom of the fuming acid absorption tower to a fuming circulating groove;
furnace gas with the temperature of 65-75 ℃ sent out from the upper part of the fuming acid absorption tower is mixed with furnace gas with the temperature of 185-195 ℃ sent out from the upper part of the other high-temperature absorption tower, then the mixture enters the bottom of the reagent acid absorption tower and is in countercurrent contact with reagent sulfuric acid with the temperature of 60-70 ℃ and the concentration of 98-98.2 percent, which enters the upper part of the reagent acid absorption tower, SO as to absorb residual SO3The dried tail gas is sent out from the upper part of the reagent acid absorption tower, and the reagent sulfuric acid with the concentration of 98.8 to 99 percent is discharged from the bottom of the reagent acid absorption tower to a reagent circulating tank;
and feeding the dried tail gas with the temperature of 65-75 ℃ sent out from the upper part of the reagent acid absorption tower into the bottom of a drying acid concentration tower, carrying out countercurrent contact with concentrated acid with the temperature of 45-55 ℃ and the concentration of 75-76% sent into the upper part of the drying acid concentration tower to absorb the water of the dried tail gas, then feeding the tail gas out from the upper part of the drying acid concentration tower to a tail absorption tower, and discharging the dried acid with the concentration of 79-80% from the bottom of the drying acid concentration tower to the side of a drying acid pump of a drying circulation tank.
5. The method for producing sulfuric acid according to claim 1, wherein: in the fifth step, desalted water is conveyed to a pure water heater through a desalted water pump, enters a deaerator to be deoxidized and heated to 102-105 ℃, then is conveyed to a fuming waste heat recoverer, a reagent waste heat recoverer and a high-temperature waste heat recoverer to recover part of sulfuric acid heat energy, and is conveyed to a water supply heater to recover high-temperature sulfuric acid heat energy through a boiler water supply pump with the pressure of 4.8MPa, and then is conveyed to a waste heat boiler, wherein one part of boiler water is conveyed to a water pipe boiler at a three-section outlet of a converter to recover heat energy at a three-section outlet of the converter, the other part of boiler water is evaporated through a steam pocket, is heated to 410-430 ℃ through a low-temperature superheater at a two-section outlet of the converter and a high-temperature superheater at a first section outlet of the converter, and has the pressure.
6. The method for producing sulfuric acid according to claim 1, wherein: in the sixth step, hydrogen peroxide with the concentration of 6-8% is added into the tail absorption tower to treat the tail gas.
7. The method for producing sulfuric acid according to claim 2, wherein: the content of hydrogen sulfide in the hydrogen sulfide-containing acid gas is 10-90%, the content of S in the liquid sulfur is 99.3-99.9%, and the adding amount of the liquid sulfur and the hydrogen sulfide-containing acid gas is 1: 0-9 in terms of the mass ratio of sulfur to sulfur.
8. The method for producing sulfuric acid according to claim 3, wherein: urea and an SCR denitration catalyst are added into a denitration reactor, vanadium sulfate catalysts are added into one section and two sections of a converter, and vanadium sulfate catalysts and cesium catalysts are added into three sections of the converter.
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