CN111689477B - Wet process and apparatus for preparing sulfuric acid from acid gas with high hydrocarbon content - Google Patents
Wet process and apparatus for preparing sulfuric acid from acid gas with high hydrocarbon content Download PDFInfo
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- CN111689477B CN111689477B CN202010703326.6A CN202010703326A CN111689477B CN 111689477 B CN111689477 B CN 111689477B CN 202010703326 A CN202010703326 A CN 202010703326A CN 111689477 B CN111689477 B CN 111689477B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 238000000034 method Methods 0.000 title claims abstract description 126
- 239000002253 acid Substances 0.000 title claims abstract description 98
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 26
- 229930195733 hydrocarbon Natural products 0.000 title claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 24
- 239000007789 gas Substances 0.000 claims abstract description 173
- 238000005406 washing Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 40
- 238000010791 quenching Methods 0.000 claims description 33
- 230000000171 quenching effect Effects 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003570 air Substances 0.000 description 57
- 239000007788 liquid Substances 0.000 description 10
- 239000003595 mist Substances 0.000 description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 238000012856 packing Methods 0.000 description 4
- 239000012080 ambient air Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
- B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treating Waste Gases (AREA)
Abstract
A process and a device for preparing sulfuric acid by a wet method from high-hydrocarbon-content acid gas are provided, wherein the high-hydrocarbon-content acid gas is combusted in an incinerator to form process gas containing SO 2, the process gas is cooled, the cooled process gas is divided into two paths, one path is converted, condensed, washed and absorbed to form finished sulfuric acid, and the other path is mixed with combustion-supporting gas to form mixed gas, and the mixed gas enters the incinerator again to form part of circulation of the process gas. The SO 2 gas generated in the incinerator is partially returned into the incinerator after heat exchange and temperature reduction through the heat exchange unit, SO that the problems that the generation rate of nitrogen oxides is increased rapidly due to overhigh temperature in the incinerator when the air intake amount is low, or the SO 2 content in process gas is too low and the exhaust emission is increased due to the fact that the air intake amount is increased to control the temperature in the incinerator are avoided.
Description
Technical Field
The invention relates to a process and a device for preparing sulfuric acid, in particular to a process and a device for preparing sulfuric acid by a high-hydrocarbon-content acid gas wet method.
Background
The pre-washing flash steam and the dimethyl ether claus gas in the coal chemical industry enterprises are rich in about 5-30 mol percent of hydrocarbon substances, 10-50 mol percent of H 2 S, and the C5 and C6 contents in the hydrocarbon composition are higher. When the sulfur recovery process is used for treatment, the incinerator is in anoxic combustion, so that insufficient hydrocarbon combustion can be caused, carbon particles generated by hydrocarbon combustion can block a catalyst bed layer, and meanwhile, the carbon particles can be brought into a sulfur product, so that the quality of the sulfur product is unqualified. In the general wet sulfuric acid production process, because the hydrocarbon content is high, a large amount of supplementary air is needed to control the temperature of the incinerator, SO that the SO 2 molar content in the process gas is low and is lower than 2%. Because a large amount of air is added, the flow of the process gas after the incinerator is increased, the equipment sizes of a subsequent conversion reactor, a condenser and tail gas treatment are increased, the manufacturing cost of the device is increased, and the operation cost is increased. The increase of the process gas volume also leads to the increase of the exhaust emission, the increase of the heat taken away by the exhaust gas leads to the reduction of the steam production of the device, the effect of the device is affected, and the increase of the exhaust gas also leads to the increase of the total amount of discharged SO 2 and sulfuric acid mist. If the supplement of dilution wind is reduced, the furnace temperature of the incinerator is increased, so that the generation rate of nitrogen oxides is increased sharply, and a denitration unit is added in the device, so that the investment of the device is increased.
The utility model patent application of the application No. CN2019201282663. X, named as a wet sulfuric acid process system for producing concentrated sulfuric acid by secondary pressurization, the utility model patent application of the application No. CN201911413284.6, named as a sulfuric acid manufacturing method, and the utility model patent application of the application No. CN201911346398.3, named as a device and a method for preparing sulfuric acid by cracking and regenerating waste sulfuric acid and or sulfur-containing waste liquid, are all used for producing sulfuric acid by means of burning, converting and re-absorbing, but the problem of overhigh temperature in an incinerator is not solved.
Foreign patent technicians inject SiO 2 -containing particles into process gas through an acid mist control unit, so that the condensation effect of sulfuric acid is improved, and the acid mist control unit is relatively expensive and subject to foreign technical monopoly.
Therefore, a new process capable of improving the concentration of sulfur dioxide in the process gas, reducing equipment investment and preventing the emission of nitrogen oxides from reaching standards due to the rise of furnace temperature is needed.
Disclosure of Invention
Aiming at the problems that the temperature in a furnace is too high or the concentration of sulfur dioxide is too low when the prior device for preparing sulfuric acid utilizes high-hydrocarbon-content acid gas to prepare sulfuric acid, the invention provides a process and a device for preparing sulfuric acid by a wet method from high-hydrocarbon-content acid gas, which can reduce the addition of dilution air, improve the concentration of SO 2 in process gas, reduce the process gas quantity and the size of treatment equipment SO as to achieve the purpose of reducing engineering investment.
The invention adopts the technical means for solving the problems that: a wet process for preparing sulfuric acid from high-hydrocarbon-content acidic gas features that the high-hydrocarbon-content acidic gas is burnt in incinerator to obtain technological gas containing SO 2, the technological gas is cooled, and the cooled technological gas is divided into two paths, one path is converted, condensed, washed and absorbed to obtain sulfuric acid product, and the other path is mixed with combustion-supporting gas to obtain mixed gas, which is then fed into incinerator to form part of technological gas for circulation.
Further, the mole content of SO 2 in the mixed gas is 2% -6%.
Further, the temperature in the incinerator is 950-1000 o ℃; the burnt process gas is cooled down twice through a waste heat boiler and a steam superheater, cooled to 440-480 o C through the waste heat boiler and cooled to 410-430 o C through the steam superheater; the temperature of the mixed gas is 180-220 o ℃.
Further, the process gas is converted into the process gas rich in SO 3 through three times of conversion sequentially through the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer, and cooling is performed after each conversion.
Further, the inlet temperature of the first catalyst bed is 405-420 o C, the inlet temperature of the second catalyst bed is 400-440 o C, and the inlet temperature of the third catalyst bed is 390-400 o C; the outlet temperature after conversion cooling is 280-300 o ℃; the condensation temperature is 85-100 o C.
Further, residual SO 2 in the condensed process gas is washed and absorbed by H 2O2 added into dilute sulfuric acid, SO that desulfurization of the process gas is realized.
The wet sulfuric acid making device for high hydrocarbon content acid gas includes one incinerator with air inlet pipe connected to the hydrocarbon content acid gas pipeline and the combustion supporting pipeline, one heat exchange unit, one converting reactor, one acid condenser and one washing unit connected successively via the technological pipeline, and one gas outlet pipe connected to the converting reactor and the other combustion supporting pipeline to form circulation.
Further, an air mixing unit is arranged on the combustion-supporting air pipeline, and the fuel gas and the SO 2 gas form mixed gas through the air mixing unit.
Further, the heat exchange unit comprises a waste heat boiler and a steam superheater which are communicated through a process gas pipeline, the waste heat boiler and the steam superheater are also respectively communicated with a steam drum through heat exchange pipelines, and the heat exchange pipeline connected with the steam superheater also passes through the conversion reactor.
Further, the conversion reactor comprises a first catalyst bed, a second catalyst bed and a third catalyst bed which are communicated, a process gas pipeline inlet of the conversion reactor is arranged at the first catalyst bed, a first inter-stage cooler is arranged between the first catalyst bed and the second catalyst bed, a second inter-stage cooler is arranged between the second catalyst bed and the third catalyst bed, and a process gas cooler is arranged between the third catalyst bed and a process gas pipeline outlet of the conversion reactor.
Further, the inlet and outlet of the process gas cooler are communicated with the steam drum through heat exchange pipelines, the inlet end of the second inter-stage cooler is connected with the steam drum through heat exchange pipelines, the outlet end of the second inter-stage cooler is connected with the inlet end of the first inter-stage cooler through heat exchange pipelines, and the outlet end of the first inter-stage cooler is a high-temperature steam outlet.
Further, ceramic acid-resistant filler and a cyclone demister are arranged in the acid condenser, wherein the ceramic acid-resistant filler is arranged at the inlet of the process gas pipeline, the cyclone demister is arranged at the outlet of the process gas pipeline, and a sulfuric acid outlet is arranged below the acid condenser.
Further, the cyclone mist eliminator cone angle was 1.5 o -20o.
Further, the sulfuric acid outlet of the acid condenser is connected to a concentrated sulfuric acid circulating unit, the concentrated sulfuric acid circulating unit comprises a concentrated acid circulating tank, a concentrated acid circulating pump and a concentrated acid cooler, an outlet pipeline of the concentrated acid cooler is divided into two paths, one path returns to the concentrated acid circulating tank to form circulation, and the other path is a concentrated acid outlet to output finished sulfuric acid.
Further, the heat exchange unit also comprises a feed water preheater, the heat exchange gas inlet of the acid condenser is connected with a cooling air blower, the outlet is communicated with the feed water preheater through a heat exchange pipeline, and the steam drum is also communicated with the feed water preheater through a heat exchange pipeline.
Further, the washing unit comprises a quenching washing tower and an electrostatic demister which are communicated, wherein an inlet of the quenching washing tower is communicated with an outlet of the acid condenser through a process air pipeline, and an outlet of the electrostatic demister is a tail gas outlet.
Further, the quenching washing tower is divided into a quenching section and a washing section, a sulfuric acid outlet is arranged below the quenching section, a sulfuric acid outlet pipeline is divided into three paths, one path returns to the quenching section to form circulation, the other path returns to the washing section to form circulation, and finished sulfuric acid is output.
Further, the quenching washing tower is also provided with a softened water inlet which is respectively communicated with the quenching section and the washing section, and the washing section is also provided with a hydrogen peroxide inlet.
Further, a silk screen demister is arranged at a position close to the electrostatic demister in the quenching washing tower.
The beneficial effects of the invention are as follows:
1. According to the invention, SO 2 gas generated in the incinerator is partially returned into the incinerator after heat exchange and temperature reduction by the heat exchange unit, SO that the problems of rapid increase of nitrogen oxide generation rate caused by overhigh temperature in the incinerator when the air intake amount is low or excessively low SO 2 content and increased exhaust emission in process gas caused by increasing the air intake amount to control the temperature in the incinerator are avoided.
2. According to the invention, the cyclone demister is arranged in the acid condenser, and the centrifugal action of the cyclone demister on liquid drops is utilized, so that the small liquid drops in the gas can be separated out and finally flow out from the bottom of the acid condenser, and the evaporated sulfuric acid is prevented from being accumulated on the demister.
Drawings
FIG. 1 is a schematic diagram of an embodiment;
In the figure: 1. the system comprises an incinerator, 11, hydrocarbon-containing acid gas, 2, a heat exchange unit, 21, a waste heat boiler, 22, a steam superheater, 23, a steam drum, 24, a feedwater preheater, 3, an air mixing unit, 31, a combustion air blower, 32, an air preheater, 33, a sulfur dioxide blower, 34, a mixed gas, 4, a conversion reactor, 41, a first catalyst bed, 42, a first stage inter-cooler, 43, a second catalyst bed, 44, a second stage inter-cooler, 45, a third catalyst bed, 46, a process gas cooler, 5, an acid condenser, 51, a cyclone mist eliminator, 52, ceramic acid-resistant packing, 53, a cooling air blower, 6, a washing unit, 7, a quenching washer, 71, a random or structured packing, 72, a wire mesh mist eliminator, 73, a spiral nozzle, 74, a washing liquid circulating pump, 75, softened water, 76, 8, an electrostatic mist eliminator, 81, a clean air blower, 82, a chimney, 9, a sulfuric acid circulating unit, 91, a concentrated acid circulating tank, 92, a concentrated acid circulating pump 93, and a concentrated acid circulating pump.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
As shown in FIG. 1, a wet sulfuric acid production device for high hydrocarbon-containing acid gas comprises a process gas pipeline connected in sequence from an inlet of the hydrocarbon-containing acid gas 11, wherein the molar content of hydrocarbon in the hydrocarbon-containing acid gas 11 is 5% -30%, and the molar content of H 2 S is 10% -50%. The method comprises the steps of burning an incinerator 1, a heat exchange unit 2, a conversion reactor 4, an acid condenser 5 and a washing unit 6, wherein hydrocarbon-containing acid gas 11 is burnt in the incinerator 1 to form process gas containing sulfur dioxide gas, the process gas enters the conversion reactor 4 for carrying out multistage conversion reaction after being cooled by the heat exchange unit 2 to form process gas containing sulfur trioxide, the process gas enters the acid condenser 5 again, sulfuric acid is formed in the acid condenser 5 to flow out from an outlet, tail gas is discharged after the unreacted complete process gas enters the washing unit 6 to continue to react, and the sulfur is converted into liquid sulfuric acid to flow out.
The heat exchange unit 2 comprises a waste heat boiler 21 and a steam superheater 22 which are sequentially communicated, wherein the process gas is cooled for the first time through the waste heat boiler 21 after coming out of the incinerator 1, the temperature of the process gas after the first time is reduced to 440-480 o C, then the process gas is cooled for the second time through the steam superheater 22, and the process gas after the second time is cooled to 410-430 o C.
An air mixing unit 3 is arranged between the steam superheater 22 and the incinerator 1, and the air mixing unit 3 comprises a combustion air blower 31, an air preheater 32 and a sulfur dioxide blower 33. The process gas pipeline subjected to the second cooling by the steam superheater 22 is divided into two paths, one path is communicated with the subsequent conversion reactor 4, and the other path enters the air mixing unit 3. The air inlet of the incinerator 1 is connected with the air inlet pipe of the hydrocarbon-containing acid gas 11 and the air outlet of the air mixing unit 3, the hydrocarbon-containing acid gas is cooled twice after being combusted in the incinerator 1, a part of process gas after cooling enters the air mixing unit 3, and enters the incinerator again after being mixed with combustion-supporting cold air, the temperature in the incinerator 1 is controlled at 950-1000 o ℃, the input amount of oxygen-containing cold air in the incinerator 1 is reduced through the circulation of the process gas, the content of sulfur dioxide in the process gas is further improved, and meanwhile, the problem that the temperature in the incinerator 1 is too high when the input amount of cold air in a non-circulating structure is low is avoided.
The cold air is boosted by the combustion-supporting air blower 31 and then passes through the air preheater 32, part of the process air after the second cooling also passes through the air preheater 32 along the process air pipeline, the cold air and the process air are subjected to heat exchange at the air preheater 32, the process air temperature is reduced, the cold air temperature is increased and then the cold air and the process air are mixed to form the mixed air 34, the mole content of SO 2 in the mixed air 34 is 2% -6%, the temperature is controlled to be 180-220 o C, and the sulfur dioxide blower 33 is arranged on the process air pipeline before or after the process air passes through the air preheater 32 to ensure the smooth progress of the process air. The cold air and the process gas are subjected to heat exchange and then mixed, the temperature difference between the cold air and the process gas is reduced, the problem that sulfuric acid dew point corrosion is generated due to sudden temperature reduction of the high-temperature process gas during direct mixing is avoided, meanwhile, the cold air and the process gas with the temperature being closer to each other can be mixed more uniformly, and further, when the formed mixed gas 34 and the hydrocarbon-containing acid gas 11 enter the incinerator 1 together, the distribution of oxygen in the gas is more uniform, so that the hydrocarbon-containing acid gas 11 can be fully combusted.
The heat exchange unit 2 further comprises a steam drum 23, the steam drum 23 is connected with the waste heat boiler 21 and the steam superheater 22 through heat exchange pipelines, and the heat exchange pipelines between the steam drum 23 and the waste heat boiler 21 form a circulating connection.
The conversion reactor 4 adopts a three-stage catalytic reaction structure and sequentially comprises a first catalyst bed 41, a first inter-stage cooler 42, a second catalyst bed 43, a second inter-stage cooler 44, a third catalyst bed 45 and a process gas cooler 46 according to the flow direction of the process gas. The process gas after twice heat exchange enters the conversion reactor 4 along a process gas pipeline, sulfur dioxide gas in the process gas is converted into sulfur trioxide through multiple catalytic reactions, heat exchange is carried out after each conversion reaction, the inlet temperature of the first catalyst bed 42 is 405-420 o C, the inlet temperature of the second catalyst bed is 400-440 o C, the inlet temperature of the third catalyst bed is 390-400 o C, the process gas temperature is prevented from being too high, and finally the sulfur dioxide gas flows out after being cooled to 280-300 o C by the process gas cooler 46, and enters the subsequent acid condenser 5.
The first inter-stage cooler 42, the second inter-stage cooler 44 and the process gas cooler 46 are all connected with the steam drum through heat exchange pipelines for heat exchange, the heat exchange pipelines between the steam drum 23 and the process gas cooler 46 form circulating connection, and the other heat exchange pipeline passes through the steam superheater 33 after coming out of the steam drum 23, enters the second inter-stage cooler 44 after heat exchange and temperature rise, enters the first inter-stage cooler 42 after heat exchange and temperature rise again, and forms high-temperature steam after heat exchange and temperature rise. The process gas in the conversion reactor 4 is gradually cooled through multiple heat exchanges, SO that the influence of the excessive temperature of the process gas on the conversion depth of SO 2 is avoided.
After the process gas rich in sulfur trioxide enters the acid condenser 5, the top temperature of the acid condenser is 85-100 o ℃, SO 3 and H 2 O are hydrated to produce gaseous sulfuric acid due to the temperature reduction, and then the gaseous sulfuric acid is cooled to form liquid sulfuric acid, and a section of ceramic acid-resistant filler 52 is arranged at the bottom of the acid condenser 5 to provide a mass and heat transfer space for hot process gas and sulfuric acid, SO that the mass fraction of the condensed sulfuric acid can be increased from 97% to 98.5%. The top of the acid condenser 5 is provided with a plurality of cyclone demisters 51, small-particle-size sulfuric acid droplets which fail to drip fall onto a top plate of the acid condenser 5 after being separated from process gas by the cyclone demisters 51, flow into the bottom of the acid condenser 5 under the action of gravity, the cone angle of the cyclone demisters 51 is 1.5 o -20o, the removal efficiency of sulfuric acid mist 3um droplets in the process gas passing through the cyclone demisters 51 is more than 95%, and the pressure drop is lower than 3KPa. The bottom of the acid condenser 5 is provided with a sulfuric acid outlet, the liquid concentrated sulfuric acid formed in the acid condenser 5 flows out along the sulfuric acid outlet and enters a concentrated sulfuric acid circulating unit 9, and the rest of process gas enters a subsequent washing unit 6.
The acid condenser 5 is also connected with a cooling air fan 53, and the ambient air is boosted by the cooling air fan 53 and then enters the acid condenser 5 to provide condensation low temperature for the sulfuric acid in the acid condenser 5.
The heat exchange unit 2 further comprises a feed water preheater 24, wherein the ambient air after heat exchange in the acid condenser 5 is connected to the feed water preheater 24 through a pipeline for emptying, the feed water preheater 24 is connected with the steam drum 23 through a heat exchange pipeline, the other end of the heat exchange pipeline, which is positioned at the feed water preheater 24, is provided with an inlet for deoxidized water 25, and the external deoxidized water 25 exchanges heat with the ambient temperature after heat exchange in the acid condenser 5 in the feed water preheater 24 and then enters the steam drum 23.
The concentrated sulfuric acid circulation unit 9 comprises a concentrated acid circulation tank 91, a concentrated acid circulation pump 92 and a concentrated acid cooler 93, wherein an outlet pipeline of the concentrated acid cooler 93 is divided into two paths, one path returns to the concentrated acid circulation tank 91 to form circulation, the other path is a concentrated acid outlet, hot concentrated sulfuric acid flowing out of the acid condenser 5 enters the concentrated sulfuric acid circulation unit 9 to be cooled, then part of the hot concentrated sulfuric acid flows out as finished sulfuric acid, and the other part of the hot concentrated sulfuric acid returns to the concentrated acid circulation tank 91 to form circulation to cool the hot sulfuric acid flowing out of the acid condenser 5. The concentrated acid circulating pump 92 pushes the concentrated sulfuric acid to advance, and the concentrated acid cooler 93 is further provided with a water cooling pipeline for exchanging heat with the concentrated sulfuric acid through cold water.
The washing unit 6 comprises a quenching washing tower 7 and an electrostatic demister 8 which are communicated from bottom to top, wherein the lower section of the quenching washing tower 7 is a quenching section, the upper section of the quenching washing tower is a washing section, spiral nozzles 73 are arranged above the quenching section and the washing section, scattered piles or structured packing 71 are arranged in the washing section, the bottom of the quenching section is a sulfuric acid outlet, a sulfuric acid outlet pipeline is divided into three paths, one path is connected to the spiral nozzles 73 of the quenching section to form circulation, the other path is connected to the spiral nozzles 73 of the washing section to form circulation, the other path is a finished sulfuric acid outlet, and a pipeline of the outlet can be extended to a finished sulfuric acid outlet of concentrated sulfuric acid, and the concentrated sulfuric acid can be diluted to output sulfuric acid with one concentration and also can be independently output, namely the whole device can output sulfuric acid with two different concentrations. And the spiral nozzles 73 of the quenching section and the washing section are both connected with a softened water 75 pipeline, the spiral nozzle 73 of the washing section is also connected with a hydrogen peroxide solution 76 pipeline, and the sulfuric acid outlet pipeline is also provided with a washing liquid circulating pump 74. The process gas from the acid condenser 5 enters the quenching section of the quenching washing tower 7, the dilute sulfuric acid mixed with the softened water 75 is circulated and returned to the spiral nozzle 73 above the quenching section, at the moment, the process gas is in countercurrent contact with the dilute sulfuric acid, the process gas is rapidly cooled through the evaporation of water in the dilute sulfuric acid, the dilute sulfuric acid liquid flows out from the bottom of the quenching section, the process gas rises to the washing section, and the contact area of sulfur dioxide and hydrogen peroxide in the process gas is enlarged by the random packing 71 in the washing section, so that the rapid removal of sulfur dioxide is facilitated. Residual sulfur dioxide in the process gas reacts with hydrogen peroxide sprayed from a spiral nozzle 73 above the washing section rapidly to generate sulfuric acid, so that desulfurization of the process gas is realized.
A silk screen demister 72 is arranged in the quenching washing tower 7 and close to the electrostatic demister 8, and a small amount of sulfuric acid mist drops entrained in the gas after the reaction are effectively removed through the silk screen demister 72 and the electrostatic demister 8 in sequence, so that clean gas is obtained.
The air outlet of the electrostatic demister 8 is connected with a clean air fan 81, and clean air is sent into a chimney 82 through the clean air fan 81 and then discharged.
As can be seen from the above embodiments, the present invention also relates to a wet process for preparing sulfuric acid from high-hydrocarbon acid gas, wherein the high-hydrocarbon acid gas is combusted in the incinerator 1 to form a process gas containing SO 2, the temperature in the incinerator 1 is 950-1000 o C, the high-temperature process gas is cooled to 440-480 o C by the waste heat boiler 21, and then cooled to 410-430 o C by the steam superheater. The cooled process gas is divided into two paths, one path of the process gas is converted and cooled for multiple times to form the process gas rich in SO 3, and the other path of the process gas is mixed with combustion-supporting gas to form mixed gas 34 and then enters the incinerator 1 again to form the circulation of part of the process gas, wherein the combustion-supporting gas can be ambient air, oxygen is provided for combustion, and meanwhile, the temperature in the incinerator can be reduced. The process gas rich in SO 3 is introduced into an acid condenser 5, the top temperature of the acid condenser 5 is 85-100 o ℃, SO 3 and H 2 O in the process gas are hydrated to generate gaseous sulfuric acid due to the temperature reduction, the gaseous sulfuric acid is condensed to generate liquid sulfuric acid, and large-particle-size sulfuric acid drops fall into the bottom of the acid condenser 5 along a glass tube of the acid condenser 5 to form finished sulfuric acid for collection. A cyclone demister 51 is arranged at the top of the acid condenser 5 to remove sulfuric acid mist droplets in the process gas. And finally, quenching and washing the process gas, and performing reaction absorption on H 2O2 added in the recycled dilute sulfuric acid and SO 2 remained in the process gas to form sulfuric acid, thereby realizing desulfurization of the process gas.
The above embodiments are only for illustrating the present invention, not for limiting the present invention, and various changes and modifications may be made by one skilled in the relevant art without departing from the spirit and scope of the present invention, so that all equivalent technical solutions shall fall within the scope of the present invention, which is defined by the claims.
Claims (4)
1. A high hydrocarbon acid gas wet process sulfuric acid making device is characterized in that: the device comprises an incinerator (1), a heat exchange unit (2), a conversion reactor (4), an acid condenser (5) and a washing unit (6) which are sequentially connected through a process gas pipeline, wherein the incinerator (1) is provided with an air inlet pipe which is simultaneously communicated with a hydrocarbon-containing acid gas pipeline and a combustion-supporting gas pipeline, an air outlet pipe of the incinerator (1) is divided into two paths after passing through the heat exchange unit (2), one path is connected to the conversion reactor (4), and the other path is connected to the combustion-supporting gas pipeline to form circulation; an air mixing unit is arranged on the combustion-supporting air pipe, and the combustion-supporting gas and SO 2 gas form a mixed gas (34) through the air mixing unit;
the heat exchange unit (2) comprises a waste heat boiler (21) and a steam superheater (22) which are communicated through a process gas pipeline, the waste heat boiler (21) and the steam superheater (22) are also respectively communicated with a steam drum (23) through heat exchange pipelines, and the heat exchange pipeline connected with the steam superheater (22) also passes through the conversion reactor (4);
The conversion reactor (4) comprises a first catalyst bed (41), a second catalyst bed (43) and a third catalyst bed (45) which are communicated, a process gas pipeline inlet of the conversion reactor (4) is formed in the first catalyst bed (41), a first inter-stage cooler (42) is arranged between the first catalyst bed (41) and the second catalyst bed (43), a second inter-stage cooler (44) is arranged between the second catalyst bed (43) and the third catalyst bed (45), and a process gas cooler (46) is arranged between the third catalyst bed (45) and a process gas pipeline outlet of the conversion reactor (4);
The inlet and outlet of the process gas cooler (46) are communicated with the steam drum (23) through a heat exchange pipeline, the inlet end of the second inter-stage cooler (44) is connected with the steam drum (23) through a heat exchange pipeline, the outlet end of the second inter-stage cooler is connected with the inlet end of the first inter-stage cooler (42) through a heat exchange pipeline, and the outlet end of the first inter-stage cooler (42) is a high-temperature steam outlet;
The acid condenser (5) is internally provided with ceramic acid-resistant filler (52) and a cyclone demister (51), wherein the ceramic acid-resistant filler (52) is arranged at the inlet of a process gas pipeline, the cyclone demister (51) is arranged at the outlet of the process gas pipeline, the cone angle of the cyclone demister (51) is 1.5 o -20o, and a sulfuric acid outlet is arranged below the acid condenser (5);
The sulfuric acid outlet of the acid condenser (5) is connected to a concentrated sulfuric acid circulating unit (9), the concentrated sulfuric acid circulating unit (9) comprises a concentrated acid circulating tank (91), a concentrated acid circulating pump (92) and a concentrated acid cooler (93), an outlet pipeline of the concentrated acid cooler (93) is divided into two paths, one path returns to the concentrated acid circulating tank (91) to form circulation, and the other path is a concentrated acid outlet to output finished sulfuric acid;
the heat exchange unit (2) further comprises a feed water preheater (24), the heat exchange gas inlet of the acid condenser (5) is connected with a cooling air blower (53), the outlet is communicated with the feed water preheater (24) through a heat exchange pipeline, and the steam drum (23) is also communicated with the feed water preheater (24) through a heat exchange pipeline;
The high-hydrocarbon-content acid gas is combusted in the incinerator (1) to form process gas containing SO 2, the process gas is cooled, the cooled process gas is divided into two paths, one path is converted, condensed, washed and absorbed to form finished sulfuric acid, and the other path is mixed with combustion-supporting gas to form mixed gas (34) and then enters the incinerator (1) again to form the circulation of part of process gas;
The process gas is cooled for the first time through a waste heat boiler (21) after coming out of the incinerator (1), the temperature of the process gas after the first time is reduced to 440-480 o ℃ and then cooled for the second time through a steam superheater (22), and the process gas after the second time is cooled to 410-430 o ℃;
An air mixing unit (3) is arranged between the steam superheater (22) and the incinerator (1), and the air mixing unit (3) comprises a combustion air blower (31), an air preheater (32) and a sulfur dioxide blower (33); the process gas pipeline after the second cooling by the steam superheater (22) is divided into two paths, one path is communicated with the subsequent conversion reactor (4), and the other path enters the air mixing unit (3) to form mixed gas (34).
2. The high hydrocarbon acid gas wet process sulfuric acid production apparatus according to claim 1, wherein: the mole content of SO 2 in the mixed gas (34) is 2-6%.
3. The high hydrocarbon acid gas wet process sulfuric acid production apparatus according to claim 1, wherein: the process gas is converted for three times through a first catalyst bed (41), a second catalyst bed (43) and a third catalyst bed (45) in sequence to form process gas rich in SO 3, and the process gas is cooled after each conversion;
The inlet temperature of the first catalyst bed (41) ranges from 405 to 420 o C, the inlet temperature of the second catalyst bed (43) ranges from 400 to 440 o C, and the inlet temperature of the third catalyst bed (45) ranges from 390 to 400 o C; the outlet temperature after conversion cooling is 280-300 o ℃; the condensation temperature is 85-100 o C.
4. The high hydrocarbon acid gas wet process sulfuric acid production apparatus according to claim 1, wherein: the washing unit (6) comprises a quenching washing tower (7) and an electrostatic demister (8) which are communicated, wherein the inlet of the quenching washing tower (7) is communicated with the outlet of the acid condenser (5) through a process gas pipeline, and the outlet of the electrostatic demister (8) is a tail gas outlet;
The quenching washing tower (7) is divided into a quenching section and a washing section, a sulfuric acid outlet is arranged below the quenching section, a sulfuric acid outlet pipeline is divided into three paths, one path returns to the quenching section to form circulation, the other path returns to the washing section to form circulation, and finished sulfuric acid is output;
The quenching washing tower (7) is also provided with a softened water (75) inlet which is respectively communicated with the quenching section and the washing section, and the washing section is also provided with a hydrogen peroxide (76) inlet;
a silk screen demister (72) is also arranged in the quenching washing tower (7) close to the electrostatic demister (8).
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| CN114275743B (en) * | 2021-12-10 | 2023-04-28 | 湖北兴福电子材料股份有限公司 | Method for producing high-purity liquid sulfur trioxide for electronic-grade sulfuric acid |
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| WO2010075027A1 (en) * | 2008-12-15 | 2010-07-01 | Katana Energy Llc | Emissions free sulfuric acid and sodium bisulfite production for desalination from gasification acid gas |
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| WO2010075027A1 (en) * | 2008-12-15 | 2010-07-01 | Katana Energy Llc | Emissions free sulfuric acid and sodium bisulfite production for desalination from gasification acid gas |
| CN102371108A (en) * | 2010-08-20 | 2012-03-14 | 中国石油化工集团公司 | Method for producing sulfuric acid by oxygen-enriched air incineration of acid gas containing hydrogen sulfide |
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