CN111689477A - Wet process and apparatus for preparing sulfuric acid from high-hydrocarbon-content acidic gas - Google Patents
Wet process and apparatus for preparing sulfuric acid from high-hydrocarbon-content acidic gas Download PDFInfo
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- CN111689477A CN111689477A CN202010703326.6A CN202010703326A CN111689477A CN 111689477 A CN111689477 A CN 111689477A CN 202010703326 A CN202010703326 A CN 202010703326A CN 111689477 A CN111689477 A CN 111689477A
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 238000000034 method Methods 0.000 title claims abstract description 127
- 230000008569 process Effects 0.000 title claims abstract description 121
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 181
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims description 96
- 238000005406 washing Methods 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 38
- 238000010791 quenching Methods 0.000 claims description 34
- 230000000171 quenching effect Effects 0.000 claims description 34
- 229930195733 hydrocarbon Natural products 0.000 claims description 27
- 150000002430 hydrocarbons Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 18
- 239000002918 waste heat Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003570 air Substances 0.000 description 49
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 11
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 9
- 239000003595 mist Substances 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
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 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
- 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
- 230000009471 action Effects 0.000 description 2
- 239000012080 ambient air Substances 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
- 238000012856 packing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 210000004072 lung Anatomy 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
- 238000005201 scrubbing Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 239000013589 supplement Substances 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
- 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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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Abstract
A wet process for preparing sulfuric acid from the high-hydrocarbon acidic gas containing SO is disclosed, which is generated by burning the high-hydrocarbon acidic gas in incinerator2The process gas is cooled, the cooled process gas is divided into two paths, one path of the process gas is converted, condensed, washed and absorbed to form finished sulfuric acid, the other path of the process gas is mixed with combustion-supporting gas to form mixed gas, and then the mixed gas enters the incinerator again to form circulation of part of the process gas. By mixing SO generated in an incinerator2The gas is cooled by the heat exchange unit and the part of the gas returns to the incinerator, thereby avoiding the over-high temperature in the incinerator when the air inlet amount is lowThe generation rate of nitrogen oxides is increased sharply, or SO in the process gas is caused when the temperature in the furnace is controlled by increasing the air inlet quantity2The content is too low and the exhaust emission is increased.
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 prewashed flash steam and dimethyl ether Claus gas in coal chemical industry enterprises contain hydrocarbon substances with about 5 to 30 mol percent and H with 10 to 50 mol percent2S, the hydrocarbon composition has higher contents of C5 and C6. When the sulfur recovery process is used for treatment, because the incinerator is in anoxic combustion, the hydrocarbon is insufficiently combusted, 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-process sulfuric acid production process, because the hydrocarbon content is high, a large amount of air needs to be supplemented for controlling the temperature of an incinerator, SO is caused in the process gas2The molar content is lower and is below 2 percent. Because of the addition of a large amount of air, the process gas flow after the incinerator is increased, the sizes of a subsequent conversion reactor, a condenser and tail gas treatment equipment are increased, the manufacturing cost of the device is increased, and the operation cost is increased. The increase of the process gas amount also leads to the increase of the exhaust emission, the heat taken away by the exhaust is increased, the steam production of the device is reduced, the benefit of the device is influenced, and the increase of the exhausted exhaust also leads to the emission of SO2And the total amount of sulfuric acid mist is increased. If the supplement of the dilution air is reduced, the temperature of the incinerator is increased, so that the generation rate of nitrogen oxides is increased rapidly.
For example, the utility model patent with the application number of CN201920128663.X, entitled "wet sulfuric acid process system for producing concentrated sulfuric acid by secondary pressurization", the invention patent application with the application number of CN201911413284.6, entitled "method for producing sulfuric acid", and the invention patent application with the application number of CN201911346398.3, entitled "apparatus and method for preparing sulfuric acid by cracking and regenerating waste sulfuric acid and/or sulfur-containing waste liquid" all produce sulfuric acid by burning, converting and absorbing firstly, but do not solve the problem of overhigh temperature in the incinerator.
Foreign patent technologists inject SiO-containing gas into the process gas through an acid mist control unit2The particle of (2) increases the condensation effect of sulfuric acid, and the acid mist control unit is expensive and is limited by foreign technical monopoly.
Therefore, a new process capable of increasing the concentration of sulfur dioxide in the process gas, reducing the equipment investment and simultaneously not causing the increase of the furnace temperature to cause the discharge of nitrogen oxides to be not up to the standard is needed.
Disclosure of Invention
The invention provides a process and a device for preparing sulfuric acid by a wet method of high-hydrocarbon-content acid gas, aiming at the problem that the temperature in a furnace is too high or the concentration of sulfur dioxide is too low when the current device for preparing sulfuric acid utilizes the high-hydrocarbon-content acid gas to prepare sulfuric acid, and the process and the device can reduce the addition of dilution air and improve the SO in process gas2The process gas amount and the size of treatment equipment are reduced so as to achieve the aim of reducing the engineering investment.
The technical means adopted by the invention to solve the problems are as follows: a wet process for preparing sulfuric acid from the acidic gas with high hydrocarbon content features that the acidic gas with high hydrocarbon content is burnt in incinerator to form SO2The process gas is cooled, the cooled process gas is divided into two paths, one path of the process gas is converted, condensed, washed and absorbed to form finished sulfuric acid, the other path of the process gas is mixed with combustion-supporting gas to form mixed gas, and then the mixed gas enters the incinerator again to form circulation of part of the process gas.
Further, SO in the mixed gas2The molar content of (A) is 2-6%.
Further, the temperature in the incinerator is 950-oC; the burned process gas is cooled twice by a waste heat boiler and a steam superheater and is cooled to 440-480-oC, cooling to 410-430 through a steam superheateroC; the temperature of the mixed gas is 180-oC。
Further, the process gas is converted for three times through the first catalyst bed layer, the second catalyst bed layer and the third catalyst bed layer in sequence to form the SO-rich gas3And cooling after each conversionAnd cooling.
Further, the inlet temperature of the first catalyst bed 405-oC, inlet temperature of the second catalyst bed 400-oC, inlet temperature of third catalyst bed 390-oC; the outlet temperature after the conversion cooling is 280-300-oC; the condensation temperature is 85-100oC。
Further, residual SO in the condensed process gas2By addition of H in dilute sulfuric acid2O2Washing and absorbing are carried out to realize the desulfurization of the process gas.
The utility model provides a high sour wet legal system sulphuric acid device that contains hydrocarbon, includes the burning furnace, heat exchange unit, conversion reactor, acid condenser and the washing unit that connect gradually through the technology gas pipeline, burns the burning furnace and is equipped with the intake pipe, and its intake pipe simultaneously with contain hydrocarbon sour gas pipeline and combustion-supporting gas pipeline intercommunication, and burns the outlet duct of burning furnace and divide into two the tunnel behind the heat exchange unit, be connected to conversion reactor, another way and be connected to combustion-supporting gas pipeline and form the circulation.
Furthermore, an air mixing unit is arranged on the combustion-supporting gas pipeline, and the combustion-supporting gas and the SO are arranged2The gas is mixed into mixed gas through the air mixing unit.
Furthermore, 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 respectively communicated with the steam drum through heat exchange pipelines, and the heat exchange pipeline connected with the steam superheater passes through the conversion reactor.
Furthermore, the conversion reactor comprises a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer which are communicated, a process gas pipeline inlet of the conversion reactor is arranged at the first catalyst bed layer, a first-stage intercooler is arranged between the first catalyst bed layer and the second catalyst bed layer, a second-stage intercooler is arranged between the second catalyst bed layer and the third catalyst bed layer, and a process gas cooler is arranged between the third catalyst bed layer and the process gas pipeline outlet of the conversion reactor.
Furthermore, 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-stage intercooler is connected with the steam drum through the heat exchange pipelines, the outlet end of the second-stage intercooler is connected with the inlet end of the first-stage intercooler through the heat exchange pipelines, and the outlet end of the first-stage intercooler 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 an inlet of the process gas pipeline, the cyclone demister is arranged at an outlet of the process gas pipeline, and a sulfuric acid outlet is arranged below the acid condenser.
Further, the cone angle of the cyclone demister is 1.5o-20o。
Furthermore, a sulfuric acid outlet of the acid condenser is connected to a concentrated acid circulating unit, the concentrated 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 of the outlet pipeline returns to the acid circulating tank to form circulation, and the other path of the outlet pipeline outputs finished sulfuric acid for the concentrated acid outlet.
Furthermore, the heat exchange unit also comprises a water supply preheater, a cooling air fan is connected at a heat exchange gas inlet of the acid condenser, an outlet is communicated with the water supply preheater through a heat exchange pipeline, and the steam drum is also communicated with the water supply preheater through a heat exchange pipeline.
Furthermore, the washing unit comprises a quenching washing tower and an electrostatic demister which are communicated, an inlet of the quenching washing tower is communicated with an outlet of the acid condenser through a process gas pipeline, and an outlet of the electrostatic demister is a tail gas outlet.
Furthermore, 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 the other path outputs finished sulfuric acid.
Furthermore, 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.
Furthermore, a wire mesh demister is arranged at a position close to the electrostatic demister in the quenching washing tower.
The invention has the beneficial effects that:
1. the invention is realized by adding SO generated in the incinerator2The part of the gas after heat exchange and temperature reduction by the heat exchange unit returns to the incinerator, thereby avoiding the rapid increase of the generation rate of nitrogen oxide caused by overhigh temperature in the incinerator when the air inlet amount is low or the SO in the process gas caused by increasing the air inlet amount to control the temperature in the incinerator2The content is too low and the exhaust emission is increased.
2. According to the invention, the swirl demister is arranged in the acid condenser, and small liquid drops in gas are separated out and finally flow out from the bottom of the acid condenser by utilizing the centrifugal action of the swirl demister on the liquid drops, so that the evaporated sulfuric acid is prevented from being accumulated on the demister.
Drawings
FIG. 1 is a schematic structural view of an embodiment;
in the figure: 1. the system comprises an incinerator 11, hydrocarbon-containing acid gas, a heat exchange unit 2, a waste heat boiler 21, a waste heat boiler 22, a steam superheater 23, a steam drum 24, a feed water preheater 3, an air mixing unit 31, a combustion-supporting gas fan 32, an air preheater 33, a sulfur dioxide fan 34, mixed gas, a conversion reactor 4, a first catalyst bed 41, a first inter-stage cooler 42, a first inter-stage cooler 43, a second catalyst bed 44, a second inter-stage cooler 45, a third catalyst bed 46, a process cooler 5, an acid condenser 51, a cyclone demister 52, ceramic acid-resistant filler 53, a cooling air fan 53, a washing unit 6, a quenching washing tower 7, a quenching washing tower 71, random or regular filler 72, a wire mesh demister 73, a spiral nozzle 74, a washing liquid circulating pump 75, softened water 76, hydrogen peroxide, 8, an electrostatic demister, 81. the system comprises a clean air fan, a chimney 82, a concentrated sulfuric acid circulating unit 9, an acid circulating tank 91, an acid circulating pump 92 and an acid cooler 93.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example one
As shown in figure 1, the wet process sulfuric acid producing apparatus with high hydrocarbon content acid gas has hydrocarbon content in acid gas 11 of 5-30 mol%, H2The mol content of S is 10-50%, and the wet-process sulfuric acid production device comprises a process gas pipeline in sequence from the inlet of the hydrocarbon-containing acid gas 11Communicated with each other: the process gas containing sulfur trioxide enters the acid condenser 5, the sulfur trioxide forms sulfuric acid in the acid condenser 5 and flows out from an outlet, the unreacted process gas enters the washing unit 6 to continue to react and then is discharged as tail gas, and the sulfur is converted into liquid sulfuric acid and flows out.
The heat exchange unit 2 comprises a waste heat boiler 21 and a steam superheater 22 which are sequentially communicated, the process gas is firstly cooled by the lung heat boiler 21 after coming out of the incinerator 1, and the temperature of the process gas after being cooled for the first time is reduced to 440-oC, then carrying out secondary temperature reduction through the steam superheater 22, and cooling the process gas after the secondary temperature reduction to 410-430-oC。
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-supporting air fan 31, an air preheater 32 and a sulfur dioxide fan 33. The process gas pipeline after the second temperature reduction by the steam superheater 22 is divided into two paths, one path is communicated to the subsequent conversion reactor 4, and the other path enters the air mixing unit 3. The air inlet of the incinerator 1 is simultaneously 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, part of the cooled process gas 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 to be 950-1000-oAnd C, the input amount of oxygen-containing cold air in the incinerator 1 is reduced through the circulation of the process gas, so that the content of sulfur dioxide in the process gas is improved, and the problem of overhigh temperature in the incinerator 1 when the input amount of the cold air in a non-circulating structure is low is solved.
The cold air passes through the air preheater 32 after being boosted by the combustion-supporting air blower 31, part of the process gas after being cooled for the second time also passes through the air preheater 32 along the process gas pipeline, and the cold air and the process gas pass through the air preheater 32Heat exchange is carried out, the temperature of the process gas is reduced, the temperature of the cold air is increased, the process gas and the cold air are mixed to form a mixed gas 34, and SO is contained in the mixed gas 342The molar content of the organic silicon compound is 2 to 6 percent, and the temperature is controlled to be 220 ℃ CoAnd C, arranging a sulfur dioxide fan 33 on a process air pipeline before or after the process gas passes through the air preheater 32 to ensure that the process gas smoothly moves forward, wherein in the embodiment, the sulfur dioxide fan 33 is arranged on the process air pipeline after the process gas passes through the air preheater 32. 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 firstly, sulfuric acid dew point corrosion caused by sudden cooling of the high-temperature process gas during direct mixing is avoided, meanwhile, the cold air and the process gas with the closer temperature can be mixed more uniformly, and 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 layer 41, a first-stage intercooler 42, a second catalyst bed layer 43, a second-stage intercooler 44, a third catalyst bed layer 45 and a process cooler 46 according to the flow direction of process gas. The process gas after the two heat exchanges enters the conversion reactor 4 along the process gas pipeline, the sulfur dioxide gas in the process gas is converted into sulfur trioxide through a plurality of catalytic reactions, heat exchange is carried out after each conversion reaction, and the inlet temperature of the first catalyst bed layer 42 is 405-420-oC, the inlet temperature of the second catalyst bed is 400-440-oC, the inlet temperature of the third catalyst bed layer is 390-oC, avoiding the over-high temperature of the process gas, and finally cooling to 280-300 ℃ by the process gas cooler 46oC then flows out into the subsequent acid condenser 5.
The first-stage intercooler 42, the second-stage intercooler 44 and the process cooler 46 are connected with the steam drum through heat exchange pipelines for heat exchange, and the steam drum is connected with the steam drum through heat exchange pipelinesThe heat exchange pipelines between the process cooler 46 and the steam drum 23 form a circulating connection, another heat exchange pipeline passes through the steam superheater 33 after coming out of the steam drum 23, enters the second-stage intercoolers 44 after heat exchange and temperature rise, enters the first-stage intercoolers 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 exchange, SO that the influence of the overhigh temperature of the process gas on SO is avoided2The depth of conversion of (a).
After the process gas rich in sulfur trioxide enters the acid condenser 5, the temperature at the top of the acid condenser is 85-100 DEGoC, SO due to temperature decrease3And H2O hydration produces gaseous sulfuric acid, and then cooling forms liquid sulfuric acid, is provided with a section of ceramic acid-resistant filler 52 at the bottom of acid condenser 5, provides the mass and heat transfer space of hot process gas and sulfuric acid, can improve the mass fraction of the condensed sulfuric acid from 97% to 98.5%. A plurality of cyclone demisters 51 are arranged at the top of the acid condenser 5, sulfuric acid droplets with small particle size which cannot drop are separated from the process gas by the cyclone demisters 51 and then fall onto the top plate of the acid condenser 5, and flow into the bottom of the acid condenser 5 under the action of gravity, and the cone angle of the cyclone demisters 51 is 1.5o-20oAnd the removal efficiency of 3um droplets of sulfuric acid mist in the process gas passing through the cyclone demister 51 is more than 95%, and the pressure drop is lower than 3 KPa. The bottom of the acid condenser 5 is provided with a sulfuric acid outlet, 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 residual process gas enters a subsequent washing unit 6.
The acid condenser 5 is also connected with a cooling air fan 53, and air in the environment enters the acid condenser 5 after being boosted by the cooling air fan 53 to provide a low condensation temperature for sulfuric acid in the acid condenser 5.
The heat exchange unit 2 further comprises a water supply preheater 24, ambient air after heat exchange is carried out in the acid condenser 5 is connected to the water supply preheater 24 through a pipeline and then is discharged to the air, the water supply preheater 24 is connected with the steam pocket 23 through a heat exchange pipeline, the other end of the heat exchange pipeline, which is located at the water supply preheater 24, is an inlet of deoxygenated water 25, the external deoxygenated water 25 and the ambient temperature after heat exchange in the acid condenser 5 are subjected to heat exchange in the water supply preheater 24 and then enter the steam pocket 23.
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 is returned to the concentrated acid circulating tank 91 to form circulation, the other path is a concentrated acid outlet, the hot concentrated sulfuric acid flowing out from the acid condenser 5 enters the concentrated sulfuric acid circulating unit 9 to be cooled, 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 circulating tank 91 to form circulation to cool the hot sulfuric acid flowing out from the acid condenser 5. The concentrated sulfuric acid is driven to move forward by the concentrated sulfuric acid circulating pump 92, and the concentrated sulfuric 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, the lower section of the quenching washing tower 7 is a quenching section, the upper section of the quenching section is a washing section, spiral nozzles 73 are arranged above the quenching section and the washing section, a random or structured packing 71 is arranged in the washing section, the bottom of the quenching section is a sulfuric acid outlet, a pipeline of the sulfuric acid outlet is divided into three paths, one path of the sulfuric acid outlet is connected to the spiral nozzles 73 of the quenching section to form circulation, the other path of the sulfuric acid outlet is connected to the spiral nozzles 73 of the washing section to form circulation, the other path of the sulfuric acid outlet is a finished sulfuric acid outlet, the pipeline of the outlet can extend to the finished sulfuric acid outlet of the concentrated sulfuric acid, the concentrated sulfuric acid is diluted and then outputs sulfuric acid with one concentration, and. And the spiral nozzles 73 of the quenching section and the washing section are connected with softened water 75 pipelines, the spiral nozzles 73 of the washing section are also connected with hydrogen peroxide 76 pipelines, and a washing liquid circulating pump 74 is also arranged on a sulfuric acid outlet pipeline. 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 the reaction between the sulfur dioxide in the process gas and the hydrogen peroxide is enlarged by random or structured packing 71 in the washing section, so that the rapid removal of the sulfur dioxide is facilitated. The residual sulfur dioxide in the process gas reacts rapidly with the hydrogen peroxide sprayed from the spiral nozzle 73 above the scrubbing section to produce sulfuric acid, thereby realizing the desulfurization of the process gas.
A wire mesh 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 droplets carried in the reacted gas are effectively removed through the wire mesh demister 72 and the electrostatic demister 8 in sequence to obtain clean gas.
The air outlet of the electrostatic demister 8 is connected with a clean air blower 81, and clean air is discharged after being sent into a chimney 82 through the clean air blower 81.
As can be seen from the above examples, the present invention also relates to a wet sulfuric acid production process using high hydrocarbon-containing acid gas, which forms SO-containing acid gas after combustion in the incinerator 12The temperature in the incinerator 1 is 950-oC, cooling the high-temperature process gas to 440-480 through the waste heat boiler 21oC, cooling to 410-430 through a steam superheateroC. Dividing the cooled process gas into two paths, wherein one path is converted and cooled for multiple times to form rich SO3The other path of the process gas is mixed with the combustion-supporting gas to form a mixed gas 34, and then the mixed gas enters the incinerator 1 again to form circulation of part of the process gas, wherein the combustion-supporting gas can be ambient air to provide oxygen for combustion, and the temperature in the incinerator can be reduced. Rich in SO3The process gas is introduced into an acid condenser 5, and the temperature at the top of the acid condenser 5 is 85-100 DEG CoC, SO in the process gas due to temperature reduction3And H2O is hydrated to generate gaseous sulfuric acid, the gaseous sulfuric acid is condensed to generate liquid sulfuric acid, and the 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 liquid drops in the process gas. Finally, the process gas is subjected to quenching washing by adding H into the circulating dilute sulfuric acid2O2With SO remaining in the process gas2Reaction and absorption are carried out to form sulfuric acid, and the desulfurization of the process gas is realized.
The above embodiments are provided for illustrative purposes only and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should fall within the scope of the present invention, and the scope of the present invention should be defined by the claims.
Claims (10)
1. A wet process for preparing sulfuric acid from high-hydrocarbon acidic gas features that the high-hydrocarbon acidic gas is burnt in incinerator (1) to form SO2The process gas is cooled and cooled, and is characterized in that: 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 the combustion-supporting gas to form mixed gas (34) and then enters the incinerator (1) again to form circulation of part of the process gas.
2. The wet sulfuric acid process with high hydrocarbon content from acid gas as claimed in claim 1, wherein: SO in the mixed gas (34)2The molar content of (A) is 2-6%.
3. The wet sulfuric acid process with high hydrocarbon content from acid gas as claimed in claim 1, wherein: the temperature in the incinerator (1) is 950-oC; the burned process gas is cooled twice by a waste heat boiler (21) and a steam superheater (22) and is cooled to 440-480 DEG by the waste heat boiler (21)oC, cooling to 410 and 430 through a steam superheater (22)oC; the temperature of the mixed gas (34) is 180-oC。
4. The wet sulfuric acid process with high hydrocarbon content from acid gas as claimed in claim 1, wherein: the process gas is converted for three times through a first catalyst bed layer (41), a second catalyst bed layer (43) and a third catalyst bed layer (45) in sequence to form the SO-rich gas3The process gas is cooled after each conversion;
inlet temperature 405-420 of the first catalyst bed (41)oC, inlet temperature 400-oC, inlet temperature 390-oC; the outlet temperature after the conversion cooling is 280-300-oC; the condensation temperature is 85-100oC。
5. A device for preparing sulfuric acid by a wet method with high-hydrocarbon-content acid gas is characterized in that: the system 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 a gas inlet pipe which is simultaneously communicated with a hydrocarbon-containing acid gas pipeline and a combustion-supporting gas pipeline, a gas 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; the combustion-supporting gas pipeline is provided with an air mixing unit, combustion-supporting gas and SO2The gas is passed through an air mixing unit to form a mixture (34).
6. The apparatus for preparing sulfuric acid by wet process of high hydrocarbon-containing acid gas according to claim 5, wherein: 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 further communicated with a steam drum (23) through heat exchange pipelines respectively, and the heat exchange pipeline connected with the steam superheater (22) passes through the conversion reactor (4).
7. The apparatus for preparing sulfuric acid by wet process of high hydrocarbon-containing acid gas according to claim 6, wherein: the conversion reactor (4) comprises a first catalyst bed layer (41), a second catalyst bed layer (43) and a third catalyst bed layer (45) which are communicated with each other, a process gas pipeline inlet of the conversion reactor (4) is arranged at the first catalyst bed layer (41), a first inter-cooler (42) is arranged between the first catalyst bed layer (41) and the second catalyst bed layer (43), a second inter-cooler (44) is arranged between the second catalyst bed layer (43) and the third catalyst bed layer (45), and a process gas cooler (46) is arranged between the third catalyst bed layer (45) and the 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 heat exchange pipelines, the inlet end of the second-stage intercooler (44) is connected with the steam drum (23) through the heat exchange pipelines, the outlet end of the second-stage intercooler is connected with the inlet end of the first-stage intercooler (46) through the heat exchange pipelines, and the outlet end of the first-stage intercooler (46) is a high-temperature steam outlet.
8. The apparatus for preparing sulfuric acid by wet process of high hydrocarbon-containing acid gas according to claim 7, wherein: a ceramic acid-resistant filler (52) and a cyclone demister (51) are arranged in the acid condenser (5), wherein the ceramic acid-resistant filler (52) is arranged at the inlet of the process gas pipeline, the cyclone demister (51) is arranged at the outlet of the process gas pipeline, and the cone angle of the cyclone demister (51) is 1.5o-20oA sulfuric acid outlet is arranged below the acid condenser (5);
the sulfuric acid outlet of the acid condenser (5) is connected to a concentrated acid circulating unit (9), the concentrated 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 acid circulating tank (91) to form circulation, and the other path outputs finished sulfuric acid for the concentrated acid outlet.
9. The apparatus for preparing sulfuric acid by wet process of high hydrocarbon-containing acid gas according to claim 6, wherein: the heat exchange unit (2) further comprises a water supply preheater (24), a cooling air fan (53) is connected to a heat exchange gas inlet of the acid condenser (5), an outlet is communicated with the water supply preheater (24) through a heat exchange pipeline, and a steam drum (23) is also communicated with the water supply preheater (24) through a heat exchange pipeline.
10. The apparatus for preparing sulfuric acid by wet process of high hydrocarbon-containing acid gas according to claim 5, wherein: the washing unit (6) comprises a quenching washing tower (7) and an electrostatic demister (8) which are communicated, 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 the other path outputs finished sulfuric acid;
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 wire mesh demister (72) is arranged in the quenching washing tower (7) close to the electrostatic demister (8).
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