CN115990392A - Coupling process and device for flue gas desulfurization and sulfur recovery - Google Patents
Coupling process and device for flue gas desulfurization and sulfur recovery Download PDFInfo
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- CN115990392A CN115990392A CN202111216408.9A CN202111216408A CN115990392A CN 115990392 A CN115990392 A CN 115990392A CN 202111216408 A CN202111216408 A CN 202111216408A CN 115990392 A CN115990392 A CN 115990392A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000011593 sulfur Substances 0.000 title claims abstract description 96
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 96
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003546 flue gas Substances 0.000 title claims abstract description 37
- 238000011084 recovery Methods 0.000 title claims abstract description 36
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 29
- 230000023556 desulfurization Effects 0.000 title claims abstract description 29
- 238000010168 coupling process Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 239000002250 absorbent Substances 0.000 claims abstract description 46
- 230000002745 absorbent Effects 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 40
- 238000010521 absorption reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007791 liquid phase Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 40
- 230000003009 desulfurizing effect Effects 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001540 sodium lactate Substances 0.000 claims description 5
- 229940005581 sodium lactate Drugs 0.000 claims description 5
- 235000011088 sodium lactate Nutrition 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- LLMOLYDGTPLUSB-UHFFFAOYSA-N 2-aminoethyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OCCN LLMOLYDGTPLUSB-UHFFFAOYSA-N 0.000 claims description 3
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 claims description 2
- LHFVAIZKWQDJJQ-UHFFFAOYSA-N (n,n-dimethylcarbamimidoyl)-dimethylazanium;2-hydroxypropanoate Chemical compound CC(O)C(O)=O.CN(C)C(=N)N(C)C LHFVAIZKWQDJJQ-UHFFFAOYSA-N 0.000 claims description 2
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 229960001518 levocarnitine Drugs 0.000 claims description 2
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 claims description 2
- 239000001521 potassium lactate Substances 0.000 claims description 2
- 235000011085 potassium lactate Nutrition 0.000 claims description 2
- 229960001304 potassium lactate Drugs 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 239000002151 riboflavin Substances 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 239000004149 tartrazine Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alcohol amine Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 230000008929 regeneration Effects 0.000 description 1
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Abstract
The invention relates to a coupling process and a device for flue gas desulfurization and sulfur recovery. The process adopts an absorbent to absorb SO 2 The obtained absorption rich liquid and H-contained in sulfur recovery device 2 S gas is subjected to liquid phase Claus reaction in a reactor to generate sulfur, the reaction product is extracted and heated to obtain liquid sulfur which is recovered as sulfur product, and the absorption lean solution enters a stripping tower to remove H dissolved in an absorbent 2 S and SO 2 . The process of the invention removes SO in flue gas 2 At the same time SO is recovered 2 Resources increase the yield of sulfur, and can be usedIn an industrial device for flue gas desulfurization and sulfur recovery. The process does not need waste water and waste gas treatment, has high operation stability, reduces the investment of the whole device and improves the yield.
Description
Technical Field
The invention relates to a desulfurization technology, in particular to a process and a device for coupling flue gas desulfurization and sulfur recovery.
Background
The H-containing matter separated out by regeneration of alcohol amine method 2 And most of acid gas of S enters a sulfur recovery device to produce sulfur, and the device mainly comprises a multi-stage Claus combustion furnace, a condenser, a reheater, a liquid sulfur tank, a sulfur forming tank, tail gas treatment and the like. The Claus reaction is 2H 2 S+SO 2 →3S+2H 2 O, where SO 2 Is warp H 2 S is prepared in a Claus furnace, which determines that the sulfur yield can theoretically only reach H in the feed gas 2 Sulfur content contained in S.
At present, companies such as Shanghai petrochemical industry, luoyang petrochemical industry, jinlin petrochemical industry and the like matched with a large-scale sulfur recovery device in China are all provided with thermoelectric parts, power and steam are provided for plants through coal-fired boilers, and the coal-fired flue gas contains low-concentration SO 2 Typically around 1000 ppm. At present this part of SO 2 Is converted into low added value desulfurized gypsum by a calcium desulfurization technology, which causes serious resource waste. Thus SO in the flue gas 2 The recovery of the reactants as a claus reaction can simultaneously achieve flue gas desulfurization and sulfur yield increase.
Liquid phase claus reaction means SO in a liquid phase reaction medium 2 And H is 2 S reacts to generate sulfur and water, the reaction can be carried out at normal temperature and normal pressure, the operation condition is mild, and SO can be realized 2 Recovering resources and increasing sulfur yield. There are two main types of liquid phase claus reaction processes, one of which contains SO 2 And H-containing gas 2 S gasSimultaneously introducing into a packed column to effect liquid phase Claus reaction in absorbent, one of which contains SO 2 Is rich in absorption liquid and contains H 2 The absorption rich liquid of S undergoes a liquid phase claus reaction in the reactor. Patent CN105521696B takes ionic liquid as absorbent, and the ionic liquid enters H in two ways 2 S absorption tower and SO 2 An absorption tower is arranged on the bottom of the absorption tower, H is respectively obtained at the bottom of the tower 2 Rich solution of S and SO 2 Mixing the two kinds of rich liquid, then entering a reactor to generate liquid phase Claus reaction, filtering, drying and washing the mixture to obtain solid sulfur after the reaction is finished, and then washing the solid sulfur with warm water to obtain a sulfur product. Patent application CN109529567A will contain H 2 S gas and SO-containing gas 2 The gas of (2) is introduced into the bottom of a packing tower through a gas distributor, the top of the packing tower is sprayed with an absorbent from a tail gas absorbing device, and SO in the gas is carried out at normal temperature and normal pressure 2 And H 2 S is subjected to liquid phase Claus reaction in a reactor, the reaction product is solid sulfur and water, reaction tail gas enters a tail gas absorption device, sulfur slurry is filtered, washed and dried for multiple times to obtain high-purity sulfur, and separated reaction solution is sent into the tail gas absorption device.
The process can well recycle SO 2 Resources, there are still some significant disadvantages: the tower is blocked due to the large washing wastewater amount and solid sulfur, the tower is difficult to operate, the tail gas absorption treatment amount is high, the absorbent consumption is large, and the tower is easy to inactivate, etc.
Disclosure of Invention
The invention aims to solve the problems and provide a coupling process and a device for flue gas desulfurization and sulfur recovery.
In order to achieve the above object, a first aspect of the present invention provides a coupling process for flue gas desulfurization and sulfur recovery, comprising the steps of:
a) Containing SO 2 The flue gas of the flue gas is contacted with sulfur dioxide absorbent in a desulfurizing tower to obtain the SO-containing gas 2 Absorbing the rich liquid;
b) Containing SO 2 Absorbing rich liquid and containing H from sulfur recovery device 2 S gas enters the reactor at the same time, H in the reactor 2 S is a kind ofContaining SO 2 Absorbing SO in rich liquid 2 Generating claus reaction to generate solid sulfur;
c) Extracting and heating the material obtained in the step b) to separate the system into gas phase and liquid phase, wherein the gas phase is dissolved H 2 S and SO 2 The liquid phase is mutually insoluble liquid sulfur and absorption lean liquid, the gas phase returns to a Claus combustion furnace in a sulfur recovery device, and the liquid phase is sent to a liquid sulfur separator;
d) The liquid sulfur separated by the liquid sulfur separator is recovered as sulfur product, the absorption lean solution enters a stripping tower to further remove H dissolved in the absorbent 2 S and SO 2 ；
e) In the step d), the top gas of the stripping tower is returned to the Claus combustion furnace in the sulfur recovery device, and part of tower bottom liquid is returned to the desulfurizing tower after being cooled to be used as a sulfur dioxide absorbent, and the other part is returned to the reactor to be used for washing.
In the above technical scheme, preferably, in step a), the catalyst comprises SO 2 SO in flue gas of (C) 2 The concentration of (a) is 0.05-10 vol%, and H is contained in the step b) 2 H in gas of S 2 The S concentration is 50-100 vol%.
In the above-described embodiment, preferably, the sulfur dioxide absorbent in step a) has a concentration of 100vol% H per kilogram of sulfur dioxide absorbent at 100kPaA and 40 DEG C 2 S has an absorption of less than 10 g and a sulfur dioxide absorbent per kilogram of SO with a concentration of 0.05vol% 2 The absorption capacity of (2) is greater than 20 g.
In the above technical solution, preferably, the sulfur dioxide absorbent in step a) is selected from one or more of sodium lactate, potassium lactate, tetramethylguanidine lactate, ethanolamine lactate, betaine, l-carnitine, imidazole, hydroxyethyl piperazine or sodium phenolate.
In the above technical scheme, preferably, the desulfurizing tower in the step a) is a packed tower, the operating temperature is 9-60 ℃, and the pressure is 0.01-1 MPaA.
In the above technical solution, preferably, the reactor in the step b) is a jacketed stirred tank reactor; the reaction temperature is 5-80 ℃, the pressure is 0.05-2 MPaA, and the molar ratio of the hydrogen sulfide to the sulfur dioxide entering the reactor is 0.5-2.5.
In the above-described embodiment, preferably, the unreacted H in step b) 2 S returns to the Claus burner in the sulfur recovery device.
In the above-described embodiment, the reactor mass withdrawn in step c) is preferably heated to 105 to 150 ℃, preferably the reactor mass is heated to 120 to 130 ℃.
In the above technical scheme, preferably, the stripping tower in the step d) is a packed tower, the operation temperature is 100-150 ℃ and the pressure is 50-300 kPaA.
In the above technical solution, preferably, the absorbent returned to the reactor for washing in step e) accounts for 1% -25% of the outlet liquid of the bottom of the stripping tower.
The second aspect of the invention provides a flue gas desulfurization and sulfur recovery device, which comprises a desulfurization tower, a reactor connected with the bottom of the desulfurization tower through a pipeline, a liquid sulfur separator connected with the bottom of the reactor through a pipeline, and a stripping tower connected with the liquid sulfur separator, wherein the bottom of the stripping tower is connected with the desulfurization tower through a pipeline.
In the above technical scheme, preferably, the reactor is a jacketed stirred tank reactor.
In the above technical solution, preferably, a heater is provided between the reactor and the liquid sulfur separator.
In the prior art, one is SO-containing 2 Flue gas and H-containing 2 S gas is simultaneously introduced into the packed tower to generate liquid phase Claus reaction in the absorbent, SO that the packed tower is easily blocked by generated solid sulfur, and SO in the flue gas 2 Low concentration and high amounts of inert components carry H out of the column head clamp 2 S and sulfur slurry cause huge pressure for tail gas treatment; one is to adopt the same absorbent to absorb SO respectively 2 And H 2 S, the obtained SO-containing 2 Is rich in absorption liquid and contains H 2 The absorption rich liquid of S is subjected to liquid phase Claus reaction in a reactor, and the process has the defect that the same absorbent is adopted for absorption, and H is used for 2 S is much less acidic than SO 2 Can efficiently remove H 2 The absorbent of S can certainly remove SO more efficiently 2 This allows the absorbent to react with SO when the Claus reaction is carried out in the absorbent 2 The strong force can reduce H 2 Conversion of S, and reaction of residual SO 2 The strong force between the adsorbent and the adsorbent makes the adsorbent difficult to desorb in the subsequent adsorbent recovery process, so that the adsorbent is deactivated. In addition, both techniques are carried over to the sulfur product by filtration-washing-drying, which produces a significant amount of organics and H 2 S, the treatment cost of the process wastewater is increased.
In the invention, H 2 S and SO-containing 2 The absorption rich liquid of (2) reacts in a stirred tank reactor with a jacket, the operation is stable, the temperature is easy to control, and the SO is easy to control 2 Absorbent pair H 2 S has no chemical action, H 2 S is only physically dissolved in the absorbent, so that the reaction conversion rate is high, and the absorbent is easy to regenerate; the reaction product is heated to make sulfur melt into liquid phase, and the melting point of sulfur is about 110 deg.C, and at this temperature the unreacted trace quantity of H is dissolved in sulfur 2 S can be better removed, and the liquid sulfur and the absorbent are not mutually dissolved, so that the high-purity sulfur can be obtained by simple separation, and a large amount of washing wastewater is avoided; due to the raw material H 2 S is derived from a bypass of a raw material pipeline in the sulfur recovery device, and unreacted H 2 S and a trace amount of H dissolved in the absorption lean solution 2 S and SO 2 The liquid sulfur is returned to the claus furnace together and directly used as a product to be returned to a liquid sulfur tank in the sulfur recovery device, so that the steady-state operation of the running sulfur recovery device is not affected.
By adopting the method of the invention, the company can save the running cost of the prior calcium desulfurization system and simultaneously lead SO in the flue gas 2 All the waste water and waste gas are converted into sulfur products, waste water and waste gas treatment is not needed, the operation stability is high, the overall investment is reduced by 30-50%, and the income is improved by 5-10%.
Drawings
FIG. 1 is a schematic diagram of a coupled process flow diagram and apparatus for flue gas desulfurization and sulfur recovery in accordance with the present invention.
In FIG. 1, R-101, the reactor; e-101, a heater; v-101, a liquid sulfur separator; t-101, stripping tower; e-102, absorbing the lean liquid cooler; t-102, a desulfurizing tower; 1, a reaction product; 2, heating the reaction product; 3, absorbing lean liquid; 4, sulfur dioxide absorbent; and 5, absorbing the rich solution containing sulfur dioxide.
Detailed Description
The invention is further illustrated by the following examples, but it should be understood that the specific examples are not to be construed as limiting the scope of the invention.
As shown in FIG. 1, the flue gas desulfurization and sulfur recovery device comprises a desulfurization tower T102, a reactor R-101 connected with the bottom of the desulfurization tower through a pipeline, a liquid sulfur separator V-101 connected with the bottom of the reactor through a pipeline, and a stripping tower T-101 connected with the liquid sulfur separator, wherein the bottom of the stripping tower is connected with the desulfurization tower through a pipeline. The reactor is a stirred tank reactor with a jacket. A heater E-101 is arranged between the reactor and the liquid sulfur separator.
The coupling process of flue gas desulfurization and sulfur recovery of the invention is illustrated below with reference to the accompanying drawings:
a) Containing SO 2 Is contacted with sulfur dioxide absorbent in a desulfurizing tower T-102 to obtain the SO-containing gas 2 Absorbing the rich liquid 5;
b) Containing SO 2 Absorbing the rich liquid 5 and containing H from the sulfur recovery device 2 S gas enters the reactor R-101 at the same time, H in the reactor 2 S and SO-containing 2 Absorbing SO in rich liquid 2 Generating claus reaction to generate solid sulfur;
c) Extracting the material obtained by the reaction in the step b) and heating the material by a heater E-101 to separate the system into gas phase and liquid phase, wherein the gas phase is dissolved H 2 S and SO 2 The liquid phase is non-compatible liquid sulfur and absorption lean liquid, the gas phase returns to a Claus combustion furnace in a sulfur recovery device, and the liquid phase is sent to a liquid sulfur separator V-101;
d) The liquid sulfur separated by the liquid sulfur separator is used as a sulfur product recovery product to return to a liquid sulfur tank in a sulfur recovery device, and the absorption lean solution enters a stripping tower T-101 to be further removed and dissolvedH in absorbent 2 S and SO 2 ；
e) In the step d), the top gas of the stripping tower is returned to the Claus combustion furnace in the sulfur recovery device, and part of tower bottom liquid is returned to the desulfurizing tower T-102 after being cooled to be used as a sulfur dioxide absorbent, and the other part is returned to the reactor to be used for washing.
[ example 1 ]
The coupling process shown in figure 1 is adopted in a refinery, and the flow rate of the coal-fired flue gas is 330000m 3 /h，SO 2 The concentration is 1000ppm SO 2 The absorbent was 50% aqueous ethanolamine lactate solution at 100kPaA,40℃for 100vol% H per 1 kg of absorbent 2 S was absorbed in an amount of 1 g for SO at a concentration of 0.05vol% 2 The absorption capacity of (2) was 80 g.
The operating pressure at the top of the desulfurizing tower is 0.11MPaA, the operating temperature is 40 ℃, and the pressure drop of the tower is 5kPaA. H entering reactor R-101 2 S concentration is 95%, H 2 S and absorbing SO in rich liquid 2 The molar ratio of (2) was 1.8:1. The reactor temperature was 25℃and the pressure was 0.3MPaA. The outlet temperature of heater E-101 was 130 ℃, the overhead pressure of stripper T-101 was 101kPaA, the bottom temperature was 120 ℃, the pressure drop across the column was 2kPaA, the outlet temperature of absorption lean cooler E-102 was 40 ℃, and the absorbent returned to the reactor was 20% of stream 4.
2000 ten thousand investment of equipment and SO 2 The removal cost is 0.3 yuan/kg SO 2 . The device runs stably and the flue gas SO is discharged 2 The concentration is less than or equal to 10ppm, the conversion rate of hydrogen sulfide is more than or equal to 90 percent, and the yield of sulfur 1275kg/h with the purity of 99.99 percent is increased.
[ example 2 ]
The coupling process experiment of flue gas desulfurization and sulfur recovery was performed using a laboratory apparatus as shown in fig. 1. Containing SO 2 SO in flue gas of (C) 2 Is 1vol%, H-containing 2 H in gas of S 2 The S concentration was 80%. SO (SO) 2 The absorbent is 50% sodium lactate aqueous solution. At 100kPaA,40℃for every 1 kg of the absorbent, H at a concentration of 100% by volume 2 S was absorbed in an amount of 2 g for SO at a concentration of 0.05vol% 2 The absorption capacity of (2) is 100 g.
Top operating pressure of desulfurizing tower0.50MPaA, operating temperature 60 ℃, column pressure drop 5kPaA. H entering reactor R-101 2 S and absorbing SO in rich liquid 2 The molar ratio of (2) was 0.8:1. The reactor temperature was 50℃and the pressure was 1.0MPaA. The outlet temperature of heater E-101 was 110℃, the overhead pressure of stripper T-101 was 250kPaA, the kettle temperature was 150℃, the pressure drop across the column was 2kPaA, the outlet temperature of absorption lean cooler E-102 was 40℃, and the absorbent returned to the reactor was 20% of stream 4.
The device runs stably and the flue gas SO is discharged 2 The concentration is less than or equal to 5ppm, the conversion rate of hydrogen sulfide is more than or equal to 95 percent, and the purity of sulfur is 99.99 percent.
[ example 3 ]
The coupling process experiment of flue gas desulfurization and sulfur recovery was performed using a laboratory apparatus as shown in fig. 1. Containing SO 2 SO in flue gas of (C) 2 Has a concentration of 8vol%, and contains H 2 H in gas of S 2 The S concentration was 80%. SO (SO) 2 The absorbent is 50% sodium lactate aqueous solution.
The operating pressure at the top of the desulfurizing tower is 0.05MPaA, the operating temperature is 20 ℃, and the pressure drop of the tower is 3kPaA. H entering reactor R-101 2 S and absorbing SO in rich liquid 2 The molar ratio of (2) is 2.5:1. The reactor temperature was 80℃and the pressure was 2.0MPaA. The outlet temperature of heater E-101 was 150℃and the overhead pressure of stripper T-101 was 150kPaA, the column bottoms temperature was 130℃and the column pressure drop was 2kPaA, the outlet temperature of absorption lean cooler E-102 was 40℃and the absorbent returned to the reactor was 20% of stream 4.
The device runs stably and the flue gas SO is discharged 2 The concentration is less than or equal to 5ppm, the conversion rate of sulfur dioxide is more than or equal to 95%, and the purity of sulfur is 99.99%.
[ example 4 ]
The coupling process experiment of flue gas desulfurization and sulfur recovery was performed using a laboratory apparatus as shown in fig. 1. Containing SO 2 SO in flue gas of (C) 2 Has a concentration of 8vol%, and contains H 2 H in gas of S 2 The S concentration was 80%. SO (SO) 2 The absorbent is 50% sodium lactate aqueous solution.
The operating pressure at the top of the desulfurizing tower is 0.05MPaA, the operating temperature is 20 ℃, and the pressure drop of the tower is 3kPaA. H entering reactor R-101 2 S and absorbing SO in rich liquid 2 Molar ratio of (2) is2.5:1. The reactor temperature was 80℃and the pressure was 2.0MPaA. The outlet temperature of the heater E-101 was 150 ℃, the overhead pressure of the stripper T-101 was 80kPaA, the column bottom temperature was 100 ℃, the column pressure drop was 2kPaA, the outlet temperature of the absorption lean cooler E-102 was 40 ℃, and the absorbent returned to the reactor was 20% of the stream 4.
The device runs stably and the flue gas SO is discharged 2 The concentration is less than or equal to 5ppm, the conversion rate of sulfur dioxide is more than or equal to 95%, and the purity of sulfur is 99.99%.
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. The coupling process for flue gas desulfurization and sulfur recovery is characterized by comprising the following steps:
a) Containing SO 2 The flue gas of the flue gas is contacted with sulfur dioxide absorbent in a desulfurizing tower to obtain the SO-containing gas 2 Absorbing the rich liquid;
b) Containing SO 2 Absorbing rich liquid and containing H from sulfur recovery device 2 S gas enters the reactor at the same time, H in the reactor 2 S and SO-containing 2 Absorbing SO in rich liquid 2 Generating claus reaction to generate solid sulfur;
c) Extracting and heating the material obtained in the step b) to separate the system into gas phase and liquid phase, wherein the gas phase is dissolved H 2 S and SO 2 The liquid phase is mutually insoluble liquid sulfur and absorption lean liquid, the gas phase returns to a Claus combustion furnace in a sulfur recovery device, and the liquid phase is sent to a liquid sulfur separator;
d) The liquid sulfur separated by the liquid sulfur separator is recovered as sulfur product, the absorption lean solution enters a stripping tower to further remove H dissolved in the absorbent 2 S and SO 2 ；
e) In the step d), the top gas of the stripping tower is returned to the Claus combustion furnace in the sulfur recovery device, and part of tower bottom liquid is returned to the desulfurizing tower after being cooled to be used as a sulfur dioxide absorbent, and the other part is returned to the reactor to be used for washing.
2. The process according to claim 1, wherein in step a) the SO-containing agent is selected from the group consisting of 2 SO in flue gas of (C) 2 The concentration of (a) is 0.05-10 vol%, and H is contained in the step b) 2 H in gas of S 2 The S concentration is 50-100 vol%.
3. The process according to claim 1, wherein in step a) the sulfur dioxide absorbent is used in a concentration of 100 vol.% H for one kg of sulfur dioxide absorbent at 100kPaA and 40 ℃ 2 S has an absorption of less than 10 g and a sulfur dioxide absorbent per kilogram of SO with a concentration of 0.05vol% 2 The absorption capacity of (2) is greater than 20 g.
4. The process according to claim 1, wherein the sulfur dioxide absorbent in step a) is selected from one or more of sodium lactate, potassium lactate, tetramethylguanidine lactate, ethanolamine lactate, betaine, l-carnitine, imidazole, hydroxyethyl piperazine or sodium phenolate.
5. The process according to claim 1, wherein the desulfurizing tower in step a) is a packed tower operated at a temperature of 9 ℃ to 60 ℃ and a pressure of 0.01mpa to 1 mpa.
6. The process of claim 1 wherein the reactor in step b) is a jacketed stirred tank reactor; the reaction temperature is 5-80 ℃, the pressure is 0.05-2 MPaA, and the molar ratio of the hydrogen sulfide to the sulfur dioxide entering the reactor is 0.5-2.5.
7. The process according to claim 1, wherein unreacted H in step b) 2 S returns to the Claus burner in the sulfur recovery device.
8. A process according to claim 1, wherein the reactor mass withdrawn in step c) is heated to 105-150 ℃, preferably the reactor mass is heated to 120-130 ℃.
9. The process according to claim 1, wherein in step d) the stripping column is a packed column operated at a temperature of 100 ℃ to 150 ℃ and a pressure of 50kPaA to 300kPaA.
10. The process according to claim 1, wherein the absorbent returned to the reactor for washing in step e) comprises 1% to 25% of the stripper bottoms outlet liquid.
11. The flue gas desulfurization and sulfur recovery device is characterized by comprising a desulfurization tower, a reactor connected with the bottom of the desulfurization tower through a pipeline, a liquid sulfur separator connected with the bottom of the reactor through a pipeline, and a stripping tower connected with the liquid sulfur separator, wherein the bottom of the stripping tower is connected with the desulfurization tower through a pipeline.
12. The apparatus of claim 11, wherein the reactor is a jacketed stirred tank reactor.
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