CN115041007A - Sulfur dioxide gas recovery system and method - Google Patents
Sulfur dioxide gas recovery system and method Download PDFInfo
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- CN115041007A CN115041007A CN202210718046.1A CN202210718046A CN115041007A CN 115041007 A CN115041007 A CN 115041007A CN 202210718046 A CN202210718046 A CN 202210718046A CN 115041007 A CN115041007 A CN 115041007A
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000011084 recovery Methods 0.000 title claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 470
- 239000000872 buffer Substances 0.000 claims abstract description 322
- 239000007788 liquid Substances 0.000 claims abstract description 207
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000010269 sulphur dioxide Nutrition 0.000 claims description 153
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 43
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 34
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 31
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 19
- 239000011152 fibreglass Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- 239000007853 buffer solution Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000004291 sulphur dioxide Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- DJGAAPFSPWAYTJ-UHFFFAOYSA-M metamizole sodium Chemical compound [Na+].O=C1C(N(CS([O-])(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 DJGAAPFSPWAYTJ-UHFFFAOYSA-M 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000005574 cross-species transmission Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
Abstract
The invention belongs to the technical field of environmental protection, and particularly relates to a sulfur dioxide gas recovery system and a method, wherein the system comprises: the absorption tower comprises a first-stage absorption tower, a second-stage absorption tower, a third-stage absorption tower and a fourth-stage absorption tower, as well as a first-stage buffer container, a second-stage buffer container, a third-stage buffer container and a fourth-stage buffer container which are used for storing absorption liquid, wherein the first-stage absorption tower, the second-stage absorption tower, the third-stage buffer container and the fourth-stage buffer container are sequentially connected along the direction of sulfur dioxide; sequentially connecting four to one-stage buffer containers along the flowing direction of the absorption liquid; the absorption liquid outlet of each absorption tower is directly connected with the corresponding inlet of the same-stage buffer container; the absorption liquid inlet of each absorption tower is connected with the corresponding outlet of the same-stage buffer container, and the absorption liquid can circularly flow between the absorption tower and the buffer container of the corresponding stage. The sulfur dioxide gas generated in the process of recovering the aminoantipyrine by using the system of the invention has the recovery rate of about 100 percent, and the content of the sulfur dioxide in the tail gas is lower than 10mg/m 3 。
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a sulfur dioxide gas recovery system and a sulfur dioxide gas recovery method.
Background
Sulfur dioxide (chemical formula: SO) 2 ) Also known as sulfurous anhydride, is the main component of the most common raw material gas of sulfur oxide and sulfuric acid. Sulfur dioxide is a colorless gas with a strong pungent odor and is one of the major atmospheric pollutants. A large amount of sulfur dioxide gas can be generated in the production process of analgin intermediate amino antipyrine, in the prior art, the treatment of the sulfur dioxide gas mainly comprises the step of taking ammonia water as absorption liquid to finish the absorption of sulfur dioxide in a single absorption tower to generate ammonium bisulfite or ammonium sulfite, in the actual operation, the ammonia water is easy to volatilize and can be discharged along with tail gas, the ammonia gas in the treated tail gas exceeds the standard, sometimes, the sulfur dioxide is not completely absorbed due to the recycling of the absorption liquid, the content of sulfur dioxide in the tail gas exceeds the standard, and the sulfur dioxide is difficult to exceed the standardThe treated tail gas is ensured to be stable and reach the standard. Furthermore, as the aminoantipyrine production increases, a single absorber column cannot meet the gas throughput requirements. Therefore, the absorption of sulfur dioxide cannot be well completed by adopting a single absorption tower, the phenomenon that the content of sulfur dioxide or ammonia exceeds the standard often occurs in tail gas, the emission standard cannot be met, and absorption solution is wasted.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a sulfur dioxide gas recovery system and a sulfur dioxide gas recovery method.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a sulphur dioxide gas recovery system, the system comprising: the absorption tower comprises a first-stage absorption tower, a second-stage absorption tower, a third-stage absorption tower and a fourth-stage absorption tower, as well as a first-stage buffer container, a second-stage buffer container, a third-stage buffer container and a fourth-stage buffer container which are used for storing absorption liquid, wherein the first-stage absorption tower, the second-stage absorption tower, the third-stage absorption tower and the fourth-stage absorption tower are sequentially connected along the trend of sulfur dioxide; along the flowing direction of the absorption liquid, the four-stage buffer container, the three-stage buffer container, the two-stage buffer container and the one-stage buffer container are sequentially connected;
the absorption liquid outlet of each absorption tower is directly connected with the corresponding inlet of the same-stage buffer container; the absorption liquid inlet of each absorption tower is connected with the corresponding outlet of the same-stage buffer container, and the absorption liquid can circularly flow between the absorption tower and the buffer container of the corresponding stage.
In the above sulfur dioxide gas recovery system, as a preferred embodiment, the primary absorption tower is configured to perform a first absorption on the sulfur dioxide gas; the secondary absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the primary absorption tower; the third-stage absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the second-stage absorption tower; the four-stage absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the three-stage absorption tower, and the tail gas is discharged into the air.
In the above-mentioned sulfur dioxide gas recovery system, as a preferred embodiment, the system further comprises a plurality of pumps, and a pump is arranged between each level of absorption tower and the buffer container, and is used for pumping the absorption liquid in the buffer container of the level into the absorption tower of the corresponding level.
In the above sulfur dioxide gas recovery system, as a preferred embodiment, the system further comprises a plurality of condensers, which are disposed between the absorption liquid inlet of the absorption tower of each stage and the pump, for cooling the absorption liquid from the buffer container of the corresponding stage; preferably, the condenser is a graphite condenser.
In the above sulfur dioxide gas recovery system, as a preferred embodiment, the absorption tower is a circulating absorption tower; preferably, the first-stage absorption tower and the second-stage absorption tower are glass fiber reinforced plastic circulating absorption towers; preferably, the third-stage absorption tower and the fourth-stage absorption tower are PVC circulating absorption towers.
In the above sulfur dioxide gas recovery system, as a preferred embodiment, the buffer container is a buffer solution storage tank; preferably, the first-stage buffer container and the second-stage buffer container are glass fiber reinforced plastic buffer solution storage tanks; preferably, the third-level buffer container and the fourth-level buffer container are PVC buffer solution storage tanks.
In a second aspect, the present invention provides a method for recovering sulfur dioxide gas using the above system, comprising the steps of:
(1) adding ammonia water as absorption liquid into the first-stage buffer container, the second-stage buffer container and the third-stage buffer container, and adding water as absorption liquid into the fourth-stage buffer container;
(2) introducing gas containing sulfur dioxide from a gas inlet of a first-stage absorption tower, sequentially absorbing the gas by the first-stage absorption tower, a second-stage absorption tower, a third-stage absorption tower and a fourth-stage absorption tower, then discharging the gas out of the recovery system, simultaneously conveying absorption liquid in each stage of buffer container into the corresponding same-stage absorption tower to absorb the sulfur dioxide gas entering the same-stage absorption tower, conveying the absorption liquid absorbing the sulfur dioxide gas from the absorption tower back to the same-stage buffer container, and enabling the absorption liquid to circularly flow between the same-stage buffer container and the absorption tower;
(3) when the total concentration of the ammonium sulfite and the ammonium bisulfite in the absorption liquid of the first-stage buffer container reaches 500-550mg/mL, the absorption liquid in the first-stage buffer container is recovered, and then the absorption liquid of the second-stage buffer container is supplemented into the first-stage buffer container, the absorption liquid of the third-stage buffer container is supplemented into the second-stage buffer container, the absorption liquid of the fourth-stage buffer container is supplemented into the third-stage buffer container, and water is supplemented into the fourth-stage buffer container.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, step (3) further includes: before the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid in the first-stage buffer container reaches 500-550mg/mL, the concentration of the absorption liquid in the second-stage buffer container, the third-stage buffer container and the fourth-stage buffer container is ensured not to exceed the upper limit, and when the concentration of the absorption liquid in the second-stage buffer container, the third-stage buffer container or the fourth-stage buffer container reaches the upper limit, the absorption liquid reaching the upper limit of the concentration is diluted.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, the dilution is: diluting the absorption liquid in the secondary buffer container to pH8.5-9.5 with ammonia water, or diluting the absorption liquid in the tertiary buffer container to pH less than or equal to 8.0 with ammonia water, or diluting the concentration of the sulfurous acid in the absorption liquid in the quaternary buffer container to below 40mg/mL with water; further preferably, the absorption liquid in the tertiary buffer container is diluted to pH 6.0-7.0 by using ammonia water.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (3), the concentrations of the absorption liquids in the primary buffer container, the secondary buffer container and the tertiary buffer container are the total concentrations of ammonium sulfite and ammonium bisulfite in the absorption liquid, and the concentration of the absorption liquid in the quaternary buffer container is the concentration of sulfurous acid; the upper limit of the concentration of the absorption liquid of the first-stage buffer container is as follows: 550 mg/mL; the upper limit of the concentration of the absorption liquid of the secondary buffer container is as follows: 300 mg/mL; the upper limit of the concentration of the absorption liquid of the third-stage buffer container is as follows: 200 mg/mL; the upper limit of the concentration of the absorption liquid of the four-stage buffer container is as follows: 50 mg/mL.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (2), when the gas containing sulfur dioxide is introduced from the gas inlet of the first-stage absorption tower and is discharged from the recovery system after being absorbed by the first-stage absorption tower, the second-stage absorption tower, the third-stage absorption tower and the fourth-stage absorption tower in sequence, the content of sulfur dioxide in the gas is less than 30mg/m 3 (ii) a More preferably the sulphur dioxide content of the gas is less than 10mg/m 3 (ii) a Further preferably, the ammonia content of said gas is lower than 30mg/m 3 。
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (2), the temperature of the absorption liquid entering the first-stage absorption tower and the second-stage absorption tower is equal to or higher than 20 ℃, more preferably 30-40 ℃; preferably, the temperature of the absorption liquid entering the third-stage absorption tower and the fourth-stage absorption tower is less than or equal to 40 ℃.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (1), the method for adding ammonia water includes introducing water into the primary buffer container, the secondary buffer container and the tertiary buffer container, and adding liquid ammonia to generate ammonia water; preferably, the pH value of the ammonia water in the primary buffer container and the secondary buffer container is 8.5-9.5; more preferably 9.0; preferably, the pH value of the ammonia water in the third-stage buffer container is 7.0-8.0.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (1), in an initial state, 1/3 to 1/2 of the volume of the absorption liquid is added into the primary buffer container, and the volume of the absorption liquid in the primary buffer container is less than or equal to 3/4 of the volume of the absorption liquid in the secondary buffer container; preferably, 2/3 with the volume of the absorption liquid being less than or equal to the volume of the absorption liquid is added into the secondary buffer container, the tertiary buffer container and the quaternary buffer container.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, in the step (3), after the absorption liquid in the secondary buffer container is supplemented into the primary buffer container, or after the absorption liquid in the tertiary buffer container is supplemented into the secondary buffer container, or after the absorption liquid in the quaternary buffer container is supplemented into the tertiary buffer container, the pH of the absorption liquid in the primary buffer container, the secondary buffer container and the tertiary buffer container is adjusted; further preferably, after the pH is adjusted, the volume of the absorption liquid in the primary buffer container accounts for 1/3-1/2 of the volume of the absorption liquid, and the volume of the absorption liquid in the primary buffer container is less than or equal to 3/4 of the volume of the absorption liquid in the secondary buffer container; preferably, the volume of the absorption liquid in the secondary buffer container and the tertiary buffer container does not exceed 2/3 of the volume thereof; preferably, in the step (3), the absorption liquid in the fourth-stage buffer container is supplemented to the third-stage buffer container, and after the water is supplemented in the fourth-stage buffer container, the volume of the absorption liquid in the fourth-stage buffer container does not exceed 2/3 of the volume of the absorption liquid.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, the adjusting the pH is adjusting the pH by adding ammonia water or liquid ammonia; preferably, the pH is adjusted to 8.5-9.5 by adjusting the pH of the absorption liquid in the first-stage buffer container and the second-stage buffer container, and the pH of the absorption liquid in the third-stage buffer container is adjusted to be less than or equal to 8.0.
In the above method for recovering sulfur dioxide gas, as a preferred embodiment, the sulfur dioxide-containing gas is sulfur dioxide gas generated in the process of preparing aminoantipyrine.
Has the advantages that:
in the enterprise production, in the reaction process of preparing the aminoantipyrine and generating the sulfur dioxide at the upstream, about 450-490 kg of sulfur dioxide is generated in each batch of reaction, 33 tons of sulfur dioxide are generated in each month, and about 90% of the sulfur dioxide in each batch of reaction is generated and discharged within two hours before the reaction. The absorption of sulfur dioxide by a single absorption tower requires frequent replacement of absorption liquid, and the machine is stopped to cool, and the content of sulfur dioxide in tail gas exceeds the standard.
By adopting the recovery method, the recovery rate of the sulfur dioxide can be improved to be close to 100 percent, a multi-stage absorption mode is adopted, the absorption liquid used by the absorption tower at the next stage can be recycled in the absorption tower at the front adjacent stage, the absorption liquid is fully utilized, the sulfur dioxide absorption effect is good, the same amount of sulfur dioxide gas is treated, compared with a single absorption tower, the system and the method can save a large amount of absorption liquid, the cost is reduced, and the sulfur dioxide content in the tail gas reaches the standard.
The last absorption tower of this application adopts water as the absorption liquid, can absorb the ammonia that comes from in preceding level gas, and the ammonia content also reaches standard in the tail gas of final emission, is less than 30mg/m 3 。
In the embodiment of the invention, the total volume of the system reaches 23000 liters, the system capacity is greatly expanded, sulfur dioxide tail gas generated by upstream preparation of aminoantipyrine of 4-5 batches can be absorbed, and then the absorption liquid is replaced or supplemented, the machine does not need to be stopped for cooling, and the production cost is reduced; compared with a single absorption tower, the method has the advantages that the amount of the ammonium sulfite and ammonium bisulfite solution with the total concentration of 500-550mg/mL recovered from each batch of sulfur dioxide gas is more, the generated economic value is larger, the economic value of the ammonium sulfite and ammonium bisulfite solution recovered from each batch of sulfur dioxide gas is about 900 yuan, the energy consumption is higher than that of the recovery system adopted by the method, and the content of sulfur dioxide in tail gas is obviously reduced (lower than 10 mg/m) 3 ) And simultaneously, the purposes of environmental protection, energy conservation and cost reduction are realized.
Drawings
FIG. 1 is a block diagram of a sulfur dioxide recovery system in example 1.
The reference numbers are as follows: 1-condenser, 2-pump, 3-first-stage absorption tower, 4-second-stage absorption tower, 5-third-stage absorption tower, 6-fourth-stage absorption tower, 7-first-stage buffer container, 8-second-stage buffer container, 9-third-stage buffer container and 10-fourth-stage buffer container.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the sulfur dioxide gas recovery system and the method thereof according to the present invention are further described in detail below with reference to the following examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are for convenience of description of the present invention only and do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. The terms "connected" and "connected" used herein should be interpreted broadly, and may include, for example, a fixed connection or a detachable connection; they may be directly connected or indirectly connected through intermediate members, and specific meanings of the above terms will be understood by those skilled in the art as appropriate.
The present invention provides a sulfur dioxide gas recovery system, in a specific embodiment of the present invention, as shown in fig. 1, the system comprises: the absorption tower comprises a first-stage absorption tower 3, a second-stage absorption tower 4, a third-stage absorption tower 5, a fourth-stage absorption tower 6, a first-stage buffer container 7, a second-stage buffer container 8, a third-stage buffer container 9, a fourth-stage buffer container 10, a pump 2 and a condenser 1, wherein the first-stage buffer container 7, the second-stage buffer container 8, the third-stage buffer container 9 and the fourth-stage buffer container 10 are used for storing absorption liquid, the pump 2 is used for pumping the absorption liquid in the buffer container into the absorption tower in the corresponding stage, and the condenser 1 is used for cooling the absorption liquid from the buffer container in the corresponding stage, and the first-stage absorption tower 3, the second-stage absorption tower 4, the third-stage absorption tower 5 and the fourth-stage absorption tower 6 are sequentially connected along the direction of sulfur dioxide; along the flowing direction of the absorption liquid, the fourth-stage buffer container 10, the third-stage buffer container 9, the second-stage buffer container 8 and the first-stage buffer container 7 are sequentially connected, so that the liquid in the fourth-stage buffer container 10 can be conveyed to the third-stage buffer container 9, the liquid in the third-stage buffer container 9 can be conveyed to the second-stage buffer container 8, and the liquid in the second-stage buffer container 8 can be conveyed to the first-stage buffer container 7; the absorption liquid outlet of each absorption tower is directly connected with the corresponding inlet of the same-stage buffer container; the absorption liquid inlet of each absorption tower is connected with the corresponding outlet of the same-stage buffer container, and the absorption liquid can circularly flow between the absorption tower and the buffer container of the corresponding stage. The circulation flow of the absorption liquid between the absorption tower and the buffer container of the corresponding grade is realized by the following specific scheme: the buffer container is connected with an inlet of a pump 2, an outlet of the pump 2 is connected with a lower opening of a condenser 1 (namely an inlet of an absorption liquid of the condenser), the absorption liquid enters the condenser 1 through the lower opening of the condenser 1, then flows out of an upper opening of the condenser 1 (namely an outlet of the absorption liquid of the condenser) to enter the absorption tower, and returns to the buffer container after passing through the absorption tower.
The following describes the devices or components involved in the system of the present invention.
The chemical reaction equation for absorbing sulfur dioxide is as follows:
SO 2 +H 2 O＝H 2 SO 3 NH 3 +H 2 O＝NH 4 OH
H 2 SO 3 +NH 4 OH＝NH 4 HSO 3
NH 4 HSO 3 +NH 4 OH＝(NH 4 ) 2 SO 3 (NH 4 ) 2 SO 3 +H 2 SO 3 ＝2NH 4 HSO 3
the primary absorption tower 3 is used for carrying out primary absorption on the sulfur dioxide gas; the secondary absorption tower 4 is used for further absorbing sulfur dioxide gas which is not absorbed by the primary absorption tower 3; the third-stage absorption tower 5 is used for further absorbing sulfur dioxide gas which is not absorbed by the second-stage absorption tower 4; the fourth-stage absorption tower 6 is used for further absorbing sulfur dioxide gas which is not absorbed by the third-stage absorption tower 5, and discharging tail gas into the air.
Preferably, each stage of absorption tower is a circulating absorption tower, and particularly can be a circulating absorption tower with sulfur dioxide tolerance, such as a glass fiber reinforced plastic circulating absorption tower and/or a PVC circulating absorption tower; preferably, the first-stage absorption tower 3 and the second-stage absorption tower 4 are glass fiber reinforced plastic circulating absorption towers; preferably, the third-stage absorption tower 5 and the fourth-stage absorption tower 6 are PVC circulating absorption towers. According to the invention, the glass fiber reinforced plastic circulating absorption tower has excellent corrosion resistance, the content of sulfur dioxide in the first two stages of absorption towers is higher, the absorption tower can be prevented from being corroded by using the glass fiber reinforced plastic circulating absorption tower, the content of sulfur dioxide in the last two stages of absorption towers is lower, and the cost can be reduced by using the PVC circulating absorption tower with lower manufacturing cost.
Preferably, the system further comprises a plurality of pumps 2, and a pump 2 is arranged between each level of absorption tower and the buffer container and is used for pumping the absorption liquid in the buffer container of the level into the absorption tower of the corresponding level.
Preferably, the system further comprises a plurality of condensers 1, the condensers 1 being disposed between the absorption liquid inlet of the absorption tower of each stage and the pump 2, for cooling the absorption liquid from the buffer container of the corresponding stage; preferably, the condenser is a graphite condenser. In the specific embodiment of the invention, the circulation flow of the absorption liquid between the absorption tower and the buffer container of the corresponding grade is realized by the following specific scheme: the buffer container is connected with an inlet of a pump 2, an outlet of the pump 2 is connected with a lower port of a condenser 1, absorption liquid enters the condenser 1 through the lower port of the condenser 1, then enters the absorption tower from an upper port of the condenser 1, and returns to the buffer container after passing through the absorption tower.
Preferably, the temperature of the absorption liquid entering the first-stage absorption tower 3 and the second-stage absorption tower 4 after being cooled by the condenser 1 is more than or equal to 20 ℃, and more preferably 30-40 ℃; preferably, the temperature of the absorption liquid entering the third-stage absorption tower 5 and the fourth-stage absorption tower 6 after being cooled by the condenser 1 is less than or equal to 40 ℃.
In the invention, the concentration of sulfur dioxide in the first-stage absorption tower 3 and the second-stage absorption tower 4 is higher, the concentration of ammonium sulfite generated by the reaction of absorption liquid is also higher, and crystallization is easy to generate due to too low temperature; the concentration of sulfur dioxide is lower in tertiary absorption tower 5 and level four absorption tower 6, does not have the crystallization problem, and the high temperature can make the absorption liquid solubility reduce, still can cause sulfur dioxide and ammonia to spill over, consequently the temperature that gets into the absorption liquid in tertiary absorption tower 5 and the level four absorption tower 6 is less than 40 ℃.
Preferably, the buffer container is a buffer storage tank; specifically, the buffer solution tank may be a buffer solution tank made of a material resistant to sulfurous acid, ammonia water, ammonium sulfite, and ammonium bisulfite, for example, a glass fiber reinforced plastic buffer solution tank. Preferably, the primary buffer container 7 and the secondary buffer container 8 are glass fiber reinforced plastic buffer solution storage tanks; preferably, the third-stage buffer container 9 and the fourth-stage buffer container 10 are PVC buffer storage tanks.
In the invention, sulfur dioxide gas passes through a first-stage absorption tower 3 and a second-stage absorption tower in sequenceThe rear parts of the stage absorption tower 4 and the third stage absorption tower 5 only contain trace sulfur dioxide, and can be completely absorbed by absorption liquid (water) in the fourth stage absorption tower 6, trace ammonia gas entering the fourth stage absorption tower 6 along with sulfur dioxide gas from the third stage absorption tower 5 can also be completely absorbed by the absorption liquid (water) in the fourth stage absorption tower 6, the trace sulfur dioxide and the water generate sulfurous acid, the concentration of the sulfurous acid in the fourth stage buffer container 6 is lower than 50mg/mL, and the content of the sulfur dioxide in tail gas is lower than 10mg/m 3 And the ammonia content is lower than 30mg/m 3 . The invention can ensure that the content of sulfur dioxide in tail gas is lower than 10mg/m by controlling the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid of a first-level buffer container 7 to be less than or equal to 550mg/mL, the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid of a second-level buffer container 8 to be less than or equal to 300mg/mL, the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid of a third-level buffer container 9 to be less than or equal to 200mg/mL and the total concentration of sulfurous acid in the absorption liquid of a fourth-level buffer container 10 to be less than or equal to 50mg/mL, thereby ensuring that the content of sulfur dioxide in tail gas is lower than 10mg/m 3 。
In the invention, water is used as the absorption liquid of the four-stage buffer container 10, thereby avoiding the overproof of substances such as ammonia water and the like in the tail gas, reducing the content of pollutants in the tail gas and directly discharging the tail gas into the air. In the tail gas absorption process, the absorption liquid absorbs a large amount of heat energy, so that the temperature of the absorption liquid is increased, and the solubility of ammonia and sulfur dioxide in the absorption liquid is reduced.
In the preferred embodiment of the invention, the volume of the absorption liquid in the primary buffer container is controlled to be 1/3-1/2 of the volume, and the volume of the absorption liquid in the primary buffer container is lower than 3/4 of the volume of the absorption liquid in the secondary buffer container, on one hand, because the absorption reaction in the primary absorption tower is violent, the volume of the absorption liquid in the primary buffer container is increased quickly in the absorption process, and more space needs to be reserved; on the other hand, the absorption liquid in the first-stage buffer container reaches the upper limit before the absorption liquid in the second-stage, third-stage and fourth-stage buffer containers, the absorption liquid in the first-stage buffer container quickly reaches the standard of recycling, and meanwhile, the absorption liquid in the second-stage, third-stage and fourth-stage buffer containers does not reach the standard of recyclingTo the upper limit of the concentration, the sulfur dioxide content in the tail gas is ensured to be lower than 30mg/m 3 And the absorption liquid in the second-stage, third-stage and fourth-stage buffer containers does not need to be diluted.
Example 1
As shown in fig. 1, according to an embodiment of the present invention, the system includes: the absorption tower comprises a first-stage absorption tower 3, a second-stage absorption tower 4, a third-stage absorption tower 5, a fourth-stage absorption tower 6, a first-stage buffer container 7, a second-stage buffer container 8, a third-stage buffer container 9, a fourth-stage buffer container 10, a condenser 1 and a pump 2, wherein the first-stage buffer container 7, the second-stage buffer container 8, the third-stage buffer container 9 and the fourth-stage buffer container 10 are used for storing absorption liquid, the condenser 1 is used for cooling the absorption liquid entering the absorption tower, and the pump 2 is used for pumping the absorption liquid in the buffer containers into the corresponding same-stage absorption tower, wherein the first-stage absorption tower 3, the second-stage absorption tower 4, the third-stage absorption tower 5 and the fourth-stage absorption tower 6 are sequentially connected along the trend of sulfur dioxide; along the flowing direction of the absorption liquid, a four-stage buffer container 10, a three-stage buffer container 9, a two-stage buffer container 8 and a one-stage buffer container 7 are connected in sequence;
the buffer container of each level links to each other with the 2 import of the pump of this level, the 1 end opening of pump 2 exit linkage condenser, absorption liquid gets into in condenser 1 through the 1 end opening of condenser, absorption liquid goes out from condenser 1 and gets into the absorption tower after the cooling, after the sulfur dioxide contact reaction in the absorption tower, absorption liquid flows back to the buffer container of corresponding level again from the absorption liquid export of absorption tower, and reciprocating cycle makes the absorption liquid in the buffer container get into the absorption tower many times and reacts with the sulfur dioxide, can fully absorb sulfur dioxide.
In this example, 2 3000L PVC buffer solution storage tanks, 2 6000L PVC circulating absorption towers, two 25-stage graphite condensers, and 2 10000L (10 m) graphite condensers were used 3 ) The system comprises a glass fiber reinforced plastic buffer solution storage tank, 2 11000L glass fiber reinforced plastic circulating absorption towers, 2 40-platform graphite condensers and 4 pumps, wherein the 2 glass fiber reinforced plastic circulating absorption towers are respectively used as a primary absorption tower 3 and a secondary absorption tower 4, the 2 glass fiber reinforced plastic absorption solution storage tanks are respectively used as a primary buffer container 7 and a secondary buffer container 8, and the primary absorption tower 3 and the secondary absorption tower 4 respectively use one 40-platform graphite condenser; wherein 2 PVC circulating absorption towers are respectively used as a three-stage absorption tower 5 and a four-stage absorption tower 62 PVC buffer solution storage tanks of 3000 liters were used as the third-stage buffer vessel 9 and the fourth-stage buffer vessel 10, and the third-stage absorption tower 5 and the fourth-stage absorption tower 6 each used a 25-stage graphite condenser.
The first-stage absorption tower 3 and the second-stage absorption tower 4 are main absorption towers, and the third-stage absorption tower 5 and the fourth-stage absorption tower 6 are insurance absorption towers and absorb trace sulfur dioxide gas.
(1) Principle of sulfur dioxide recovery system
The reaction process is as follows:
SO 2 +H 2 O＝H 2 SO 3 NH 3 +H 2 O＝NH 4 OH
H 2 SO 3 +NH 4 OH＝NH 4 HSO 3
NH 4 HSO 3 +NH 4 OH＝(NH 4 ) 2 SO 3 (NH 4 ) 2 SO 3 +H 2 SO 3 ＝2NH 4 HSO 3
(2) absorption process
Respectively adding drinking water into four levels of buffer containers, then introducing liquid ammonia into a first level buffer container 7 and a second level buffer container 8 to generate ammonia water with the pH value of 9.0, introducing liquid ammonia into a third level buffer container 9 to generate ammonia water with the pH value of 7.5, wherein the volume of the ammonia water in the first level buffer container 7 is 4000L, the volume of the ammonia water in the second level buffer container 8 is 6000L, the volume of the ammonia water in the third level buffer container 9 is 2000L, and the volume of the water in the fourth level buffer container 10 is 2000L, introducing sulfur dioxide-containing gas from a first level absorption tower 3, sequentially passing through the first level absorption tower 3, a second level absorption tower 4, a third level absorption tower 5 and a fourth level absorption tower 6, and discharging tail gas from the fourth level absorption tower 6 to a recovery system after passing through the fourth level absorption tower 6. The content of sulfur dioxide in the tail gas is lower than 10mg/m 3 。
By adjusting the pH value of the absorption liquid in the primary buffer container 7 and the secondary buffer container 8 to 8.5-9.5, the concentration of ammonia water can be controlled to be 15% -20%, and the effect of absorbing sulfur dioxide is insufficient when the concentration of ammonia water is too high; on the other hand, the reaction for absorbing sulfur dioxide is too violent, a large amount of heat is emitted, the temperature of the absorption liquid is increased, and the solubility of ammonia and sulfur dioxide in the absorption liquid is reduced.
Passing a gas comprising sulfur dioxide through the recovery system:
(a) the sulfur dioxide is firstly absorbed by the absorption liquid from the primary buffer container 7 in the primary absorption tower 3, and the absorption liquid absorbing the sulfur dioxide returns to the primary buffer container 7 to generate a mixed solution of ammonium bisulfite and ammonium sulfite; (b) then a small amount of sulfur dioxide which is not absorbed in the first-stage absorption tower 3 is further absorbed by the absorption liquid from the second-stage buffer container 8 in the second-stage absorption tower 4, the absorption liquid which absorbs the sulfur dioxide returns to the second-stage buffer container 8, the absorbed sulfur dioxide is continuously increased along with the increase of the circulation times of the absorption liquid in the second-stage buffer container 8 in the second-stage absorption tower 4, and a mixed solution of ammonium bisulfite and ammonium sulfite is slowly formed in the second-stage buffer container 8; (c) similar to the reaction process of the absorption liquid in the secondary buffer container 8, a mixed solution of ammonium bisulfite and ammonium sulfite is also obtained in the tertiary buffer container 9; (d) after the absorption of the first-stage absorption tower 3, the second-stage absorption tower 4 and the third-stage absorption tower 5, the content of sulfur dioxide in the gas entering the fourth-stage absorption tower 6 is very low, so that the absorption liquid of the fourth-stage buffer container 10 is water, the absorption liquid from the fourth-stage buffer container 10 generates a sulfurous acid solution after absorbing the sulfur dioxide in the fourth-stage absorption tower 6, and the concentration of sulfurous acid in the fourth-stage buffer container 10 is lower than 50 mg/ml.
When the total amount of ammonium sulfite and ammonium bisulfite in the absorption liquid of the primary buffer container 7 reaches 500-550mg/ml, the absorption liquid in the primary buffer container 7 is recycled to a reducing agent storage tank to be used as a raw material of analgin intermediate aminoantipyrine, then part of the absorption liquid of the secondary buffer container 8 is supplemented to the primary buffer container 7, part of the absorption liquid of the tertiary buffer container 9 is supplemented to the secondary buffer container 8, part of the absorption liquid of the quaternary buffer container 10 is supplemented to the tertiary buffer container 9, water is added to the quaternary buffer container 10, then water and liquid ammonia are respectively added to the primary buffer container 7 and the secondary buffer container 8 to adjust the pH value to 9.0, water and liquid ammonia are added to the tertiary buffer container 9 to adjust the pH value to 7.5, the volume of the absorption liquid in each stage of buffer container after the pH value is adjusted is the same as the initial state (the volume of the absorption liquid in the primary buffer container 7 is 4000L, the volume of the absorption liquid in the secondary buffer container 8 is 6000L, the volume of the absorption liquid in the tertiary buffer container 9 is 2000L, and the volume of the absorption liquid in the quaternary buffer container 10 is 2000L).
In the process, the absorption liquid in the secondary buffer container 8 absorbs sulfur dioxide to obtain a mixed solution of ammonium bisulfite and ammonium sulfite, the mixed solution is transferred to the primary buffer container 7, liquid ammonia is introduced into the primary buffer container, the pH value is adjusted to be 9, the liquid ammonia generates ammonia water when meeting water, the ammonia water reacts with the ammonium bisulfite to generate ammonium sulfite, at the moment, the solution contains a small amount of ammonium bisulfite, a large amount of ammonium sulfite and ammonia water, and the solution can be stored in the primary buffer container 7 to be continuously used for absorbing sulfur dioxide. The pump 2 pumps the absorption liquid in the primary buffer container 7 to the primary absorption tower 3, the sulfur dioxide pumped in by the fan reacts with the absorption liquid in the primary absorption tower 3 to generate sulfurous acid when meeting water, the sulfurous acid reacts with ammonium sulfite to generate ammonium bisulfite, and the sulfurous acid and ammonia water also generate ammonium bisulfite, so that the effect of continuously recovering the sulfur dioxide is achieved. When the total amount of ammonium sulfite and ammonium bisulfite in the absorption liquid in the primary buffer container 3 reaches again 500-550mg/ml, the absorption liquid is recovered again, and the absorption liquid in the secondary buffer container 8 is supplemented into the primary buffer container 7, the pH value is adjusted, and then the absorption liquid is continuously used for absorbing sulfur dioxide. The sulfur dioxide is mainly absorbed in the first-stage absorption tower 3.
In the above process, the absorption liquid of the third-stage buffer container 9 absorbs sulfur dioxide to obtain a mixed solution of ammonium bisulfite and ammonium sulfite, the mixed solution is transferred to the second-stage buffer container 8, liquid ammonia is introduced into the second-stage buffer container, the pH value is adjusted to 9, the liquid ammonia generates ammonia water when meeting water, and the ammonia water reacts with the ammonium bisulfite to generate ammonium sulfite. The solution thus contains a small amount of ammonium bisulfite and a large amount of ammonium sulfite and ammonia water, and can be stored in the secondary buffer container 8 for continuous absorption of sulfur dioxide. The sulfur dioxide that the first-order absorption tower 3 can not absorb gets into second grade absorption tower 4, here with by pump 2 from the absorption liquid reaction that second grade buffer container 8 was taken out to second grade absorption tower 4, the sulfur dioxide meets water and generates sulfurous acid, sulfurous acid reacts with ammonium sulfite and generates ammonium bisulfite, sulfurous acid also generates ammonium bisulfite with the aqueous ammonia to reach the effect of continuing to retrieve sulfur dioxide, the sulfur dioxide that fails to absorb in first-order absorption tower 3 mainly absorbs in second grade absorption tower 4.
In the above process, the absorption liquid in the four-stage buffer container 10 is a sulfurous acid solution with the concentration of less than 50 mg/ml. Transferring the ammonium sulfite solution into a third-stage buffer container 9, adding ammonia water into the third-stage buffer container, adjusting the pH value to 7.5, and reacting the ammonia water with sulfurous acid to generate ammonium sulfite, wherein the solution mainly contains the ammonium sulfite and the ammonia water and can be stored in the third-stage buffer container 9 for continuously absorbing sulfur dioxide. The sulfur dioxide which cannot be absorbed by the second-stage absorption tower 4 enters the third-stage absorption tower 5, and reacts with the absorption liquid pumped into the third-stage absorption tower 5 from the third-stage buffer container 9 by the pump 2, and the sulfur dioxide meets ammonium sulfite and ammonia water to generate ammonium bisulfite, so that the effect of continuously recovering the sulfur dioxide is achieved. After the sulfur dioxide is absorbed by the first-stage absorption tower 3 and the second-stage absorption tower 4, a small amount of sulfur dioxide is still not absorbed, the small amount of sulfur dioxide is mainly absorbed by the third-stage absorption tower 5, and less sulfur dioxide enters the fourth-stage absorption tower 6. Water is added into the four-stage buffer container 10, sulfur dioxide which cannot be absorbed by the three-stage absorption tower 5 generates sulfurous acid when meeting water in the four-stage absorption tower 6, and the effect of completely absorbing the sulfur dioxide is achieved. The trace sulfur dioxide which cannot be absorbed by the third-level absorption tower 5 is completely absorbed by the fourth-level absorption tower 6, and the steps are repeated in sequence, so that the purpose of complete absorption of the sulfur dioxide is achieved.
In this embodiment, before the absorption liquid in the first-stage buffer container 7 reaches the recovery standard, the concentrations of the absorption liquid in the second-stage buffer container 8, the third-stage buffer container 9, and the fourth-stage buffer container 10 do not exceed the upper concentration limit, and dilution is not required. After the gas containing high-concentration sulfur dioxide is recovered, the content of sulfur dioxide in tail gas is lower than 10mg/m 3 And does not contain ammonia gas, and the recovery rate of sulfur dioxide can reach 100 percent.
The above embodiments are merely examples for clearly illustrating the present invention and do not limit the present invention. Other variants and modifications of the invention, which are obvious to those skilled in the art and can be made on the basis of the above description, are not necessary or exhaustive for all embodiments, and are therefore within the scope of the invention.
Claims (10)
1. A sulfur dioxide gas recovery system, the system comprising: the absorption tower comprises a first-stage absorption tower, a second-stage absorption tower, a third-stage absorption tower and a fourth-stage absorption tower, as well as a first-stage buffer container, a second-stage buffer container, a third-stage buffer container and a fourth-stage buffer container which are used for storing absorption liquid, wherein the first-stage absorption tower, the second-stage absorption tower, the third-stage absorption tower and the fourth-stage absorption tower are sequentially connected along the trend of sulfur dioxide; along the flowing direction of the absorption liquid, the four-stage buffer container, the three-stage buffer container, the two-stage buffer container and the one-stage buffer container are sequentially connected;
the absorption liquid outlet of each absorption tower is directly connected with the corresponding inlet of the same-stage buffer container; the absorption liquid inlet of each absorption tower is connected with the corresponding outlet of the same-stage buffer container, and the absorption liquid can circularly flow between the absorption tower and the buffer container of the corresponding stage.
2. The sulfur dioxide gas recovery system of claim 1, wherein the primary absorber is configured to absorb the sulfur dioxide gas for a first time; the secondary absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the primary absorption tower; the third-stage absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the second-stage absorption tower; the four-stage absorption tower is used for further absorbing sulfur dioxide gas which is not absorbed by the three-stage absorption tower, and the tail gas is discharged into the air.
3. The sulfur dioxide gas recovery system of claim 1, further comprising a plurality of pumps, a pump being provided between each level of absorption tower and the surge vessel for pumping the absorption liquid in the level of surge vessel into the corresponding level of absorption tower; preferably, the system further comprises a plurality of condensers provided between the absorption liquid inlet of the absorption tower of each stage and the pump for cooling the absorption liquid from the buffer container of the corresponding stage; preferably, the condenser is a graphite condenser; preferably, the absorption tower is a circulating absorption tower; preferably, the first-stage absorption tower and the second-stage absorption tower are glass fiber reinforced plastic circulating absorption towers; preferably, the third-stage absorption tower and the fourth-stage absorption tower are PVC circulating absorption towers; preferably, the buffer container is a buffer storage tank; preferably, the first-stage buffer container and the second-stage buffer container are glass fiber reinforced plastic buffer solution storage tanks; preferably, the third-level buffer container and the fourth-level buffer container are PVC buffer solution storage tanks.
4. A method for recovering sulfur dioxide gas with a recovery system according to any one of claims 1 to 3, comprising the steps of:
(1) adding ammonia water as absorption liquid into the first-stage buffer container, the second-stage buffer container and the third-stage buffer container, and adding water as absorption liquid into the fourth-stage buffer container;
(2) introducing gas containing sulfur dioxide from a gas inlet of a first-stage absorption tower, sequentially absorbing the gas by the first-stage absorption tower, a second-stage absorption tower, a third-stage absorption tower and a fourth-stage absorption tower, then discharging the gas out of the recovery system, simultaneously conveying absorption liquid in each stage of buffer container into the corresponding same-stage absorption tower to absorb the sulfur dioxide gas entering the same-stage absorption tower, conveying the absorption liquid absorbing the sulfur dioxide gas from the absorption tower back to the same-stage buffer container, and enabling the absorption liquid to circularly flow between the same-stage buffer container and the absorption tower;
(3) when the total concentration of the ammonium sulfite and the ammonium bisulfite in the absorption liquid of the first-stage buffer container reaches 500-550mg/mL, the absorption liquid in the first-stage buffer container is recovered, and then the absorption liquid of the second-stage buffer container is supplemented into the first-stage buffer container, the absorption liquid of the third-stage buffer container is supplemented into the second-stage buffer container, the absorption liquid of the fourth-stage buffer container is supplemented into the third-stage buffer container, and water is supplemented into the fourth-stage buffer container.
5. The method for recovering sulfur dioxide gas as claimed in claim 4, wherein in the step (3), further comprising: before the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid in the primary buffer container reaches 500-550mg/mL, ensuring that the concentration of the absorption liquid in the secondary buffer container, the tertiary buffer container and the quaternary buffer container does not exceed the upper limit, and when the concentration of the absorption liquid in the secondary buffer container, the tertiary buffer container or the quaternary buffer container reaches the upper limit, diluting the absorption liquid reaching the upper limit of the concentration; preferably, the dilution is: diluting the absorption liquid in the secondary buffer container to pH8.5-9.5 with ammonia water, or diluting the absorption liquid in the tertiary buffer container to pH less than or equal to 8.0 with ammonia water, or diluting the concentration of the sulfurous acid in the absorption liquid in the quaternary buffer container to below 40mg/mL with water; further preferably, ammonia water is used for diluting the absorption liquid in the tertiary buffer container to pH6.0-7.0; preferably, in the step (3), the concentration of the absorption liquid in the first-stage buffer container, the second-stage buffer container and the third-stage buffer container is the total concentration of ammonium sulfite and ammonium bisulfite in the absorption liquid, and the concentration of the absorption liquid in the fourth-stage buffer container is the concentration of sulfurous acid; the upper limit of the concentration of the absorption liquid of the first-stage buffer container is as follows: 550 mg/mL; the upper limit of the concentration of the absorption liquid of the secondary buffer container is as follows: 300 mg/mL; the upper limit of the concentration of the absorption liquid of the third-stage buffer container is as follows: 200 mg/mL; the upper limit of the concentration of the absorption liquid of the four-stage buffer container is as follows: 50 mg/mL.
6. The method for recovering sulfur dioxide gas as claimed in claim 4, wherein in the step (2), the sulfur dioxide-containing gas is introduced from the gas inlet of the first absorption tower, and when the gas is discharged from the recovery system after passing through the first absorption tower, the second absorption tower, the third absorption tower and the fourth absorption tower in sequence, the content of sulfur dioxide in the gas is less than 30mg/m 3 (ii) a More preferably the sulphur dioxide content of the gas is less than 10mg/m 3 (ii) a Further preferably, the ammonia content of said gas is lower than 30mg/m 3 (ii) a Preferably, in the step (2), the temperature of the absorption liquid entering the first-stage absorption tower and the second-stage absorption tower is more than or equal to 20 ℃, and more preferably 30-40 ℃; preferably, the temperature of the absorption liquid entering the three-stage absorption tower and the four-stage absorption tower is less than or equal to40℃。
7. The method for recovering sulfur dioxide gas as claimed in claim 4, wherein in the step (1), the ammonia water is added by introducing water into the primary buffer container, the secondary buffer container and the tertiary buffer container, and then adding liquid ammonia to produce ammonia water; preferably, the pH value of the ammonia water in the primary buffer container and the secondary buffer container is 8.5-9.5; more preferably 9.0; preferably, the pH value of the ammonia water in the third-stage buffer container is 7.0-8.0; preferably, in the step (1), in an initial state, 1/3-1/2 of the volume of the absorption liquid is added into the primary buffer container, and the volume of the absorption liquid in the primary buffer container is less than or equal to 3/4 of the volume of the absorption liquid in the secondary buffer container; preferably, 2/3 with the volume of the absorption liquid being less than or equal to the volume of the absorption liquid is added into the secondary buffer container, the tertiary buffer container and the quaternary buffer container.
8. The method for recovering sulfur dioxide gas as claimed in claim 4, wherein in the step (3), after the absorption liquid of the secondary buffer container is replenished into the primary buffer container, or after the absorption liquid of the tertiary buffer container is replenished into the secondary buffer container, or after the absorption liquid of the quaternary buffer container is replenished into the tertiary buffer container, the pH of the absorption liquid in the primary buffer container, the secondary buffer container and the tertiary buffer container is adjusted; further preferably, after the pH is adjusted, the volume of the absorption liquid in the primary buffer container accounts for 1/3-1/2 of the volume of the absorption liquid, and the volume of the absorption liquid in the primary buffer container is less than or equal to 3/4 of the volume of the absorption liquid in the secondary buffer container; preferably, the volume of the absorption liquid in the secondary buffer container and the tertiary buffer container does not exceed 2/3 of the volume thereof; preferably, in the step (3), the absorption liquid in the fourth-stage buffer container is supplemented to the third-stage buffer container, and after the water is supplemented in the fourth-stage buffer container, the volume of the absorption liquid in the fourth-stage buffer container does not exceed 2/3 of the volume of the absorption liquid.
9. The method for recovering sulfur dioxide gas as claimed in claim 8, wherein said adjusting the pH is adjusting the pH by adding ammonia water or liquid ammonia; preferably, the pH is adjusted to 8.5-9.5 by adjusting the pH of the absorption liquid in the first-stage buffer container and the second-stage buffer container, and the pH of the absorption liquid in the third-stage buffer container is adjusted to be less than or equal to 8.0.
10. The method for recovering sulfur dioxide gas as claimed in claim 4, wherein said sulfur dioxide-containing gas is sulfur dioxide gas generated in the process for preparing aminoantipyrine.
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