CN103301718B - The device of a kind of recovery, concentrated sulfur dioxide in tail gas - Google Patents
The device of a kind of recovery, concentrated sulfur dioxide in tail gas Download PDFInfo
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- CN103301718B CN103301718B CN201310246739.6A CN201310246739A CN103301718B CN 103301718 B CN103301718 B CN 103301718B CN 201310246739 A CN201310246739 A CN 201310246739A CN 103301718 B CN103301718 B CN 103301718B
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- tail gas
- gas
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- deoxidation reactor
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Abstract
A kind of recovery, the device of concentrated sulfur dioxide in tail gas comprises: deoxidation reactor, Quench tank, tail gas absorber, absorbing liquid circulating pump, lean pump, lean solution tank and gas-liquid separator, tail gas enters deoxidation reactor and connects Quench tank by pipeline, gas in deoxidation reactor after deoxidation enters tail gas absorber from bottom to top after Quench cooling, go out the tail gas of tail gas absorber by qualified discharge, the bottom of tail gas absorber is connected with absorbing liquid circulating pump, absorbing liquid circulating pump connects gas-liquid separator and component loops liquid is delivered to gas-liquid separator, and send cycles left liquid back to tail gas absorber, the circulation fluid delivering to gas-liquid separator discharges sulfur dioxide gas and lean solution after resolving.
Description
Technical field
The present invention relates to a kind of recovery and concentrated device, especially for reclaiming and the device of concentrated sulfur dioxide in tail gas.
Background technology
It is a large amount of containing SO that the fields such as metallurgy, thermal power generation and Coal Chemical Industry produce
2tail gas severe contamination is caused to environment.In recent years, country is to SO
2discharge propose more and more stricter requirement, especially " overall control " requirement, even if the enterprise having reached discharging standards also will carry out the desulfurization of the more degree of depth, reduce SO further
2concentration.Meanwhile, because China's Sulphur ressource lacks relatively, for meeting industrial production needs, need a large amount of imported sulphur.Data in recent years show, the demand of China to sulphur is increasing, and major part all will depend on import; Therefore in the case, the more SO reclaimed in tail gas
2just seem particularly economical, make tail gas can qualified discharge on the one hand; Reclaim SO on the other hand
2, turn waste into wealth.
In current tail gas desulfurization technology, Wet Flue Gas Desulfurization Technique is the most ripe and desulfurization degree is the highest, is therefore used widely.And in Wet Flue Gas Desulfurization Technique, most widely used is limestone/lime-gypsum doctor treatment, account for 70% of desulfurization total installed capacity amount.This method is simple, easy, desulfuration efficiency is high.But its major defect is: desulfurization product is gypsum, is mainly used as cement raw material, industrial chemicals, filler etc., utilizes limited, market price only dozens of yuan one ton, stack volume large, be easy to cause secondary pollution, and there is problems such as absorbing wastewater treatment.Especially, this method is at process low concentration SO
2there is desulfuration efficiency during flue gas to reduce, process operation is unstable, the problems such as economic benefit is low.
In order to solve traditional desulfur technology for process low concentration SO
2the deficiency of tail gas, some the relevant SO also in succession occurred both at home and abroad
2recycling technology; Mainly contain WellmanLord doctor treatment, LABSORB regenerating desulfurization method, ClausMaster doctor treatment, CANSOLV regenerable amine process, activated coke method, ionic liquid absorption cycle etc.Wherein, WellmanLord doctor treatment utilizes sodium sulfite solution absorption SO
2, then heat resolve reclaims, and this method desulfuration efficiency is high, but more difficult to the control of oxidation side reaction in sweetening process, and power consumption is higher; LABSORB regenerating desulfurization method adopts the sodium radio-phosphate,P-32 solution prepared by NaOH and phosphoric acid to absorb SO
2, solution thermal regeneration and reclaim high concentration SO
2, this mature technology, absorbent expense is lower, but technological process is long, investment cost is high, electric and steam consumption is relatively high; ClausMaster doctor treatment adopts non-water physical solvent absorption SO
2, then by thermal regeneration, this technique absorption efficiency is high, environmental friendliness, operating cost are low; CANSOLV regenerable amine process adopts reproducible By Amine Solutions as SO
2absorbent, this method advantage is absorbent reusable edible, desulfuration efficiency is high, process gas flow and concentration range is large, by-product SO
2concentration is high, but low-pressure steam and power consumption higher, and need when processing flue gas during smelting to carry out preliminary clearning process to flue gas; Activated coke method is Shanghai Ke Liu environmental protection company desulfurization by dry method newly developed, and its advantage desulfurizing agent can Reusability, desulfurization and efficiency of dust collection is higher, strong adaptability after thermal regeneration, but activated coke loss is large, water, electricity and gas etc. consumes high; Ionic liquid absorption cycle and CANSOLV regenerable amine process type, absorbent adds the aqueous solution of a small amount of activator, antioxidant and corrosion inhibiter composition with organic cation and inorganic anion for main component, this method is applicable to the little tail gas for the treatment of capacity, technique is simple, desulfuration efficiency is high, absorbent loss is little, by-product concentration of SO 2 gas is high, but there is the shortcoming the same with amine method too.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defect existed in above-mentioned prior art, and provides.
For solving the problems of the technologies described above, the device of a kind of recovery, concentrated sulfur dioxide in tail gas, it is characterized in that comprising: deoxidation reactor, Quench tank, tail gas absorber, absorbing liquid circulating pump, lean pump, lean solution tank and gas-liquid separator, tail gas enters deoxidation reactor and connects Quench tank by pipeline, by being equipped with the deoxidation reactor of efficient dehydrogenation catalyst after entering the mix with a certain proportion of H2 containing the tail gas of low-concentration sulfur dioxide of deoxidation reactor, occur wherein to react as follows:
H
2+O
2→H
2O
This reaction more easily occurs, even if do not need heating can carry out at normal temperatures yet, and the deoxidation degree of depth can reach below remaining oxygen 0.1ppm, deoxidation reactor connects Quench tank and Quench tank pipeline connects into tail gas absorber, gas in deoxidation reactor after deoxidation enters tail gas absorber from bottom to top after Quench cooling, contacts with the absorption cycle liquid containing natrium citricum lower from top spray is reverse; Compared to pure water, containing the natrium citricum meeting in the aqueous solution of natrium citricum and H
+form resiliency solution, thus the reduction of restriction pH value, make SO
2solubility increase.Its absorption reaction process can represent by following series reaction:
SO
2(gas) → SO
2(liquid)
SO
2(liquid)+H
2o → H
++ HSO
3 -
Cit
3 -+H
+→HCit
2 -
HCit
2 -+H
+→H
2Cit
-
H
2Cit
-+H
+→H
3Cit
3SO
2+3H
2O+Na
3Cit→3NaHSO
3+H
3Cit
By reflecting the tail gas of tail gas absorber above by qualified discharge, the bottom of tail gas absorber is connected with absorbing liquid circulating pump, and by the pH value of controlled circulation liquid, absorbing liquid circulating pump connects gas-liquid separator
Component loops liquid is delivered to gas-liquid separator, and sends cycles left liquid back to tail gas absorber; The circulation fluid delivering to gas-liquid separator discharges sulfur dioxide gas and lean solution after resolving, and lean solution is delivered to lean solution tank by pipeline and collected, and lean solution tank is connected with lean pump, lean pump is delivered to tail gas absorber and recycles.
Also comprise preheater, preheater is connected between tail gas air inlet and described deoxidation reactor, catalyst carrier in described deoxidation reactor is activated alumina, and before described deoxidation reactor device preheater, activated alumina is a kind of good drier, good hydrophilic property, water is a kind of polar molecule, be easy to be adsorbed to catalyst surface, the active surface of covering catalyst, and hydrogen and Oxygen Adsorption ability are all not as water, so just make catalyst lose activity, before deoxidation reactor, preheater is installed, mist is carried out preheating.
Also comprise rich solution heater, gas product cooler, crystallization tank; Rich solution heater is connected between absorbing liquid circulating pump and gas-liquid separator, the component loops absorbing liquid extracted out from tail gas absorber passes through the Steam Heating of rich solution heater to required resolution temperature, and then by described gas-liquid separator separates, gas product cooler is connected with described gas-liquid separator, the SO of higher temperature
2gas, through supercooling, cooling and separation, obtains the SO that purity is higher
2gas products; The pipeline that lean pump is connected to described tail gas absorber is connected with crystallization tank simultaneously, and a small amount of sodium sulphate byproduct that the oxidation of a small amount of sulfur dioxide dissolving and oxygen in tail gas in plant running process is produced enters crystallization tank and isolates Na
2sO
410H
2o, the lean solution after being separated is back to lean solution groove.
The device of recovery provided by the invention, concentrated sulfur dioxide in tail gas, is applicable to containing low concentration (0.5%-15%) SO
2the process of tail gas; The rate of recovery is high, can reach more than 99%; The tail gas entering device by deoxidation reactor, by tail gas the overwhelming majority (> 99%) O
2remove, citric acid has complexing SO in addition
2effect and make oxygenation efficiency be less than 1%, this just makes absorption tower without the need to adding antioxidant again, decreases accessory substance Na
2sO
410H
2the generation of O; Technological process is simple, easy to operate, and equipment structure is few, and gross investment economizes; Absorbent is renewable, only need be interrupted supplementary in practical operation; By-product SO
2purity is high, and economic benefit is obvious.In view of the needs of China's modernization construction, this invention has wide market prospects, and its release must bring good economic benefit and social benefit.
Accompanying drawing illustrates:
Fig. 1 is the schematic flow sheet reclaiming, concentrate sulfur dioxide in tail gas device.
Detailed description of the invention:
Below in conjunction with accompanying drawing, inventive embodiment is described in further detail.
Embodiment 1: as shown in Figure 1, the device of a kind of recovery, concentrated sulfur dioxide in tail gas comprises: deoxidation reactor 2, Quench tank 3, tail gas absorber 4, absorbing liquid circulating pump 5, lean pump 6, lean solution tank 7 and gas-liquid separator 9, tail gas enters deoxidation reactor 2 and connects Quench tank 3 by pipeline, enters the tail gas containing low-concentration sulfur dioxide of deoxidation reactor 2 and a certain proportion of H
2by being equipped with the deoxidation reactor 2 of efficient dehydrogenation catalyst after mixing, there is following reaction wherein:
H
2+O
2→H
2O
This reaction more easily occurs, even if do not need heating can carry out at normal temperatures yet, and the deoxidation degree of depth can reach below remaining oxygen 0.1ppm, deoxidation reactor 2 connects Quench tank 3 and Quench tank 3 pipeline connects into tail gas absorber, gas in deoxidation reactor 2 after deoxidation enters tail gas absorber 4 from bottom to top after Quench cooling, contacts with the absorption cycle liquid containing natrium citricum lower from top spray is reverse; Compared to pure water, containing the natrium citricum meeting in the aqueous solution of natrium citricum and H
+form resiliency solution, thus the reduction of restriction pH value, make SO
2solubility increase.Its absorption reaction process can represent by following series reaction:
SO
2(gas) → SO
2(liquid)
SO
2(liquid)+H
2o → H
++ HSO
3 -
Cit
3 -+H
+→HCit
2 -
HCit
2 -+H
+→H
2Cit
-
H
2Cit
-+H
+→H3Cit
3SO
2+3H
2O+Na
3Cit→3NaHSO
3+H
3Cit
By reflecting the tail gas of tail gas absorber 4 above by qualified discharge, the bottom of tail gas absorber 4 is connected with absorbing liquid circulating pump 5, by the pH value of controlled circulation liquid, absorbing liquid circulating pump 5 connects gas-liquid separator 9, component loops liquid is delivered to gas-liquid separator 9, and sends cycles left liquid back to tail gas absorber 4; The circulation fluid delivering to gas-liquid separator 9 discharges sulfur dioxide gas and lean solution after resolving, and lean solution is delivered to lean solution tank 7 by pipeline and collected, and lean solution tank 7 is connected with lean pump 6, lean solution 6 is pumped to tail gas absorber 4 and recycles.
Embodiment 2: difference from Example 1 also comprises preheater 1 as shown in Figure 1, preheater 1 is connected between tail gas air inlet and deoxidation reactor 2, catalyst carrier in deoxidation reactor 2 is activated alumina, and before described deoxidation reactor 2 device preheater 1, activated alumina is a kind of good drier, good hydrophilic property, water is a kind of polar molecule, be easy to be adsorbed to catalyst surface, the active surface of covering catalyst, and hydrogen and Oxygen Adsorption ability are all not as water, catalyst is so just made to lose activity, before deoxidation reactor, preheater is installed, mist is carried out preheating.
Embodiment 3: difference from Example 2 also comprises rich solution heater 8, gas product cooler 10, crystallization tank 11 as shown in Figure 1; Rich solution heater 8 is connected between absorbing liquid circulating pump 5 and gas-liquid separator 9, the component loops absorbing liquid extracted out from tail gas absorber 4 passes through the Steam Heating of rich solution heater 8 to required resolution temperature, and then be separated by gas-liquid separator 9, gas product cooler 10 is connected with described gas-liquid separator 9, the SO of higher temperature
2gas, through supercooling, cooling and separation, obtains the SO that purity is higher
2gas products; The pipeline that lean pump is connected to described tail gas absorber is connected with crystallization tank simultaneously, and a small amount of sodium sulphate byproduct that the oxidation of a small amount of sulfur dioxide dissolving and oxygen in tail gas in plant running process is produced enters crystallization tank and isolates Na
2sO
410H
2o, the lean solution after being separated is back to lean solution groove.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the present patent application scope change and improve, and all should still belong within patent covering scope of the present invention.
Claims (2)
1. the device of a recovery, concentrated sulfur dioxide in tail gas, it is characterized in that comprising: deoxidation reactor, Quench tank, tail gas absorber, absorbing liquid circulating pump, lean pump, lean solution tank and gas-liquid separator, tail gas enters deoxidation reactor and connects Quench tank by pipeline, enters the tail gas containing low-concentration sulfur dioxide of deoxidation reactor and a certain proportion of H
2by being equipped with the deoxidation reactor of efficient dehydrogenation catalyst after mixing, there is following reaction wherein:
H
2+O
2→H
2O
This reaction more easily occurs, even if do not need heating can carry out at normal temperatures yet, and the deoxidation degree of depth can reach below remaining oxygen 0.1ppm, deoxidation reactor connects Quench tank and Quench tank pipeline connects into tail gas absorber, gas in deoxidation reactor after deoxidation enters tail gas absorber from bottom to top after Quench cooling, contacts with the absorption cycle liquid containing natrium citricum lower from top spray is reverse; Compared to pure water, containing the natrium citricum meeting in the aqueous solution of natrium citricum and H
+form resiliency solution, thus the reduction of restriction pH value, make SO
2solubility increase, its absorption reaction process can represent by following series reaction:
SO
2(gas) → SO
2(liquid)
SO
2(liquid)+H
2o → H
++ HSO
3 -
Cit
3-+H
+→Hcit
2-
Hcit
2-+H
+→H
2Cit
-
H
2Cit
-+H
+→H
3Cit
3SO
2+3H
2O+Na
3Cit→3NaHSO
3+H
3Cit
By reflecting the tail gas of tail gas absorber above by qualified discharge, the bottom of tail gas absorber is connected with absorbing liquid circulating pump, by the pH value of controlled circulation liquid, absorbing liquid circulating pump connects gas-liquid separator and component loops liquid is delivered to gas-liquid separator, and sends cycles left liquid back to tail gas absorber; The circulation fluid delivering to gas-liquid separator discharges sulfur dioxide gas and lean solution after resolving, and lean solution is delivered to lean solution tank by pipeline and collected, and lean solution tank is connected with lean pump, lean pump is delivered to tail gas absorber and recycles; Also comprise preheater, preheater is connected between tail gas air inlet and described deoxidation reactor, catalyst carrier in described deoxidation reactor is activated alumina, and before described deoxidation reactor device preheater, activated alumina is a kind of good drier, good hydrophilic property, water is a kind of polar molecule, be easy to be adsorbed to catalyst surface, the active surface of covering catalyst, and hydrogen and Oxygen Adsorption ability are all not as water, so just make catalyst lose activity, before deoxidation reactor, preheater is installed, mist is carried out preheating.
2., according to the device of the recovery described in claim 1, concentrated sulfur dioxide in tail gas, it is characterized in that: also comprise rich solution heater, gas product cooler, crystallization tank; Rich solution heater is connected between absorbing liquid circulating pump and gas-liquid separator, the component loops absorbing liquid extracted out from tail gas absorber passes through the Steam Heating of rich solution heater to required resolution temperature, and then by described gas-liquid separator separates, gas product cooler is connected with described gas-liquid separator, the SO of higher temperature
2gas, through supercooling, cooling and separation, obtains the SO that purity is higher
2gas products; The pipeline that lean pump is connected to described tail gas absorber is connected with crystallization tank simultaneously, and a small amount of sodium sulphate byproduct that the oxidation of a small amount of sulfur dioxide dissolving and oxygen in tail gas in plant running process is produced enters crystallization tank and isolates Na
2sO
410H
2o, the lean solution after being separated is back to lean solution groove.
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|---|---|---|---|
| CN201310246739.6A CN103301718B (en) | 2013-06-21 | 2013-06-21 | The device of a kind of recovery, concentrated sulfur dioxide in tail gas |
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|---|---|---|---|
| CN201310246739.6A CN103301718B (en) | 2013-06-21 | 2013-06-21 | The device of a kind of recovery, concentrated sulfur dioxide in tail gas |
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| CN103301718B true CN103301718B (en) | 2016-03-02 |
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| CN103708427A (en) * | 2013-12-19 | 2014-04-09 | 中国平煤神马集团开封兴化精细化工有限公司 | Method for recycling sulfur dioxide tail gas in saccharin production process |
| CN106986313A (en) * | 2017-04-11 | 2017-07-28 | 付永全 | A kind of flue gas desulfurization with citrate solution and sulfur dioxide process for reclaiming |
| CN111450672A (en) * | 2020-03-31 | 2020-07-28 | 陕西聚能新创煤化科技有限公司 | Environment-friendly treatment system and treatment method for desulfurization tail gas and ammonia nitrogen liquid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202046881U (en) * | 2011-03-16 | 2011-11-23 | 建业庆松集团有限公司 | Device for preparing high-concentration liquid SO2 with waste gas containing H2S of rectisol |
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- 2013-06-21 CN CN201310246739.6A patent/CN103301718B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN202046881U (en) * | 2011-03-16 | 2011-11-23 | 建业庆松集团有限公司 | Device for preparing high-concentration liquid SO2 with waste gas containing H2S of rectisol |
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Effective date of registration: 20160511 Address after: 214200, Jiangsu, Wuxi province Yixing Xinzhuang Street industrial concentration zone Patentee after: JIANGSU HENGXIN ENERGY TECHNOLOGY CO., LTD. Address before: 214200, 22 floor, International Economic & Trade Building, 21 education West Road, Yixing, Jiangsu Patentee before: Shao Zhihui |