CN1152734C - Desulfurizing process and apparats with regeneratable desulfurizing agent - Google Patents
Desulfurizing process and apparats with regeneratable desulfurizing agent Download PDFInfo
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- CN1152734C CN1152734C CNB01104022XA CN01104022A CN1152734C CN 1152734 C CN1152734 C CN 1152734C CN B01104022X A CNB01104022X A CN B01104022XA CN 01104022 A CN01104022 A CN 01104022A CN 1152734 C CN1152734 C CN 1152734C
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Abstract
The present invention provides a desulfurizing method and a desulfurizing device thereof. In the method, a desulfurizing agent can be regenerated. The present invention has the advantages of low investment, low operation cost, high desulfurizing efficiency and no secondary pollution and is particularly suitable for the occasions with low electricity price (such as desulphurization in a thermal power station, etc.).
Description
The invention relates to a desulfurization method and a desulfurization device for removing sulfur dioxide in waste gas, in particular to a desulfurization method and a desulfurization device with a reproducible desulfurizing agent.
In boilers and kilns commonly used in the industries of electric power, chemical industry, metallurgy and the like, exhaust gas contains a large amount of sulfur dioxide, which causes serious pollution to the atmosphere and is a main pollution source formed by acid rain. At present, the research of flue gas desulfurization is actively developed at home and abroad, certain progress is made, and some desulfurization technologies and processes are applied and popularized in practical engineering. For example, the lime/limestone-gypsum method is most commonly used, which utilizes the characteristic that lime or limestone can react with sulfur dioxide to perform wet desulfurization and washing on flue gas so as to achieve the purpose of purifying the flue gas; there are other methods such as spray drying, electron beam, etc. However, the methods popularized and applied at present have the defects, for example, the final desulfurization byproduct of the lime/limestone-gypsum method is gypsum which is restricted by the process and the market, cannot be commercialized usually, only occupies land and is discarded to form secondary pollution; in the method for regenerating the desulfurizer by electrolyzing sodium sulfate mentioned in some foreign documents, the defects of difficult treatment of a large amount of by-product dilute sulfuric acid, high cost for purifying to commercial concentrated sulfuric acid, secondary pollution and the like exist; in other desulfurization process methods, some methods have high initial investment, some methods have high operation cost, some methods form secondary pollution, and some methods have low desulfurization efficiency. These disadvantages restrict the development of the desulfurization environmental protection industry.
The invention aims to provide a method for desulfurizing and desulfurizing agent regeneration, which has the advantages of low investment, low operation cost, high desulfurizing efficiency, no secondary pollution, easy recovery of byproducts and high commercial value, and is particularly suitable for occasions with low electricity price (such as power station desulfurization and the like).
In order to achieve the purpose, the technical scheme of the invention is as follows:
a desulfurization method with renewable desulfurizing agents comprises the following steps:
(A) with NaOH and Na2SO3The mixed solution as the main component is used as a desulfurizer to wash and desulfurize the waste gas;
(B) and (3) electrolyzing the desulfurized wastewater to regenerate NaOH, and returning the generated NaOH as a desulfurizer to the step (A) for recycling.
In a preferred embodiment of the present invention, after the step (a) is completed, the desulfurized wastewater is precipitated or filtered, and then the step (B) is performed.
The device for implementing the method of the invention comprises:
at least one desulfurization scrubber 1;
at least one trans-form double-membrane three-chamber electrolytic tank 2, wherein the electrolytic tank 2 consists of an anode chamber, a cathode chamber and an intermediate chamber, the anode chamber and the intermediate chamber are separated by a cation exchange membrane, and the cathode chamber and the intermediate chamber are separated by an anion exchange membrane; the inlet of the anode chamber of the electrolytic cell 2 is connected to the desulfurization scrubber 1 via a first conduit 6, and the outlet of the anode chamber is connected to the top of the desulfurization scrubber 1 via a second conduit 7.
In a preferred embodiment of the present invention, the apparatus further comprises:
at least one wastewater collection tank 3 connected to the bottom end of the desulfurization scrubber 1 through a third conduit 8;
at least one filter 4, into which filter 4 the waste water from the waste water collecting tank 3 is introduced through a fourth conduit 9 equipped with a pump 11, the filter 4 being connected to the inlet of the anode compartment of the electrolytic cell 2 through a first conduit 6.
At least one intermediate tank 5 for introducing the solution in the anode compartment of the electrolytic cell 2 into the intermediate tank 5 through a second conduit 7, the intermediate tank 5 being connected to the desulfurization scrubber 1 through a fifth conduit 10 equipped with a pump 12.
The top of the desulfurization scrubber is provided with at least one gas outlet pipe 13, and the bottom is provided with at least one gas pipeline 14 to be treated.
The intermediate tank 5 is provided with a supplementary conduit 15.
The anode chamber of the electrolytic cell 2 is provided with a gas O2 A delivery pipe 16, a middle chamber provided with a gas SO2A delivery pipe 17, a gas H is arranged in the cathode chamber2And a delivery tube 18.
The outlet and inlet of the intermediate chamber of the electrolytic cell 2 may be connected to form a circuit or may be sealed.
The lead-out port and the lead-in port of the cathode chamber of the electrolytic cell 2 may be connected to each other as a circuit or may be sealed.
By adopting the method and the device, the whole desulfurization and desulfurizing agent electrolysis regeneration process does not generate solid waste and secondary pollution, and the byproduct is high-purity O2、H2、SO2The gas can be processed into various downstream products, so that the market demand is large and the commercial value is high; in addition, the high-concentration NaOH solution is adopted as a desulfurizer to carry out desulfurization, and the desulfurization efficiency is far higher than that of other common desulfurizers; the initial investment of the whole desulfurization and desulfurizer electrolysis regeneration system is relatively low; in addition, it avoids the disadvantage of producing large amounts of dilute sulfuric acid which is difficult to handle in conventional sodium sulfate electrolytic regeneration processes.
FIG. 1 is a flow chart of the apparatus of the present invention.
The invention is explained in more detail below with reference to the figures and examples:
using sodium hydroxide (NaOH) and/or sodium sulfite (Na)2SO3) The solution as the main component is used as a desulfurizer to perform wet scrubbing desulfurization on the flue gas to be treated, and the purified flue gas is discharged to the atmosphere. The desulfurization washing equipment can be any desulfurization equipment capable of using the desulfurizing agentA sulfur tower. The sulfur dioxide in the flue gas and the desulfurizer react as follows:
when CO is present in the flue gas2Then, the following reaction takes place:
when the NaOH is completely consumed, Na2SO3Can be mixed with SO2Further reaction takes place:
it can be seen that Na is contained in the desulfurized wastewater2SO3And NaHSO3Is a solution of main components, and of course, depending on the components in the flue gas, there may be some suspended solids and small amounts of other impurity ions such as SO in the desulfurization waste water4 2-And the like.
In order to ensure better efficiency of electrolytic regeneration of the desulfurizer and reduce electrolytic energy consumption, the high-concentration desulfurizer can be used in a desulfurization washing tower for multiple times of self-circulation or multi-stage washing so as to ensure NaOH and Na2SO3All consumption becomes NaHSO3(ii) a The high-concentration desulfurizer is preferably not diluted, which causes Na in the desulfurization wastewater2SO3And NaHSO3Is lower, thereby increasing the energy consumption of electrolysis.
And introducing the desulfurized wastewater into a trans-form double-membrane three-chamber electrolytic cell for electrolytic regeneration. In order to prolong the service life of the ionic membrane, solid suspended matters in the desulfurization wastewater are separated as far as possible by adopting methods such as filtration and the like before entering the electrolytic bath.
The trans-form double-membrane three-chamber electrolytic cell consists of a cathode chamber, an intermediate chamber and an anode chamber; the cathode chamber and the intermediate chamber are separated by an anion exchange membrane, and the intermediate chamber and the anode chamber are separated by a cation exchange membrane; the electrolytic cathode plate is arranged in the cathode chamber, and the electrolytic anode plate is arranged in the anode chamber; the cathode chamber, the middle chamber and the anode chamber are respectively provided with a liquid inlet, a liquid outlet and a gas outlet; when the electrolytic cell works, the cathode chamber, the intermediate chamber and the anode chamber are respectively provided with certain gas-liquid separation spaces to ensure the escape of gas and the gas-liquid separation, or the gas-liquid separation space of any one of the cathode chamber, the intermediate chamber and the anode chamber can be arranged outside the electrolytic cell, all the chambers of the electrolytic cell are liquid spaces, the gas-liquid separation is realized by adopting an external gas bag, the circulation of liquid is realized by adopting a natural circulation or forced circulation method, and at the moment, a liquid outlet and a gas outlet can be combined into a whole.
Introducing desulfurization wastewater into cathode chamber of electrolytic cellThe outlet solution of the cathode chamber after electrolysis contains NaOH and/or Na2SO3Is used as a main component and is led back to the desulfurization washing tower to be recycled as a desulfurizing agent. The cathode compartment undergoes the following electrolysis reactions:
at the same time, part of the SO3 2-And/or HSO3 -And/or OH-The ions migrate to the intermediate chamber under the influence of the electric field. Due to OH-The ions are recycled as a desulfurizing agent, and OH is reduced for reducing ineffective energy consumption-The proportion of ions migrating to the intermediate chamber. On the premise of ensuring the desulfurization efficiency, the OH content of the cathode chamber is reduced as much as possible-Or by direct use of NaOH and NaHSO3Na formed after neutralization2SO3Is used as a desulfurizing agent for desulfurization.
Dilute sulfuric acid is led into the anode chamber of the electrolytic cell, and water is divided and consumed after electrolysis, so that water needs to be supplemented to the anode chamber, or concentrated sulfuric acid is led out from the liquid leading-out port and led back to the electrolytic cell after water is supplemented. Because the anode chamber solution system of the electrolytic cell forms closed cycle, partial impurity ions will permeate through the ionic membrane to accumulate and concentrate after the electrolytic cell operates for a long time, and therefore, the impurity ions need to be led out by shunting periodically or continuously for treatment so as to ensure the relative stability of the components of the anode chamber solution. The anode compartment undergoes the following electrolytic reactions:
at the same time, H in solution+The ions migrate to the intermediate chamber under the influence of the electric field.
In order to ensure the conductivity of the solution in the anode chamber and reduce energy consumption, a proper amount of neutral conductive medium such as 5% dilute sulfuric acid and the like can be added into the introduced liquid in the anode chamber.
The outlet liquid of the anode chamber can be pumped back to the liquid inlet of the anode chamber after adding a proper amount of water, so as to form a closed cycle.
H transferred from the anode chamber in the intermediate chamber of the electrolytic cell+Can not pass through the anion exchange membrane and is retained in the middle chamber; SO migrating from the cathode compartment3 2-Cannot pass through the cation exchange membrane and is retained in the intermediate chamber. H+And SO3 2-The higher the concentration of (A), the higher the formation of H2SO3Due to H2SO3Low solubility in water to escape SO2. The reaction formula is as follows:
due to H of the intermediate chamber2The more O sets, the more partial export is needed for additional processing.
In order to ensure the conductivity of the solution in the intermediate chamber and reduce energy consumption, a proper amount of neutral conductive medium such as 1% dilute sulfuric acid or dilute sodium sulfate solution can be added into the introduced liquid in the intermediate chamber.
Heating of the intermediate chamber solution may be used to assist in SO2Escape of (3). Produced SO2Has high percentage content, and can be processed into liquid SO after simple treatment2Or 108% oleum. SO (SO)2The post-treatment process of (a) is not included in the scope of the present invention.
The gas-liquid mixture in the intermediate chamber can be separated by an external gas-liquid separation device such as a steam drum, and at the moment, the liquid can be conveyed back to the intermediate chamber by adopting a natural circulation or forced circulation method.
The solution system of the middle chamber of the electrolytic cell forms a closed loop circulation, so that the electrolytic cell operates for a long timeThen part of the impurities such as SO will be generated4 2-Since the ion membrane is permeated and accumulated and concentrated, the ion membrane needs to be periodically or continuously separated and discharged for treatment.
NaOH taken out of the cathode chamber andNa2SO3and returning the obtained product as a desulfurizing agent to the desulfurization washing tower for recycling.
Because the electrolysis process of the anode chamber and the cathode chamber is exothermic reaction, in order to maintain the ideal electrolysis working condition of the electrolytic cell, the temperature of the liquid in the anode chamber, the intermediate chamber and the cathode chamber in the electrolytic cell needs to be controlled, for example, the liquid flow method is controlled and the liquid is cooled in the external circulation process, and the temperature in the electrolytic cell of the catholyte, the intermediate liquid and the anolyte is controlled between 80 ℃ and 85 ℃.
Since the solution is lost during the processes of desulfurization washing, filtration and the like, sodium ions andwater are reduced, so that NaOH and water need to be supplemented in the whole desulfurization and desulfurizer regeneration system.
Containing SO2The flue gas to be treated is led into the desulfurization washing tower 1 through a pipeline 14, and 20 percent of Na2SO3And 1% NaOH mixed solution as a desulfurizer is introduced into the desulfurizer washing tower 1 through the pump 12, and the desulfurizer reacts with sulfur dioxide in flue gas, so that the purposes of washing and purifying the desulfurizer are achieved. The purified flue gas is led out through a pipeline 13.
Containing NaHSO after desulfurization3The main desulfurization waste water is led into the cathode chamber of the electrolytic cell 2 after passing through a waste water collecting tank 3, a pump 11 and a filter 4, meanwhile, 1% dilute sulfuric acid is led into the middle chamber of the electrolytic cell through a pipeline 19, and 5% dilute sulfuric acid is led into the anode chamber of the electrolytic cell 2 through a pipeline 21.
Electrifying for electrolysis, and regenerating desulfurizing agents NaOH and Na in cathode chamber2SO3The mixed solution is introduced into the intermediate tank 5, and introduced into the desulfurization scrubber 1 by the pump 12 for recycling. During electrolysis, it is ensured that the gas-liquid spaces of the cathode chamber, the intermediate chamber and the anode chamber are relatively stable, the liquid in the intermediate chamber is led out in an overflow mode through a pipeline 20, the liquid in the anode chamber is led out in an overflow mode through a pipeline 22, the hydrogen gas is led out through a pipeline 18, the oxygen gas is led out through a pipeline 16, and the SO is led out2The gas is conducted out through a pipe 17.
Make-up water and make-up NaOH solution are led from line 15 to intermediate tank 5 to make up for the reduction due to run-off.
Claims (10)
1. A desulfurization method with renewable desulfurizing agents comprises the following steps:
(A) with NaOH and Na2SO3The mixed solution as the main component is used as a desulfurizer to wash and desulfurize the waste gas;
(B) and (3) electrolyzing the desulfurized wastewater to regenerate NaOH, and returning the generated NaOH as a desulfurizer to the step (A) for recycling.
2. The desulfurization method with regenerable desulfurization agent according to claim 1, characterized in that after said step (A) is completed, the desulfurized waste water is precipitated or filtered and then subjected to said step (B).
3. An apparatus for implementing the method of claim 1, the apparatus comprising:
at least one desulfurization scrubber (1);
at least one trans-form double-membrane three-chamber electrolytic tank (2), wherein the electrolytic tank (2) consists of an anode chamber, a cathode chamber and an intermediate chamber, the anode chamber and the intermediate chamber are separated by a cation exchange membrane, and the cathode chamber and the intermediate chamber are separated by an anion exchange membrane; the inlet of the anode chamber of the electrolytic cell (2) is connected with the desulfurization washing tower (1) through a first conduit (6), and the outlet of the anode chamber is connected with the top end of the desulfurization washing tower (1) through a second conduit (7).
4. The apparatus of claim 3, further comprising:
at least one waste water collection tank (3) connected to the bottom end of the desulfurization scrubber (1) by a third conduit (8);
at least one filter (4) into which the waste water from the waste water collecting tank (3) is introduced by means of a fourth conduit (9) equipped with a pump (11), the filter (4) being connected to the inlet of the anode compartment of the electrolytic cell (2) by means of a first conduit (6).
5. The apparatus of claim 3, further comprising:
at least one intermediate tank (5) for introducing the solution in the anode compartment of the electrolytic cell (2) into the intermediate tank (5) through a second conduit (7), the intermediate tank (5) being connected to the desulfurization scrubber (1) through a fifth conduit (10) equipped with a pump (12).
6. The apparatus according to claim 3, characterized in that the desulfurization scrubber is provided with at least one gas outlet duct (13) at the top and at least one gas duct (14) to be treated at the bottom.
7. The apparatus as claimed in claim 3, characterised in that the intermediate tank (5) is provided with a supplementary conduit (15).
8. The apparatus according to claim 3, characterized in that the anode compartment of the electrolytic cell (2) is provided with a gas O2A delivery pipe (16), the intermediate chamber being provided with a gas SO2A delivery pipe (17), a gas H is arranged in the cathode chamber2A delivery pipe (18).
9. The apparatus according to claim 3, characterized in that the outlet and inlet of the intermediate chamber of the electrolytic cell (2) are connected with conduits (19), (20), respectively.
10. The apparatus according to claim 3, characterized in that the outlet and inlet of the cathode chamber of the electrolytic cell (2) are connected with the conduits (21) and (22), respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01104022XA CN1152734C (en) | 2001-02-16 | 2001-02-16 | Desulfurizing process and apparats with regeneratable desulfurizing agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01104022XA CN1152734C (en) | 2001-02-16 | 2001-02-16 | Desulfurizing process and apparats with regeneratable desulfurizing agent |
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| CN1369325A CN1369325A (en) | 2002-09-18 |
| CN1152734C true CN1152734C (en) | 2004-06-09 |
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| CN103691276B (en) * | 2013-12-10 | 2016-03-16 | 武汉钢铁(集团)公司 | A kind of method and device improving vacuum potassium carbonate desulfurization technique alkali wash section alkali lye utilization rate |
| CN106731562B (en) * | 2015-11-19 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of integrated conduct method and device of high concentration organic exhaust gas containing chlorine |
| CN105413428B (en) * | 2015-11-27 | 2018-05-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Amine process flue gas desulfurization technique |
| CA3226605A1 (en) * | 2021-08-06 | 2023-02-09 | Sebastian Nis Bay Villadsen | System and method for purification of gasses such as fuel gasses |
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Owner name: SHENZHEN KELEIEN BLUE-SKY TECHNOLOGY CO., LTD Free format text: FORMER OWNER: SHENZHEN KELEIEN ENVIRONMENTAL TECHNOLOGY CO., LTD Effective date: 20030326 |
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