CN1382513A - Desulfurizing process and equipment able to regenerates sulfurizing agent - Google Patents
Desulfurizing process and equipment able to regenerates sulfurizing agent Download PDFInfo
- Publication number
- CN1382513A CN1382513A CN 01115418 CN01115418A CN1382513A CN 1382513 A CN1382513 A CN 1382513A CN 01115418 CN01115418 CN 01115418 CN 01115418 A CN01115418 A CN 01115418A CN 1382513 A CN1382513 A CN 1382513A
- Authority
- CN
- China
- Prior art keywords
- chamber
- desulfurization
- conduit
- anode
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
A desulfurizing process and equipment features that its desulfurizing agent can be regenerated. Its advantages are high desulfurizing efficiency and no secondary pollution.
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 double-anode membrane three-chamber electrolytic cell 2, wherein the electrolytic cell 2 consists of a cathode chamber, an intermediate chamber and an anode chamber, the cathode chamber and the intermediate chamber are separated by a cation exchange membrane, and the intermediate chamber and the anode chamber are separated by another cation exchange membrane; the inlet of the intermediate chamber of the electrolytic cell 2 is connected to the desulfurization scrubber 1 via a first conduit 6, the outlet of the intermediate chamber is connected to the inlet of the cathode chamber via a second conduit 7, and the outlet of the cathode chamber leads the regenerated desulfurization agent back to the desulfurization scrubber via a third conduit 8.
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 fourth conduit 9;
at least one filter 4, into which filter 4 the waste water from the waste water collecting tank 3 is introduced through a fifth conduit 10 equipped with a pump 12, the filter 4 being connected to the inlet of the intermediate chamber of the electrolytic cell 2 through a first conduit 6.
At least one intermediate tank 5 for introducing the solution in the cathodic compartment of the electrolyzer 2 into the intermediate tank 5 through a third conduit 8, the intermediate tank 5 being connected to the desulfurization scrubber 1 through a sixth conduit 11 equipped with a pump 13.
The top of the desulfurization washing tower is provided with at least one gas outlet pipe 14, and the bottom of the desulfurization washing tower is provided with at least one gas pipeline 15 to be treated.
The intermediate tank 5 is provided with a supplementary conduit 16.
The cathode chamber is provided with a hydrogen gas outlet pipe 20, and the middle chamber is provided with a gas SO2An oxygen delivery pipe 21 is arranged on the anode chamber of the delivery pipe 17.
The outlet and inlet of the anode chamber of the electrolytic cell 2 are respectively connected with a conduit 18 and a conduit 19.
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 systemis 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 apparatus may be any desulfurization tower capable of using the desulfurizing agent. 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 double-anode 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 double-anode 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 a cation exchange membrane, and the intermediate chamber and the anode chamber are also 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 so as 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, the chambers of the electrolytic cell are all liquid spaces, the gas-liquid separation is realized by adopting an external gas bag, the circulation of the liquid is realized by adopting a natural circulation or forced circulation method, and at the moment, the liquid outlet and the gas outlet can be integrated into a whole, and the arrangement method is more suitable for the arrangement of the anode chamber.
The desulfurized wastewater is introduced into an intermediate chamber of the electrolytic cell, Na in the intermediate chamber+And migrate to the cathode compartment under the influence of the electric field.
The desulfurized wastewater is led to the cathode chamber from the intermediate chamber, and after electrolysis, the outlet solution of the cathode chamber 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:
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 anode chamber solution 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+HSO with intermediate chamber3 2-、SO3 2-Generation of H2SO3Due to H2SO3Low solubility in water to escape SO2. The reaction formula is as follows:
in order to ensure the conductivity of the solution in theintermediate 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)2Is not included in the scope of the inventionAnd (5) enclosing.
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.
NaOH and Na derived from the cathode compartment2SO3And returning the obtained product as a desulfurizing agent to the desulfurization washing tower for recycling.
Since the solution is lost during the processes of desulfurization washing, filtration and the like, sodium ions and water are reduced, so that NaOH and water need to be supplemented in the whole desulfurization and desulfurizer regeneration system.
The whole desulfurization process is shown in figure 1 and contains SO2The flue gas to be treated is led into the desulfurization washing tower 1 through a pipeline 15, and 20 percent of Na2SO3And 1% NaOH as a desulfurizing agent is introduced into the desulfurizing washing tower 1 through a sixth conduit 11 with a pump 13, wherein the desulfurizing agent and the flue gas are mixedThe sulfur dioxide is reacted to achieve the aim of desulfurization, washing and purification. The cleaned flue gas is led out through a duct 14.
Containing NaHSO after desulfurization3The main desulfurization waste water is guided into the middle chamber of the electrolytic cell 2 and then into the cathode chamber after passing through a waste water collecting tank 3, a pump 12 and a filter 4, and meanwhile, 5 percent dilute sulfuric acid is guided into the anode chamber of the electrolytic cell 2 through a pipeline 19.
Electrifying for electrolysis, and regenerating desulfurizing agents NaOH and Na in cathode chamber2SO3The mixed solution is led into an intermediate storage tank 5 through a third conduit 8, and led into a desulfurization washing tower 1 through a sixth conduit 11 with a pump 13 for recycling. During electrolysis, it is necessary to ensure that the gas-liquid spaces of the cathode chamber, the intermediate chamber and the anode chamber are relatively stable, the liquid in the anode chamber is led out in an overflow mode through a pipeline 18, the hydrogen is led out through a pipeline 20, the oxygen is led out through a pipeline 21, and the SO is led out through a pipeline 212The gas is conducted out through a pipe 17.
Make-up water and make-up NaOH solution are led from line 16 to intermediate tank 5 to make up for the reduction due to run-off.
Claims (9)
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 double-anode-membrane three-chamber electrolytic tank (2), wherein the electrolytic tank (2) consists of a cathode chamber, an intermediate chamber and an anode chamber, the cathode chamber and the intermediate chamber are separated by a cation exchange membrane, the intermediate chamber and the anode chamber are separated by another cation exchange membrane, an electrolytic cathode plate is arranged in the cathode chamber, and an anode plate is arranged in the anode chamber; the inlet of the intermediate chamber of the electrolytic cell (2) is connected with the desulfurization scrubber (1) through a first conduit (6), the outlet of the intermediate chamber is connected with the inlet of the cathode chamber through a second conduit (7), and the outlet of the cathode chamber leads the regenerated desulfurizer back to the desulfurization scrubber through a third conduit (8).
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 fourth conduit (9);
at least one filter (4) into which the waste water from the waste water collection tank (3) is introduced by means of a fifth conduit (10) equipped with a pump (12), the filter (4) being connected by means of a first conduit (6) to the inlet of the intermediate chamber ofthe electrolytic cell (2).
5. The apparatus of claim 3, further comprising:
at least one intermediate tank (5) to which the solution in the cathodic compartment of the electrolytic cell (2) is introduced by means of a third conduit (8), the intermediate tank (5) being connected to the desulfurization scrubber (1) by means of a sixth conduit (11) equipped with a pump (13).
6. The plant according to claim 3, characterized in that said desulfurization scrubber is equipped with at least one gas outlet duct (14), at least one duct (15) for the gas to be treated.
7. The apparatus as claimed in claim 3, characterised in that the intermediate tank (5) is provided with a supplementary conduit (16).
8. The apparatus according to claim 3, characterized in that the cathode compartment of the electrolytic cell (2) is provided with a hydrogen gas outlet (20) and the intermediate compartment is provided with a gaseous SO2An outlet pipe (17), and an oxygen outlet pipe (21) is arranged on the anode chamber.
9. The apparatus according to claim 3, characterized in that the outlet and inlet of the anode chamber of the electrolytic cell (2) are connected with conduits (18), (19), respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01115418 CN1248770C (en) | 2001-04-24 | 2001-04-24 | Desulfurizing process and equipment able to regenerates sulfurizing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01115418 CN1248770C (en) | 2001-04-24 | 2001-04-24 | Desulfurizing process and equipment able to regenerates sulfurizing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1382513A true CN1382513A (en) | 2002-12-04 |
| CN1248770C CN1248770C (en) | 2006-04-05 |
Family
ID=4661956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01115418 Expired - Fee Related CN1248770C (en) | 2001-04-24 | 2001-04-24 | Desulfurizing process and equipment able to regenerates sulfurizing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1248770C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985069A (en) * | 2010-09-25 | 2011-03-16 | 湖南涟钢申达环保科技有限公司 | Harmless treatment process of waste desulfurizer |
| CN104722177A (en) * | 2015-02-04 | 2015-06-24 | 中国华能集团清洁能源技术研究院有限公司 | Carbon dioxide capturing system for concentration conversion and electrolysis regeneration |
| CN109758878A (en) * | 2019-04-02 | 2019-05-17 | 余海晏 | A kind of industrially desulfurized device of high-efficiency circulation type based on ion exchange |
-
2001
- 2001-04-24 CN CN 01115418 patent/CN1248770C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985069A (en) * | 2010-09-25 | 2011-03-16 | 湖南涟钢申达环保科技有限公司 | Harmless treatment process of waste desulfurizer |
| CN104722177A (en) * | 2015-02-04 | 2015-06-24 | 中国华能集团清洁能源技术研究院有限公司 | Carbon dioxide capturing system for concentration conversion and electrolysis regeneration |
| CN104722177B (en) * | 2015-02-04 | 2017-05-31 | 中国华能集团清洁能源技术研究院有限公司 | A kind of carbon dioxide capture system for concentrating conversion and electrolytic regeneration |
| CN109758878A (en) * | 2019-04-02 | 2019-05-17 | 余海晏 | A kind of industrially desulfurized device of high-efficiency circulation type based on ion exchange |
| CN109758878B (en) * | 2019-04-02 | 2021-08-27 | 邢台嘉泰环保科技有限公司 | High-efficiency circulating industrial desulfurization device based on ion exchange |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1248770C (en) | 2006-04-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102502993B (en) | Method for treating acidic heavy metal wastewater and recycling treated wastewater | |
| CN111924807A (en) | Method and device for trapping carbon dioxide and simultaneously producing sulfuric acid by sodium bisulfate | |
| CN102101010B (en) | Electrolysis circulating flue gas desulfurization method utilizing reclamation semidry method | |
| CN106630027A (en) | Method and system for treating high-chlorine desulfurization waste water by electrolytic method and performing flue gas mercury pollution control | |
| JP2006326458A (en) | Desulfurization method and apparatus of exhaust gas containing sulfur oxide | |
| CN102205203A (en) | Desulfuration and mercury-removing combined smoke purifying process and system based on magnesium oxide method desulfuration process | |
| CN102992351A (en) | Method and device for purifying ammonia recovered from coal chemical industry wastewater | |
| CN104773864A (en) | Pretreatment technology of industrial wastewater with high sulfur content | |
| CN1572359A (en) | Desulfurizing method and apparatus of sulfur coated oxide | |
| CN1339332A (en) | Sulphur dioxide removing electrolysis process | |
| CN1152734C (en) | Desulfurizing process and apparats with regeneratable desulfurizing agent | |
| CN1248770C (en) | Desulfurizing process and equipment able to regenerates sulfurizing agent | |
| CN1974430A (en) | Method of recovering and regenerating waste gas desulfurizing and defluorinating absorbent liquid continuously | |
| CN1225303C (en) | Method for controlling flue gas contaiing SO2 with NaCl and producing high concentratino SO2 | |
| CN1706538A (en) | Regeneration process of pregnant absorbing solution and washing solution for the alkaline desulfurizing procedure of SO2 containing gas | |
| CN1243598C (en) | Waste gas desulfurizing method and apparatus | |
| CN1159086C (en) | Desulphurizing method and device with regenerable desulfurising agent | |
| CN214437868U (en) | Two-stage tandem type alkali washing treatment equipment for copper smelting waste gas | |
| CN1223399C (en) | Desulfurizing process and equipment with regeneratable sulfurizing agent | |
| CN114684794B (en) | Claus tail gas treatment system and treatment method | |
| CN212383460U (en) | Treatment system for absorbing tail gas sulfur dioxide gas | |
| CN209193691U (en) | A kind of equipment handling industrially desulfurized waste water using stack gases | |
| CN113213685A (en) | Desulfurization product sulfur recycling treatment process | |
| CN1311054A (en) | Electrolytic method for removing sulfur from gas | |
| CN1382515A (en) | Electrolyzing process and equipment for desulfurizing sodium chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN KELEIEN BLUE-SKY TECHNOLOGY CO., LTD Free format text: FORMER OWNER: SHENZHEN KELEIEN ENVIRONMENTAL TECHNOLOGY CO., LTD Effective date: 20030313 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20030313 Applicant after: Shenzhen Kelein Lantian Technology Co., Ltd. Applicant before: Keleien Environment Science and Technology Co Ltd, Shenzhen City |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060405 Termination date: 20130424 |