CN209276170U - A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the device of calcium sulfate - Google Patents
A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the device of calcium sulfate Download PDFInfo
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- CN209276170U CN209276170U CN201821925824.XU CN201821925824U CN209276170U CN 209276170 U CN209276170 U CN 209276170U CN 201821925824 U CN201821925824 U CN 201821925824U CN 209276170 U CN209276170 U CN 209276170U
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Abstract
The calcium sulfite that the utility model provides in a kind of flue gas desulfurization lime-ash prepares the device of calcium sulfate, including reaction kettle, acid mist absorbing device and acid cycle device, the top of the reaction kettle connect the bottom of the acid mist absorbing device by pipeline；The outlet connection of the acid cycle device is located at the acid solution atomizing nozzle on the acid mist absorbing device top, the entrance connection of the acid cycle device is located at the acid solution recovery port of the acid mist absorbing device bottom, the reaction kettle, acid mist absorbing device and acid cycle device are provided with oxidizing gas entrance, and connect gas source by the oxidizing gas entrance.Entire lime-ash treatment process does not have any pollution.And reaction process is simple and quick, is suitable for industrial applications.
Description
Technical field
The utility model relates to the device that the cigarette calcium sulfate in a kind of flue gas desulfurization lime-ash prepares calcium sulfate, belong to environmental protection and
Waste handles reutilization technology field.
Background technique
Currently, the industries such as China's mandatory requirement electric power, building materials carry out desulfurized treatment to sulfur dioxide (SO2) emissions, it is now existing
Desulfurization technology includes Gypsum Wet, recirculating fluidized bed, Sea water respiratory distress syndrome, desulphurizing and dust-removing integral, semidry method, rotation
Spray drying process, in-furnace calcium spraying tail flue gas humidification activation method, active coke absorption method, electronic beam method etc., in many desulfurization works
In skill technology.It is estimated that the desulfurized gypsum that China is urgently handled reaches tens million of tons or more, the output of recirculating fluidized bed desulfurization ash
Amount is also increasing, and the discharge of desulfurized gypsum and desulfurization ash accumulates land occupation and causes environmental pollution.
In recent years, the comprehensive utilization of desulfurization ash is increasingly by national departments concerned, scientific research institutions and the attention of enterprise,
It not only solves the problems, such as its discharge and the pollution of environment, and is the recycling of resource, mended to a certain extent in certain fields
Fill one of the effective way of china natural resources scarcity.
The comprehensive utilization of desulfurization ash at present is in initial stage, and a large amount of desulfurization ash is temporarily banked up, this disposition
There are the hidden danger of secondary environmental pollution for mode.It is, in general, that the calcium sulfate in Desulphurization is relatively stable, but calcium sulfite is in outside
It may be decomposed under temperature change and acid condition and generate SO2Gas causes secondary atmosphere pollution.In order to accelerate the development of desulfurization technology
And the paces of desulfurized gypsum, desulfurization ash comprehensive utilization, promote health, the fast development of Environmental Protection in China cause, we are most right
Power plant, glass factory, ceramics factory, cement plant semi-dry desulphurization lime-ash in high calcium high-sulfur, main object phase constituent is by CaCO3、
CaSO3·5H2O、Ca(OH)2The characteristics of with the composition such as flyash or silica flour；Calcium sulfite in desulfurization ash is how quick
It is effectively converted into calcium sulfate technical matters and is classified as a special subject study and researched and developed finally by prolonged research and development
The method and device that a kind of cigarette calcium sulfate using in flue gas desulfurization lime-ash prepares calcium sulfate is gone out；To meet China's electric power, build
Demand of the industries such as material to flue gas desulfurization ash Slag treatment.Moreover, the technology and device also can be directly used for calcium sulfite system
Standby calcium sulfate product.
Utility model content
The purpose of this utility model is to provide one kind quickly and effectively to convert sulphur for the calcium sulfite in desulfurization ash
The device of sour calcium.
The utility model solves scheme used by above-mentioned technical problem:
A kind of cigarette calcium sulfate in flue gas desulfurization lime-ash prepares the device of calcium sulfate, including reaction kettle, acid mist absorbing device
With acid cycle device, the top of the reaction kettle connects the bottom of the acid mist absorbing device by pipeline；The acid solution is followed
The outlet connection of loop device is located at the acid solution atomizing nozzle on the acid mist absorbing device top, and the entrance of the acid cycle device connects
Connect the acid solution recovery port positioned at the acid mist absorbing device bottom, the reaction kettle, acid mist absorbing device and acid cycle device
It is provided with oxidizing gas entrance, and gas source is connected by the oxidizing gas entrance.
Preferably, the first oxidizing gas entrance, the outlet of the first emergent gas, slurry are respectively arranged at the top of the reaction kettle
Expect entrance and acid solution entrance, the first emergent gas outlet connects the bottom of the acid mist absorbing device by pipeline, described
First oxidizing gas entrance connection be located at the reactor bottom bubbling device, the reaction kettle be additionally provided with agitating device with
And thermometer and pH meter for monitoring reaction condition.
Preferably, the acid mist absorbing device includes concatenated first grade absorption tower and two-level absorption tower, the first order absorption
Tower is disposed with the second oxidizing gas entrance, the first acid solution recovery port, the first emergent gas entrance, the first acid solution from lower to upper
Atomizing nozzle and the outlet of the second emergent gas；The two-level absorption tower is disposed with third oxidizing gas entrance, from lower to upper
Two acid solution recovery ports, the second emergent gas entrance, the second acid solution atomizing nozzle and the outlet of third emergent gas；The first evolution gas
Body entrance connects the first emergent gas outlet, and the second emergent gas outlet connects the second emergent gas entrance；
The third emergent gas outlet is communicated or is connect three-level absorption tower, the three-level absorption tower Yi Shui with atmosphere by air-introduced machine
As absorbing liquid, it is mainly used for absorbing the ClO that the outlet kind of third emergent gas may be discharged2Gas.
Preferably, the first acid solution atomizing nozzle, the second acid solution atomizing nozzle pass through acid-proof pump and connect the acid cycle
The outlet of device.
Preferably, the acid cycle device includes the first acid solution storage tank, the second acid solution storage tank, third acid solution storage tank and the
Four acid solution storage tanks, first acid solution storage tank and the second acid solution storage tank are in parallel and connect the first acid solution recovery port and the spray of the first acid solution
Mist mouth, the third acid solution storage tank and the 4th acid solution storage tank are in parallel and connect the second acid solution recovery port and the second acid solution atomizing nozzle.
Preferably, the acid cycle device is additionally provided with discharge gate, is provided with blow-off valve at the discharge gate.
Sulfuric acid in reaction kettle with CaCO in lime-ash3、Ca(OH)2Neutralization reaction occurs, generates calcium sulfate, CO2Gas and
H2O；With CaSO3·5H2O reaction generates calcium sulfate and generates SO2Gas, the SO2Gas a part may be hydrolyzed into rapidly
H2SO3, the sulfurous acid is using being passed through ClO2ClO is added dropwise in gas2After the method for aqueous solution makes it be oxidized to sulfate ion, then
With in calcium ion and generate calcium sulfate；Another part, which then escapes reaction kettle, to be brought by air-introduced machine and is absorbed acid solution in acid fog absorption tower
In ClO2Oxidation generates sulfate ion and chloride ion, and the sulfate ion and chloride ion can be used as after reaching certain concentration
Our acid solution uses or corresponding salt can be obtained after directly being neutralized with calcium ion.CO2Gas can be discharged into air,
Entire lime-ash treatment process does not have any pollution.And reaction process is simple and quick, is suitable for industrial applications.
Detailed description of the invention
Fig. 1 is the dress that the utility model one kind quickly and effectively converts the calcium sulfite in desulfurization ash in calcium sulfate
It sets.
Attached drawing mark in figure are as follows:
1, reaction kettle；2, the first oxidizing gas entrance；3, the outlet of the first emergent gas；4, slurry inlet；5, acid solution entrance；
6, bubbling device；7, agitating device；8, thermometer；9, pH meter；10, first grade absorption tower；11, two-level absorption tower；12, the second oxidation
Gas access；13, the first acid solution recovery port；14, the first emergent gas entrance；15, the first acid solution atomizing nozzle；16, the second evolution
Gas vent；17, third oxidizing gas entrance；18, the second acid solution recovery port；19, the second emergent gas entrance；20, the second acid
Liquid atomizing nozzle；21, the outlet of third emergent gas；22, acid-proof pump；23, the first acid solution storage tank；24, the second acid solution storage tank；25, the
Three acid solution storage tanks；26, the 4th acid solution storage tank；27, discharge gate；28, blow-off valve；29, manhole；30, feed opening；31, blow valve；
32, liquidometer.
Specific embodiment
To better understand the utility model, the following examples are the further explanations to the utility model, but this reality
The following examples are not limited solely to novel content.
It is as shown in Figure 1 that the calcium sulfite in desulfurization ash is converted device used by calcium sulfate by the utility model.Packet
Reaction kettle 1, acid mist absorbing device and acid cycle device are included, the top of the reaction kettle 1 connects the acid mist by pipeline and inhales
The bottom of receiving apparatus；The outlet connection of the acid cycle device is located at the acid solution atomizing nozzle on the acid mist absorbing device top,
The entrance connection of the acid cycle device is located at the acid solution recovery port of the acid mist absorbing device bottom, the reaction kettle 1, acid
Mist absorption plant and acid cycle device are provided with oxidizing gas entrance, and connect gas source by the oxidizing gas entrance.
The top of the reaction kettle 1 is respectively arranged with the first oxidizing gas entrance 2, the first emergent gas exports 3, slurry and enters
Mouthfuls 4 and acid solution entrance 5, the first emergent gas outlet 3 connects the bottoms of the acid mist absorbing device by pipeline, and described the
The connection of one oxidizing gas entrance 2 is located at the bubbling device 6 of 1 bottom of reaction kettle, and the reaction kettle 1 is additionally provided with agitating device
7 and thermometer 8 and pH meter 9 for monitoring reaction condition.The acid mist absorbing device includes concatenated first grade absorption tower 10
With two-level absorption tower 11, the first grade absorption tower 10 is disposed with the second oxidizing gas entrance 12, the first acid solution from lower to upper
Recovery port 13, the first emergent gas entrance 14, the first acid solution atomizing nozzle 15 and the second emergent gas outlet 16；The second level absorbs
Tower 11 be disposed with from lower to upper third oxidizing gas entrance 17, the second acid solution recovery port 18, the second emergent gas entrance 19,
Second acid solution atomizing nozzle 20 and third emergent gas outlet 21；The first emergent gas entrance 14 connects the first evolution gas
Body outlet 3,16 connection the second emergent gas entrance 19 of the second emergent gas outlet；The third emergent gas outlet
21 connection atmosphere.The first acid solution atomizing nozzle 15, the second acid solution atomizing nozzle 20 connect the acid solution by acid-proof pump 22 and follow
The outlet of loop device.
The acid cycle device includes the first acid solution storage tank 23, the second acid solution storage tank 24, third acid solution storage tank 25 and the
Four acid solution storage tanks 26, first acid solution storage tank 23 and the second acid solution storage tank 24 are in parallel and connect the first acid solution recovery port 13 and the
One acid solution atomizing nozzle 15, the third acid solution storage tank 25 and 26 parallel connection of the 4th acid solution storage tank simultaneously connect 18 He of the second acid solution recovery port
Second acid solution atomizing nozzle 20.
The acid cycle device is additionally provided with discharge gate 27, is provided with blow-off valve 28 at the discharge gate 27, acid solution is followed
Acid solution in loop device can be recycled or use pulverized limestone or light calcium carbonate powder to neutralize with recovery section sulphur by discharge gate discharge
Sour calcium.
The top of the reaction kettle 1 is provided with manhole 29 and cooling water outlet 30 for observing internal state, instead
The bottom of kettle is answered to be provided with corresponding cooling water inlet.First acid solution storage tank 23, the second acid solution storage tank 24, the storage of third acid solution
The top of tank 25 and the 4th acid solution storage tank 26 is provided with manhole 29 and the blow valve 31 for air-discharging, prevents in pump fluid
During form negative pressure.The liquidometer 32 for monitoring tank level is additionally provided in above-mentioned storage tank.
First acid solution storage tank 23, the second acid solution storage tank 24, third acid solution storage tank 25 and the 4th acid solution storage tank 26 are
The plastic tank of acid corrosion-resistant.
Third emergent gas outlet 21 connects air-introduced machine by pipeline, and is connected to atmosphere by the air-introduced machine.Third ease
Gas vent 21 can also connect three-level absorption tower according to actual needs out, which, as absorbing liquid, is used using water
In the ClO that absorption part may escape2Gas.
By taking certain coal-burning power plant's semi-dry desulphurization lime-ash as an example
1, analyze the CaCO in desulfurization ash3、CaSO3·5H2O、Ca(OH)2Ingredient；It weighs good certain
The lime-ash of quality, and the quality of acid solution needed for full response has been calculated on the basis of calcium content；Excess sulfuric acid
10-30%；
2, it is spare that the concentrated sulfuric acid is made into the sulfuric acid that mass fraction is 20%.
3, resulting amount is calculated according to step 1, dilute sulfuric acid is put into reaction kettle, open acid mist while opening stirring and inhale
Receiving apparatus.
4, according to step 1 calculate resulting amount by Desulphurization ground-slag being added in reaction kettle slowly, sulfuric acid is anti-at this time
Answer kettle interior and CaCO in lime-ash3、Ca(OH)2Neutralization reaction occurs, generates calcium sulfate, CO2Gas and H2O；Sulfuric acid and CaSO3·
5H2O reaction generates calcium sulfate and generates SO2Gas and H2O；Generated SO2A part of SO in gas2Gas reacts life with water
At H2SO3；It adds to be stirred to react after material and is passed through the ClO that volume ratio is 10% after 45 minutes again2Gas；In the environment of strong acid,
SO2Gas or H2SO3Or HSO3 ˉDeng by ClO2Quickly it is oxidized to sulfate ion and chloride ion；It is being passed through ClO2Gas 10 divides
The content of sampling and testing material sulfite in clock, when material sulfite content is lower than 0.5%；Stopping is passed through gas or drop
Add aqueous solution, and continue stir 10-15 minute test kettles in pH value, in sierozem power with kettle in sulfate ion and chlorine from
After son is neutral to pH value, it is pressed into filter cake with filter press, then be beaten washing with tap water is that we obtain three times, after dehydration and drying
To the additive calcium sulfate product that can be used as in cement or ceramics, through detection calcium sulphate content be greater than 97%.Above-mentioned anti-
During answering, perhaps have a small amount of not by ClO2The SO of oxidation2Gas by air-introduced machine brings acid mist into after escaping in whipping process
The ClO being absorbed in absorption tower in acid solution2Oxidation generates sulfate ion and chloride ion；It can be used as me after reaching certain concentration
Acid solution use；CO2Gas is then discharged into air, detects the SO in air-introduced machine exit2Concentration is less than 10mg/M3, entire lime-ash
Treatment process does not have any pollution.
By taking certain glass factory's semi-dry desulphurization lime-ash as an example
1, first analyze the CaCO in desulfurization ash3、CaSO3·5H2O、Ca(OH)2Ingredient, and calculated on the basis of calcium content
The quality and excessive 30% of sulfuric acid needed for reacting completely；
2, the concentration that the concentrated sulfuric acid is made into 30% is spare；
3, resulting amount is calculated according to step 1, dilute sulfuric acid is put into reaction kettle, open stirring while opening acid mist absorption
Device.
4, according to step 1 calculate resulting amount Desulphurization ground-slag being added in reaction kettle slowly, sulfuric acid is anti-at this time
Answer kettle interior and CaCO in lime-ash3、Ca(OH)2Neutralization reaction occurs, generates calcium sulfate, CO2Gas and H2O；With CaSO3·5H2O is anti-
Calcium sulfate should be generated and generate SO2Gas；The SO2Gas a part may be hydrolyzed into rapidly H2SO3；It is a part of then escape reaction
Kettle is brought into absorption tower by air-introduced machine；It after adding material, stirs 30 minutes, the aqueous solution of chlorine dioxide of 20g/l is added into kettle；
Under strong acidic environment, sulfurous acid is promptly by ClO2It is oxidized to sulfate ion and chloride ion；The later period is reacted on a small quantity light
Calcium powder neutralizes these excessive ions；Sulfurous acid after being added aqueous solution of chlorine dioxide 10 minutes, in sampling and testing material
Content stops that aqueous solution of chlorine dioxide is added dropwise after being lower than 0.5%；It is further continued for stirring 15 minutes, pH value is tested, is adjusted with sierozem power
After pH value is in neutrality, with filter press filters pressing, then three times with tap water washing material, dehydration, it is dry after be we to be
It can be used as the additive calcium sulfate product in cement or ceramics, through detecting: calcium sulphate content is greater than 97%.
In above-mentioned reaction process, perhaps have a small amount of not by ClO2The SO of oxidation2After gas overflows in whipping process
Brought in acid fog absorption tower into the ClO being absorbed in acid solution by air-introduced machine2Oxidation generates sulfate ion and chloride ion；The sulfate radical
Ion and chloride ion, which reach, can be used as our acid solution after certain concentration and uses or can obtain after directly being neutralized with calcium ion
To corresponding salt；CO2Gas is then discharged into air, and the content of sulfur dioxide detected in after air-introduced machine is vented is less than 10mg/
m3, entire lime-ash treatment process do not have any pollution.
The above is preferred embodiments of the present invention, certainly cannot with this come limit the utility model it
Interest field, it is noted that for those skilled in the art, before not departing from the utility model principle
It puts, several improvement and variation can also be made, these, which improve and change, is also considered as the protection scope of the utility model.
Claims (6)
1. the device that the calcium sulfite in a kind of flue gas desulfurization lime-ash prepares calcium sulfate, which is characterized in that including reaction kettle, acid mist
Absorption plant and acid cycle device, the top of the reaction kettle connect the bottom of the acid mist absorbing device by pipeline；Institute
The outlet connection for stating acid cycle device is located at the acid solution atomizing nozzle on the acid mist absorbing device top, the acid cycle device
Entrance connection be located at the acid mist absorbing device bottom acid solution recovery port, the reaction kettle, acid mist absorbing device and acid solution
Circulator is provided with oxidizing gas entrance, and connects gas source by the oxidizing gas entrance.
2. device as described in claim 1, which is characterized in that be respectively arranged with the first oxidizing gas at the top of the reaction kettle
Entrance, the outlet of the first emergent gas, slurry inlet and acid solution entrance, the first emergent gas outlet pass through described in pipeline connection
The bottom of acid mist absorbing device, the first oxidizing gas entrance connection is located at the bubbling device of the reactor bottom, described
Reaction kettle is additionally provided with agitating device and thermometer and pH meter for monitoring reaction condition.
3. device as claimed in claim 2, which is characterized in that the acid mist absorbing device include concatenated first grade absorption tower and
Two-level absorption tower, the first grade absorption tower are disposed with the second oxidizing gas entrance, the first acid solution recovery port, from lower to upper
One emergent gas entrance, the first acid solution atomizing nozzle and the outlet of the second emergent gas；The two-level absorption tower is successively set from lower to upper
It is equipped with third oxidizing gas entrance, the second acid solution recovery port, the second emergent gas entrance, the second acid solution atomizing nozzle and third evolution
Gas vent；The first emergent gas entrance connects the first emergent gas outlet, and the second emergent gas outlet connects
Connect the second emergent gas entrance；The third emergent gas outlet is communicated or is connect three-level suction with atmosphere by air-introduced machine
Receive tower.
4. device as claimed in claim 3, which is characterized in that the first acid solution atomizing nozzle, the second acid solution atomizing nozzle are logical
Cross the outlet that acid-proof pump connects the acid cycle device.
5. device as described in claim 3 or 4, which is characterized in that the acid cycle device includes the first acid solution storage tank, the
Two acid solution storage tanks, third acid solution storage tank and the 4th acid solution storage tank, first acid solution storage tank and the second acid solution storage tank are in parallel and connect
Connect the first acid solution recovery port and the first acid solution atomizing nozzle, the third acid solution storage tank and the 4th acid solution storage tank are in parallel and connect second
Acid solution recovery port and the second acid solution atomizing nozzle.
6. device as described in claim 3 or 4, which is characterized in that the acid cycle device is additionally provided with discharge gate, described
Blow-off valve is provided at discharge gate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201821925824.XU CN209276170U (en) | 2018-11-22 | 2018-11-22 | A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the device of calcium sulfate |
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| CN201821925824.XU CN209276170U (en) | 2018-11-22 | 2018-11-22 | A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the device of calcium sulfate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384256A (en) * | 2018-11-22 | 2019-02-26 | 黄冈师范学院 | A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the method and device of calcium sulfate |
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- 2018-11-22 CN CN201821925824.XU patent/CN209276170U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109384256A (en) * | 2018-11-22 | 2019-02-26 | 黄冈师范学院 | A kind of calcium sulfite in flue gas desulfurization lime-ash prepares the method and device of calcium sulfate |
| CN109384256B (en) * | 2018-11-22 | 2023-11-07 | 黄冈师范学院 | Method and device for preparing calcium sulfate from calcium sulfite in flue gas desulfurization ash |
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