CN116139675A - Dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower and operation treatment method thereof - Google Patents

Dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower and operation treatment method thereof Download PDF

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CN116139675A
CN116139675A CN202111391314.5A CN202111391314A CN116139675A CN 116139675 A CN116139675 A CN 116139675A CN 202111391314 A CN202111391314 A CN 202111391314A CN 116139675 A CN116139675 A CN 116139675A
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slurry
tower
aeration
pipe
dry
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赵岩
邵春岩
王坚
陈刚
陈明
曾乐
张广鑫
裴江涛
赵阳
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Shenyang Academy Environmental Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/346—Controlling the process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80—Semi-solid phase processes, i.e. by using slurries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/608—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention relates to a dry method and semi-dry method desulfurization ash double-tank aeration oxidation tower and an operation treatment method thereof, which are characterized in that: the whole device consists of an aeration tower and SO 2 The device comprises an absorption tower, a first aeration disc, a second aeration disc, a first slurry pump, a second slurry pump, a first blower, a second blower, an acid liquid pump, a first stirrer, a second stirrer and the like; decomposing the conventional one-step oxidation process into multiple steps, precisely controlling the pH of the slurry in each step, and simultaneouslyBinding SO 2 Reabsorption measures not only avoid CaSO 3 Large scale decomposition and SO 2 Secondary pollution and ensure sufficient amount of CaSO 3 In a liquid phase reaction system, the problem of slow oxidation rate caused by high alkalinity of the dry method and the semi-dry method desulfurization ash is finally solved, and the clean and efficient modification is creatively realized.

Description

Dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower and operation treatment method thereof
Technical Field
The invention belongs to the technical field of resources and environment, relates to stabilization modification and resource utilization of dry and semi-dry desulfurization ash, in particular to a double-tank aeration oxidation tower for the dry and semi-dry desulfurization ash, and also provides a working method of the device.
Background
In recent years, because of the high importance of China on ecological environment protection and SO 2 The emission requirements are becoming strict, and the flue gas desulfurization process is widely popularized and applied in industries such as coal-fired power plants, steel sintering, industrial boilers, petrochemical industry and the like, wherein the dry-method and semi-dry-method desulfurization process represented by CFB, LIFAC, NID, SDA, CDSI has the advantages of small occupied area, low investment, low operation cost, low energy consumption, no wastewater and waste acid emission and the like, and has become the trend of the future development of the flue gas desulfurization technology.
The dry and semi-dry desulfurizing process features that powdered or granular calcium-base absorbent is used to remove SO from fume 2 The desulfurization product is dry powder and mainly comprises CaSO 3 ·1/2H 2 O、CaCO 3 、CaSO 4 ·2H 2 O and small amounts of unreacted Ca (OH) 2 Etc. Compared with wet desulfurization process, the dry desulfurization process and the semi-dry desulfurization process produce the de-sulfurizationThe sulfur ash has much more complex components, has the characteristics of high sulfur, high calcium and high alkalinity, and is especially CaSO 3 The components with poor chemical stability cause the dry method and the semi-dry method desulfurization ash to show unusual physicochemical properties. Because the research on the properties, reaction characteristics and action mechanisms of the solid waste is not enough and deep, at present, people have a plurality of judicious attitudes on comprehensive utilization of the solid waste, and no effective utilization way is formed, so that the dry and semi-dry desulfurization ash is accumulated in a large amount or is simply buried, a large amount of precious land resources are occupied, the burden of enterprises is increased, and the further popularization and application of the dry and semi-dry desulfurization process are restricted. In addition, due to CaSO 3 Instability of (C) is extremely prone to SO after long-term stacking 2 Is a potential threat to the environment; meanwhile, as the particle size of the dry method and the semi-dry method desulfurization ash is smaller, the mass is lighter, and once the desulfurization ash is blown by wind, dust pollution can be generated.
For the comprehensive utilization of dry and semi-dry desulfurization ash, the related work at home and abroad at present does not form a complete system, the obtained results belong to research properties, any large-scale industrialized application technology is not formed yet, and the reason is mainly that the method comprises the following four aspects:
(1) The chemical composition of the desulphurized ash is very complex. The phase composition of the common dry method and semi-dry method desulfurization ash comprises CaSO 4 、CaSO 3 、CaCO 3 、Ca(OH) 2 、CaO、MgCO 3 The components are complex and various in chemical properties, so that the comprehensive utilization is more limited and more difficult.
(2) The content of each component of the desulfurized fly ash fluctuates greatly. Due to the differences of operation, running and management levels of different enterprise equipment, the differences of different raw material types and batching schemes, the differences of desulfurization efficiency of different desulfurization processes and the differences of coal-fired components of different batches, the contents of components of desulfurization ash generated by different desulfurization equipment and different time periods of the same equipment can be greatly fluctuated. Such fluctuations bring about frequent changes in the overall chemical properties, which make its comprehensive utilization very difficult.
(3) The chemical nature of the various components in the desulphurized ash is not stable. CaSO in desulfurized fly ash 3 、Ca(OH) 2 And CaO, are unstable in chemical properties and change with environmental and time changes. CaSO (Caso-like conductor) 3 In an acidic environment or under the high temperature condition of neutral or reducing atmosphere, the SO is decomposed easily 2 And released again to cause secondary pollution of the environment, and simultaneously CaSO 3 Will oxidize to CaSO in air 4 Resulting in instability of the properties of the desulfurized ash material over long periods of use. CaO absorbs water very easily to generate Ca (OH) 2 Causes volume non-uniform expansion, ca (OH) 2 Reabsorption of CO from air 2 To generate CaCO 3 . These instabilities create a major obstacle to the comprehensive utilization of the desulfurization ash.
(4) CaSO in desulfurized fly ash 3 Is very high in CaSO 3 The effect and mechanism of the action of (a) are not clear. CaSO in dry and semi-dry desulfurization ash 3 Can be up to 50% or more, and CaSO 3 The influence on the overall mechanical properties and stability of the material is yet to be further studied and confirmed. For example, when the desulfurized fly ash is used as a cement retarder, caSO 3 The retarding effect of (2) and the influence on the cement mechanical property are still in great dispute.
In summary, under the new background of the huge promotion of the construction of the 'no-waste city' and 'double-carbon' targets in China, the harmless and deep recycling of the desulfurization ash by the dry method and the semi-dry method are realized by large-scale scientific treatment, so that the method is not only the technical problems to be solved in the industries of coal-fired power plants, steel sintering, industrial boilers, petrochemical industry and the like in China, but also the promotion of ecological civilization construction in China, the promotion of high-quality development and the realization of the necessary requirements of comprehensive resource conservation and recycling are promoted.
Based on the basic chemical principles of acid-base neutralization and oxidation reduction, the dry-method and semi-dry-method desulfurization ash is subjected to forced oxidation modification in a sulfuric acid environment, so that the four problems of limiting the large-scale comprehensive utilization of the solid waste can be solved at one time: caCO in desulfurized fly ash under the action of acid-base neutralization reaction 3 、Ca(OH) 2 Alkaline components such as CaOAll are rapidly converted into CaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the Under the action of oxidation reaction, caSO with poor stability 3 Will also be converted into CaSO 4 . Thus, the dry method and semi-dry method desulfurization ash with complex and various original components and unstable contents and chemical properties of various components is converted into a stable CaSO 4 As a major component, the chemical properties of the solid waste are similar to those of wet desulfurization gypsum. Because the technical problems of all links in the comprehensive utilization of the wet desulfurization gypsum are basically solved, the modified dry desulfurization ash and the modified semi-dry desulfurization ash can be comprehensively utilized on a large scale according to various technical routes of the wet desulfurization gypsum, thereby thoroughly solving the increasingly urgent treatment problem of the bulk solid waste. Meanwhile, the recycling of the waste sulfuric acid is realized.
However, due to SO 3 2- Will be in excess of H + Bind to form pollutant SO 2 The pH of the reaction solution must not be too low; at the same time, the dissolution process of the desulfurization ash can lead the pH value of the solution to be rapidly increased due to the strong alkalinity of the desulfurization ash, while the CaSO 3 The solubility of (c) is low and further decreases with increasing pH, so that the oxidation rate decreases considerably, and the solid-to-liquid ratio of the dissolution process, i.e. the pH of the solution, cannot be too high. In conclusion, the high-efficiency oxidation of the dry-method and semi-dry-method desulfurization ash is realized in a one-step method and conventional slurry mode, and meanwhile, SO is not contained 2 Release is very difficult and there is a need to develop innovative oxidative modification devices and methods that adapt to the characteristics of the desulfurization ash.
Disclosure of Invention
In order to solve the technical problems in the background technology, the invention provides the dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower which has the advantages of low cost, stable operation, convenient construction and flexible operation and the operation treatment method thereof.
In order to achieve the purpose, the invention provides a dry method and semi-dry method desulfurization ash double-tank aeration oxidation tower, which has the technical key points that:
the whole device consists of an aeration tower and SO 2 Absorption tower, first aeration disc, second aeration disc, first slurry pump, second slurry pump, first blower, second drumFan, acid-liquid pump, first agitator, second agitator, first desulfurization ash inlet pipe, second desulfurization ash inlet pipe, first flexible joint, second flexible joint, first oxidation tuber pipe, second oxidation tuber pipe, first blast pipe, second blast pipe, first liquid level meter flange, second liquid level meter flange, first manometer flange, second manometer flange, first pH probe flange, second pH probe flange, first thermometer flange, second thermometer flange, first densimeter flange, second densimeter flange, reabsorption thick liquid merging pipe, first thick liquid discharge pipe, second thick liquid discharge pipe, acidizing fluid inlet pipe, first clear water inlet pipe, second clear water inlet pipe, first manhole, second manhole are constituteed.
The first aeration disc and the second aeration disc are respectively arranged on the aeration tower and the SO 2 An inner bottom surface of the absorption tower; the first stirrer and the second stirrer are respectively arranged on the aeration tower and the SO 2 The inner low position of the absorption tower is respectively positioned above the first aeration disc and the second aeration disc; the first desulfurization ash feeding pipe, the first flexible joint, the first exhaust pipe, the first liquid level meter flange and the first pressure meter flange are arranged at the top of the aeration tower; the second desulfurized ash feed pipe, the second flexible joint, the second exhaust pipe, the second liquid level meter flange and the second pressure meter flange are arranged on the SO 2 The top of the absorption tower; the first pH probe flange and the second pH probe flange are respectively and equidistantly arranged on the aeration tower and the SO from top to bottom 2 The side wall of the absorption tower; the first thermometer flange and the second thermometer flange are respectively arranged on the aeration tower and the SO 2 The side wall of the middle part of the absorption tower; the first densimeter flange and the second densimeter flange are respectively arranged on the aeration tower and the SO 2 The side wall of the middle lower part of the absorption tower; the reabsorption slurry merging pipe, the acid liquid feeding pipe, the first clear water feeding pipe and the first manhole are all arranged on the side wall of the lower part of the aeration tower; the second clear water feeding pipe and the second manhole are arranged on the SO 2 The lower side wall of the absorption tower; the first oxidation air pipe and the first slurry discharge pipe are arranged at the bottom of the aeration tower; the second oxidation air pipe and the second slurry discharge pipe are all arranged on the SO 2 The bottom of the absorption tower.
The inlet of the first slurry pump is connected with the first slurry discharge pipe and the clear water pipe through a three-way pipeline, and the outlet of the first slurry pump is connected with the first clear water feed pipe and the gypsum dehydration unit through a three-way pipeline; the inlet of the second slurry pump is connected with a second slurry discharge pipe and a clear water pipe through a three-way pipeline, and the outlet of the second slurry pump is connected with a second clear water feed pipe and a reabsorption slurry merging pipe through a three-way pipeline; the outlets of the first blower and the second blower are respectively connected with the first aeration disc and the second aeration disc through the first oxidation air pipe and the second oxidation air pipe; the inlet of the second air blower is connected with the first exhaust pipe; the outlet of the acid liquor pump is connected with an acid liquor feeding pipe; the first flexible joint and the second flexible joint are respectively connected with the first desulfurization ash feeding pipe and the second desulfurization ash feeding pipe.
The aeration tower and SO 2 The absorption towers are all vertical cylinders, and the height-diameter ratio is 2-10.
The first aeration disc and the second aeration disc are arranged in a rectangular array, a circumferential array or a radial array.
The first stirrer and the second stirrer are both bottom-in type.
The first blower and the second blower are respectively Roots blower or centrifugal blower.
The acid liquid pump adopts a metering pump.
The first flexible joint and the second flexible joint are both made of rubber corrugated pipes.
The number of the first pH probe flange and the second pH probe flange is 3-10, and the first pH probe flange and the second pH probe flange are respectively arranged along the aeration tower and the SO 2 The absorption towers are arranged at equal intervals from top to bottom in the height direction.
The second exhaust pipe is provided with SO 2 And an on-line monitoring device.
The invention also provides a working method of the double-tank aeration oxidation tower for the dry and semi-dry desulfurization ash, which is characterized in that: the method comprises the following eleven steps:
step one: and (5) analyzing and testing raw materials. Analyzing and testing the components of the dry and semi-dry desulfurization ash to determine CaSO therein 3 And the content of various strongly basic compounds.
Step two: alkali liquor preparation. Only open the inlet and outlet clear water pipelines of the second slurry pump, and utilize the second slurry pump to feed the SO 2 Injecting clear water into the absorption tower when the liquid level is higher than the total liquid levelAfter 2/3~3/4 of (2), stopping feeding clear water; feeding the desulfurized fly ash into the SO through the second flexible joint and the second desulfurized fly ash feed pipe by using a pipe chain or a screw conveyor 2 An absorption tower; continuously operating the second stirrer to ensure that the desulfurized fly ash and the clean water are quickly and fully mixed and dissolved to finally form the pH value>10, and thereafter stopping the desulfurized fly ash feed.
Step three: acid liquor preparation. Waste sulfuric acid with low heavy metal and organic pollutant content and mass fraction of 1% -95% is gradually injected into the aeration tower by using the acid pump; only opening a clear water pipeline at the inlet and outlet of the first slurry pump, and injecting clear water into the aeration tower by using the first slurry pump; continuously operating the first stirrer to enable the waste sulfuric acid and the clean water to be quickly and fully mixed and dissolved; and stopping feeding the waste sulfuric acid and the clean water after the pH value of the solution in the tower is stabilized between 2.2 and 4.2 and the liquid level is higher than 2/3~3/4 of the total liquid level.
Step four: and (5) desulfurizing and acidifying. Feeding the desulfurization ash into an aeration tower through the first flexible joint and a first desulfurization ash feeding pipe by utilizing a pipe chain or a screw conveyor; under the action of the first stirrer, the desulfurized fly ash entering the tower is subjected to the rapid and sufficient mixing, dissolving and reacting processes with the acid liquor; and stopping feeding the desulfurization ash when the pH value of the solution is raised to 3.1-6.2 and is kept stable.
Step five: and (5) forced oxidation. Continuously operating the first blower, wherein the first blower sends air into the first aeration disc through a first oxidation air pipe, and the air is injected into the solution in the step four in the form of a large number of tiny bubbles; under the action of the first stirrer, the bubbles rise in a spiral manner, so that the contact time with the solution is further increased, and the full mass transfer process is completed; HSO in solution at this time 3 - Will be O 2 Oxidation to SO 4 2- Releasing H + Thereby lowering the pH of the solution.
Step six: and (5) secondary acidification. When the pH value of the solution in the fifth step tends to be stable, starting the acid liquid pump, and gradually adding the waste sulfuric acid in the third step into the aeration tower; under the action of the first stirrer, the waste sulfuric acid entering the tower is rapidly and fully mixed with the solution, the reaction process is completed, the pH value of the solution is reduced to 2.2-4.2 again, and then the acid liquid pump is turned off.
Step seven: a multi-step cycle. Repeating the steps four to six continuously to ensure that the solution in the step six gradually has solid-phase CaSO 4 Separating out and finally forming the slurry with the solid content of 6% -30%.
Step eight: and partially discharging slurry. When the slurry liquid level or density in the step seven reaches a certain value, only opening an inlet slurry pipeline and an outlet dehydration unit pipeline of the first slurry pump, discharging a part of slurry by using the first slurry pump, and delivering the slurry into a dehydration unit to produce gypsum products; in the pulp discharging process, the liquid level in the aeration tower is kept to be 2/3~3/4 higher than the total liquid level; and after the slurry discharge is completed, the first slurry pump is closed, and an inlet slurry pipeline and an outlet dehydration unit pipeline of the first slurry pump are closed.
Step nine: SO (SO) 2 And (5) re-absorption. In multi-step cyclic oxidation, especially secondary acidification, there may be local pH of the slurry that is too low, resulting in incompletely oxidized SO 3 2- With excess H + Binding to release SO 2 In the case of (a), this part of SO 2 Discharging through said first exhaust pipe; continuously operating the second blower to make the part of SO through the second oxidation air pipe 2 Feeding into said second aeration tray, which carries SO 2 Injecting the alkaline slurry of the second step in the form of a plurality of fine bubbles; under the action of the second stirrer, the bubbles rise in a spiral shape, further increasing the contact time with the slurry, thereby completing SO 2 And (3) a reabsorption process.
Step ten: and (5) merging the reabsorption slurry. With the alkaline slurry of the second step continuously absorbing SO 2 The pH value of the water is gradually reduced; and when the alkaline slurry is reduced to below 8.5, after the secondary acidification in the step six is completed, only opening an inlet slurry pipeline and an outlet reabsorption slurry merging pipeline of the second slurry pump, and sending the alkaline slurry into an aeration tower by using the second slurry pump for merging oxidation treatment.
Step eleven: and finishing the modification. And continuously repeating the second step, the fourth step and the tenth step, and finally finishing the oxidative modification of all the dry-method and semi-dry-method desulfurized ash.
Compared with the prior art, the invention has the following beneficial effects:
(1) Based on the optimal solid-liquid ratio, the pH value of the acidified slurry in the whole oxidation process is always controlled to be 2.2-6.2, so that the CaSO in the desulfurized fly ash can be avoided to the maximum extent 3 Decompose to release SO 2 And can ensure enough CaSO 3 In a liquid phase reaction system, thereby remarkably improving the reaction rate of the whole oxidation process.
(2) The conventional one-step oxidation process is decomposed into multiple steps, and the problem of slow oxidation rate caused by the high alkalinity of the dry method and the semi-dry method desulfurization ash is solved by precisely controlling the solid-to-liquid ratio and the slurry pH of each step of oxidation process, so that the high-efficiency oxidation of the high alkalinity desulfurization ash is creatively realized.
(3) The method can realize the resource utilization of the dry method and the semi-dry method desulfurization ash and the waste sulfuric acid at the same time, thereby achieving the purposes of treating waste with waste and cooperatively recycling, and obtaining better economic and environmental benefits.
(4) Adopts a double-tank reactor type, utilizes a second tank body to make SO 2 And reabsorption is carried out, so that the risk of secondary pollution is further reduced.
(5) The flexible joint can effectively relieve harmful vibration transferred between the desulfurization ash conveying equipment and the reaction tower while ensuring the tightness of the system, and improves the safety and stability of the operation of the system.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a cross-sectional view taken along line A-A of FIG. 1;
FIG. 3 shows a semi-dry desulfurization ash and 80% concentrated H in a certain iron and steel plant 2 SO 4 The reagent is used as raw material, the pH regulation acidification and forced oxidation laboratory test is carried out according to the step method of the invention, and when the solid content of the final slurry reaches 10%, the slurry is derived from CaSO 3 S balance diagram of (2).
The reference numerals in fig. 1 are as follows: 1-aeration tower, 2-SO 2 Absorption tower, 3-first aerationThe tray, 4-second aeration tray, 5-first slurry pump, 6-second slurry pump, 7-first blower, 8-second blower, 9-acid pump, 10-first stirrer, 11-second stirrer, 12-first desulfurization ash feed pipe, 13-second desulfurization ash feed pipe, 14-first flexible joint, 15-second flexible joint, 16-first oxidation air pipe, 17-second oxidation air pipe, 18-first exhaust pipe, 19-second exhaust pipe, 20-first liquid level meter flange, 21-second liquid level meter flange, 22-first pressure meter flange, 23-second pressure meter flange, 24-first pH probe flange, 25-second pH probe flange, 26-first thermometer flange, 27-second thermometer flange, 28-first densimeter flange, 29-second densimeter flange, 30-reabsorption slurry merging pipe, 31-first slurry outlet pipe, 32-second slurry outlet pipe, 33-acid feed pipe, 34-first clear water, 35-second inlet pipe, 36-second manhole, 37-second inlet pipe.
Detailed Description
The invention will be further described with reference to the drawings and the specific examples.
As shown in figures 1-2, the invention relates to a dry method and semi-dry method desulfurization ash double-tank aeration oxidation tower, which comprises an aeration tower 1 and SO 2 The absorption tower 2, the first aeration disc 3, the second aeration disc 4, the first slurry pump 5, the second slurry pump 6, the first blower 7, the second blower 8, the acid liquid pump 9, the first stirrer 10, the second stirrer 11, the first desulfurized ash feed pipe 12, the second desulfurized ash feed pipe 13, the first flexible joint 14, the second flexible joint 15, the first oxidation air pipe 16, the second oxidation air pipe 17, the first exhaust pipe 18, the second exhaust pipe 19, the first liquid level meter flange 20, the second liquid level meter flange 21, the first pressure meter flange 22, the second pressure meter flange 23, the first pH probe flange 24, the second pH probe flange 25, the first thermometer flange 26, the second thermometer flange 27, the first densimeter flange 28, the second densimeter flange 29, the reabsorption slurry merging pipe 30, the first slurry exhaust pipe 31, the second slurry exhaust pipe 32, the acid liquid feed pipe 33, the first clear water 34, the second clear water 35, the first person hole 36, the second person inlet pipe 37.
A first aeration disc 3 and a second aeration disc 4 are respectively arranged on the aeration tower 1 and the SO 2 An inner bottom surface of the absorption tower 2; the first stirrer 10 and the second stirrer 11 are respectively arranged on the aeration tower 1 and the SO 2 The lower part of the absorber 2 is respectively positioned above the first aeration disc 3 and the second aeration disc 4; the first desulfurized ash feed pipe 12, the first flexible joint 14, the first exhaust pipe 18, the first liquid level meter flange 20 and the first pressure meter flange 22 are arranged at the top of the aeration tower 1; the second desulfurized ash feed pipe 13, the second flexible joint 15, the second exhaust pipe 19, the second liquid level meter flange 21 and the second pressure meter flange 23 are arranged on the SO 2 The top of the absorption tower 2; the first 24 and the second pH probe flange 25 are respectively and equidistantly arranged on the aeration tower 1 and the SO from top to bottom 2 The side wall of the absorption tower 2; a first thermometer flange 26 and a second thermometer flange 27 are respectively arranged on the aeration tower 1 and the SO 2 The middle side wall of the absorption tower 2; a first 28 and a second densimeter flange 29 are respectively arranged on the aeration tower 1 and the SO 2 The middle lower side wall of the absorption tower 2; the reabsorption slurry merging pipe 30, the acid liquid feeding pipe 33, the first clear water feeding pipe 34 and the first manhole 36 are all arranged on the side wall of the lower part of the aeration tower 1; the second clean water inlet pipe 35 and the second manhole 37 are all arranged on the SO 2 The lower side wall of the absorption tower 2; the first oxidation air pipe 16 and the first slurry discharge pipe 31 are arranged at the bottom of the aeration tower 1; the second oxidation air pipe 17 and the second slurry discharge pipe 32 are all arranged at SO 2 The bottom of the absorption column 2.
The inlet of the first slurry pump 5 is connected with the first slurry discharge pipe 31 and the clean water pipe through a three-way pipeline, and the outlet is connected with the first clean water feed pipe 34 and the gypsum dehydration unit through a three-way pipeline; the inlet of the second slurry pump 6 is connected with a second slurry discharge pipe 32 and a clear water pipe through a three-way pipeline, and the outlet is connected with a second clear water feed pipe 35 and a reabsorption slurry merging pipe 30 through a three-way pipeline; the outlets of the first blower 7 and the second blower 8 are respectively connected with the first aeration disc 3 and the second aeration disc 4 through a first 16 and a second oxidation air pipe 17; the inlet of the second blower 8 is connected with a first exhaust pipe 18; the outlet of the acid pump 9 is connected with an acid liquid feeding pipe 33; the first 14 and the second flexible joint 15 are respectively connected with the first 12 and the second desulfurization ash feeding pipe 13.
The aeration tower 1 andSO 2 the absorption towers 2 are all vertical cylinders, and the height-diameter ratio is 2-10.
The first aeration disc 3 and the second aeration disc 4 are arranged in a rectangular array, a circumferential array or a radial array.
The first stirrer 10 and the second stirrer 11 are both bottom-in type.
The first blower 7 and the second blower 8 are respectively a Roots blower or a centrifugal blower.
The acid liquid pump 9 adopts a metering pump.
The first flexible joint 14 and the second flexible joint 15 are both made of rubber corrugated pipes.
The number of the first 24 and the second pH probe flanges 25 is 3-10, and the first and the second pH probe flanges are respectively arranged along the aeration tower 1 and the SO 2 The absorption towers 2 are arranged at equal intervals from top to bottom in the height direction.
The second exhaust pipe 19 is provided with SO 2 And an on-line monitoring device.
A working method of a dry method and semi-dry method desulfurization ash double-tank aeration oxidation tower is characterized in that: the method comprises the following eleven steps:
step one: and (5) analyzing and testing raw materials. Analyzing and testing the components of the dry and semi-dry desulfurization ash to determine CaSO therein 3 And the content of various strongly basic compounds.
Step two: alkali liquor preparation. Only open the inlet and outlet clear water pipelines of the second slurry pump 6, and utilize the second slurry pump 6 to feed the SO 2 Injecting clear water into the absorption tower 2, and stopping feeding the clear water when the liquid level is higher than 2/3~3/4 of the total liquid level; feeding the desulfurization ash into the SO through the second flexible joint 15 and the second desulfurization ash feeding pipe 13 by using a pipe chain or a screw conveyor 2 An absorption tower 2; continuously operating the second stirrer 11 to make the desulfurized fly ash and the clean water quickly and fully mixed and dissolved, and finally forming the pH value>10, and thereafter stopping the desulfurized fly ash feed.
Step three: acid liquor preparation. Waste sulfuric acid with low heavy metal and organic pollutant content and mass fraction of 1% -95% is gradually injected into the aeration tower 1 by utilizing the acid pump 9; only the clean water inlet pipeline and the clean water outlet pipeline of the first slurry pump 5 are opened, and clean water is injected into the aeration tower 1 by using the first slurry pump 5; continuously operating the first stirrer 10 to enable the waste sulfuric acid and the clean water to be quickly and fully mixed and dissolved; and stopping feeding the waste sulfuric acid and the clean water after the pH value of the solution in the tower is stabilized between 2.2 and 4.2 and the liquid level is higher than 2/3~3/4 of the total liquid level.
Step four: and (5) desulfurizing and acidifying. Feeding the desulfurization ash into the aeration tower 1 through the first flexible joint 14 and the first desulfurization ash feeding pipe 12 by using a pipe chain or a screw conveyor; under the action of the first stirrer 10, the desulfurized fly ash entering the tower is subjected to rapid and sufficient mixing, dissolving and reacting processes with the acid liquor; and stopping feeding the desulfurization ash when the pH value of the solution is raised to 3.1-6.2 and is kept stable.
Step five: and (5) forced oxidation. Continuously operating the first blower 7, wherein the first blower 7 sends air into the first aeration disc 3 through a first oxidation air pipe 16, and the air is injected into the solution in the step four in the form of a large number of tiny bubbles; under the action of the first stirrer 10, the bubbles rise in a spiral shape, further increasing the contact time with the solution, thereby completing the full mass transfer process; HSO in solution at this time 3 - Will be O 2 Oxidation to SO 4 2- Releasing H + Thereby lowering the pH of the solution.
Step six: and (5) secondary acidification. When the pH value of the solution in the fifth step tends to be stable, starting the acid liquid pump 9, and gradually adding the waste sulfuric acid in the third step into the aeration tower 1; under the action of the first stirrer 10, the waste sulfuric acid entering the tower is rapidly and fully mixed with the solution and reacted, the pH value of the solution is reduced to 2.2-4.2 again, and then the acid liquid pump 9 is closed.
Step seven: a multi-step cycle. Repeating the steps four to six continuously to ensure that the solution in the step six gradually has solid-phase CaSO 4 Separating out and finally forming the slurry with the solid content of 6% -30%.
Step eight: and partially discharging slurry. When the slurry liquid level or density in the step seven reaches a certain value, only opening an inlet slurry pipeline and an outlet dehydration unit pipeline of the first slurry pump 5, discharging a part of slurry by using the first slurry pump 5, and delivering the slurry into a dehydration unit to produce a gypsum product; in the pulp discharging process, the liquid level in the aeration tower 1 is kept to be 2/3~3/4 higher than the total liquid level; after the slurry discharge is completed, the first slurry pump 5 and the inlet slurry pipeline and the outlet dewatering unit pipeline thereof are closed.
Step nine: SO (SO) 2 And (5) re-absorption. In multi-step cyclic oxidation, especially secondary acidification, there may be local pH of the slurry that is too low, resulting in incompletely oxidized SO 3 2- With excess H + Binding to release SO 2 In the case of (a), this part of SO 2 Will be discharged through said first exhaust pipe 18; continuously operating the second blower 8, and the second blower 8 uses the second oxidation air pipe 17 to make the part of SO 2 Into said second aeration tray 4, which carries SO 2 Injecting the alkaline slurry of the second step in the form of a plurality of fine bubbles; under the action of the second agitator 11, the bubbles rise in a spiral, further increasing the contact time with the slurry, thus completing the SO 2 And (3) a reabsorption process.
Step ten: and (5) merging the reabsorption slurry. With the alkaline slurry of the second step continuously absorbing SO 2 The pH value of the water is gradually reduced; when the temperature is reduced to below 8.5, and after the secondary acidification in the step six is completed, only an inlet slurry pipeline and an outlet reabsorption slurry merging pipeline of the second slurry pump 6 are opened, and alkaline slurry is sent into the aeration tower 1 by using the second slurry pump 6 for merging oxidation treatment.
Step eleven: and finishing the modification. And continuously repeating the second step, the fourth step and the tenth step, and finally finishing the oxidative modification of all the dry-method and semi-dry-method desulfurized ash.
The raw components of semi-dry desulfurization ash in a certain iron and steel plant are shown in table 1. The pH regulation acidification and forced oxidation test are carried out according to the step method of the invention, and when the solid content of the final slurry reaches 10%, the final slurry is derived from CaSO 3 The S balance of (2) is shown in figure 3. Table 2 shows the components of the oxidized products obtained. It can be seen that the main component in the original semi-dry desulfurization ash is CaSO 3 And CaCO (CaCO) 3 39.65% and 32.77%, respectively, of thisIn addition to a certain amount of MgCO 3 And Ca (OH) 2 Iso-overbased components, caSO 4 Is very low. By the step method, almost all CaSO in the original semi-dry desulfurization ash 3 ，CaCO 3 And Ca (OH) 2 Are all converted into dihydrate CaSO 4 Simultaneous SO 2 Has little escape amount, and the dihydrate CaSO in the oxidized product 4 The content of the modified polyethylene reaches 93.97%, and a good modification effect is obtained.
TABLE 1 raw ingredients of semi-dry desulfurization ash (dry basis)
Figure DEST_PATH_IMAGE002
TABLE 2 composition of oxidized products (dry basis)
Figure DEST_PATH_IMAGE004
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The embodiments described above are intended to facilitate a thorough understanding and enabling use of the invention by those skilled in the art. It will be apparent to those having ordinary skill in the art that the general principles described herein may be applied to other embodiments without the need for inventive faculty by various modifications to these embodiments. Therefore, the present invention is not limited to the above-described embodiments, and modifications made by those skilled in the art without departing from the scope of the invention should be included in the scope of the invention in light of the present teachings.

Claims (9)

1. A dry method, semi-dry method desulfurization ash double tank body aeration oxidation tower, its characterized in that: the whole device consists of an aeration tower and SO 2 The absorption tower, the first aeration disc, the second aeration disc, the first slurry pump, the second slurry pump, the first blower, the second blower, the acid liquid pump, the first stirrer, the second stirrer, the first desulfurization ash feeding pipe, the second desulfurization ash feeding pipe, the first flexible joint, the second flexible joint, the first oxidation air pipe, the second oxidation air pipe, the first exhaust pipe, the second exhaust pipe, the first liquid level meter flange and the firstThe device comprises a second liquid level meter flange, a first pressure meter flange, a second pressure meter flange, a first pH probe flange, a second pH probe flange, a first thermometer flange, a second thermometer flange, a first densimeter flange, a second densimeter flange, a reabsorption slurry merging pipe, a first slurry discharge pipe, a second slurry discharge pipe, an acid liquid feed pipe, a first clear water feed pipe, a second clear water feed pipe, a first manhole and a second manhole;
the first aeration disc and the second aeration disc are respectively arranged on the aeration tower and the SO 2 An inner bottom surface of the absorption tower; the first stirrer and the second stirrer are respectively arranged on the aeration tower and the SO 2 The inner low position of the absorption tower is respectively positioned above the first aeration disc and the second aeration disc; the first desulfurization ash feeding pipe, the first flexible joint, the first exhaust pipe, the first liquid level meter flange and the first pressure meter flange are arranged at the top of the aeration tower; the second desulfurized ash feed pipe, the second flexible joint, the second exhaust pipe, the second liquid level meter flange and the second pressure meter flange are arranged on the SO 2 The top of the absorption tower; the first pH probe flange and the second pH probe flange are respectively and equidistantly arranged on the aeration tower and the SO from top to bottom 2 The side wall of the absorption tower; the first thermometer flange and the second thermometer flange are respectively arranged on the aeration tower and the SO 2 The side wall of the middle part of the absorption tower; the first densimeter flange and the second densimeter flange are respectively arranged on the aeration tower and the SO 2 The side wall of the middle lower part of the absorption tower; the reabsorption slurry merging pipe, the acid liquid feeding pipe, the first clear water feeding pipe and the first manhole are all arranged on the side wall of the lower part of the aeration tower; the second clear water feeding pipe and the second manhole are arranged on the SO 2 The lower side wall of the absorption tower; the first oxidation air pipe and the first slurry discharge pipe are arranged at the bottom of the aeration tower; the second oxidation air pipe and the second slurry discharge pipe are all arranged on the SO 2 The bottom of the absorption tower;
the inlet of the first slurry pump is connected with the first slurry discharge pipe and the clear water pipe through a three-way pipeline, and the outlet of the first slurry pump is connected with the first clear water feed pipe and the gypsum dehydration unit through a three-way pipeline; the inlet of the second slurry pump is connected with a second slurry discharge pipe and a clear water pipe through a three-way pipeline, and the outlet of the second slurry pump is connected with a second clear water feed pipe and a reabsorption slurry merging pipe through a three-way pipeline; the outlets of the first blower and the second blower are respectively connected with the first aeration disc and the second aeration disc through the first oxidation air pipe and the second oxidation air pipe; the inlet of the second air blower is connected with the first exhaust pipe; the outlet of the acid liquor pump is connected with an acid liquor feeding pipe; the first flexible joint and the second flexible joint are respectively connected with the first desulfurization ash feeding pipe and the second desulfurization ash feeding pipe.
2. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the aeration tower and SO 2 The absorption towers are all vertical cylinders, and the height-diameter ratio is 2-10.
3. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the first aeration disc and the second aeration disc are arranged in a rectangular array, a circumferential array or a radial array.
4. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the first blower and the second blower are respectively Roots blower or centrifugal blower.
5. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the first flexible joint and the second flexible joint are both made of rubber corrugated pipes.
6. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the number of the first pH probe flange and the second pH probe flange is 3-10, and the first pH probe flange and the second pH probe flange are respectively arranged along the aeration tower and the SO 2 The absorption towers are arranged at equal intervals from top to bottom in the height direction.
7. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the second exhaust pipe is provided with SO 2 And an on-line monitoring device.
8. The double-tank aeration oxidation tower for dry and semi-dry desulfurization ash according to claim 1, which is characterized in that: the acid liquid pump adopts a metering pump.
9. The method for operating and treating the dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower according to claim 1, which is characterized in that: the method comprises the following eleven steps:
step one: analyzing and testing raw materials, and analyzing and testing components of dry-method and semi-dry-method desulfurization ash to determine CaSO therein 3 And the content of various strong alkaline compounds;
step two: alkali liquor configuration, namely only opening clear water pipelines at the inlet and outlet of the second slurry pump, and utilizing the second slurry pump to feed the SO 2 Injecting clear water into the absorption tower, and stopping feeding the clear water when the liquid level is higher than 2/3~3/4 of the total liquid level; feeding the desulfurized fly ash into the SO through the second flexible joint and the second desulfurized fly ash feed pipe by using a pipe chain or a screw conveyor 2 An absorption tower; continuously operating the second stirrer to ensure that the desulfurized fly ash and the clean water are quickly and fully mixed and dissolved to finally form the pH value>10, and thereafter stopping the desulfurized fly ash feed;
step three: acid liquor preparation, namely gradually injecting waste sulfuric acid with low heavy metal and organic pollutant content and mass fraction of 1% -95% into the aeration tower by using the acid liquor pump; only opening a clear water pipeline at the inlet and outlet of the first slurry pump, and injecting clear water into the aeration tower by using the first slurry pump; continuously operating the first stirrer to enable the waste sulfuric acid and the clean water to be quickly and fully mixed and dissolved; stopping feeding the waste sulfuric acid and the clean water when the pH value of the solution in the tower is stable between 2.2 and 4.2 and the liquid level is higher than 2/3~3/4 of the total liquid level;
step four: acidifying the desulfurized ash, and conveying the desulfurized ash into an aeration tower through the first flexible joint and the first desulfurized ash feed pipe by utilizing a pipe chain or a screw conveyor; under the action of the first stirrer, the desulfurized fly ash entering the tower is subjected to the rapid and sufficient mixing, dissolving and reacting processes with the acid liquor; stopping feeding the desulfurized fly ash when the pH value of the solution rises to 3.1-6.2 and keeps stable;
step five: forced oxidation, continuously operating the first blower, and feeding air into the first aeration disc through a first oxidation air pipe by the first blower, wherein the air is injected into the solution in the step four in the form of a large number of tiny bubbles; under the action of the first stirrer, the bubbles rise in a spiral manner, so that the contact time with the solution is further increased, and the full mass transfer process is completed; HSO in solution at this time 3 - Will be O 2 Oxidation to SO 4 2- Releasing H + Thereby lowering the pH of the solution;
step six: when the pH value of the solution in the fifth step tends to be stable, starting the acid liquid pump, and gradually adding the waste sulfuric acid in the third step into the aeration tower; under the action of the first stirrer, the waste sulfuric acid entering the tower is rapidly and fully mixed with the solution, the pH value of the solution is reduced to 2.2-4.2 again, and then the acid liquid pump is closed;
step seven: a multi-step circulation is carried out, the steps four to six are repeated continuously, so that the solution in the step six gradually has solid-phase CaSO 4 Separating out and finally forming slurry with the solid content of 6% -30%;
step eight: when the slurry liquid level or density in the step seven reaches a certain value, only opening an inlet slurry pipeline and an outlet dehydration unit pipeline of the first slurry pump, discharging a part of slurry by using the first slurry pump, and delivering the slurry to a dehydration unit to produce gypsum products; in the pulp discharging process, the liquid level in the aeration tower is kept to be 2/3~3/4 higher than the total liquid level; after the slurry discharge is completed, the first slurry pump is closed, and an inlet slurry pipeline and an outlet dehydration unit pipeline of the first slurry pump are closed;
step nine: SO (SO) 2 Reabsorption, in the course of multi-step cyclic oxidation, especially secondary acidification, may occur where the local pH of the slurry is too low, resulting in incompletely oxidized SO 3 2- With excess H + Binding to release SO 2 In the case of (a), this part of SO 2 Discharging through said first exhaust pipe; continuously operating the second air blower through a second oxidation air pipeThe part of SO 2 Feeding into said second aeration tray, which carries SO 2 Injecting the alkaline slurry of the second step in the form of a plurality of fine bubbles; under the action of the second stirrer, the bubbles rise in a spiral shape, further increasing the contact time with the slurry, thereby completing SO 2 A reabsorption process;
step ten: and (3) merging the reabsorption slurry, and continuously absorbing SO along with the alkaline slurry in the second step 2 The pH value of the water is gradually reduced; when the alkaline slurry is reduced to below 8.5, and after the secondary acidification in the step six is completed, only opening an inlet slurry pipeline and an outlet reabsorption slurry merging pipeline of the second slurry pump, and sending the alkaline slurry into an aeration tower by using the second slurry pump for merging oxidation treatment;
step eleven: and (3) finishing the modification, namely continuously repeating the second step, the fourth step and the tenth step, and finally finishing the oxidation modification of all the dry-method and semi-dry-method desulfurized ash.
CN202111391314.5A 2021-11-23 2021-11-23 Dry-method and semi-dry-method desulfurization ash double-tank aeration oxidation tower and operation treatment method thereof Pending CN116139675A (en)

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