CN1101718C - Wet catalytic fume desulfurizing method and equipment - Google Patents
Wet catalytic fume desulfurizing method and equipment Download PDFInfo
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- CN1101718C CN1101718C CN00128209A CN00128209A CN1101718C CN 1101718 C CN1101718 C CN 1101718C CN 00128209 A CN00128209 A CN 00128209A CN 00128209 A CN00128209 A CN 00128209A CN 1101718 C CN1101718 C CN 1101718C
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Abstract
The present invention relates to a method for the wet dust removal and liquid-phase catalytic desulfurization of flue gas of coal-fired furnaces and a device. In the method, Fe2O3 in coal-fired ash is used as desulfurization reactant, and a venturi and a water film are used as a gas and liquid mass transfer device for increasing systems of a cyclone hydraulic separator; SO2 in flue gas is converted into water insoluble solid sulfur compounds through media or called catalysts or iron-corroding bacteria of G. Compared with a limestone paste method, the investment is reduced by 97 to 95%, operation cost is reduced below 0.2 min/KW. n, and the desulfurization efficiency reaches 95 to 99%.
Description
The invention belongs to a flue gas dust removal and desulfurization method and equipment, and particularly relates to a coal-fired furnace flue gas moisture dust removal liquid-phase catalytic desulfurization method and equipment.
At present, the flue gas desulfurization technology of a coal-fired thermal boiler is characterized by acid-base neutralization in developed countries in the world, namely, SO in flue gas is neutralized by limestone or lime which is most compatible in the nature2. The chemical reaction conditions need many stages, and the investment is very large due to the addition of auxiliary systems and automatic control equipment, the investment of the imported system in China is more than 2 hundred million for 20 ten thousand KW units, and the running cost is 400 yuan/tSO due to the consumption of lime or limestone and the depreciation cost of high investment amount2Above, the US is $ 370-2. In the technical field of environmentalprotection, the desulfurization of flue gas is daunting for the nation because of large investment and high operating cost.
The invention aims to provide a liquid-phase catalytic desulfurization method and equipment for removing dust from flue gas moisture of a coal-fired furnace, which are changed from the basic principle of desulfurization reaction and achieve the aims of reducing the investment amount and expensive operation cost of flue gas desulfurization.
The purpose of the invention is realized as follows:
a liquid phase catalytic desulfurization method for removing dust from flue gas moisture of a coal-fired furnace is characterized by comprising the following steps: the invention is to burn FeS in coal2Decomposition product SO after thermal decomposition2With Fe2O3This is accompanied by the emission of smokeSome SO2With Fe2O3Reacting the iron-corroding bacteria with sulfuric acid to generate Fe2(SO4)3Then continuously reacts with sulfuric acid to generate FeS2；
Which is reacted by
Wherein the sulfuric acid generation process participating in the reaction is as follows: when the gas-solid-liquid flue gas mixture contains SO2，O2And the smoke dust contains Fe2O3Solid-state powder particles are subjected to chemical power mass transfer of Venturi velocity field, and solid-state Fe is obtained through medium action2O3The molecule will be partially changed into ion to Fe3+G forms a liquid phase catalyst, and the ferric ion concentration will continue to increase to a constant value in a closed cycle continuous operation. Become a pairSO2Strong liquid phase catalyst for removing SO from flue gas2And O2Catalytic formation of SO3Transferring to liquid phase to become sulfuric acid.
A hydrocyclone is adopted, the upper part of a conical pipe is connected with a large short round pipe, one side of the large short round pipe is tangentially connected with an inlet pipe with a conical section, the top of the large short round pipe is provided with an end cover, an outlet pipe which is led into the conical pipe is arranged in the middle of the end cover, and the lower part of the conical pipe is connected with a small short round pipe which is a slag discharge pipe.
The inlet pipe with a conical section can also be a square R-angle reducer.
The inlet tube with a conical cross-section may also be a circular reducer.
The lower parts of the Venturi tube and the water film tower are connected with a reaction tank, the reaction tank is connected with an inlet pipe with a conical section of a front hydrocyclone through a front acid-proof mortar pump, the lower part of the front hydrocyclone is connected with a small short circular pipe and connected with a dedusting make-up water tank, an outlet pipe at the upper part of the front hydrocyclone is connected with a dedusting water tank, and the dedusting water tank is connected with the Venturi tube through a deduster water supply pump, an inlet of a Venturi diffusion pipe of the water film tower and an upper inlet of the water; the dust removal water supply tank is connected with a conical inlet pipe of the rear hydrocyclone through a rear acid-proof ash slurry pump, the lower part of the rear hydrocyclone is connected witha small short circular pipe to be connected with an ash flushing ditch, and an outlet pipe at the upper part of the rear hydrocyclone is connected with a dust removal water tank.
The invention has the advantages that:
1. due to greatly simplifying the system and using the heat decomposition product Fe of the pyrite in the coal2O3As a desulfurizing reactant, the investment of a flue gas desulfurization device is reduced by 97-95 percent compared with a limestone-gypsum method, the running cost is reduced to 0.07-0.2 min/KW.n, and if a byproduct is recycled, the method is profitable.
2. The occupied area is small, and for a 10 ten thousand KW unit, the occupied area is less than 100m2If no venturi-water film dust remover unit is available, the floor area of the set-shaped venturi-water film of the capacity unit needs to be increased. Is particularly suitable for the old factories to add coal-fired thermal boilers.
3. The desulfurization cost is not increased along with the increase of the sulfur content of the fuel coal, and the method is particularly suitable for medium-high sulfur coal types of the fuel pyrite sulfur and the sulfate sulfur.
4. Because the system is simple, the chemical reaction of the system is self-reacting, and the manual control is not needed, so a special post is not needed, and only a dedusting attendant can take charge of the system.
5. The scaling problem of the ash flushing system which is headache for years in a thermal power plant is eliminated.
6. The desulfurization efficiency can meet domestic requirements, and the experimental value shows that the desulfurization efficiency reaches 95-99%.
7. Recoverable water purifying agent primary product Fe2(SO4)3And a sulphur resource FeS2And solves the problem of import of sulfur in China.
The embodiments are described below with reference to the accompanying drawings:
FIG. 1 is a structural system diagram of a liquid-phase catalytic desulfurization method for removing dust from flue gas moisture of a coal-fired furnace
FIG. 2 is a side view of a hydrocyclone of a liquid phase catalytic desulfurization apparatus for removing dust from flue gas moisture of a coal-fired furnace
FIG. 3 is the top view of the hydrocyclone of the liquid phase catalytic desulfurization device for wet gas dust removal of flue gas from coal-fired furnace
Drawing reference numbers:
1) a dust remover water supply pump, 2) a dust removal water tank, 3) a venturi and a water film, 4) a reaction tank, 5) a front acid-proof mortar pump, 6) a front hydrocyclone separator, 7) a washing tank, 8) dust removal make-up water, 9) a rear acid-proof mortar pump, 10) a rear hydrocyclone separator and 11 ash flushing ditches).
The invention is to burn FeS in coal2Decomposition product SO after thermal decomposition2With Fe2O3These SO2With Fe2O3Reacting the iron-corroding bacteria with sulfuric acid to generate Fe2(SO4)3Then continuously reacting with sulfuric acid to generate FeS2. Namely SO in the flue gas2With Fe in ash2O3The compounds converted into water-insoluble solid sulphur are discharged as a mixture in ash, or as Fe from steel mill industrial waste2O3FeSO4Iron filings, etc. are reacted with dust-free flue gas in the system to obtain the primary product of iron sulfate as water-purifying agent, and if it is continuously reacted with sulfuric acid, FeS is obtained2Recovering by-products or sulfur resources.
Wherein the sulfuric acid generation process participating in the reaction is as follows: when the flue gas mixture contains SO2，O2And the smoke dust contains Fe2O3When the solid powder particles meet water through the Venturi tube, the chemical power mass transfer in a velocity field is realized, and the solid Fe is realized through the medium action2O3The molecule will be partially changed into ion to Fe3+G forms a liquid phase catalyst, and the ferric ion concentration will continue to increase to a constant value in a closed cycle continuous operation. Become to SO2Strong liquid phase catalyst for removing SO from flue gas2And O2Catalytic formation of SO3Transferring to liquid phase to become sulfuric acid. The generated sulfuric acid participates in the flue gas desulfurization process of the present invention.
Which is reacted by
The equipment of the coal-fired furnace flue gas wet gas dust removal liquid phase catalytic desulfurization method is as follows: the lower parts of the Venturi tube and the water film tower are connected with a reaction tank, the reaction tank is connected with a conical inlet pipe of a front hydrocyclone through a front acid-resistant mortar pump, the lower part of the front hydrocyclone is connected with a small short circular pipe and connected with a dedusting make-up water tank, an outlet pipe at the upper part of the front hydrocyclone is connected with a dedusting water tank, and the dedusting water tank is connected with the Venturi tube through a deduster water supply pump, is connected with an inlet of a Venturi tube water distribution device of the Venturi tube and the water film tower and; the dust removal water supply tank is connected with a conical inlet pipe of the rear hydrocyclone through a rear acid-proof ash slurry pump, the lower part of the rear hydrocyclone is connected with a small short circular pipe and connected with an ash flushing ditch, and an outlet pipe at the upper part of the rear hydrocyclone is connected with a dust removal water tank.
A liquid-phase catalytic desulfurizing method for removing dust from fume and moisture in coal-burning furnace features that a cyclone separator is used to separate liquid from solid, which is a centrifugal force converted from speed force.
Example (b):
the present invention uses a Venturi-water film dust remover as gas and liquid mass transfer equipment, and a reaction tank is arranged behind a water film so as to provide the time (about 0.5-3h) required by chemical reaction, and the ash water in the reaction tank is pressurized by an acid-resistant ash slurry pump and is integrated by a hydrocyclone into a flat belt which is cut into the vertical wall of the hydrocyclone to form a centrifugal force rotating along the inner wall of the hydrocyclone. Converting the speed force into centrifugal force for liquid-solid separation, returning the separated ash water to a dust-removing water tank to form closed cycle for dust removal and desulfurization, discharging the separated thick ash into a washing tank, supplementing dust-removing make-up water, pressurizing by an acid-resistant ash slurry pump, pumping into a rear hydrocyclone separator, and feeding the separated ash water into the dust-removing water tank or into a reaction tank to recover FeS which has not reacted2
Fe (b) of3+Soluble substances such as ions, a mediator and the like and thick ash are discharged to an ash flushing ditch.
The present invention uses Venturi dust collector to replace all flue gas through-flow equipment for flue gas desulfurization, so that its investment only accounts for 3-5% of that of lime-gypsum method. The desulfurizing reactant is Fe in ash of decomposed product of thermally decomposing pyrite in coal2O3(Fe produced under other conditions)2O3Equivalent), mediated by a mediator and the thermal decomposition product SO2Then converted into pyrite to become water-insoluble solid sulfur, and the intermediate product of the conversion process is Fe2(SO4)4Fe in dilute sulphuric acid3+Is a liquid phase catalyst, so the cost of flue gas desulfurization is reduced to below 0.2 min/kwn from about 0.12 yuan/kw.n. It is slightly profitable to recover the by-products.
The industrial implementation system is shown in figure 1, smoke rotates and rises from a venturi to a water film to throw dust particles to the peripheral wall and is washed down by the liquid film, the smoke passes through a wet section and a dry section of the water film and reaches a top water discharging film device to enter a discharge flue, meanwhile, a dust remover water supply pump 1) pumps water in a dust removing water tank 2) to be supplied to the venturi and the water film, a water distribution device 3) carries dust carrying water to fall to the bottom of the water film and is discharged to a reaction tank 4) through a dust water outlet, the dust carrying water is pressurized by a front acid-resistant dust pump5) and is supplied to a front hydrocyclone 6) (a branch can be arranged to be used for anti-sedimentation circulation), and the separated water is sent to a dust removing water. The separated thick ash is discharged into a washing tank 7) and is mixed with dedusting make-up water 8) through a post-acid-resistant ash pump 9), and the mixture is supplied to a post-hydrocyclone 10) and can also be provided with a branch for anti-settling circulation, and the water separated by the post-hydrocyclone 10) is sent to a dedusting water tank 2) and can also be sent to a reaction tank 4) through a branch, and the separated thick ash is discharged into an ash flushing system 11) and is discharged.
It is characterized by that it is a Venturi-water film dust-removing equipment, and is used as gas-liquid-solid mass transfer equipment, and utilizes the chemical power mass transfer function produced by Venturi tube speed field, and at the same time, it also includes a parallel-flow jet tower with speed field, and a jet cup type three-phase mixing tower is used for liquid-phase catalytic system whose absorption liquid pH value is less than 3.0. The closed circulation system contains trace (about 10 micrograms per project) of iron-corroding bacteriaFe in grey water due to the proliferation and mediation of iron-eroding bacteria2O3The molecules are gradually ionized and dissolved in the grey water to become Fe3+G ion transport to SO in liquid phase2.O2The catalyst has a catalytic effect, the flue gas desulfurization efficiency is improved along with the increase of the concentration of ferric ions in a liquid phase, and the dedusting and desulfurization system is formed after the ferric ions are dissolved in the dedusting circulating water. Until the desulfurization efficiency reaches the desired value and then stabilizes to that value. Characterized in that the liquid phase catalyst is ferric ion (Fe)3+) The iron-corroding bacteriais an activator or mediator, which is the catalyst in Fe during the operation of the system2O3Molecule and rare H2SO4Fe produced by the reaction3+. It is characterized by that in the closed circulation system, along with the continuous operation time and raising flue gas desulfurization efficiency, the sulfuric acid concentration in the grey water can be continuously raised from zero to some extent, and Fe2O3Conversion to Fe2(SO4)3The speed is increased, and FeS is converted and generated under the catalyst along with the increase of the concentration of sulfuric acid and ferric sulfate in the closed circulation liquid2Then precipitate out to become a stable compound. This is a self-reacting process, requiring no manual adjustment. The liquid phase catalyst also comprises iron, cobalt, nickel and other metals of iron series elements, oxides and compounds thereof, and SO is catalyzed by Venturi liquid phase of gas-liquid mass transfer2、O2Catalyzing the mixed solution with water to form sulfuric acid, and adding the sulfuric acid and Fe into a reaction tank2O3Ferric sulfate is generated under the catalyst, and the ferric sulfate and the sulfuric acid continue to react to form pyrite (FeS)2) Completes the removal of SO in the flue gas2Conversion to FeS2And the water-insoluble sulfur compounds are mixed in the ash and discharged.
An acid-proof reaction pool for providing dilute sulfuric acid (liquid) and Fe2O3(solid) reaction time under catalyst.
The acid-proof reaction tank discharges ash or thick ash outwards at any time, and the hydrocyclone is a liquid-solid separation device which converts speed force into centrifugal force and is used for maintaining the liquid-solid ratio in the reaction tankto be stable at about 5-10% or below 30%. The liquid-solid separation equipment also comprises separation equipment such as a sedimentation tank, a clarifier, a concentration tank, an inclined tube sedimentation tank and the like.
The washing pool is carried in the thick ash residual liquid discharged from the recovery reaction pool and is not converted into FeS2Of ion Fe3+And a medium agent, and the arrangement of a plurality of stages of washing tanks and even whether the washing tank is arranged or not are different according to the requirements of the demander. The hydrocyclone of the stage plays a role. The washed ash or thick ash is separated and discharged, and the grey water is sent to a dust removal water tank or a reaction tank to be used as dust removal make-up water.
In the system, when iron is used as a desulfurization reactant and ferric ions are used as a liquid phase catalyst, oxides and grey acidized substances Al of alkali metals and alkaline earth metals2O3Only with acid reactants under these conditions.
In the system, the oxides of alkali metals and alkaline earth metals, such as common alkali metal potassium, sodium, alkali earth metal calcium, magnesium, strontium, barium, ammonia and ammonium salt can participate in the desulfurization reaction when the PH value is more than 5, and certain desulfurization efficiency can be obtained.
At present, most large and medium-sized thermal power generating units in China are replaced by dry dust removal. The invention can arrange a Venturi-water film behind the dry dust collector, and lead the dust after dry dust collection into the reaction tank, thereby obtaining the same effect, and further throwing the steel mill garbage Fe into the reaction tank2O3Iron filings, ferrous sulfate, etc. for desulfurizing dust-free fume, recovering by-product and primary product of polyferric sulfate, and iron sulfate or further reaction to obtain FeS2And separating out sulfur resources.
Implementation requirements and equipment market:
1. the Venturi-water film dust remover is designed by most electric power design institutes and electric power scientific research institutes of shaped products.
2. The reaction tank and the washing tank can be constructed according to design. Only considering acid resistance, seepage resistance and the fact that some products do not need special anti-freezing requirements, common users can solve the problems automatically and can also include other people.
3. The hydrocyclone separator is specially provided for technical inventors, as shown in the figure, the parameters are as follows, the inlet pipe is a square R-angle reducing pipe, D1The inner wall can be cut or a circular reducing pipe. Or an inlet pipe with a conical cross-section, D1Flow rate of 10-40m/S, D2The flow speed is 2-16m/S,H2taper angle of 4-30, D3The flow velocity is 0.5-10m/S
Claims (6)
1. A liquid phase catalytic desulfurization method for removing dust from flue gas moisture of a coal-fired furnace is characterized by comprising the following steps: the invention is to burn FeS in coal2Decomposition product SO after thermal decomposition2With Fe2O3The SO emitted with the flue gas2With Fe2O3Reacting with sulfuric acid to generate Fe2(SO4)3Then continuously reacting with sulfuric acid to generate FeS2；
Which is reacted by
2. The coal-fired furnace flue gas wet dust removal liquid-phase catalytic desulfurization method as set forth in claim 1, characterized in that: wherein the sulfuric acid generation process participating in the reaction is as follows: when the flue gas mixture contains SO2，O2And the smoke dust contains Fe2O3Solid-state powder particles are subjected to chemical power mass transfer of Venturi velocity field, and solid-state Fe is obtained through medium action2O3The molecule will be partially changed into ion to Fe3+G forms a liquid phase catalyst, and the ferric ion concentration will continuously increase to a constant value as SO in the continuous operation of the closed cycle2Strong liquid phase catalyst for removing SO from flue gas2And O2Catalytic formation of SO3Transferring to liquid phase to become sulfuric acid.
3. The apparatus for liquid-phase catalytic desulfurization of coal-fired furnace flue gas with moisture removal according to claim 1, characterized in that: the dust removal water tank is connected with a dust remover water supply pump, the dust remover water supply pump is connected with a venturi and a water distribution device of a water film, the bottom of the water film is connected with a reaction tank, the reaction tank is connected with an acid-proof mortar pump, the acid-proof mortar pump is connected with a front hydrocyclone, and the upper part of the front hydrocyclone is connected with a dust removal water tank 2) to form closed circulation of dust removal water; a washing tank is arranged below the front hydrocyclone separator, the washing tank is connected with an acid-proof mortar pump, the acid-proof mortar pump is connected with a rear hydrocyclone separator, the rear hydrocyclone separator is connected with a dust removal water tank, and the lower part of the rear hydrocyclone separator is connected with a dust washing system; the hydrocyclone adopted is a conical pipe, the upper part of the conical pipe is connected with a large short round pipe, one side of the large short round pipe is tangentially connected with an inlet pipe with a conical section, the top of the large short round pipe is provided with an end cover, the middle of the end cover is provided with an outlet pipe which is led into the conical pipe, and the lower part of the conical pipe is connected with a small short round pipe which is a slag discharge pipe.
4. The apparatus for liquid-phase catalytic desulfurization of coal-fired furnace flue gas with moisture removal according to claim 3, characterized in that: the cyclone separator is adopted, and the inlet pipe with the conical section can also be a square R-angle reducing pipe.
5. The apparatus for liquid-phase catalytic desulfurization of coal-fired furnace flue gas with moisture removal according to claim 3, characterized in that: the inlet pipe with a conical section can also be a circular reducer by adopting a hydrocyclone separator.
6. The apparatus for liquid-phase catalytic desulfurization of coal-fired furnace flue gas with moisture removal according to claim 3, characterized in that: the lower parts of the Venturi tube and the water film tower are connected with a reaction tank, the reaction tank is connected with an inlet pipe with a conical section of a front hydrocyclone through a front acid-proof mortar pump, the lower part of thefront hydrocyclone is connected with a small short circular pipe and connected with a dedusting make-up water tank, an outlet pipe at the upper part of the front hydrocyclone is connected with a dedusting water tank, and the dedusting water tank is connected with the Venturi tube through a deduster water supply pump, an inlet of a Venturi diffusion pipe of the water film tower and an upper inlet of the water; the dust removal water supply tank is connected with a conical inlet pipe of the rear hydrocyclone through a rear acid-proof ash slurry pump, the lower part of the rear hydrocyclone is connected with a small short circular pipe to be connected with an ash flushing ditch, and an outlet pipe at the upper part of the rear hydrocyclone is connected with a dust removal water tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00128209A CN1101718C (en) | 2000-06-16 | 2000-12-15 | Wet catalytic fume desulfurizing method and equipment |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00113845.6 | 2000-06-16 | ||
| CN 00113845 CN1278455A (en) | 2000-06-16 | 2000-06-16 | Wet dedusting and liquid catalytic desulfurizing process and equipment for fume treatment in thermal power plant |
| CN00128209A CN1101718C (en) | 2000-06-16 | 2000-12-15 | Wet catalytic fume desulfurizing method and equipment |
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| Publication Number | Publication Date |
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| CN1310037A CN1310037A (en) | 2001-08-29 |
| CN1101718C true CN1101718C (en) | 2003-02-19 |
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| CN00128209A Expired - Fee Related CN1101718C (en) | 2000-06-16 | 2000-12-15 | Wet catalytic fume desulfurizing method and equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104307349B (en) * | 2014-10-24 | 2023-07-25 | 重庆庆龙精细锶盐化工有限公司 | Flushable serial strontium slurry desulfurization system |
| CN104324601B (en) * | 2014-10-24 | 2023-07-25 | 重庆庆龙精细锶盐化工有限公司 | Energy-saving strontium slurry desulfurization system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2006758A1 (en) * | 1970-02-14 | 1971-08-19 | Gastechnik GmbH, 4200 Oberhausen | Gas-desulphurizing material |
| CN85104062A (en) * | 1985-05-22 | 1986-07-16 | 太原工业大学 | Catalytic desulfurizing agent for flue gas and preparation method thereof |
| US5041693A (en) * | 1989-08-10 | 1991-08-20 | Uop | Separation of normal paraffins and the regeneration of zeolitic molecular sieves used therein |
| CN1196971A (en) * | 1998-03-18 | 1998-10-28 | 北京三聚化工技术有限公司 | Sweetening agent and its prepn. method |
| DE19913645A1 (en) * | 1998-05-20 | 1999-11-25 | Voest Alpine Ind Anlagen | Desulphurizing slag regeneration |
-
2000
- 2000-12-15 CN CN00128209A patent/CN1101718C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2006758A1 (en) * | 1970-02-14 | 1971-08-19 | Gastechnik GmbH, 4200 Oberhausen | Gas-desulphurizing material |
| CN85104062A (en) * | 1985-05-22 | 1986-07-16 | 太原工业大学 | Catalytic desulfurizing agent for flue gas and preparation method thereof |
| US5041693A (en) * | 1989-08-10 | 1991-08-20 | Uop | Separation of normal paraffins and the regeneration of zeolitic molecular sieves used therein |
| CN1196971A (en) * | 1998-03-18 | 1998-10-28 | 北京三聚化工技术有限公司 | Sweetening agent and its prepn. method |
| DE19913645A1 (en) * | 1998-05-20 | 1999-11-25 | Voest Alpine Ind Anlagen | Desulphurizing slag regeneration |
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| CN1310037A (en) | 2001-08-29 |
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