CN110385011A - A kind of carbon fiber fixed bed flue gas desulfurization and denitration technique and device - Google Patents
A kind of carbon fiber fixed bed flue gas desulfurization and denitration technique and device Download PDFInfo
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- CN110385011A CN110385011A CN201910740639.6A CN201910740639A CN110385011A CN 110385011 A CN110385011 A CN 110385011A CN 201910740639 A CN201910740639 A CN 201910740639A CN 110385011 A CN110385011 A CN 110385011A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0407—Constructional details of adsorbing systems
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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Abstract
The invention discloses a kind of carbon fiber fixed bed flue gas desulfurization and denitration techniques, successively sequentially include the following steps: (1) and pre-process to flue gas, contain SO in the flue gas2, NOx；(2) flue gas is adsorbed by carbon fiber fixed cell, the flue gas direct emission after the completion of adsorbing；(3) it desorbs；(4) Reduction of NOx；(5) SO is absorbed2.A kind of carbon fiber fixed bed flue gas desulfurization and denitrification device is also disclosed simultaneously, for realizing above-mentioned carbon fiber fixed bed flue gas desulfurization and denitration technique, it is characterized in that, the desulfuring and denitrifying apparatus is successively arranged preprocessor, adsorptive reactor, desorption apparatus, reduction apparatus and SO from upstream side to downstream side2Adsorbent equipment；Wherein, include the changeable carbon fiber adsorption component of at least two groups in the adsorptive reactor, used for rotation, the downstream of the adsorptive reactor is additionally provided with an exhanst gas outlet.
Description
Technical field
The present invention relates to environment protection field, especially a kind of carbon fiber fixed bed flue gas desulfurization and denitration technique and equipment.
Background technique
The discharge of sulfur dioxide, nitrogen oxides causes serious Acid Rain Pollution and ecological damage.China is a coal
The country of resource very abundant, and maximum coal production state and country of consumption in the world；The principal mode of coal utilization is straight
Burning is connect, 80% or more of coal total amount, the pollutants such as a large amount of coal-fired a large amount of sulfur dioxide of generation, the row of sulfur dioxide are occupied
It high-volume ranks first in the world, brings about great losses to national economy and people's property, while also resulting in the big of China's Sulphur ressource
Amount is lost.Therefore it reduces and control is polluted, the discharge of sulphur is the needs of global sustainable development when prevention and treatment is coal-fired, outstanding to China
To be important and urgent, and most critical is that there is an urgent need to develop technologically advanced, economically feasible, the suitable Prevention Techniques of environment.Cigarette
Desulfurization denitration technology is the measure that China presently the most effectively curbs environmental pollution.
In recent years, as the continuous enhancing of China's economic strength and environmental standard are gradually stringent, sulfur dioxide, nitrogen oxides
Disposal of pollutants management continues to increase, and many thermal power plants, Metallurgical Factory have successively introduced foreign countries according to respective actual conditions
Various flue gas desulfurization and denitrification technologies, and Gypsum Wet has been built up, rotating spraying semidry method, in-furnace calcium spraying tailing portion increases
Wet activation dry method, sea water desulfuration, electron-beam desulfurization and flue gas circulating fluidized bed desulfurization technology, SNCR and SCR denitration technology, activity
The demonstrative project and engineering project of burnt desulfurization and denitrification integral technology etc..These flue gas desulfurization and denitrification technologies exist to some extent
Investment is big, and operating cost height and the problems such as needing to administer secondary pollution and sulphur renewable resources, wide according to China region, unit is numerous
Miscellaneous, medium and coal distribution situation are complicated, the national conditions such as Sulphur ressource shortage and water shortage, it is necessary to the more advanced desulphurization denitration skill of development
Art.
Activated carbon fiber desulphurization denitration technology be a kind of absorption principle by physical-chemical based on dry desulfurization denitration skill
Art.The activated carbon fiber adsorbed can obtain sulfuric acid, sulfur dioxide liquid through regenerating, and the products such as elemental sulfur also can be generated
Sulfuric acid, calcium sulfate, magnesium sulfate or ammonium sulfate, nitrogen oxides are reduced to nitrogen and water.In this way, activated carbon fiber desulphurization denitration work
Skill can not only be used to control the discharge of sulfur dioxide, nitrogen oxides, but also can recycle Sulphur ressource, be that a kind of development prospect is preferable
Desulfurizing and denitrifying process.
From in the 1980s, foreign countries expand a large amount of research and development.
The active carbon desulfurization Lurgi technology of Germany, gas-liquid contact in Lurgi method, washing water disperse unevenness in bed
Even, water consumption is big, and sulfuric acid concentration is low in water lotion, and difficulty is big when concentrate, and desulfuration efficiency is lower, and it is small to be suitable for treating capacity, dioxy
Change the lower situation of sulphur concentration；
Hitachi-east electricity Hitachi Seesakujoo Ltd.Co.and Tokyo Tenryooku Ltd.Co. of Japan
Method active carbon desulfurization technique, compared with Lurgi method, sulfuric acid concentration is higher in the washing lotion which obtains, continuity less with water
Preferably.But the device is complicated, need to repeatedly switch, operate it is more numerous, though and can be used for the biggish occasion for the treatment of capacity, require pipeline very
Slightly, every corollary equipment size also accordingly increases, and thus bring equipment investment and maintenance difficulty increase；
Method, adsorption plant are ground in rotary shower bath method-change of Japanization Yan Ji work Co., Ltd. Kaken Kiikoo Ltd.Co.
The advantages of being skillfully constructed, having concentrated Hitachi-east electrical method of Lurgi method and Japan, but active carbon (coke) utilization rate is distributed in bed
Unevenly, overall utilization efficiency is not high, and when treating capacity is big, equipment will also be increased with increase, space hold, works as dust content
When big, bed resistance can continuity at any time and increase, therefore, need to install cleaner before absorber, when operation, absorption
SO in the flue gas crossed2, NOx/ fluctuation of concentration it is larger, continuity is poor；
Hitachi's Hitachi Zoosen Ltd.Co. ship construction method of Japan obtains its advantage is that vapor is easily isolated
Gas is purer, low operation temperature, avoids active carbon under high temperature (coke) itself thermal decomposition, and waste is reduced, operational safety；
The powered-down Sumitomo Heavy Induetry and EDPC PowerPlant in Sumitomo-of Japan
Takehara method, it is similar with Hitachi's ship construction method, vapor only is substituted with inert gas, desorption temperature is higher, is 370
DEG C or more, leave the rich SO of desorption device2Gas is for producing sulfuric acid；
The BF/Uhde flue gas desulfurization and denitrification ammonia process of Germany, can save water source, will not cause secondary pollution, available
Rich SO2Gas can not only be used to produce sulfuric acid, but also can produce elemental sulfur, and washability is larger.But due to mechanical wear, sulfuric acid
A part of charcoal need to be consumed when reduction, therefore, need regular supply.
Because in consideration of it, need it is a kind of China's applicability it is stronger, using the wider out of stock technology of carbon fiber flue gas desulfurization
And the desulfurizer adaptable with it, while reducing the consumption of water as far as possible and improving the thermal efficiency of the device.
Summary of the invention
The object of the present invention is to provide a kind of equipment is simple, occupied area is small, and construction cost is lower, and operating cost is cheap
Carbon fiber fixed bed flue gas desulfurization and denitrification device and process matched therewith.
To achieve the goals above, a kind of carbon fiber fixed bed flue gas desulfurization and denitration technique provided by the invention, is successively pressed
Following steps carry out:
(1) flue gas is pre-processed, contains SO in the flue gas2, NOx；
(2) flue gas is adsorbed by carbon fiber fixed cell, the flue gas direct emission after the completion of adsorbing；
(3) it desorbs；
(4) Reduction of NOx；
(5) SO is absorbed2。
Preferably, pre-treatment step is dust removal process in step (1), and dustiness of the flue gas after dust removal process is little
In 0.1g/Nm3.
Preferably, the mode desorbed in step (3) is heating desorption, and the desorption temperature is 200~600 DEG C.
Preferably, catalytic reduction step is NO in step (4)xReducing catalyst surface contact with ammonia generate nitrogen and
Water.
Preferably, SO is absorbed in step (5)2It is carried out using liquefied ammonia, ammonium hydroxide or carbonic acid hydrogen ammonium.
On the other hand, the present invention also provides a kind of carbon fiber fixed bed flue gas desulfurization and denitrification devices, for realizing above-mentioned
Carbon fiber fixed bed flue gas desulfurization and denitration technique, which is characterized in that the desulfuring and denitrifying apparatus from upstream side to downstream side according to
It is secondary to be equipped with preprocessor, adsorptive reactor, desorption apparatus, reduction apparatus and SO2Adsorbent equipment；
Wherein, include the changeable carbon fiber adsorption component of at least two groups in the adsorptive reactor, make for rotation
With the downstream of the adsorptive reactor is additionally provided with an exhanst gas outlet；
The desorption apparatus is used to desorb the substance of carbon fiber adsorption component absorption；
The reduction apparatus is used for the NO that reductive desorption goes outx, it is also provided with an ammonia adding apparatus thereon；
The SO2Adsorbent equipment is used for the SO that adsorption-desorption goes out2。
Preferably, the preprocessor is deduster.
Preferably, the deduster is any one in electric precipitator, electrostatic fabric filter or bag filter.
Preferably, carbon fiber used on the carbon fiber adsorption component contains N-And S-Functional group.
Preferably, the desorption apparatus is desorber, and the desorber passes through in the inert gas circulation pipe of desorber
Hot steam heated.
Apparatus structure provided by the invention is simple, and resistance is small, stable, and continuity is good, desulphurization denitration high dust collection efficiency,
It can reach national emission standard, while removing heavy metal, dioxin, hydrogen chloride, hydrogen fluoride etc.；
Technique provided by the invention and device use activated carbon fiber as adsorbent material, high mechanical strength, service life
It is long；It is not needed in technique using a large amount of water, it is without secondary pollution；Desulfurization product can be selected according to actual needs, be easy to store,
Transport, economic value are considerable；It is small to the corrosivity of equipment, high reliablity.
Detailed description of the invention
Fig. 1 is carbon fiber fixed bed flue gas desulfurization and denitrification schematic device in the embodiment of the present invention one.
Wherein: 1. preprocessor, 2. adsorptive reactor, 21. carbon fiber adsorption component, 3. desorption apparatus, 4. reduction apparatus 41.
Ammonia adding apparatus 5.SO2Adsorbent equipment
Specific embodiment
Embodiment one
Referring to FIG. 1, the embodiment of the invention provides a kind of carbon fiber fixed bed flue gas desulfurization and denitrification devices.
The carbon fiber fixed bed flue gas desulfurization and denitrification device includes the pretreatment set gradually from upstream side to downstream side
Device 1, adsorptive reactor 2, desorption apparatus 3, reduction apparatus 4 and SO2Adsorbent equipment 5.
Flue gas enters from the upstream side of the desulfuring and denitrifying apparatus.
The preprocessor 1 removes the particulate matter in most of flue gas, especially for pre-processing to flue gas to mention
It rises the service life of follow-up equipment and extends the maintenance period of follow-up equipment.
Therefore, the preprocessor 1 is deduster, is appointed preferably in electric precipitator, electrostatic fabric filter or bag filter
It anticipates one kind.
It include the changeable carbon fiber adsorption component 21 of at least two groups, every group of absorbing carbon fiber in the adsorptive reactor 2
Attached group of 21 equal independent operatings improve the working efficiency of whole device to carry out subsequent alternation operation.
The downstream of the adsorptive reactor 2 is additionally provided with an exhanst gas outlet, and flue gas adsorbs completion in adsorptive reactor and reaches
Pass through this exhanst gas outlet outlet after to discharge standard.
Further, carbon fiber used on the carbon fiber adsorption component 21 also contains N-And S-Functional group, for removing
The harmful substances such as the heavy metal and dioxin that may contain in flue gas.
The desorption apparatus 3 is used to desorb the carbon fiber adsorption component 21 that absorption is completed, and makes carbon fiber adsorption group
21 absorption property of part regeneration, to recycle.Meanwhile desorbing the high concentration SO released2, NOxConducive to progress subsequent job
Progress.
The desorption apparatus 3 is desorber, and in the present embodiment, carbon fiber adsorption component 21 passes through heating in desorber
Mode desorbed.
Further, the desorber is heated by the hot steam in the inert gas circulation pipe of desorber, with
Boiler waste heat is utilized to greatest extent, it is energy saving.
The reduction apparatus 4 is used for the NO that reductive desorption goes outx, it is provided with an ammonia adding apparatus 41, also thereon will pass through
Reduction reaction generates nitrogen and water.
The SO2Adsorbent equipment 5 is used for the SO that adsorption-desorption goes out2.Wherein, SO is adsorbed2Adsorbent used is by actual demand
Product and determine, can be adsorbed using such as ammonium hydroxide, ammonium hydrogen carbonate, lime stone or vapor or other reagents, this
Invention is not specifically limited in this embodiment.
Embodiment two
Further, the present invention also provides a kind of carbon fiber fixed bed flue gas desulfurization and denitration technique, embodiment is relied on
A kind of carbon fiber fixed bed flue gas desulfurization and denitrification device realization.
The carbon fiber fixed bed flue gas desulfurization and denitration technique successively clicks step progress:
(1) flue gas is pre-processed, contains SO in the flue gas2, NOx；
(2) flue gas is adsorbed by carbon fiber fixed cell, the flue gas direct emission after the completion of adsorbing；
(3) it desorbs；
(4) Reduction of NOx；
(5) SO is absorbed2。
Wherein, step (1) is mainly carried out by the preprocessor of device in embodiment one.The dust in flue gas is removed, is made
Dustiness in flue gas is not more than 0.1g/Nm3。
Excessively high dustiness be unfavorable for subsequent adsorbtion work progress, while also can shortening device maintenance period, reduce
Working efficiency.
Pretreated flue gas is adsorbed by the carbon fiber adsorption component in adsorptive reactor, the cigarette after the completion of adsorbing
Gas meets discharge standard, wherein SO2Content is 12~30mg/Nm3, NOXContent is 20~35mg/Nm3, therefore can direct emission.
The desorption procedure of step (3) carries out in the desorption apparatus of device in example 1, adsorbs the absorbing carbon fiber of completion
Attached component carries out desorption and regeneration in a manner of heating, and desorption temperature is 200~600 DEG C.Desorption can discharge carbon fiber adsorption component
The SO of middle absorption2And NOx.The carbon fiber adsorption component that desorption is completed returns to adsorptive reactor and continues to use.Simultaneously as carbon fiber
Carbon fiber used also contains N in dimension absorbent module-And S-Functional group, therefore, the nocuousness such as heavy metal and dioxin in flue gas
Substance also can be decomposed or convert removal.
Desorb the high concentration SO generated2And NOxCarry out the processing of subsequent step.
Firstly, first passing through the reduction apparatus of device in embodiment one to NO in step (4)xIt is handled.NOxBy with
Reducing catalyst surface of the ammonia of ammonia adding apparatus addition inside reduction apparatus is reduced into nitrogen and water.
Remove NOxGas enter SO2Adsorbent equipment is to carry out step (5), in SO2Adsorbent equipment using liquefied ammonia, ammonium hydroxide,
Ammonium hydrogen carbonate, lime stone or vapor carry out, specific adsorbent can product as needed selected, the present invention is to this
It is not specifically limited.
Below with reference to specifically used example to carbon fiber fixed bed flue gas desulfurization and denitrification device provided by the present invention and technique
Technical effect be illustrated.
Use example one
Certain steel mill 90m2Sintering machine, station boiler are put 54 ten thousand steres of flue gas/hour, and flue-gas temperature is 80~160 DEG C, cigarette
Sulfur-bearing 6000mg/Nm in gas3, NOx300mg/Nm3.Using activated carbon fiber desulfurization and denitrification integral process, adsorptive reactor is set
5 × 6 × 12 meters are calculated as, activated carbon fiber desorption apparatus volume is 360 cubic metres；Activated carbon fiber is selected, total amount is 70 tons.
Detailed process are as follows:
Flue gas from sintering machine tail portion enters pre-duster after electrostatic precipitator, and adsorption reaction is entered after dedusting
Device, preset wherein 70 tons of activated carbon fibers, flue gas flow through activated carbon fiber, are stripped of dust, SO2And NOxDeng flue gas enter master
Exhaust fan, chimney discharge；The reactor of the built-in activated carbon fiber of changeable two sets is set；The carbon fiber foundation of dust is adsorbed
Pressure difference soot blowing or timing soot blowing, dust fall into following ash bucket, timing outlet；SO is adsorbed2And NOxDeng activated carbon fiber connect
Activated carbon fiber desorption apparatus is connect, adsorptive reactor is switched to after desorption and continues to adsorb；In activated carbon fiber desorption apparatus (3)
The SO of desorption2And NOxInto reduction apparatus and SO2Absorption plant, before the ammonia of ammonia adding apparatus is added to reduction apparatus.The system
Design desulfuration efficiency be 99.5%, SO2Discharge is 30mg/Nm3；Designing efficiency of dust collection is 90%, dust emission 5mg/
Nm3；Design denitration efficiency is 90%, NOxDischarge is 30mg/Nm3。
In conclusion apparatus structure provided by the invention is simple, resistance is small, stable, and continuity is good, and desulphurization denitration removes
Dirt is high-efficient, can reach national emission standard, while removing heavy metal, dioxin, hydrogen chloride, hydrogen fluoride etc.；
Technique provided by the invention and device use activated carbon fiber as adsorbent material, high mechanical strength, service life
It is long；It is not needed in technique using a large amount of water, it is without secondary pollution；Desulfurization product can be selected according to actual needs, be easy to store,
Transport, economic value are considerable；It is small to the corrosivity of equipment, high reliablity.
Specific case used herein elaborates inventive concept, the explanation of above example is only intended to
Help understands core of the invention thought.It should be pointed out that for those skilled in the art, not departing from this
Under the premise of inventive concept, any obvious modification, equivalent replacement or the other improvements made should be included in the present invention
Protection scope within.
Claims (10)
1. a kind of carbon fiber fixed bed flue gas desulfurization and denitration technique, which is characterized in that successively sequentially include the following steps:
(1) flue gas is pre-processed, contains SO in the flue gas2, NOx；
(2) flue gas is adsorbed by carbon fiber fixed cell, the flue gas direct emission after the completion of adsorbing；
(3) it desorbs；
(4) Reduction of NOx；
(5) SO is absorbed2。
2. carbon fiber fixed bed flue gas desulfurization and denitration technique according to claim 1, which is characterized in that pre- in step (1)
Processing step is dust removal process, and dustiness of the flue gas after dust removal process is not more than 0.1g/Nm3。
3. carbon fiber fixed bed flue gas desulfurization and denitration technique according to claim 1, which is characterized in that solution in step (3)
The mode of suction is heating desorption, and the desorption temperature is 200~600 DEG C.
4. carbon fiber fixed bed flue gas desulfurization and denitration technique according to claim 1, which is characterized in that step is urged in (4)
Change reduction step is NOxIt is contacted on reducing catalyst surface with ammonia and generates nitrogen and water.
5. carbon fiber fixed bed flue gas desulfurization and denitration technique according to claim 1, which is characterized in that inhaled in step (5)
Receive SO2It is carried out using liquefied ammonia, ammonium hydroxide or carbonic acid hydrogen ammonium.
6. a kind of carbon fiber fixed bed flue gas desulfurization and denitrification device, is fixed for realizing carbon fiber as claimed in claims 1-5
Bed flue gas desulphurization denitrating technique, which is characterized in that the desulfuring and denitrifying apparatus is successively arranged pretreatment from upstream side to downstream side
Device, adsorptive reactor, desorption apparatus, reduction apparatus and SO2Adsorbent equipment；
Wherein, include the changeable carbon fiber adsorption component of at least two groups in the adsorptive reactor, used for rotation, institute
The downstream for stating adsorptive reactor is additionally provided with an exhanst gas outlet；
The desorption apparatus is used to desorb the substance of carbon fiber adsorption component absorption；
The reduction apparatus is used for the NO that reductive desorption goes outx, it is also provided with an ammonia adding apparatus thereon；
The SO2Adsorbent equipment is used for the SO that adsorption-desorption goes out2。
7. carbon fiber fixed bed flue gas desulfurization and denitrification device according to claim 6, which is characterized in that the preprocessor
For deduster.
8. carbon fiber fixed bed flue gas desulfurization and denitrification device according to claim 7, which is characterized in that the deduster is
Any one in electric precipitator, electrostatic fabric filter or bag filter.
9. carbon fiber fixed bed flue gas desulfurization and denitrification device according to claim 6, which is characterized in that the absorbing carbon fiber
Carbon fiber used contains N on attached component-And S-Functional group.
10. carbon fiber fixed bed flue gas desulfurization and denitrification device according to claim 6, which is characterized in that the desorption dress
It is set to desorber, the desorber is heated by the hot steam in the inert gas circulation pipe of desorber.
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| FR3135212A1 (en) * | 2022-05-09 | 2023-11-10 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and apparatus for purifying a gas flow containing at least one nitrogen oxide |
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Application publication date: 20191029 |