CN107497295A - The method of dry flue gas desulphurization denitration - Google Patents

The method of dry flue gas desulphurization denitration Download PDF

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Publication number
CN107497295A
CN107497295A CN201710939480.1A CN201710939480A CN107497295A CN 107497295 A CN107497295 A CN 107497295A CN 201710939480 A CN201710939480 A CN 201710939480A CN 107497295 A CN107497295 A CN 107497295A
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flue gas
absorbent
weight
magnesia
catalyst
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童裳慧
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Microtek Blue Industrial Co Ltd
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Microtek Blue Industrial Co Ltd
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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
    • 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
    • B01D53/14—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 absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • 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
    • B01D53/81—Solid phase 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
    • B01D53/86—Catalytic processes
    • B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/14—Waste materials; Refuse from metallurgical processes
    • C04B18/141—Slags
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/16—Waste materials; Refuse from building or ceramic industry
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
    • C04B22/142—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The invention discloses a kind of method of dry flue gas desulphurization denitration, comprise the following steps：(1) pre- dust removal step：Pending flue gas is subjected to pre- dedusting to remove most of dust granules, so as to form pre- dedusting flue gas；(2) catalytic oxidation stage：Use catalyst by the oxidizing sulfur dioxide in pre- dedusting flue gas for sulfur trioxide, and be nitrogen dioxide by oxidation of nitric oxide, so as to form pretreated fumes；(3) absorption step：The absorbent using magnesia as main component is used to carry out dry desulfurization denitration to pretreated fumes, so as to form flue gas after processing.The denitrification efficiency of the method for the present invention is high, and technological process is simple, and water consumption is less, and investment and operating cost are relatively low.

Description

The method of dry flue gas desulphurization denitration
Technical field
The present invention relates to a kind of method of dry flue gas desulphurization denitration.
Background technology
In recent years, air pollution problems inherent increasingly aggravates.China is as a developing country, significant period of time from now on The interior situation that will be faced air pollution and constantly aggravate.As energy demand is continuously increased, the pollution caused by fume emission is asked Topic becomes increasingly conspicuous, and air environmental pollution control problem has caused the great attention of the people of the world.Development is efficient, energy-conservation, height The flue gas purifying method of cost performance can fundamentally solve development and environmentally friendly, current and long-range different demands.At present, combine Flue gas desulfurization and denitrification technology receives significant attention.Traditional joint flue gas desulfurization and denitration technique is to install one additional behind desulfurizer Denitrification apparatus is covered, such as SCR (SCR) or SNCR (SNCR), so as to realize that combined desulfurization takes off Nitre.But not only floor space is big for this classification administration way, and investment and operating cost are high, and one is brought to popularization and application Fixed difficulty.Large-scale wet method, semidry method, dry flue gas desulphurization device are used widely in the stove of China's every profession and trade, but Ability of the technique without denitration simultaneously.If setting up denitration device again, investment and operating cost are huge.
For flue gas desulfurization technique, both at home and abroad largely using calcium base particle as desulfurizing agent, circulating fluidization is carried out Dry flue gas desulphurization.The composition of desulfurizing byproduct after gas cleaning is mainly calcium sulfite CaSO3, it is difficult to be subject to profit again With, thus as the biggest obstacle in the application of current dry flue gas desulphurization engineering.
For gas denitrifying technology, the current domestic low NO primarily directed to combustion processxProduce and carry out a large amount of Research, passes through various low NOxTechnology design goes out various low NOxBurner, but above-mentioned combustion technology can not meet cleaning well The environmental requirement of flue gas, and influenceed by factors such as coal characteristic, service conditions, the distance with increasingly strict environmental requirement It is more and more remote.At present used by the denitrating flue gas project of domestic operation technique mainly introduce Europe, the United States, Deng developed countries and Regional gas denitrifying technology, the denitrating technique mainly applied at present are divided into SCR methods and SNCR methods.SCR method denitration efficiencies are higher, row The standard of putting can reach 90%, but complex process, system investments expense and follow-up operation processing cost are high；SNCR method small investments, Follow-up operation processing cost is relatively low, but denitration efficiency can only achieve 60%, can not meet increasingly strict emission request.
The Chinese patent application of Application No. 201120250204.2 discloses a kind of device of desulphurization denitration, including：Pot Fire grate smoke pipe connection economizer, economizer connects denitrating tower, denitrating tower connects deduster, and deduster connects desulfurizing tower through air-introduced machine, and give up cigarette Gas enters back into denitrating tower denitration from boiler exhaust gas pipeline by economizer, and after dust arrester dedusting, is introduced by air-introduced machine Desulfurizing tower carries out desulfurization.Faveolate denitration filling block is provided with denitrating tower, ammonifying device is provided with desulfurizing tower and bottom exposes Device of air.But the denitration efficiency of the device is only 30%~50%, it is difficult to meets emission request.
The content of the invention
In order to overcome drawbacks described above, present inventor has made intensive studies.It is an object of the invention to provide one The method of kind of dry flue gas desulphurization denitration, its denitrification efficiency is significantly improved, and technological process is simple, water consumption compared with Few, investment and operating cost are relatively low.Further aim of the present invention is to provide a kind of method of dry flue gas desulphurization denitration, cigarette Byproduct of reaction after gas purification can be utilized directly, thus have preferable economic benefit.The present invention adopts the following technical scheme that Realize above-mentioned purpose.
The present invention provides a kind of method of dry flue gas desulphurization denitration, comprises the following steps：
(1) pre- dust removal step：Pending flue gas is subjected to pre- dedusting to remove most of dust granules, so as to form pre- remove Cloud of dust gas；
(2) catalytic oxidation stage：In bed apparatus is catalyzed, using catalyst by the oxidizing sulfur dioxide in pre- dedusting flue gas For sulfur trioxide, and it is nitrogen dioxide by oxidation of nitric oxide, so as to form pretreated fumes；The catalyst include carrier and Active component；The carrier is nanoscale amphoteric oxide, selected from TiO2、ZrO2Or HfO2In one or more；The activity Composition includes KMnO4And nanosize metal oxide, the nanosize metal oxide include V2O5、CoO、Co2O3、Fe2O3With MnO2；With
(3) absorption step：In absorption equipment, the absorbent using magnesia as main component is used to enter pretreated fumes Row dry desulfurization denitration, so as to form flue gas after processing.
Method in accordance with the invention it is preferred that in step (1), the content of sulfur dioxide of the pending flue gas for 300~ 20000mg/Nm3, amount of nitrogen oxides be 100~500mg/Nm3, oxygen content be 10~20vol%, flow velocity be 2~5m/s, And temperature is 95~160 DEG C.
Method in accordance with the invention it is preferred that in step (1), pre- efficiency of dust collection is more than 90%.
Method in accordance with the invention it is preferred that in step (2), the catalysis bed apparatus includes shell, and the front portion of shell is set There is gas outlet, the rear portion of shell is provided with air inlet, and the inside of shell is provided with least two Catalytic Layers being arranged above and below；It is described pre- to remove Cloud of dust gas enters the Catalytic Layer by the air inlet, and is discharged from the gas outlet.
Method in accordance with the invention it is preferred that in step (2), based on 100 part by weight of catalyst, the catalyst include with Lower component：
Method in accordance with the invention it is preferred that in step (2), based on 100 part by weight of catalyst, the catalyst include with Lower component：
Method in accordance with the invention it is preferred that in step (3), the absorption equipment is recirculating fluidized bed absorption tower, described The time of contact of absorbent and the pretreated fumes is in more than 30min.
Method in accordance with the invention it is preferred that in step (3), the absorbent also includes calcium oxide and silica；Institute Stating magnesia includes 70~85wt% activated magnesia, and content of the nanoscale magnesium in the magnesia be 10~ 20wt%.
Method in accordance with the invention it is preferred that it also comprises the following steps：
(4) dust removal step：Flue gas after the processing is separated in sack cleaner, so as to obtain purifying smoke, The absorbent and main component not being fully utilized are the powdered accessory substance of sulfate and nitrate；
(5) absorbent circulation step：The absorbent not being fully utilized is recycled to absorption equipment.
Method in accordance with the invention it is preferred that it also comprises the following steps：
(6) by-product utilized step：Raw material including the powdered accessory substance and industrial solid wastes is mixed, so as to Form construction material.
The present invention carries out flue gas desulfurization and denitrification using catalyst and absorbent substep, and its denitrification efficiency is significantly carried Height, and technological process is simple, and water consumption is less, and investment and operating cost are relatively low.Compared with wet desulphurization denitration, the present invention is also Industrial wastewater discharge can be reduced.The method of the present invention is by the byproduct of reaction after gas cleaning directly using obtaining Building wood Material, thus there is preferable economic benefit.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to This.
The method that the method for dry flue gas desulphurization denitration is referred to as flue gas dry desulfurizing denitration, is represented without using slurries The method that desulphurization denitration is carried out to flue gas.The dry flue gas desulphurization denitration of the present invention is different from wet process of FGD denitration, and it is not A large amount of slurries are needed to use, thus the generation of a large amount of industrial wastes can be avoided.
The method of the dry flue gas desulphurization denitration of the present invention includes：(1) pre- dust removal step；(2) catalytic oxidation stage；(3) Absorption step.This method can also include (4) dust removal step；(5) absorbent circulation step；(6) by-product utilized step.Below Describe in detail.
<Pre- dust removal step>
The pre- dust removal step of the present invention is that pending flue gas is carried out into pre- dedusting to remove most of dust granules, so as to shape Into pre- dedusting flue gas.Above-mentioned steps can be carried out in pre- cleaner, and the concrete structure of the pre- cleaner can use this Known to field those.It is for instance possible to use electrostatic precipitator is as pre- cleaner.The pre- efficiency of dust collection of the present invention can be More than 90%, preferably more than 95%, the load of process below can be so reduced, improves the operation stability of desulphurization denitration.
In the present invention, the content of sulfur dioxide of pending flue gas can be 300~20000mg/Nm3, be preferably 500~ 10000mg/Nm3, more preferably 1000~3000mg/Nm3.The amount of nitrogen oxides of the flue gas can be 100~500mg/ Nm3, be preferably 150~500mg/Nm3, more preferably 300~500mg/Nm3.Oxygen content can be 10~20vol%, preferably For 15~18vol%.Temperature can be 95~160 DEG C；Preferably 120~135 DEG C.In addition, the flow velocity of flue gas can be 2~ 5m/s, preferably 2.5~3.5m/s.Above-mentioned Gas Parameters represent the parameter at smoke inlet；The parameter root of smoke outlet Factually depending on border desulphurization denitration situation.Using above-mentioned technological parameter, be advantageous to improve denitrification efficiency.
<Catalytic oxidation stage>
The catalytic oxidation stage of the present invention is to use catalyst by the oxidizing sulfur dioxide in pre- dedusting flue gas for three oxidations Sulphur, and be nitrogen dioxide by oxidation of nitric oxide, so as to form pretreated fumes.Above-mentioned steps are carried out in bed apparatus is catalyzed. Catalysis bed apparatus includes shell, and the front portion of shell is provided with gas outlet, and the rear portion of shell is provided with air inlet, and the inside of shell is provided with extremely Few two Catalytic Layers being arranged above and below.Pre- dedusting flue gas enters the Catalytic Layer by the air inlet, and is discharged from the gas outlet. Catalyst is provided with Catalytic Layer.The shape of catalyst can be cylinder, spheroid or Raschig ring body；Preferably spheroid.This Sample is advantageous to fill up the Catalytic Layer for being catalyzed bed apparatus.
In the present invention, catalyst includes carrier and active component, and active component is supported on carrier, for by flue gas Oxidizing sulfur dioxide be sulfur trioxide, and be nitrogen dioxide by oxidation of nitric oxide.Carrier can be that nanoscale both sexes aoxidize Thing.For example, carrier is selected from TiO2、ZrO2Or HfO2In one or more；Preferably TiO2And ZrO2Combination.Active component bag Include nanosize metal oxide and KMnO4.The nanosize metal oxide includes V2O5、CoO、Co2O3、Fe2O3And MnO2。V2O5 It is main to be responsible for SO2Catalysis oxidation is SO3, CoO, Co2O3、Fe2O3、MnO2And KMnO4It is main to be responsible for NO catalysis oxidations being NO2。 Such combination can be sulfur trioxide and nitrogen dioxide fully by the sulfur dioxide in flue gas and oxidation of nitric oxide.
According to an embodiment of the invention, based on 100 part by weight of catalyst, the catalyst includes 30~60 parts by weight TiO2, 10~30 parts by weight ZrO2, 2~10 parts by weight V2O5, 2~10 parts by weight CoO, 1~5 parts by weight Co2O3, 3~10 weight Part Fe2O3, 5~15 parts by weight MnO2With 2~10 parts by weight KMnO4.Preferably, the catalyst includes 40~56 parts by weight TiO2, 12~20 parts by weight ZrO2, 5~10 parts by weight V2O5, 3~8 parts by weight CoO, 2~5 parts by weight Co2O3, 3~8 parts by weight Fe2O3, 6~10 parts by weight MnO2With 3~8 parts by weight KMnO4.It is highly preferred that the catalyst includes 46~50 parts by weight TiO2, 13~15 Parts by weight ZrO2, 8~10 parts by weight V2O5, 5~6 parts by weight CoO, 3~5 parts by weight Co2O3, 5~7 parts by weight Fe2O3, 7~9 weights Measure part MnO2With 6~8 parts by weight KMnO4.Above-mentioned active component is controlled in above range, it can be significantly improved in flue gas Sulfur dioxide and nitric oxide production oxidation effectiveness, so as to improve desulfurization off sulfide effect.According to an embodiment of the invention, The catalyst is only made up of said components.
The catalyst of the present invention can use conventional method to obtain, such as infusion process.Nanosize metal oxide can be adopted Synthesized with conventional methods such as sol-gel process, Hydrolyze method, hydrothermal synthesis methods.Here repeat no more.Nanosize metal oxide Particle diameter can be 2~100nm, and specific surface area is 100~300m2/g.Potassium permanganate can impregnate in the form of a solution.
<Absorption step>
The absorption step of the present invention is to use the absorbent using magnesia as main component to carry out dry method to pretreated fumes Desulphurization denitration, so as to form flue gas after processing.Above-mentioned steps can be carried out in absorption equipment.Absorption equipment can be recycle stream Change bed absorption tower, so absorbent can fully be contacted with pretreated fumes, improve desulfurization off sulfide effect.Absorbent and pre- place The time of contact for managing flue gas can be in more than 30min, for example, 30~60min, preferably in 35~50min.It can so take into account Desulfurization off sulfide effect and fume treatment efficiency.
In the present invention, absorbent includes magnesia.Magnesia can include light calcined magnesia, micron order magnesia and/ Or nanoscale magnesium.According to an embodiment of the invention, the magnesia includes 70~85wt% activated magnesia, Preferably 80~85% activated magnesia；It is excellent and content of the nanoscale magnesium in the magnesia is 10~20wt% Elect 15~20wt% as.By using the exclusive property of some nanoparticles of nanoscale magnesium, desulphurization denitration can be improved Efficiency.The formation of magnesium sulfate is so more beneficial for, so as to improve flue gas desulfurization and denitrification effect.In the present invention, the absorbent Magnesia can only be included, the modifying agent such as calcium oxide and silica can also be comprised additionally in.Modifying agent is micron order, nanoscale Metal oxide.In order to improve removal efficiency, absorbent of the invention is powdered.Its particle diameter can be 0.5~10 micron, Preferably 1~5 micron.Directly absorbent can so be mixed with flue gas, and then sulfur dioxide and nitrogen oxidation are carried out to flue gas The removing of thing, so as to complete the desulphurization denitration of flue gas in the case where not needing a large amount of water, and a large amount of industrial wastes is not produced. For example, absorbent dry powder is sufficiently mixed with flue gas in flue, desulphurization denitration processing, processing are carried out subsequently into absorption tower Flue gas is discharged by chimney afterwards.
In the present invention, the bottom of absorption equipment can be provided with smoke inlet, for the pretreated fumes to be introduced To the absorption equipment.The bottom of absorption equipment can be provided with nozzle, for supplying water to absorption equipment.In the effect of water Under, absorbent is more fully contacted and reacted with flue gas, improves desulfurization off sulfide effect.
<Dedusting and absorbent circulation step>
The dust removal step of the present invention is is separated flue gas after the processing in sack cleaner, so as to be purified Flue gas, the absorbent not being fully utilized and main component are the powdered accessory substance of sulfate and nitrate.Absorbent circulation step The rapid absorbent not to be fully utilized in the bottom collection of sack cleaner, and the absorbent not being fully utilized is recycled to Absorption equipment.
In the present invention, the bottom of sack cleaner can be provided with absorbent collector and accessory substance collector.Absorb Agent collector is connected by the smoke inlet of pipeline and absorption equipment, for the absorbent not being fully utilized to be recycled into the suction Receiving unit.Absorbent can be so reused, reduces operating cost.Accessory substance collector is set by pipeline and by-product recovery Standby connection, for accessory substance to be delivered into the by-product recovery equipment.Absorbent collector can be it is at least one, such as two More than individual.
<By-product utilized step>
The by-product utilized step of the present invention is to mix the raw material including the powdered accessory substance and industrial solid wastes Close, so as to form construction material.Powdered accessory substance comes from by-product recovery equipment.For example, by accessory substance and magnesia, industry Solid waste and additive, which are well mixed, obtains binder materials.In the present invention, accessory substance, magnesia, industrial solid can be given up Thing and additive are respectively ground to more than 200 mesh in advance, preferably more than 250 mesh, are then mixed；By accessory substance, oxygen Change magnesium, industrial solid wastes and additive, which are well mixed, obtains mixture, and then gained mixture is ground to more than 200 mesh, Preferably more than 250 mesh；Or mix the accessory substance after grinding, magnesia, industrial solid wastes and additive, then enter one Step grinding obtains binder materials.
In the present invention, the weight ratio of accessory substance and magnesia, industrial solid wastes and additive can be 50~100: 50~100:30~80:2~10.Preferably, their weight ratio is 60~80:60~80:50~60:5~10.So can be with Fully ensure that the combination property of binder materials.
In the present invention, the industrial solid wastes can be selected from one kind in flyash, slag powders or building waste powder It is or a variety of；Preferably flyash and/or slag powders.The example of the slag powders of the present invention includes but is not limited to the stove after ball milling Slag, slag, slag or scum.Flyash is the fine ash that catching is got off from the flue gas after coal combustion, and flyash is coal-burning power plant The primary solids waste of discharge.Slag is ironmaking, the slag charge of steel-making discharge.Building waste powder is the powder using building waste as raw material The broken industrial solid wastes formed.Using above-mentioned industrial solid wastes, be advantageous to obtain the binder materials of steady quality.Industrial Solid The granularity of body waste is preferably more than 200 mesh, more preferably more than 250 mesh.According to an embodiment of the invention, the work Industry solid waste is selected from slag powders and flyash of the granularity more than 200 mesh.
In the present invention, the additive is selected from dihydric phosphate, dibasic alkaliine, tartaric acid, tartrate or amino One or more in trimethylene phosphonic；Preferably dihydric phosphate or dibasic alkaliine.Specific example includes but unlimited In sodium dihydrogen phosphate or disodium-hydrogen.Using above-mentioned additive, the combination property of binder materials can be fully ensured that.
According to an embodiment of the invention, it is 10~35 that the industrial solid wastes, which can be selected from weight ratio,:30~ The composition of 50 slag powders and flyash composition；Preferably weight ratio is 20~25:30~35 slag powders and flyash group Into composition.
" part " in following preparation example and embodiment represents parts by weight, unless specifically stated otherwise.
Embodiment 1
By V2O5、CoO、Co2O3、Fe2O3、MnO2And KMnO4As active component, TiO2And ZrO2As carrier using leaching Stain method obtains catalyst A1.
Table 1, catalyst A1 formulas
TiO2 56.0 parts by weight
ZrO2 15.0 parts by weight
V2O5 4.0 parts by weight
CoO 5.0 parts by weight
Co2O3 5.0 parts by weight
Fe2O3 3.0 parts by weight
MnO2 7.0 parts by weight
KMnO4 5.0 parts by weight
Table 2, smoke inlet parameter
Sequence number Parameter Unit Numerical value
1 Inlet flue gas amount (operating mode) m3/h 180000
2 Inlet flue gas amount (mark condition wet basis) Nm3/h 120441
3 Inlet flue gas temperature ℃ 135
4 SO2Entrance concentration mg/Nm3 2400
5 Entrance nitric oxide concentration mg/Nm3 480
6 Humidity of flue gas % 5.8
Table 3, exhanst gas outlet parameter
Sequence number Project Quantity Unit
1 Exiting flue gas amount (operating mode) 99543 m3/h
2 Exhaust gas temperature 65 ℃
3 Sulfur dioxide emissioning concentration 45 mg/Nm3
4 Desulfuration efficiency 98.75 %
5 Discharged nitrous oxides concentration 50 mg/Nm3
6 Denitration efficiency 96 %
7 The quantum of output of accessory substance 5.34 t/h
The flow velocity of pending flue gas is 2.5m/s, oxygen content 15vol%,；The other specification of smoke inlet, flue gas go out The parameter of mouth is as shown in tables 2 and 3.
Pending flue gas removes most of dust granules in advance by pre-duster, obtains pre- dedusting flue gas, pre- dedusting effect Rate is more than 90%.Pre- dedusting flue gas is by catalysis bed apparatus, and the equipment includes two Catalytic Layers being arranged above and below, wherein filling up Catalyst A1.V2O5By SO2Catalysis oxidation is SO3, CoO, Co2O3、Fe2O3、MnO2And KMnO4It is NO by NO catalysis oxidations2, so as to Form pretreated fumes.Using absorbent, (magnesium oxide powder, it contains 80wt% activated magnesia, nano oxidized content of magnesium For 15wt%) carry out dry desulfurization denitration.Absorbent dry powder is well mixed into flue with pretreated fumes, and is entered and followed In ring fluid bed absorption tower, then the water sprayed into nozzle is sufficiently mixed, so as to complete flue gas desulfurization and denitrification.Flue gas passes through after processing The absorbent and purifying smoke that cloth bag deduster is separated into powdered accessory substance, is not fully utilized, purifying smoke are arranged by chimney Go out, accessory substance then enters accessory substance collector, and the absorbent not being fully utilized is recycled in absorption tower.
By industrial solid wastes (flyash, slag powders) more than accessory substances more than 200 mesh and magnesia, 200 mesh and Additive (sodium dihydrogen phosphate) is well mixed to obtain the binder materials.Binder materials material proportion and the performance test results such as table 4 and table 5.The performance of binder materials is measured using GB/T50448-2008.Wherein, density, water absorption rate are maintenance 28d Test result.
The material proportion of table 4, binder materials
Specification Accessory substance Magnesia Slag Flyash Additive
g 80 60 20 35 5
The testing result of table 5, binder materials
The concentration of the sulfur dioxide of purifying smoke is 45mg/Nm3, the concentration of nitrogen oxides is 50mg/Nm3.Desulfuration efficiency reaches To 98.75%, denitration efficiency 96%.
Embodiment 2
Increase V2O5And Fe2O3Dosage, catalyst A2 is obtained using the formula of table 6, other conditions are same as Example 1.Cigarette Gas outlet parameter is referring to table 7.
Table 6, catalyst A2 formulas
TiO2 52.0 parts by weight
ZrO2 15.0 parts by weight
V2O5 6.0 parts by weight
CoO 5.0 parts by weight
Co2O3 5.0 parts by weight
Fe2O3 5.0 parts by weight
MnO2 7.0 parts by weight
KMnO4 5.0 parts by weight
Table 7, exhanst gas outlet parameter
Sequence number Project Quantity Unit
1 Exiting flue gas amount (operating mode) 98834 m3/h
2 Exhaust gas temperature 65 ℃
3 Sulfur dioxide emissioning concentration 37 mg/Nm3
4 Desulfuration efficiency 98.98 %
5 Discharged nitrous oxides concentration 43 mg/Nm3
6 Denitration efficiency 96.02 %
7 The quantum of output of accessory substance 5.43 t/h
The concentration of the sulfur dioxide of purifying smoke is 37mg/Nm3, the concentration of nitrogen oxides is 43mg/Nm3.Desulfuration efficiency reaches To 98.98%, denitration efficiency 96.02%.
Embodiment 3
Catalyst A3 is obtained using the formula of table 8, other conditions are same as Example 1.Exhanst gas outlet parameter is referring to table 9.
Table 8, catalyst A3 formulas
TiO2 46.0 parts by weight
ZrO2 15.0 parts by weight
V2O5 8.0 parts by weight
CoO 5.0 parts by weight
Co2O3 5.0 parts by weight
Fe2O3 7.0 parts by weight
MnO2 7.0 parts by weight
KMnO4 7.0 parts by weight
Table 9, exhanst gas outlet parameter
Sequence number Project Quantity Unit
1 Exiting flue gas amount (operating mode) 97345 m3/h
2 Exhaust gas temperature 65 ℃
3 Sulfur dioxide emissioning concentration 24 mg/Nm3
4 Desulfuration efficiency 99.34 %
5 Discharged nitrous oxides concentration 29 mg/Nm3
6 Denitration efficiency 97.39 %
7 The quantum of output of accessory substance 5.7 t/h
The concentration of the sulfur dioxide of purifying smoke is 24mg/Nm3, the concentration of nitrogen oxides is 29mg/Nm3.Desulfuration efficiency reaches To 99.34%, denitration efficiency 97.39%.
The present invention is not limited to above-mentioned embodiment, in the case of without departing substantially from the substantive content of the present invention, this area skill Any deformation, improvement, the replacement that art personnel are contemplated that each fall within the scope of the present invention.

Claims (10)

  1. A kind of 1. method of dry flue gas desulphurization denitration, it is characterised in that comprise the following steps：
    (1) pre- dust removal step：Pending flue gas is subjected to pre- dedusting to remove most of dust granules, pre- the cloud of dust is removed so as to be formed Gas；
    (2) catalytic oxidation stage：In bed apparatus is catalyzed, use catalyst by the oxidizing sulfur dioxide in pre- dedusting flue gas for three Sulfur oxide, and be nitrogen dioxide by oxidation of nitric oxide, so as to form pretreated fumes；The catalyst includes carrier and activity Composition；The carrier is nanoscale amphoteric oxide, selected from TiO2、ZrO2Or HfO2In one or more；The active component Including KMnO4And nanosize metal oxide, the nanosize metal oxide include V2O5、CoO、Co2O3、Fe2O3And MnO2；With
    (3) absorption step：In absorption equipment, the absorbent using magnesia as main component is used to do pretreated fumes Method desulphurization denitration, so as to form flue gas after processing.
  2. 2. according to the method for claim 1, it is characterised in that in step (1), the sulfur dioxide of the pending flue gas contains Measure as 300~20000mg/Nm3, amount of nitrogen oxides be 100~500mg/Nm3, oxygen content be 10~20vol%, flow velocity be 2~5m/s and temperature are 95~160 DEG C.
  3. 3. according to the method for claim 1, it is characterised in that in step (1), pre- efficiency of dust collection is more than 90%.
  4. 4. according to the method for claim 1, it is characterised in that in step (2), the catalysis bed apparatus includes shell, outside The front portion of shell is provided with gas outlet, and the rear portion of shell is provided with air inlet, and the inside of shell is provided with least two catalysis being arranged above and below Layer；The pre- dedusting flue gas enters the Catalytic Layer by the air inlet, and is discharged from the gas outlet.
  5. 5. according to the method for claim 1, it is characterised in that in step (2), based on 100 part by weight of catalyst, the catalysis Agent includes following components：
  6. 6. according to the method for claim 1, it is characterised in that in step (2), based on 100 part by weight of catalyst, the catalysis Agent includes following components：
  7. 7. according to the method for claim 1, it is characterised in that in step (3), the absorption equipment is inhaled for recirculating fluidized bed The time of contact of receipts tower, the absorbent and the pretreated fumes is in more than 30min.
  8. 8. according to the method for claim 1, it is characterised in that in step (3), the absorbent also includes calcium oxide and two Silica；The magnesia includes 70~85wt% activated magnesia, and nanoscale magnesium containing in the magnesia Measure as 10~20wt%.
  9. 9. according to the method described in any one of claim 1~8, it is characterised in that it also comprises the following steps：
    (4) dust removal step：Flue gas after the processing is separated in sack cleaner, so as to obtain purifying smoke, not complete The absorbent and main component of complete utilization are the powdered accessory substance of sulfate and nitrate；With
    (5) absorbent circulation step：The absorbent not being fully utilized is recycled to absorption equipment.
  10. 10. according to the method for claim 9, it is characterised in that it also comprises the following steps：
    (6) by-product utilized step：Raw material including the powdered accessory substance and industrial solid wastes is mixed, so as to be formed Construction material.
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CN108714425A (en) * 2018-05-11 2018-10-30 华南理工大学 A kind of desulfurization catalyst of flue gas and the application in new dry process rotary kiln dore furnace flue gas desulfurization
WO2019062449A1 (en) * 2017-09-30 2019-04-04 中晶环境科技股份有限公司 Dry desulfurization and denitration agent, and production method therefor and application thereof
CN109806882A (en) * 2019-03-18 2019-05-28 山东大业联合新能源设备有限公司 A kind of SCO denitration new energy composite material
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CN111944557A (en) * 2019-05-17 2020-11-17 中国石油化工股份有限公司 FCC method for reducing NO concentration in regenerated flue gas
CN113117513A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Integrated process for flue gas treatment and cement preparation
CN113117498A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Integrated process for flue gas treatment and cementing material preparation
CN113121130A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Preparation method of cementing material

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CN113117513A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Integrated process for flue gas treatment and cement preparation
CN113117498A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Integrated process for flue gas treatment and cementing material preparation
CN113121130A (en) * 2019-12-30 2021-07-16 中晶新材料有限公司 Preparation method of cementing material

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