CN107441932A - Fume desulfurizing agent and its production method and application - Google Patents
Fume desulfurizing agent and its production method and application Download PDFInfo
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- CN107441932A CN107441932A CN201710918985.XA CN201710918985A CN107441932A CN 107441932 A CN107441932 A CN 107441932A CN 201710918985 A CN201710918985 A CN 201710918985A CN 107441932 A CN107441932 A CN 107441932A
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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
- B01D53/508—Sulfur oxides by treating the gases with solids
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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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
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Abstract
The invention discloses a kind of fume desulfurizing agent and its production method and application.Based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components:The parts by weight of MgO 70~90;The parts by weight of CaO0.5~4;SiO22~10 parts by weight;V2O50.15~0.6 parts by weight;CeO20.1~0.4 parts by weight;Al2O30.15~0.6 parts by weight;MnO25~10 parts by weight.The desulfuration efficiency of the fume desulfurizing agent of the present invention is very high.
Description
Technical field
The present invention relates to a kind of fume desulfurizing agent and its production method and application, especially a kind of dry-desulphurizer and its life
Production method and flue gas dry desulfurizing method.
Background technology
With the fast development of basic industries, China's economy makes great progress;The ring caused by industrial pollution simultaneously
Border pollution is also increasingly severe.Using coal-fired and fuel oil as the oxysulfide SO included in the waste gas that power source dischargesx, nitrogen
Oxide NOx, the pollutant such as dust and heavy metal exacerbate the generation of haze weather.In China's energy system, coal accounts for
The 75% of whole energy system, much larger than oil, natural gas and waterpower.National SO2The 90% of discharge capacity carrys out spontaneous combustion coal.Therefore,
Reduce SO2Discharge capacity turn into the task of top priority.
Current sulfur method is roughly divided into three classes:(1) wet method, washed using liquid-absorbant (such as water or aqueous slkali)
Wash;(2) semidry method, the moisture in lime slurry, while lime and SO are evaporated using obvious heat of smoke2Reaction generation dry powder-shaped sulfurous
Sour calcium, the characteristics of having wet method and dry method concurrently;(3) dry method, with powdery or granular absorbent, adsorbent or catalyst to remove SO2。
Wet Flue Gas Desulfurization Technique comparative maturity, there is the business application history of decades, but had that freight charges are high, water consumption is big, by-product
Thing easily causes secondary pollution problems.Dry method and semi-dry process have that cost is low, technique is simple, easy to maintenance, desulfuration efficiency
The advantages that scope is wide, reliable, strong adaptability, gets more and more people's extensive concerning.But semidry method does not solve fundamentally
The certainly reproducible utilization problem of resource.
Dry desulfurization process majority belongs to gas-solid reaction, relatively lower speed, and flue gas in the reactor grow by the reaction time, takes off
Flue gas after sulphur does not cool, it is not necessary to heats, you can meets the requirement of discharge diffusion.In addition, desulfurization by dry method also has nothing
The advantages that fouling, condensation, blocking, reliability height, secondary pollution are lacked.
Existing frequently-used dry-desulphurizer is based on activated carbon or activated coke.It is a kind of cost-effective with active carbon desulfurization
Sulfur method.Simple to operate because active carbon desulfurization temperature is low, caused sulfuric acid is also used as byproduct recycling, because
This is a kind of very promising sulfur method with active carbon desulfurization.Application No. 99104245.X Chinese patent application discloses
A kind of method that desulfurizing agent is prepared by the use of activated carbon or NACF as carrier loaded cupric oxide, but because carbon material is strong
Low, abrasion height is spent, the number of recycling is few, and production cost is high.
For the activated coke of commercial sizeization application at present there is also desulfurization capacity is relatively low, regeneration is frequent, and usage amount is big etc. asks
Topic.Therefore, the dry-desulphurizer of developing low-cost, high activity is highly desirable, to improve desulfurization performance, reduces usage amount, drop
Low investment and operating cost.
The content of the invention
The defects of in order to overcome prior art, present inventor have carried out in-depth study repeatedly, so as to complete this
Invention.
It is an object of the present invention to provide a kind of desulfurizing agent, its desulfuration efficiency are very high.
It is another object of the present invention to provide a kind of production method of desulfurizing agent, its technique is simple, and cost is cheap.
It is yet a further object of the present invention to provide a kind of method of flue gas dry desulfurizing, and it can improve making for desulfurizing agent
Use effect.
The present invention, which adopts the following technical scheme that, realizes above-mentioned purpose.
The present invention provides a kind of fume desulfurizing agent, and based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components:
According to the desulfurizing agent of the present invention, it is preferable that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components:
According to the desulfurizing agent of the present invention, it is preferable that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components:
According to the desulfurizing agent of the present invention, it is preferable that MgO is made up of micron order magnesia and nanoscale magnesium, and nanometer
Level magnesia is 10~20 parts by weight;CaO is made up of micron order calcium oxide and nanoscale calcium, and nanoscale calcium is
0.5~2 parts by weight;SiO2It is made up of micron silica and nanometer grade silica, and nanometer grade silica is 2~5
Parts by weight;V2O5Including nanoscale vanadic anhydride, and nanoscale vanadic anhydride is 0.15~0.5 parts by weight;CeO2By micron
Level ceria and nanoscale ceria composition, and nanoscale ceria is 0.1~0.3 parts by weight;Al2O3Including nanometer
Level alundum (Al2O3), and nanoscale alundum (Al2O3) is 0.15~0.5 parts by weight;And MnO2Including nanometer electrode manganese dioxide, and
Nanometer electrode manganese dioxide is 5~8 parts by weight.
According to the desulfurizing agent of the present invention, it is preferable that nanoscale magnesium is 15~20 parts by weight;Nanoscale calcium is 1
~2 parts by weight;Nanometer grade silica is 3~5 parts by weight;Nanoscale vanadic anhydride is 0.2~0.3 parts by weight;Nanoscale
Ceria is 0.15~0.2 parts by weight;Nanoscale alundum (Al2O3) is 0.2~0.3 parts by weight;And nanometer electrode manganese dioxide is
6~7 parts by weight.
According to the desulfurizing agent of the present invention, it is preferable that the active oxidation content of magnesium in MgO is 50~75wt%.
According to the desulfurizing agent of the present invention, it is preferable that the active oxidation content of magnesium in MgO is 62~75wt%.
According to the desulfurizing agent of the present invention, it is preferable that described desulfurizing agent is flue gas dry desulfurizing agent.
The present invention also provides a kind of production method of desulfurizing agent, including the step that the component is well mixed.
The present invention a kind of method of flue gas dry desulfurizing is also provided, by above-mentioned desulfurizing agent formed dry powder-shaped, then with flue gas
Fully contact more than 30min, so as to remove the sulfur dioxide in flue gas;Wherein, the content of sulfur dioxide of flue gas be 1000~
3000mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
The present invention is by magnesia and metal oxide and inorganic non-metallic oxide organic assembling, so as to form desulfuration efficiency
Very high fume desulfurizing agent.According to currently preferred technical scheme, the nano level metal oxide of suitable amounts and inorganic
Nonmetal oxide can further improve flue gas desulfurization effect.
Embodiment
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
In the present invention, micron order represents 1~100 μm, preferably 2~10 μm;Nanoscale represents 1~100nm, is preferably
10~60nm.
<Desulfurizing agent and production method>
The desulfurizing agent of the present invention includes magnesia and modifying agent.Magnesia include light calcined magnesia, micron order magnesia with
And nanoscale magnesium.Modifying agent includes micron order and nano level metal oxide and inorganic non-metallic oxide.Metal oxygen
Compound includes nanoscale and micron-sized calcium oxide, alundum (Al2O3), manganese dioxide, vanadic anhydride, ceria.It is inorganic non-
Metal oxide includes nanoscale and micron-sized silica.It is a discovery of the invention that these modifying agent are combined with magnesia, can
To significantly improve flue gas desulfurization effect.
With V2O5Exemplified by, V2O5Oxygen and vanadium tetraoxide, SO are broken down at high temperature2Urged in the presence of oxygen obtained by decomposition
Change is oxidized to SO3.Subsequent elementary reaction is then that the oxygen absorbed in gas phase is participated in instead together with it and so as to supplement
The oxygen answered.V2O5Reduce SO2It is oxidized to SO3Course of reaction activation energy, so as to accelerate reaction rate.SO3Further and oxygen
Change reactive magnesium generation sulfate, so as to reach desulfurized effect.
In the desulfurizing agent of the present invention, MgO is 70~90 parts by weight, preferably 80~90 parts by weight, more preferably 85~
88 parts by weight.Active oxidation content of magnesium in MgO can be 50~75wt%, preferably 62~75wt%, more preferably 65~
70wt%.So be advantageous to improve its assimilation effect to sulfur trioxide, so as to improve desulfurized effect.MgO can be by micron order
Magnesia and nanoscale magnesium composition, and nanoscale magnesium is 10~20 parts by weight;Preferably 15~20 parts by weight.So
Desulfurized effect can further be improved.
In the desulfurizing agent of the present invention, CaO is 0.5~4 parts by weight, preferably 0.8~3 parts by weight, more preferably 2~3
Parts by weight.CaO is made up of micron order calcium oxide and nanoscale calcium, and nanoscale calcium is 0.5~2 parts by weight;It is preferred that
For 1~2 parts by weight.Calcium oxide can with assist absorption sulfur trioxide, so as to improving desulfurized effect.
In the desulfurizing agent of the present invention, SiO2For 2~10 parts by weight, preferably 3~8.5 parts by weight, more preferably 5~8
Parts by weight.SiO2It is made up of micron silica and nanometer grade silica, and nanometer grade silica is 2~5 parts by weight;
Preferably 3~5 parts by weight.Silica promotes catalytic effect, and then improves desulfurized effect.
In the desulfurizing agent of the present invention, V2O5For 0.15~0.6 parts by weight, preferably 0.2~0.4 parts by weight, it is more preferably
0.35~0.4 parts by weight.V2O5Including nanoscale vanadic anhydride, and nanoscale vanadic anhydride is 0.15~0.5 parts by weight;
Preferably 0.2~0.3 parts by weight.Vanadic anhydride is controlled in above range, desulfurized effect and usage amount can be taken into account, so as to
Reduce cost.
In the desulfurizing agent of the present invention, CeO2For 0.1~0.4 parts by weight, preferably 0.15~0.3 parts by weight, more preferably
For 0.2~0.3 parts by weight.CeO2It is made up of micron order ceria and nanoscale ceria, and nanoscale ceria is
0.1~0.3 parts by weight;Preferably 0.15~0.2 parts by weight.Ceria is controlled in above range, desulfurization effect can be taken into account
Fruit and usage amount, so as to reduce cost.
In the desulfurizing agent of the present invention, Al2O3For 0.15~0.6 parts by weight, preferably 0.2~0.4 parts by weight, more preferably
For 0.2~0.3 parts by weight.Al2O3Including nanoscale alundum (Al2O3), and nanoscale alundum (Al2O3) is 0.15~0.5 weight
Part;Preferably 0.2~0.3 parts by weight.Alundum (Al2O3) can improve catalytic effect, and then improve desulfuration efficiency.
In the desulfurizing agent of the present invention, MnO2For 5~10 parts by weight, preferably 6~9 parts by weight, more preferably 6~7 weights
Measure part.MnO2Including nanometer electrode manganese dioxide, and nanometer electrode manganese dioxide is 5~8 parts by weight;Preferably 6~7 parts by weight.Will
Manganese dioxide is controlled in above range, desulfurized effect and usage amount can be taken into account, so as to reduce cost.
In the present invention, described desulfurizing agent is flue gas dry desulfurizing agent.Flue gas dry desulfurizing is also referred to as dry method flue gas
Desulfurization, represent to carry out desulfurization to flue gas without using slurries.The dry flue gas desulphurization of the present invention is different from wet process of FGD, and it is not
A large amount of slurries are needed to use, thus can avoid producing a large amount of industrial wastes.
The production method of the desulfurizing agent of the present invention includes the step for being well mixed above-mentioned each component.For example, magnesia,
Calcium oxide, alundum (Al2O3), manganese dioxide, vanadic anhydride, ceria and silica are well mixed, so as to obtain dry powder
Shape desulfurizing agent.
<Flue gas dry desulfurizing>
The method of the present invention includes flue gas desulfurization step:Above-mentioned desulfurizing agent is formed into dry powder-shaped, it is then (such as pre- with flue gas
Dedusting flue gas) fully contact more than 30min, so as to remove the sulfur dioxide in flue gas.The content of sulfur dioxide of flue gas is 1000
~3000mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
In the method for the invention, before flue gas desulfurization step, pre- dust removal step is preferably included:Flue gas is removed in advance
Dirt is to remove most of dust granules, so as to form pre- dedusting flue gas.Above-mentioned steps can be carried out in pre- cleaner, and this is pre-
The concrete structure of cleaner can use it is well known in the art those, such as electrostatic precipitator.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 stable of desulfurization
Property.
In the method for the invention, the content of sulfur dioxide of flue gas can be 1000~3000mg/Nm3, be preferably 1500
~2800mg/Nm3, more preferably 1600~2600mg/Nm3.Oxygen content can be 10~25vol%, be preferably 15~
20vol%.Temperature can be 105~160 DEG C;Preferably 120~135 DEG C.In addition, the flow velocity of flue gas can be 2~5m/s, it is excellent
Elect 2.5~3.5m/s as.Above-mentioned Gas Parameters represent the parameter at smoke inlet;The parameter of smoke outlet is according to actual de-
Depending on sulphur situation.Using above-mentioned technological parameter, be advantageous to improve desulfuration efficiency.
The flue gas desulfurization step of the present invention can be carried out in desulfurizer.Desulfurizer can be that recirculating fluidized bed absorbs
Tower, so desulfurizing agent can fully be contacted with pre- dedusting flue gas, improve desulfurized effect.Desulfurizing agent contact with pre- dedusting flue gas
Time can be in more than 30min, for example, 30~60min, preferably in 35~50min.Desulfurized effect and cigarette can so be taken into account
Gas disposal efficiency.For example, desulfurizing agent dry powder and pre- dedusting flue gas are sufficiently mixed in flue, carried out subsequently into absorption tower
Desulfurization process, the flue gas after desulfurization are discharged by chimney.
In the method for the invention, after flue gas desulfurization, dust removal step can also be included:Flue gas after the desulfurization is existed
Separated in bag-type dust collector, so as to obtain purifying smoke and powdered accessory substance.
Embodiment 1
Each component is well mixed by the formula according to table 1, obtains desulfurizing agent D1.Dry desulfurization is carried out using the desulfurizing agent,
The flow velocity of flue gas is 2.5m/s;The other specification of smoke inlet, the parameter of exhanst gas outlet are as shown in tables 2 and 3.Flue gas after purification
The concentration 45mg/Nm of sulfur dioxide3, desulfuration efficiency 99.03%.
The formula of table 1, desulfurizing agent D1
Table 2, smoke inlet parameter
Sequence number | Parameter | Numerical value | Unit |
1 | Inlet flue gas amount (operating mode) | 1780000 | m3/h |
2 | Inlet flue gas amount (mark condition) | 1148790 | Nm3/h |
3 | Inlet flue gas temperature | 135 | ℃ |
4 | SO2Entrance concentration | 2600 | mg/Nm3 |
5 | Entrance flue dust | 110 | mg/Nm3 |
Table 3, exhanst gas outlet parameter
Sequence number | Project | Quantity | Unit |
1 | Desulfurizing tower exiting flue gas amount (operating mode) | 824493 | m3/h |
2 | Exhaust gas temperature | 65 | ℃ |
3 | Sulfur dioxide emissioning concentration | 45 | mg/Nm3 |
4 | Desulfuration efficiency | 99.03 | % |
5 | The quantum of output of accessory substance | 36.80 | t/h |
Embodiment 2
Each component is well mixed by the formula according to table 4, obtains desulfurizing agent D2.Dry desulfurization is carried out using the desulfurizing agent,
The concentration of the sulfur dioxide of flue gas is 27mg/Nm after purification3, desulfuration efficiency 99.42%.The same embodiment of parameter of smoke inlet
1, the parameter of exhanst gas outlet is as shown in table 5.
The formula of table 4, desulfurizing agent D2
Table 5, exhanst gas outlet parameter
Embodiment 3
Each component is well mixed by the formula according to table 6, obtains desulfurizing agent D3.Dry desulfurization is carried out using the desulfurizing agent,
The concentration of the sulfur dioxide of flue gas is 15mg/Nm after purification3, desulfuration efficiency 99.68%.The same embodiment of parameter of smoke inlet
1, the parameter of exhanst gas outlet is as shown in table 7.
The formula of table 6, desulfurizing agent D3
Table 7, exhanst gas outlet parameter
Sequence number | Project | Quantity | Unit |
1 | Exiting flue gas amount (operating mode) | 808579 | m3/h |
2 | Exhaust gas temperature | 64 | ℃ |
3 | Sulfur dioxide emissioning concentration | 15 | mg/Nm3 |
4 | Desulfuration efficiency | 99.68 | % |
5 | The quantum of output of accessory substance | 37.07 | t/h |
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 fume desulfurizing agent, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent includes following components:
2. desulfurizing agent according to claim 1, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent include with
Lower component:
3. desulfurizing agent according to claim 1, it is characterised in that based on 100 parts by weight desulfurizing agents, the desulfurizing agent include with
Lower component:
4. desulfurizing agent according to claim 1, it is characterised in that:
MgO is made up of micron order magnesia and nanoscale magnesium, and nanoscale magnesium is 10~20 parts by weight;
CaO is made up of micron order calcium oxide and nanoscale calcium, and nanoscale calcium is 0.5~2 parts by weight;
SiO2It is made up of micron silica and nanometer grade silica, and nanometer grade silica is 2~5 parts by weight;
V2O5Including nanoscale vanadic anhydride, and nanoscale vanadic anhydride is 0.15~0.5 parts by weight;
CeO2It is made up of micron order ceria and nanoscale ceria, and nanoscale ceria is 0.1~0.3 parts by weight;
Al2O3Including nanoscale alundum (Al2O3), and nanoscale alundum (Al2O3) is 0.15~0.5 parts by weight;With
MnO2Including nanometer electrode manganese dioxide, and nanometer electrode manganese dioxide is 5~8 parts by weight.
5. desulfurizing agent according to claim 4, it is characterised in that:
Nanoscale magnesium is 15~20 parts by weight;
Nanoscale calcium is 1~2 parts by weight;
Nanometer grade silica is 3~5 parts by weight;
Nanoscale vanadic anhydride is 0.2~0.3 parts by weight;
Nanoscale ceria is 0.15~0.2 parts by weight;
Nanoscale alundum (Al2O3) is 0.2~0.3 parts by weight;With
Nanometer electrode manganese dioxide is 6~7 parts by weight.
6. according to the desulfurizing agent described in any one of claims 1 to 3, it is characterised in that the active oxidation content of magnesium in MgO is 50
~75wt%.
7. desulfurizing agent according to claim 6, it is characterised in that the active oxidation content of magnesium in MgO is 62~75wt%.
8. according to the desulfurizing agent described in any one of claims 1 to 3, it is characterised in that described desulfurizing agent takes off for dry fume
Sulphur agent.
9. the production method of the desulfurizing agent according to any one of claim 1~8, it is characterised in that including by the component
Well mixed step.
A kind of 10. method of flue gas dry desulfurizing, it is characterised in that form the desulfurizing agent described in any one of claim 1~8
Dry powder-shaped, more than 30min is fully then contacted with flue gas, so as to remove the sulfur dioxide in flue gas;Wherein, the titanium dioxide of flue gas
Sulfur content is 1000~3000mg/Nm3, flow velocity is 2~5m/s and temperature is 105~160 DEG C.
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Cited By (4)
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CN108404651A (en) * | 2018-02-01 | 2018-08-17 | 中海油天津化工研究设计院有限公司 | A kind of desulfurizing agent for new dry process rotary kiln smoke catalytic desulfurization |
CN109012075A (en) * | 2018-08-24 | 2018-12-18 | 中惠科银河北科技发展有限公司 | A kind of flue gas dry desulfurizing desulfurizing agent and preparation method thereof |
WO2019062451A1 (en) * | 2017-09-30 | 2019-04-04 | 中晶环境科技股份有限公司 | Flue gas desulfurization agent, and production method therefor and application thereof |
CN112403254A (en) * | 2020-11-20 | 2021-02-26 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
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CN105779074A (en) * | 2016-03-08 | 2016-07-20 | 广东万引科技发展有限公司 | Calcium-based catalytic desulfurization agent for cement kiln |
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