CN105107373B - Composite desulfurizer for oxidizing elemental mercury and removing HCl and preparation method thereof - Google Patents
Composite desulfurizer for oxidizing elemental mercury and removing HCl and preparation method thereof Download PDFInfo
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- CN105107373B CN105107373B CN201510552204.0A CN201510552204A CN105107373B CN 105107373 B CN105107373 B CN 105107373B CN 201510552204 A CN201510552204 A CN 201510552204A CN 105107373 B CN105107373 B CN 105107373B
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 28
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 20
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 65
- 230000003009 desulfurizing effect Effects 0.000 claims description 61
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000000779 smoke Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- -1 hydrogen salt Chemical class 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 41
- 230000023556 desulfurization Effects 0.000 abstract description 30
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 238000002347 injection Methods 0.000 abstract 1
- 239000007924 injection Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- 230000008569 process Effects 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000019738 Limestone Nutrition 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 4
- 235000010261 calcium sulphite Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241001625808 Trona Species 0.000 description 1
- DLDMZEIIMBQMAM-UHFFFAOYSA-N [Ca].[Na].[Ba] Chemical compound [Ca].[Na].[Ba] DLDMZEIIMBQMAM-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
Abstract
For oxidizing simple substanceThe composite desulfurizer for removing mercury and HCl comprises 15-30% of bicarbonate and BaCO by mass percent32～5％，KMnO40.5～2％，CeO20.5 to 2 percent, and the balance of Ca (OH)2. During preparation, the calcium hydroxide, the sodium bicarbonate, the barium carbonate and the potassium permanganate are respectively crushed, and then the raw materials are uniformly mixed according to the mass percentage. The preparation method of the composite desulfurizer is simple and feasible, and the requirements of desulfurization and demercuration can be met only by one set of feeding and injection system in practical engineering application. The composite desulfurizer of the invention has good medium-temperature desulfurization efficiency, and SO is in the temperature range of 300-420 DEG C2The removal efficiency is more than 95 percent, and SO3The removal efficiency is more than 90%; the oxidation efficiency of the elemental mercury reaches 80-95%; the HCl removing efficiency reaches more than 90 percent.
Description
Technical field
The present invention relates to a kind of desulfurizing agent for removing the SOx in flue gas, HCl, Elemental Mercury, and in particular to one kind is used for
Oxidizing simple substance mercury, the composite desulfurizing agent for removing HCl and preparation method thereof.
Background technology
It is that a large amount of flue gases are discharged in the boiler of fuel or thermal power plant every year using coal, oil.These flue gases contain SOx,
The harmful substances such as NOx, HCl and HF, its sulphur oxide includes SO2And SO3, they are the main matters to form acid rain.
With China's industrial expansion, the sulfur dioxide (SO2) emissions in industrial smoke are increasingly serious, sulfur dioxide to environment and
The infringement that human body is caused gradually is paid attention to by country and society, therefore a variety of flue gas desulfurization technique technologies are just arisen at the historic moment, these skills
Art can be divided into wet method, half either from foreign countries' introduction, or independent research by its operating feature or using the type of desulfurizing agent
Three kinds of dry method and desulfurization by dry method.Wherein wet process of FGD is because of its safe operation, the features such as desulfuration efficiency is high, accounts for flue gas and takes off
The leading position of sulphur technique.
It is main to use limestone-gypsum doctor treatment in traditional wet desulfurizing process, its operation principle be with lime stone or
Lime stone slurry absorbs the SO in flue gas as absorbent2, calcium sulfite is generated, calcium sulfite is empty by compression in oxidizing tower
Gas is oxidized to calcium sulfate.Dry method and the main component of semi-dry desulphurization agent are the emulsus desulfurizing agent (hydrogen that quick lime and water are configured to
Calcium oxide), adverse current is carried out to flue gas or following current is sprayed, generation gypsum is reclaimed with regard to desulfurization generally by dedusting and solid, is done
Method and semi-dry desulphurization efficiency are very low, and general desulfuration efficiency can only achieve 70% or so.
Desulfurizing agent can substantially be divided into natural prodcuts (containing alkaline waste) and the class of chemicals two, natural production by its source
Product include lime stone, natural rock phosphate in powder, carbide slag (waste material) etc., and chemicals includes lime, calcium hydroxide, magnesia, hydroxide
Sodium, sodium sulfite, sodium sulphate, basic aluminum sulfate, ammoniacal liquor etc..Desulfurizing agent must also meet some conditions, such as desulfurizing agent to flow
The SO in flue gas can largely be absorbed2, and can also be reclaimed with simple method or regeneration treatment, still needing in addition, it is good to possess some
Good chemical characteristic, such as workability, nontoxic, low-viscosity, corrosion-free, thermally-stabilised, loss are low.Conventional several desulfurizing agents
Have：Calcium-based desulfurizing agent, sodium base desulfurizer, Mg-base desulfurizing agent, amino desulfurizing agent etc..
Sodium alkali removes SO2It is a kind of efficient sulfur method, with advantages such as fast, the alkali utilization rate height of reaction rate, but
Because the soda market price is higher, desulphurization cost is caused to increase, the desulphurization cost particularly operated for a long time is larger.Industrially
NaHCO3Production cost it is higher, therefore use NaHCO3The research and application of desulfurization are less.Inner mongolia autonomous region Ih Ju League etc.
Ground has abundant trona mineral reserve, the NaHCO as made from trona3Cost is relatively low, or even raw ore can be applied directly.
It is simple too high using sodium alkali desulfurization agent operating cost, and desulfurization product is not disposable, merely using Ca-base adsorbent,
Desulfuration efficiency does not reach requirement, and the two contradiction is mutually highlighted, and Sodium/Calcium dual alkali scrubbing FGD process can solve above-mentioned contradiction.Sodium base
Desulfurizing agent alkalescence is strong, and compared with lime stone or Wet Lime Desulfurization technique, Sodium/Calcium dual alkali scrubbing FGD process technology has operation can
Lean on, the advantages of operating cost is low, desulfuration efficiency is high.
The higher wet desulfurization system of desulfuration efficiency is more complicated, and running cost is higher, and operates relatively convenient pass
Unite dry method and semi-dry desulphurization, its desulfurizing agent desulfuration efficiency again than relatively low, therefore find it is a kind of can high-efficiency desulfurization dry desulfurization
Agent, needs the artificial and cost input of desulfurization industry to have important economical and environmentally friendly meaning for attenuating.
Adsorption process is an exothermic process in itself, and high temperature is a unfavorable factor to the process, also results in desulfuration efficiency
Decline.If temperature is to NaHCO3Sweetening process influence it is larger, temperature be less than 150 DEG C in the case of desulfurized effect preferably, when
When temperature brings up to 300 DEG C, desulfuration efficiency can be significantly reduced, it is impossible to meet SO2Environmental protection index.At present to coal-fired flue-gas condition
Under simple substance mercury removal adsorbent or catalyst mainly have carbon-based adsorbents such as flying dust, activated carbon and modified activated carbon etc.,
Their active temperature windows are narrower, and demercuration efficiency is relatively low under middle temperature (300~420 DEG C), it is impossible to for the temperature range
The removing of mercury.
The content of the invention
The purpose of the present invention be in view of the shortcomings of the prior art there is provided it is a kind of for oxidizing simple substance mercury, removing HCl it is compound
Desulfurizing agent and preparation method thereof, the composite desulfurizing agent can under middle temperature (300~420 DEG C) efficiently, stably oxidizing simple substance mercury,
Remove HCl, SO2。
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of composite desulfurizing agent for being used for oxidizing simple substance mercury, removing HCl, by mass percentage, including bicarbonate 15
~30%, BaCO32~5%, KMnO40.5~2%, CeO20.5~2%, remaining is Ca (OH)2。
It is preferred that, the bicarbonate is NaHCO3。
It is preferred that, by mass percentage, including NaHCO320~30%, BaCO32~3%, KMnO41~2%,
CeO21~2%, remaining is Ca (OH)2。
A kind of preparation method for oxidizing simple substance mercury, the composite desulfurizing agent for removing HCl, first by calcium hydroxide, bicarbonate
Sodium, barium carbonate, potassium permanganate are respectively crushed into the powder that granularity is less than 2mm, then according to by mass percentage, by bicarbonate
Salt 15~30%, BaCO32~5%, KMnO40.5~2%, CeO20.5~2%, remaining is Ca (OH)2It is well mixed, obtain
To the composite desulfurizing agent for oxidizing simple substance mercury, removing HCl.
Compared with prior art, the invention has the advantages that：
(1) present invention is with bicarbonate, Ca (OH)2For desulfurization host, reliable, desulfuration efficiency is high, it is to avoid simple
It is too high using sodium alkali desulfurization agent operating cost, and desulfurization product is not disposable, merely using Ca-base adsorbent, desulfuration efficiency is not up to
To the problem of requirement.
(2) present invention is due to by BaCO3It is introduced into desulfurizing agent, so can promote to form barium sulfate, sulphur in desulfurization product
The thing phase of the low aqueous solubilities such as sour calcium, calcium sulfite, the recycling of lime-ash is not influenceed, reduces secondary pollution.
(3) a set of feed and spray are only needed in the preparation method simple possible of the composite desulfurizing agent, actual engineer applied
The need for penetrating system and just can meeting desulfurization, demercuration.
(4) composite desulfurizing agent of the invention has preferable moderate temperature desulphurization efficiency, within the temperature range of 300~420 DEG C,
SO2Removal efficiency is more than 95%, SO3Removal efficiency is more than 90%；Elemental mercury oxidation efficiency can reach 80%-95%；
HCl removal efficiency can reach more than 90%.
(5) by composite desulfurizing agent to SO3Removing can be greatly reduced the acid dew point of flue gas, mitigate to upstream device
There is the phenomenon of blue smoke in corrosion and chimney emission.
Further, it is sodium acid carbonate based on bicarbonate, by BaCO3Composition calcium-sodium-barium base in desulfurizing agent is introduced into be combined
Desulfurizing agent, can improve desulfurization rate and stability of the calcium-sodium base composite desulfurizing agent within the temperature range of 300~420 DEG C.
Further, calcium-based desulfurizing agent of the present invention, sodium base desulfurizer are combined with active component, by BaCO3、KMnO4、
CeO2It is incorporated into as active component in desulfurizing agent, active component can improve the desulphurization reaction speed of desulfurizing agent, reduction reaction is lived
Change energy, there is preferable catalytic action to desulphurization reaction.Meanwhile, promote to be formed stable sulfureous phase in desulfurization product, from basic
On solve HCl, SO under middle temperature (300~420 DEG C)2、SO3Removal efficiency is not high, desulfurization product can cause asking for secondary pollution
Topic.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
The composite desulfurizing agent of the present invention, by mass percentage, including bicarbonate 15%, BaCO33%, KMnO4
1%, CeO22%, remaining is Ca (OH)2。
Embodiment 2
The composite desulfurizing agent of the present invention, by mass percentage, including bicarbonate 20%, BaCO32%, KMnO4
0.5%, CeO21%, remaining is Ca (OH)2。
Embodiment 3
The composite desulfurizing agent of the present invention, by mass percentage, including bicarbonate 25%, BaCO35%, KMnO4
1.5%, CeO20.5%, remaining is Ca (OH)2。
Embodiment 4
The composite desulfurizing agent of the present invention, by mass percentage, including bicarbonate 30%, BaCO34%, KMnO4
2%, CeO21.5%, remaining is Ca (OH)2。
The preparation method of composite desulfurizing agent of the present invention is：First by calcium hydroxide, sodium acid carbonate, barium carbonate, potassium permanganate point
The powder that granularity is less than 2mm is not ground into, then according to by mass percentage, by bicarbonate 15~30%, BaCO32~
5%, KMnO40.5~2%, CeO20.5~2%, remaining is Ca (OH)2It is well mixed, obtain being used for oxidizing simple substance mercury, removing
HCl composite desulfurizing agent.
The present invention by mass percentage, including NaHCO315~30%, BaCO32~5%, KMnO40.5~2%,
CeO20.5~2%, remaining is Ca (OH)2.The present invention is with Ca (OH)2And NaHCO3As the desulfurization host at 300~420 DEG C,
SO can directly be removed2、SO3、HCl；Meanwhile, addition partial desulfurization agent can efficient oxidation Elemental Mercury, and the desulfurization effect stabilized and increased
Rate.The oxidation efficiency of Elemental Mercury can be significantly improved using the composite desulfurizing agent, removal efficiency and desulfurization effect with higher HCl
Rate.Desulfurization product is mainly calcium sulfate, barium sulfate, does not result in the secondary pollution to water body and soil, does not interfere with lime-ash
Value.
The desulfuration efficiency and its economy of the composite desulfurizing agent of different component are different, and desulfurizing agent of the same race adds in different
Under dosage, cost performance is also different.Because the unit price of composite desulfurizing agent is than Ca (OH)2It is monovalent much higher, so composite desulfurizing agent
Monovalent increment be almost directly proportional to addition.Oxidable Elemental Mercury proposed by the present invention, the composite desulfurizing agent for removing HCl, contain
There are calcium hydroxide, sodium acid carbonate, barium carbonate, potassium permanganate, ceria.
The preparation technology of the composite desulfurizing agent of the present invention is first by calcium hydroxide, sodium acid carbonate, barium carbonate, potassium permanganate point
The powder that granularity is less than 2mm is not ground into, is then matched according to the mass percent of desulfurizing agent component, and be well mixed.
Directly the composite desulfurizing agent is added in flue by feed and spraying system when using, desulfurizing agent and smoke contacts, desulfurizing agent
With the Elemental Mercury in flue gas, HCl, SO2The stable compound of reaction generation, these products and unreacted desulfurizing agent and dust one
Rise and be captured down in dust arrester.Due to KMnO4With CeO2It is catalyst, consumption seldom, will not cause harm to environment.
The composite desulfurizing agent is used within the temperature range of 300~420 DEG C, the oxygenation efficiency of Elemental Mercury can bring up to 80%-
95%, SO2Removal efficiency is more than 95%, SO3, HCl removal efficiency more than 90%.
Calcium-based desulfurizing agent, sodium base desulfurizer are combined by the present invention with active component, by BaCO3、KMnO4、CeO2It is used as work
Property component be incorporated into desulfurizing agent, active component can improve the desulphurization reaction speed of desulfurizing agent, reduce reaction activity, to desulfurization
Reaction has preferable catalytic action.Meanwhile, promote to form stable sulfureous phase in desulfurization product, fundamentally solve in
HCl, SO under warm (300~420 DEG C)2、SO3The problem of removal efficiency is not high, desulfurization product can cause secondary pollution.
Ca (OH) in desulfurizing agent2、BaCO3With SO2Reaction generates calcium sulfite (CaSO respectively3), calcium sulfate (CaSO4)、
Barium sulfate (BaSO4), see reaction equation (1)~(3)；NaHCO3With SO2Reaction generation Na2SO3、Na2SO4, see reaction equation (4)~
(7)。Ca(OH)2、BaCO3、NaHCO3Also it can be reacted with HCl, HCl is removed while desulfurization, see reaction equation (8)~(10).
BaCO3(s)+SO2(g)+1/2O2(g)→BaSO4(s)+CO2(g) (1)
Ca(OH)2(s)+SO2(g)→CaSO3(s)+H2O(g) (2)
2Ca(OH)2(s)+2SO2(g)+O2(g)→2CaSO4(s)+2H2O(g) (3)
2NaHCO3(s)→Na2CO3(s)+H2O(g)+CO2(g) (4)
Na2CO3(s)+SO2(g)→Na2SO3(s)+CO2(g) (5)
2Na2CO3(s)+2SO2(g)+O2(g)→2Na2SO4(s)+2CO2(g) (6)
Na2CO3(s)+SO3(g)→Na2SO4(s)+CO2(g) (7)
Ca(OH)2(s)+2HCl(g)→CaCl2(s)+2H2O(g) (8)
Na2CO3(s)+2HCl(g)→2NaCl(s)+H2O(g)+CO2(g) (9)
NaHCO3(s)+HCl(g)→NaCl(s)+H2O(g)+CO2(g) (10)
KMnO4Played an important role in the oxidizing process of Elemental Mercury, see reaction equation (11)~(13), the oxygen of Elemental Mercury
Change process has electro transfer, gaseous Hg0Can be with metal oxide (KMnO4) Lattice Oxygen react generation HgO, disappear
The Lattice Oxygen of consumption can be fed by gaseous oxygen.CeO2With powerful oxygen storage capacity, it is possible to realize Ce under different atmosphere3 +/Ce4+Conversion.CeO2Adjuvant can be played a part of in the oxidizing process of Elemental Mercury, Lacking oxygen can be both provided, also may be used
To widen the active temperature range of catalyst.KMnO4With CeO2Combination can produce more activity for being beneficial to elemental mercury oxidation
Oxygen.
KMnO4(s)+Hg0(g)→KMnO3(s)+HgO(s) (11)
KMnO3(s)+0.5O2(g)→KMnO4(s) (12)
KMnO4(s)+HgO(s)→KHgMnO5(s) (13)。
Claims (3)
1. it is a kind of for oxidizing simple substance mercury, removing HCl composite desulfurizing agent, it is characterised in that by mass percentage, including carbon
Sour hydrogen salt 15~30%, BaCO32~5%, KMnO40.5~2%, CeO20.5~2%, remaining is Ca (OH)2；
The bicarbonate is NaHCO3。
2. it is according to claim 1 a kind of for oxidizing simple substance mercury, removing HCl composite desulfurizing agent, it is characterised in that to press
Mass percent meter, including NaHCO320~30%, BaCO32~3%, KMnO41~2%, CeO21~2%, remaining is
Ca(OH)2。
3. a kind of preparation method as claimed in claim 1 for oxidizing simple substance mercury, the composite desulfurizing agent for removing HCl, it is special
Levy and be, calcium hydroxide, sodium acid carbonate, barium carbonate, potassium permanganate are first respectively crushed into the powder that granularity is less than 2mm, then
According to by mass percentage, by bicarbonate 15~30%, BaCO32~5%, KMnO40.5~2%, CeO20.5~
2%, remaining is Ca (OH)2It is well mixed, obtain the composite desulfurizing agent for oxidizing simple substance mercury, removing HCl；Directly will when using
The composite desulfurizing agent is added in flue by feed and spraying system, desulfurizing agent and smoke contacts, desulfurizing agent and the list in flue gas
Matter mercury, HCl, SO2The stable compound of reaction generation, these products and unreacted desulfurizing agent are together with dust in dust arrester
In be captured down.
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| CN108939904B (en) * | 2018-07-04 | 2021-06-15 | 华润水泥技术研发有限公司 | Desulfurizing agent composition and application thereof in cement clinker production |
| CN109173687B (en) * | 2018-10-09 | 2021-01-15 | 清华大学 | Method for removing sulfur trioxide in flue gas |
| CN109622204A (en) * | 2018-11-12 | 2019-04-16 | 南京环境再生能源有限公司 | A kind of garbage burning factory fume treatment sodium bicarbonate flouring technology |
| CN112495157A (en) * | 2020-09-30 | 2021-03-16 | 山东大学 | Device and process for cooperatively removing sulfur trioxide and hydrogen chloride |
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| CN101440328A (en) * | 2008-12-24 | 2009-05-27 | 李政 | Environment-protecting synergistic agent for fuel coal |
| CN103194294B (en) * | 2013-04-25 | 2014-12-17 | 甘肃黑马石化工程有限公司 | Boiler coal combustion-improving desulfurizing agent composition and preparation method thereof |
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