CN101734875B - Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method - Google Patents
Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method Download PDFInfo
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- CN101734875B CN101734875B CN2009102639216A CN200910263921A CN101734875B CN 101734875 B CN101734875 B CN 101734875B CN 2009102639216 A CN2009102639216 A CN 2009102639216A CN 200910263921 A CN200910263921 A CN 200910263921A CN 101734875 B CN101734875 B CN 101734875B
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- 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
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Abstract
The invention relates to a method for the catalytic oxidation of calcium sulfite in desulphurization ash by a dry method and a semi-dry method, which is carried out according to the following steps: (a) preparing a manganese salt solution with the concentration of 0.2-4%; (b) adding the manganese salt solution into desulphurization ash proportionally; (c) taking a hydrogen peroxide solution with the concentration of 1-10% and adding into the mixture of the manganese salt solution and the desulphurization ash proportionally; and (d) keeping the temperature of the mixture of the desulphurization ash, the manganese salt solution and the hydrogen peroxide solution and digesting for 0.5-2 hours. The invention uses manganese salt and hydrogen peroxide as a catalyst and an oxidant to oxidize the calcium sulfite in the desulphurization ash and has simple method, low implementation cost and easy realization. The invention can enhance the oxidation speed and limit of the calcium sulfite, solves the adverse effect of the instability caused by the slow oxidation of the calcium sulfite in air on the quality of an autoclaved brick and provides an approach which is easy to realize for the mass utilization of the desulphurization ash.
Description
Technical field
The present invention relates to a kind of lime-ash treatment process, especially for the catalysed oxidation processes of calcium sulfite in dry method, the semi-dry desulphurization ash.
Background technology
Along with industry is fast-developing, environmental pollution problems is more and more outstanding, and various countries are increasing to control, management that obnoxious flavour such as oxynitride, sulfurous gas in the flue gas pollutes at present.Fume desulphurization method has wet method and dry method, semidrying; Dry method, semi-dry method flue gas desulfurization technique have that compact construction, floor space are little, power consumption and the water consumption is low, once invest little, advantages such as running cost is low, non-wastewater discharge; In the water-deficient area, aspect such as little unit and old unit transformation is widely used, and has the good technical economy.Yet the disposal of dry method, semi-dry process flue gas desulphurization sub product---desulfurized ash still lacks effective solution with comprehensive utilization, becomes the focus that the insider pays close attention to.Dry method, semi-dry process flue gas desulphurization ash; It is the mixture of calcium sulfite, calcium sulfate, flyash and unreacted sweetening agent; Discharged together by cleaning apparatus, the relevant person has carried out many researchs, and desulfurized ash is applied to fire calcium sulphoaluminate cement, cement additire, building materials etc.But owing to there is calcium sulfite that quantity do not wait and a spot of unreacted sweetening agent completely in the desulfurized ash; Therefore; It utilizes mode, scope and approach to receive strict limitation and restriction, is difficult to be widely used in traditional construction material industries such as cement, concrete, vitrified brick.If it is improper to utilize, the sulphur that solidifies in calcium sulfite is discharged once more, all that has been achieved is spoiled to make desulfurization, causes secondary pollution.In addition, the unstable that slow oxidation causes in air of the calcium sulfite in the desulfurized ash can have a negative impact to the autoclaved brick quality; Moreover excessive sulfur content has limited it as the application in cement mixed material and the concrete admixture in the desulfurized ash.Therefore dry method, semi-dry desulphurization ash are abandoned processing mostly at present; This not only need drop into substantial contribution, take the part soil builds storage ash; And pay the solid waste effluent charge of great number by storing up quantity, and storing up for a long time of desulfurized powder coal ash exists bigger environmental influence and security risk to ambient atmosphere environment and underground water etc.
Summary of the invention
The present invention is used for solving the problem of above-mentioned prior art and catalysed oxidation processes that a kind of dry method, semi-dry desulphurization ash calcium sulfite are provided; It can quicken the oxidation process of calcium sulfite in dry method, the semi-dry desulphurization ash, solves the dry method semi-dry desulphurization ash and is applied to calcium sulfite problem of unstable in the autoclaved brick production.
The alleged problem of the present invention is solved by following technical scheme:
The catalysed oxidation processes of calcium sulfite in a kind of dry method, the semi-dry desulphurization ash, it carries out according to following step:
A. get manganese salt, configuration quality concentration is the 0.2%-4% manganese salt solution;
B. add the ratio of 40-100ml manganese salt solution according to every kg dry method, semi-dry desulphurization ash, manganese salt solution is added in the desulfurized ash in whipping process, mix;
C. getting concentration is the 1%-10% superoxol, in the mixture with manganese salt solution and desulfurized ash among its adding step b in whipping process, mixes; The superoxol add-on is that every kg dry method, semi-dry desulphurization ash add the 50-100ml superoxol;
D. the mixture insulation with above-mentioned desulfurized ash, manganese salt solution, superoxol digested 0.5-2 hour.
The catalysed oxidation processes of calcium sulfite in above-mentioned dry method, the semi-dry desulphurization ash, said manganese salt are a kind of or its mixture in manganous sulfate, manganous nitrate, manganese halide, the potassium permanganate.
The catalysed oxidation processes of calcium sulfite in above-mentioned dry method, the semi-dry desulphurization ash carries out heat treated in the mixing process of said step b and step c, and Heating temperature is 30-50 ℃.
The present invention is directed to dry method, semi-dry desulphurization ash is difficult to utilize problem, and a kind of method that is used for catalyzed oxidation dry method, semi-dry desulphurization ash calcium sulfite is provided.This method uses manganese salt cheap and easy to get and hydrogen peroxide as catalyzer and oxygenant, the calcium sulfite in the oxidation sweetening ash, and method is simple, implementation cost is low, be easy to realization.The inventive method can be with the very fast at normal temperatures oxidation of the calcium sulfite in the desulfurized ash; Using desulfurized ash to prepare in the material humidification hybrid technique of autoclaved brick; Introduce method provided by the present invention, can improve the oxidation rate and the limit of calcium sulfite in the desulfurized ash, solve the disadvantageous effect of the calcium sulfite volumetric expansion that slow oxidation causes in air the autoclaved brick quality; For a large amount of utilizations of desulfurized ash provide an approach that is easy to realize, the inventive method can not pollute environment in addition.
Embodiment
The present invention is directed to the problem of oxidation of calcium sulfite in dry method, the semi-dry desulphurization ash, the method for calcium sulfite in a kind of quick catalysis oxidation dry method, the semi-dry desulphurization ash is provided.Said method is being used in combination of manganese salt and hydrogen peroxide; According to a certain percentage manganese salt solution and hydrogen peroxide are blended in dry method, the semi-dry desulphurization ash; Improve the oxidation rate and the limit of calcium sulfite in the desulfurized ash; Make it be converted into calcium sulfate, solve the calcium sulfite instability problem that slow oxidation causes in air, when eliminating desulfurized ash and being used to prepare autoclaved brick to the disadvantageous effect of its quality.The mechanism of action of the present invention is: manganese salt solution is joined in the desulfurized ash Mn in the manganese salt solution
2+Can make the calcium sulfite in the desulfurized ash in the concentration range of broad and in the long time, keep higher catalyzed oxidation speed, and ydrogen peroxide 50 is a kind of oxygenant, can promote the carrying out of the catalytic oxidation of calcium sulfite.The addition that it is pointed out that manganese salt and hydrogen peroxide should be controlled at suitable scope, and addition is not enough, and the rate of oxidation of calcium sulfite will reduce, and oxidation effectiveness is bad; And addition is too much, the unnecessary waste that then not only can not improve the rate of oxidation of calcium sulfite but also can make raw material.Manganese salt of the present invention is manganous sulfate, manganous nitrate, manganese halide, potassium permanganate a kind of or its mixture wherein.Test shows that the inventive method raw material consumption is few, active high, and the rate of oxidation that can make calcium sulfite in the dry method semi-dry desulphurization ash is than improving more than 2 times under the on-catalytic condition.Below improve several concrete embodiment:
Embodiment 1: get certain dry desulfurization ash 1kg of power plant, configuration concentration is 0.2% manganese sulfate solution 60ml, and concentration is 1% superoxol 90m1; Manganese sulfate solution is added in the desulfurized ash in whipping process, mix; Again superoxol is added in the mixture of manganese sulfate solution and desulfurized ash in whipping process, mix; Behind the insulation digestion 2h, measuring desulfurization ash Central Asia calcium sulphate content is 5.5%, has reduced by 19.4% than former desulfurized ash Central Asia calcium sulphate content.
Embodiment 2: get certain dry desulfurization ash 1kg of power plant, configuration concentration is 0.5% manganese nitrate solution 80ml, and concentration is 4% superoxol 100ml; Manganese nitrate solution is added in the desulfurized ash in whipping process, mix; Again superoxol is added in the mixture of manganese nitrate solution and desulfurized ash in whipping process, mix; Behind the insulation digestion 1h, measuring desulfurization ash Central Asia calcium sulphate content is 2.1%, has reduced by 12.5% than former desulfurized ash Central Asia calcium sulphate content.
Embodiment 3: get certain dry desulfurization ash 1kg of power plant, configuration concentration is 1% manganese halide solution 60ml, and concentration is 6% superoxol 80ml; Manganese halide solution is added in the desulfurized ash in whipping process, mix; Again superoxol is added in the mixture of manganese halide solution and desulfurized ash in whipping process, mix; Behind the insulation digestion 1.5h, measuring desulfurization ash Central Asia calcium sulphate content is 3.7%, has reduced by 10.3% than former desulfurized ash Central Asia calcium sulphate content.
Embodiment 4: get certain semi-dry desulphurization ash 1kg of power plant, configuration concentration is 4% potassium permanganate 40ml, and concentration is 10% superoxol 50ml; Potassium permanganate solution is added in the desulfurized ash in whipping process, mix; Again superoxol is added in the mixture of potassium permanganate solution and desulfurized ash in whipping process, mix; Behind the insulation digestion 2h, measuring desulfurization ash Central Asia calcium sulphate content is 5.7%, has reduced by 19.2% than former desulfurized ash Central Asia calcium sulphate content.
Embodiment 5: get dry desulfurization ash 1kg of certain power plant, configuration concentration is 2% manganous sulfate, potassium permanganate mixing solutions 50ml, and manganous sulfate in the mixing solutions, permanganic acid are identical in quality, and concentration is 2% superoxol 60ml; Manganous sulfate, potassium permanganate mixing solutions are added in the desulfurized ash in whipping process, mix; Again superoxol is added in whipping process in the mixture of manganous sulfate, potassium permanganate mixing solutions and desulfurized ash, mix; Behind the insulation digestion 1h, measuring desulfurization ash Central Asia calcium sulphate content is 4.6%, has reduced by 20.7% than former desulfurized ash Central Asia calcium sulphate content.
Embodiment 6: get dry desulfurization ash 10kg of certain power plant, configuration concentration is 3% manganous sulfate, manganese halide mixing solutions 700ml, and manganous sulfate in the mixing solutions, manganese halide are identical in quality, and configuration concentration is 3% superoxol 500ml; Manganous sulfate, manganese halide mixing solutions are added in the desulfurized ash in whipping process, mix, the whipping process temperature remains on normal temperature; Superoxol is added in whipping process in the mixture of manganous sulfate, manganese halide mixing solutions and desulfurized ash again, mix, the whipping process temperature remains on normal temperature; Behind the insulation digestion 0.5h, measuring desulfurization ash Central Asia calcium sulphate content is 2.6%, has reduced by 18.7% than former desulfurized ash Central Asia calcium sulphate content.
Show that by the foregoing description the inventive method is calcium sulfite in the oxidation sweetening ash fast, obviously reduce the Central Asia calcium sulphate content of desulfurized ash.The inventive method is introduced the use desulfurized ash prepare in the material humidification hybrid technique of autoclaved brick, can effectively solve the autoclaved brick quality instability problem that causes because of the calcium sulfite slow oxidation.
Claims (3)
1. the catalysed oxidation processes of calcium sulfite in a dry method, the semi-dry desulphurization ash is characterized in that it carries out according to following step:
A. get manganese salt, configuration quality concentration is the 0.2%-4% manganese salt solution;
B. add the ratio of 40-100ml manganese salt solution according to every kg dry method, semi-dry desulphurization ash, manganese salt solution is added in the desulfurized ash in whipping process, mix;
C. getting mass concentration is the 1%-10% superoxol; In the mixture with manganese salt solution and desulfurized ash among its adding step b in whipping process; Mix, the superoxol add-on is that every kg dry method, semi-dry desulphurization ash add the 50-100ml superoxol;
D. the mixture insulation with above-mentioned desulfurized ash, manganese salt solution, superoxol digested 0.5-2 hour.
2. the catalysed oxidation processes of calcium sulfite in dry method according to claim 1, the semi-dry desulphurization ash is characterized in that: said manganese salt is manganous sulfate, manganous nitrate, manganese halide, potassium permanganate one or more mixture wherein.
3. the catalysed oxidation processes of calcium sulfite in dry method according to claim 2, the semi-dry desulphurization ash is characterized in that: carry out heat treated in the mixing process of said step b and step c, Heating temperature is 30-50 ℃.
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