CN110436506A - Using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes - Google Patents
Using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A method of using industrial waste sulfuric acid to semi-dry desulphurization ash oxidation processes, belongs to the useless resource reclaim of solid waste, liquid and recycle field；Preparation method: slurry is made in semi-dry desulphurization ash and water, industrial waste sulfuric acid solution is added, is stirred, slurry is stood after the reaction was completed, removes upper water, repeated flushing is carried out to product, is stood, until supernatant liquor is clear, colorless to get to product after semi-dry desulphurization ash oxidation processes；The content of calcium sulfate is 85~96.13% in product after semi-dry desulphurization ash oxidation processes；The method is by there are the more calcium oxide and calcium hydroxide for having neither part nor lot in desulphurization reaction in Desulphurization, and calcium sulfite, Efficient Conversion is at calcium sulfate, also the problem of calcium sulfite in Desulphurization can only be made to be oxidized to calcium sulfate in air, other compositions cannot be made to be converted to calcium sulfate due to calcined oxide method is solved.
Description
Technical field
The present invention relates to solid waste, the useless resource reclaims of liquid to recycle field, and in particular to a kind of to utilize double of industrial waste sulfuric acid
The method of dry-process desulfurized ash oxidation processes.
Background technique
One of the emphasis of efforts at environmental protection is placed on prevention and treatment sulfur dioxide gas body pollution by country, and that prevents and treats focuses on controlling
Thermal power plant processed, three opium gas source of kiln and Industrial Boiler.And the sulfur dioxide of coal-burning power plant's discharge is in the row of China's sulfur dioxide
It puts and accounts for 50% or more in total amount, be the most important thing for administering sulfur dioxide pollution.
The policy of state control sulfur dioxide (SO2) emissions all the time is increasingly stringent, and many large enterprises research and develop and use cigarette
Desulfurization system, all kinds of desulfurizers are installed successively.Flue gas desulfurization had entered Rapid development stage in recent years, these desulphurization systems
After putting into operation, another environmental problem is produced --- a large amount of desulfurization product processing problem.With flue gas desulfurization device
Operation successively, desulfurization product is more and more, and the comprehensive utilization of desulfurization product becomes urgent problem, and solve it is good
The bad further development for directly influencing desulfurization technology.
Wet desulfurizing process application earliest, due to its with corrosivity and waste water it is difficult, semi-dry desulfurizing process is slow
Slowly replaced.For desulfurization product based on grey calcium sulfite, comprehensive utilization difficulty is big, and the Desulphurization generated in sweetening process is only
There is small part to be utilized, the remaining overwhelming majority is abandoned, and causes serious secondary pollution, and occupy a large amount of land resource.
Semi-dry desulphurization product is than wet processing product much less, but complicated component, and nature difference is very big, and containing free calcium oxide and
Calcium sulfite, most semi-dry desulphurization products take the method for disposal of stacking and landfill, not only occupy a large amount of soils,
Fugitive dust can also cause serious secondary pollution to environment, be detrimental to health.Semi-dry desulphurization product largely belongs to sulfurous acid
Calcium type Desulphurization, Desulphurization sulfite calcium is extremely unstable, can recycling to Desulphurization and using causing to seriously affect, therefore mesh
The preceding research emphasis to Desulphurization is concentrated mainly on processing calcium sulfite type desulphurization ash, the effective use of semi-dry desulphurization ash at
For research hotspot.Effective use Desulphurization can not only make waste resource be utilized, but also can solve thus solid waste
Accumulate the environmental problem generated.
Titanium dioxide is considered as current performance white pigment the most superior in the world, excellent compared to other pigment performances,
It is widely used in the industry such as coating, papermaking, ceramics, food and medicine, referred to as " industrial monosodium glutamate ".China produces titanium dioxide at present
Mainly based on sulfuric acid process, sulfuric acid method titanium pigment production capacity and yield are up to 90% or more.In Titanium White Production By Sulfuric Acid Process technique
There is a large amount of spent acid to generate.For finally obtained sulfuric acid waste, large enterprise substantially utilizes devil liquor recovery, medium and small enterprise
There are problems that the row of stealing and pollution transportation.The illegal dumping of Waste Sulfuric Acid and illegal burial, it has also become the risk factor of environmental accident is given up
Sulfuric acid not only pollutes environment, wastes Sulphur ressource, also has security risk.China's Waste Sulfuric Acid processing at present mainly has concentration, cracking
6 kinds of approach such as regeneration, production chemical fertilizer, chemical oxidation, extraction, neutralisation treatment, sulphur-bearing waste solution processing mainly have concentration salt extraction, cracking
The approach such as regeneration.
Currently, the research of calcium sulfite oxidation concentrates on electrochemical oxidation, catalyst oxidation, high-temperature oxydation.Wherein Anhui
The method of Zhou Haofeng of building material Co., Ltd, Ma Gangjia China et al. invention reconciles flue gas desulfurization ash with water by a certain percentage,
It is passed through direct current by inert electrode, utilizes electrochemical method oxidative calcium.It is that power consumption is big at its deficiency, it should not be big
It is applied in technical scale production, and it is slow to be electrolysed rate.
Sun Jiling of North China Electric Power University et al. has studied the catalysis that calcium sulfite oxidation can be effectively catalyzed under low temperature
Agent --- manganese sulfate.And from influence factors such as catalyst loading, reaction temperature, reaction time to manganese sulfate catalysis oxidation sulfurous
The influence of sour calcium has carried out experimental study.It is the sulfuric acid Mn catalyst since reaction temperature is low in catalytic oxidation process at its deficiency
It is slow to calcium sulfite oxidation speed, oxygenation efficiency is low, and manganese impurity has been mixed into product, influence the purity of product calcium sulfate and white
Degree etc..
Guo Bin of Hebei University of Science and Technology et al. is for semidry method sintering flue gas desulfurization ash because of CaSO3Content is high-leveled and difficult with effectively comprehensive
Close the problem of utilizing, temperature be 400~500 DEG C, gas-solid ratio (volume of air flow and Desulphurization mass ratio) be 0.02~
0.06m3/ (gh), reaction time be 30~60min, without extra catalyst when, CaSO in Desulphurization3Oxygenation efficiency be 40.4~
100.0%；Temperature is at 450 DEG C or more, CaSO3Oxygenation efficiency is 80% or more.This method energy consumption is high, is unfavorable for energy conservation and subtracts
Row.
Using spent acid oxidation processes Desulphurization sulfite calcium, it is effectively utilized solid waste resource Desulphurization and the useless resource of liquid is useless
Acid, has at low cost, and degree of oxidation is good, the high feature of utilization rate.Desulphurization and spent acid are all wastes in need of immediate treatment, and at present
Two kinds of changing rejected material to useful resource methods are limited, therefore, are badly in need of developing a kind of using spent acid oxidation processes Desulphurization sulfite calcium
Technique.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of using industrial waste sulfuric acid to semi-dry desulphurization ash oxidation processes
Method, solve the problems, such as that semi-dry desulphurization ash sulfite calcium aoxidizes that at high cost, treating capacity is insufficient；Make semi-dry desulphurization ash
In the more calcium oxide for having neither part nor lot in desulphurization reaction and calcium hydroxide it is so efficient that be converted to calcium sulfate；Also it is asked for solid waste and the useless processing of liquid
Topic provides new approaches.
It is provided by the invention it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, through the method
Calcium sulphate content is 85~96.13% in the semi-dry desulphurization ash of oxidation processes.
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
It is 5~20% slurries that semi-dry desulphurization ash and water, which are configured to mass concentration, and it is 20 that mass concentration is added in slurry
~30% industrial waste sulfuric acid solution, wherein industrial waste sulfuric acid dosage is 1~3 times of semi-dry desulphurization ash quality, and solution is stirred,
Whipping temp is 30~80 DEG C, and mixing time is 2~8h；
Step 2, it filters:
After the completion of stirring, slurry is filtered, washs, obtains solid material cake；
Step 3, dry:
Filtered material biscuit is dry, it is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
In the step 1, the ingredient that industrial waste sulfuric acid solution contains, by quality-volumetric concentration in terms of: Ti < 3g/L, Fe
< 50g/L, Al < 2.5g/L, Mn < 2g/L, Ca < 0.5g/L, Mg < 7.5g/L.
In affiliated step 1, semi-dry desulphurization ash contains ingredient by percentage to the quality, and CaO content >=50%, S content >=
8%, Al2O3Content < 0.4%, SiO2Content < 0.7%, content of MgO < 2.1%, ZrO2Content < 0.01%, Fe content <
0.3%.
In the step 1, semi-dry desulphurization ash and water are configured to the slurry that mass concentration is 5~20%.
In the step 1, industrial waste sulfuric acid dosage is 2 times of semi-dry desulphurization ash quality；Whipping temp is 30~80 DEG C.
In the step 1, mixing time is 2~8h.
In the step 1, stirring uses heat collecting type constant temperature blender with magnetic force.
In the step 2, the instrument of slurry filtration washing is vacuum filter.
In the step 3, material biscuit is dry to dry for natural air drying or baking oven, and it is dry not need vacuum for drying temperature≤50 DEG C
It is dry.
There are the more calcium oxide and calcium hydroxide for having neither part nor lot in desulphurization reaction in semi-dry desulphurization ash of the invention, and
Calcium sulfite.
Industrial waste acid used in the present invention is the Waste Sulfuric Acid of generation when using production of titanium dioxide by sulfuric acid method in steel mill.
Present invention oxidation product obtained can be to prepare calcium sulfate crystal whiskers, thus real under hydrothermal synthesizing condition
The high value added utilization of existing waste resource.
Technical solution of the present invention certain density waste sulfuric acid solution is first added into semi-dry desulphurization ash slurry, then
It in the case where temperature is 30~80 DEG C, is stirred, to realize the oxidation pre-treatment to semi-dry desulphurization ash.Sulfuric acid can with do not join
It is reacted with the calcium oxide of desulphurization reaction and calcium hydroxide, by adjusting pulp density and sulfuric acid dosage, reaches reaction rate
To maximum, to make calcium oxide and calcium hydroxide Efficient Conversion calcium sulfate；Calcium sulfite in slurries in acid condition with
Oxygen reacts to obtain calcium sulfate, and reaction includes the processes such as dissolution, dissociation, acidification, oxidation, crystallization, adjusts concentration of slurry, makes to react
Rate is best, and the oxygenation efficiency of the calcium sulfite in semi-dry desulphurization ash is promoted, and the oxygen dissolved in unit volume sufficiently reacts.Instead
Slurry should be stood after the completion, remove upper water, repeated flushing is carried out to product, is stood, until supernatant liquor is clear, colorless.
A small amount of product is taken out, it is dried；Product drying can also can be dried with natural air drying using baking oven, and drying temperature≤
It is 50 DEG C, sufficiently loose to it after the product after drying is cooled to room temperature, the high Desulphurization of calcium sulphate content is obtained, after promotion
The conversion ratio of calcium sulfate in continuous hydrothermal synthesis reaction.
Some is active calcium oxide by CaO in Desulphurization, is that the deduster that unreacted is complete in absorbent is collected
Part, some is non-active calcium oxide, mainly with CaCO3、CaSO3And CaSO4Form exist, wherein active oxidation
Calcium is a kind of substance with reactivity.
Semi-dry desulphurization ash sulfite calcium, calcium oxide and calcium hydroxide chemically react in whipping process, reaction
Shown in equation such as formula (1), (2):
CaO+H2O=Ca (OH)2 (1)
Ca(OH)2+H2SO4=CaSO4·2H2O (2)
It is insufficient with the calcium oxide content of sulfuric acid reaction and calcium hydroxide amount in unit volume solution when concentration of slurry is too low,
So reaction equation (1), (2) carry out slowly, calcium sulphate content is low.With the increase of concentration of slurry, slurries internal oxidition calcium and hydrogen-oxygen
Change calcium concentration to increase, calcium sulphate content constantly increases in oxidation product.Sulphur when pulp density is more than certain value, in unit volume
Acid amount is certain, limits reaction, calcium sulphate content is not further added by oxidation product, and excessive concentration leads to the solid in unit volume
Amount increases, and slurry fluidity is deteriorated, and the calcium sulfate for reacting generation cannot be rapidly separated reaction surface, sulfuric acid and calcium hydroxide it is anti-
It answers contact surface to become smaller, can not react completely.Calcium sulfite in slurries reacts to obtain calcium sulfate in acid condition with oxygen,
Reaction includes the processes such as dissolution, dissociation, acidification, oxidation, crystallization, as shown in formula (3)~(8).
CaSO3(s)=CaSO3(aq) (3)
CaSO3(aq)=Ca2++SO3 2- (4)
H++SO3 2-=HSO3 - (5)
Ca2++SO4 2-=CaSO4(aq) (7)
CaSO4(aq)+2H2O=CaSO4·2H2O(s) (8)
When concentration of slurry is low, unit volume calcium sulfite content is low, limits reaction, fails to react completely；With slurries
Concentration increases, and calcium sulfite oxidation rate improves.When concentration increase to a certain extent when, reaction conversion ratio reaches maximum, obtains
Calcium sulphate content highest.Concentration of slurry is continued growing, slurry fluidity is deteriorated, and whipping process plays oxygenation, unit volume
The amount of oxygen of interior dissolution reduces, and reaction conversion ratio reduces, and the calcium sulfite in Desulphurization can not react completely, and then obtain
Calcium sulphate content reduce.
Calcium sulphate content first increases reduce afterwards as the temperature rises in Desulphurization.As the temperature rises, calcium sulfite
Solubility reduces, and equilibrium concentration reduces.Reaction temperature is excessively high, extremely low by the inferior sulfate radical concentration for reacting (4) generation, oxidation reaction
It slows.The inferior sulfate radical that reaction equation (3), (4) generate generates HSO according to reaction (5)3 -, with the progress of reaction, HSO3 -
Concentration gradually rises, and the practical oxidation process of calcium sulfite mainly presses reaction (6) progress, when liquidus temperature is excessively high, Ca
(HSO3)2Can decompose reaction, shown in reaction equation such as formula (9).Crystal of calcium sulfate process is formula (7)~(8).In order to mention
The content of calcium sulfate in high semi-dry desulphurization ash oxidation product, and reduce sulfur dioxide evolution as far as possible and cause secondary pollution, instead
Answer temperature unsuitable excessively high.
Ca(HSO3)2=CaSO3+SO2+H2O (9)
With the increase of sulfuric acid dosage, the content of calcium sulfate increases in semi-dry desulphurization ash oxidation product.When with stirring
Between increase, the content of calcium sulfate increases in Desulphurization.In low concentration, calcium sulphate content is with concentration of slurry in Desulphurization
It increases and increases.At high concentrations, calcium sulphate content is reduced with the raising of concentration of slurry in Desulphurization.
Innovation of the present invention is to efficiently use solid waste resource semi-dry desulphurization ash and the useless resource industrial waste sulfuric acid of liquid, symbol
National changing rejected material to useful resource policy is closed, the more other methods of production cost are low, and treating capacity is much larger than other methods.
It is provided by the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, be based on specified conditions
Test method, by regulate and control test parameters, make the content of calcium sulfate in the semi-dry desulphurization ash after spent acid aoxidizes by other
The 80% of method increases to 85~96.13%, and production cost is far below high-temperature oxidation, catalyst oxidizing process and electrochemical oxidation
Method, easy to operate compared with method for oxidation in the prior art, operating condition is easily controllable, and the method efficiently uses solid waste
Resource semi-dry desulphurization ash and the useless resource industrial waste sulfuric acid of liquid, meet national changing rejected material to useful resource policy.
Specific embodiment
Following embodiment first carries out deferrization to semi-dry desulphurization ash, then recycles industrial waste sulfuric acid to semi-dry desulphurization ash
Oxidation processes；Wherein deferrization process uses the Wet-type strong magnetic separator of model XCSQ-50 × 70, and background magnetic field intensity is 795kA/
M, except the yield of Desulphurization after iron is 90.0~99.6%, the content of impurity iron is 0.10~0.16%.Work is used in embodiment
The ingredient and content of industry waste sulfuric acid solution, by quality-volumetric concentration be in terms of: Ti:2.92g/L, Fe:46g/L, Al:2.2g/L,
Mn:1.7g/L, Ca:0.2g/L, Mg:7.1g/L.
Embodiment 1
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 5%, is added into slurry
Enter 1 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, and whipping temp is 30 DEG C, right
Slurry solution stirs 4h respectively；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 85% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 2
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 10%, is added into slurry
Enter 2 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, and whipping temp is 40 DEG C, right
Slurry solution stirs 4h；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper
Layer clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 91.20% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 3
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Desulphurization 30g after semidry method deferrization is configured to slurry with water, preparing pulp density is 10%, is added into slurry
Enter 2 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, and whipping temp is 40 DEG C, right
Slurry solution stirs 6h；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 92.82% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 4
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 20%, is added into slurry
Entering 1.5 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, and whipping temp is 80 DEG C,
8h is stirred respectively to slurry solution；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 40 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 90% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 5
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 10%, is added into slurry
Enter 3 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, is stirred, stirs to slurry
Mixing the time is 4h, and whipping temp is 50 DEG C；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 91.83% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 6
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 10%, is added into slurry
Enter 2 times of semi-dry desulphurization ash quality of industrial waste sulfuric acid solution, industrial waste sulfuric acid concentration is 20%, is stirred, stirs to slurry
Mixing the time is 4h, and whipping temp is 50 DEG C；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 96.13% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Embodiment 7
It is of the invention using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, comprising the following steps:
Step 1, it stirs:
Semi-dry desulphurization ash 30g after deferrization is configured to slurry with water, preparing pulp density is 10%, is divided into slurry
Industrial waste sulfuric acid solution that Jia Ru be 2 times of semi-dry desulphurization ash quality, industrial waste sulfuric acid concentration are 20%, are stirred slurry
It mixes, mixing time 4h, whipping temp is 75 DEG C；
Step 2, it filters:
Slurry is stood after the completion of stirring, slurry is filtered, repeated flushing, standing, flushing, standing, until upper layer
Clear liquid is clear, colorless, obtains solid material cake；
Step 3, dry:
Material cake is dried in 50 DEG C of baking ovens, is cooled to room temperature, obtains product after semi-dry desulphurization ash oxidation processes.
Calcium sulphate content is 94.19% in product after the finally obtained semi-dry desulphurization ash oxidation processes of the present embodiment.
Semi-dry desulphurization ash raw material used in above embodiments contains ingredient and is shown in Table 1 by mass percentage.
Semi-dry desulphurization ash material chemical component used in 1 above embodiments of table is by mass percentage
| Component | Al2O3 | SiO2 | CaO | MgO | ZrO2 | S | Na | F | TFe |
| Content/% | 0.37 | 0.64 | 50.92 | 2.04 | <0.01 | 8.04 | 0.24 | 0.98 | 0.24 |
Claims (7)
1. it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, which comprises the steps of:
Step 1, it stirs:
Semi-dry desulphurization ash and water are configured to the slurry that mass concentration is 5~20%, be added in slurry mass concentration be 20~
30% industrial waste sulfuric acid solution, wherein industrial waste sulfuric acid dosage is 1~3 times of semi-dry desulphurization ash quality；Solution is stirred, is stirred
Mixing temperature is 30~80 DEG C, and mixing time is 2~8h；
Step 2, it filters:
After the completion of stirring, slurry is filtered, washs, obtains solid material cake；
Step 3, dry:
It will expect that biscuit is dry, is cooled to room temperature, and obtain product after semi-dry desulphurization ash oxidation processes.
2. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, in the step 1, the ingredient that industrial waste sulfuric acid solution contains, by quality-volumetric concentration in terms of: Ti < 3g/L, Fe <
50g/L, Al < 2.5g/L, Mn < 2g/L, Ca < 0.5g/L, Mg < 7.5g/L.
3. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, in the step 1, semi-dry desulphurization ash contains ingredient by percentage to the quality, CaO content >=50%, S content >=
8%, Al2O3Content < 0.4%, SiO2Content < 0.7%, content of MgO < 2.1%, ZrO2Content < 0.01%, Fe content <
0.3%.
4. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, in the step 1, stirring uses heat collecting type constant temperature blender with magnetic force.
5. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, in the step 2, the instrument of slurry filtration washing is vacuum filter.
6. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, in the step 3, material biscuit is dry to dry for natural air drying or baking oven, and it is dry not need vacuum for drying temperature≤50 DEG C
It is dry.
7. it is according to claim 1 it is a kind of using industrial waste sulfuric acid to the method for semi-dry desulphurization ash oxidation processes, it is special
Sign is, the content for obtaining calcium sulfate in product after semi-dry desulphurization ash oxidation processes is 85~96.13%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014230A (en) * | 2019-11-15 | 2020-04-17 | 鞍钢集团矿业有限公司 | Low-temperature oxidation method of dry-method and semi-dry-method desulfurized ash |
| CN111661865A (en) * | 2020-05-25 | 2020-09-15 | 沈阳环境科学研究院 | Continuous dry method/semi-dry method desulfurization ash stabilization treatment system and method |
| CN111747438A (en) * | 2020-05-25 | 2020-10-09 | 沈阳环境科学研究院 | pH regulation and control multistep stabilization modification method for dry/semi-dry desulfurized fly ash |
| CN112279287A (en) * | 2020-10-16 | 2021-01-29 | 中冶南方都市环保工程技术股份有限公司 | Treatment process and treatment system for semi-dry desulfurized fly ash |
| CN112501634A (en) * | 2020-12-04 | 2021-03-16 | 鞍钢集团矿业有限公司 | Electrochemical oxidation method for sulfite in desulfurized fly ash |
| CN112877777A (en) * | 2021-03-04 | 2021-06-01 | 沈阳大学 | Method for preparing calcium sulfate hemihydrate crystal whisker by using semidry desulfurization ash |
| CN112939050A (en) * | 2021-02-19 | 2021-06-11 | 北京铝能清新环境技术有限公司 | Resource utilization process suitable for semi-dry desulfurization waste ash in electrolytic aluminum industry |
| CN114226421A (en) * | 2021-12-23 | 2022-03-25 | 上海电气电站环保工程有限公司 | Treatment method of semidry desulfurization ash |
| CN115448350A (en) * | 2022-08-01 | 2022-12-09 | 芜湖新兴铸管有限责任公司 | Combined oxidation method of semi-dry desulfurized fly ash and industrial waste sulfuric acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623592A (en) * | 2009-07-31 | 2010-01-13 | 攀枝花新钢钒股份有限公司 | Process for comprehensively treating waste acid and desulphurized ash |
| CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
| CN104096707A (en) * | 2014-06-27 | 2014-10-15 | 武汉钢铁(集团)公司 | Resource utilization method of half-dry desulfurized fly ash |
-
2019
- 2019-08-14 CN CN201910746803.4A patent/CN110436506A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623592A (en) * | 2009-07-31 | 2010-01-13 | 攀枝花新钢钒股份有限公司 | Process for comprehensively treating waste acid and desulphurized ash |
| CN102912445A (en) * | 2012-10-22 | 2013-02-06 | 浙江天蓝环保技术股份有限公司 | Process and device for preparing gypsum whisker by semi-dry desulfurized fly ash and waste acid |
| CN104096707A (en) * | 2014-06-27 | 2014-10-15 | 武汉钢铁(集团)公司 | Resource utilization method of half-dry desulfurized fly ash |
Non-Patent Citations (1)
| Title |
|---|
| 郝海青: "利用半干法脱硫灰制备硫酸钙晶须", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111014230A (en) * | 2019-11-15 | 2020-04-17 | 鞍钢集团矿业有限公司 | Low-temperature oxidation method of dry-method and semi-dry-method desulfurized ash |
| CN111661865A (en) * | 2020-05-25 | 2020-09-15 | 沈阳环境科学研究院 | Continuous dry method/semi-dry method desulfurization ash stabilization treatment system and method |
| CN111747438A (en) * | 2020-05-25 | 2020-10-09 | 沈阳环境科学研究院 | pH regulation and control multistep stabilization modification method for dry/semi-dry desulfurized fly ash |
| CN111747438B (en) * | 2020-05-25 | 2022-12-06 | 沈阳环境科学研究院 | pH regulation and control multistep stabilization modification method for dry/semi-dry desulfurized fly ash |
| CN112279287A (en) * | 2020-10-16 | 2021-01-29 | 中冶南方都市环保工程技术股份有限公司 | Treatment process and treatment system for semi-dry desulfurized fly ash |
| CN112501634A (en) * | 2020-12-04 | 2021-03-16 | 鞍钢集团矿业有限公司 | Electrochemical oxidation method for sulfite in desulfurized fly ash |
| CN112939050A (en) * | 2021-02-19 | 2021-06-11 | 北京铝能清新环境技术有限公司 | Resource utilization process suitable for semi-dry desulfurization waste ash in electrolytic aluminum industry |
| CN112939050B (en) * | 2021-02-19 | 2023-08-22 | 北京铝能清新环境技术有限公司 | Resource utilization process suitable for semi-dry desulfurization waste ash in electrolytic aluminum industry |
| CN112877777A (en) * | 2021-03-04 | 2021-06-01 | 沈阳大学 | Method for preparing calcium sulfate hemihydrate crystal whisker by using semidry desulfurization ash |
| CN114226421A (en) * | 2021-12-23 | 2022-03-25 | 上海电气电站环保工程有限公司 | Treatment method of semidry desulfurization ash |
| CN114226421B (en) * | 2021-12-23 | 2024-03-15 | 上海电气电站环保工程有限公司 | Treatment method of semi-dry desulfurization ash |
| CN115448350A (en) * | 2022-08-01 | 2022-12-09 | 芜湖新兴铸管有限责任公司 | Combined oxidation method of semi-dry desulfurized fly ash and industrial waste sulfuric acid |
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