CN109718658A - A kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization - Google Patents
A kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization Download PDFInfo
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- CN109718658A CN109718658A CN201910148787.9A CN201910148787A CN109718658A CN 109718658 A CN109718658 A CN 109718658A CN 201910148787 A CN201910148787 A CN 201910148787A CN 109718658 A CN109718658 A CN 109718658A
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- solid waste
- calcium carbide
- carbide factory
- reutilization
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Abstract
A kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization, comprising the following steps: calcium carbide factory's solid waste granularity is reduced by pretreatment, then by dipping, filter and isolate maceration extract and filter cake, contain Mg (OH) in maceration extract2、Ca(OH)2, it is used for boiler tail flue gas desulfurization.Filter cake is made of magnesia, calcium oxide, aluminium oxide and the silica not dissociated, and the water solubility of aluminium oxide can be activated by addition cosolvent, further completes the desulfurization of calcium carbide factory's solid waste and cycling and reutilization.
Description
Technical field
The invention belongs to Industrial Solid Waste processing and fume environment protection process field more particularly to a kind of calcium carbide factory's solid waste desulfurization and
The method of cycling and reutilization.
Background technique
At present to SO in flue gas2The control of discharge mainly uses wet process limestone/gypsum method, MgO method flue gas desulfurization technique.
Have many advantages, such as that raw material sources are abundant, low in cost using limestone/gypsum method flue gas desulfurization technique, but up-front investment
Greatly, equipment blocks seriously corroded.Mg-base desulfurizing agent activity is higher than calcium-based desulfurizing agent, and by-product chemical property is stablized, but insufficient
Place are as follows: Mg-base desulfurizing agent price is more expensive, and raw material sources are few.
The Industrial Solid Waste that most of enterprise, calcium carbide factory is generated pours into cinder field and is filled, and is not recycled.
These calcium carbide factory's solid wastes stack not only appropriation of land for a long time, cause dust from flying, and by the immersion of rainwater, in lime-ash can
Dissolubility alkali meeting polluted underground water and surface water, and keep the pH value of soil unbalance.
Summary of the invention
The purpose of the present invention is to provide a kind of calcium carbide factory's solid waste desulfurization and the methods of cycling and reutilization, to solve above-mentioned ask
Topic.
To achieve the above object, the invention adopts the following technical scheme:
A kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization, comprising the following steps:
Step 1, calcium carbide factory's solid waste granularity is reduced by pretreatment, obtains Yu Chu calcium carbide factory solid waste waste residue, calcium carbide factory's solid waste
Waste residue includes MgO, CaO, Al2O3And SiO2；
Step 2, water and pretreated calcium carbide factory's solid waste waste residue are mixed, mixed substance filter and is divided
Separate out maceration extract and filter cake；
Step 3, flue gas desulfurization is carried out respectively to isolated maceration extract and filter cake；
Step 4, the product in collection step 3 after flue gas desulfurization, and it is filtered.
Further, 20 mesh are crushed to hereinafter, obtaining Yu Chu calcium carbide factory by after the drying of calcium carbide factory's solid waste waste residue in step 1
Solid waste waste residue.
Further, water is mixed as leaching solvent with Yu Chu calcium carbide factory solid waste waste residue in step 2, stirring at normal temperature dipping,
It is filtered using Suction filtration device, obtains maceration extract and filter cake；The dosage of water and the dosage of Yu Chu calcium carbide factory solid waste waste residue meet every gram
The corresponding water that 100mL is added of calcium carbide factory's solid waste；Room temperature refers to 10~30 DEG C；Dip time is 30min.
Further, maceration extract isolated in step 3 carries out flue gas desulfurization, the specific steps are as follows:
1. maceration extract is pumped into absorption tower after nozzle atomization, flue gas enters absorption tower, flue gas and absorption by air-introduced machine
Liquid counter current contacting, calcium hydroxide in sulfur dioxide and absorbing liquid and magnesium hydroxide in flue gas react；
2. absorb the bottom of the tower is stirred continuously by blender, and blasts air, oxidation step 1. middle desulfurization by air blower
Product after reaction；
3. absorption tower is discharged in the slurries of absorb the bottom of the tower by slurry discharge pump, collect.
Further, step 1. in, the pH value of absorbing liquid: 10~11.8, step 3. in slurries pH value are as follows: 8.5~
10。
Further, filter cake isolated in step 3 carries out flue gas desulfurization, the specific steps are as follows:
1. adding cosolvent in filter cake, stirring at normal temperature impregnates in aqueous solution, the lysigenous aluminium hydroxide of filter cake, hydrogen
Maceration extract is pumped into absorption tower by calcium oxide and magnesium hydroxide maceration extract after nozzle atomization, and flue gas reacts with absorbing liquid；Water
The dosage water that 100mL is added corresponding with the filter cake that the dosage of Yu Chu calcium carbide factory solid waste waste residue meets every gram；Room temperature refers to 10~
30℃；Dip time is 3h；
2. collecting the slurries after oxidation.
Further, step 1. in, the pH value of absorbing liquid: 8~10, step 2. in slurries pH value are as follows: 5.5~8.
Further, by the slurries collected in step 3 from absorb the bottom of the tower by the way that aluminum sulfate solution, magnesium sulfate is obtained by filtration
Adlerika is obtained epsom salt by evaporation and concentration, crystallisation by cooling by solution and calcium sulphate solid, and aluminum sulfate solution is used
In being further processed into required aluminium compound；Crystallisation by cooling refers in -8~0 DEG C of crystallisation by cooling.
Compared with prior art, the present invention has following technical effect:
The present invention is by component separating treatment, and calcium carbide factory's solid waste is mainly by MgO, CaO, Al2O3And SiO2Group
At, solid waste maceration extract, solid waste filter cake aqueous solution can be used as absorbent and carry out flue gas desulfurization by aqueous solution in alkalinity, with
SO in flue gas2Reaction generates the products such as corresponding stable compound calcium sulphate dihydrate, epsom salt, silica, realizes
Flue gas harmless treatment, and realize solid waste harmless treatment, to realize the cycling and reutilization of calcium carbide factory's solid waste.
Detailed description of the invention
Fig. 1 is the pH value of calcium carbide factory's Industrial Solid Waste of the invention maceration extract at different temperatures.
Fig. 2 is the desulphurization reaction speed of calcium carbide factory's Industrial Solid Waste of the invention for different initial pH value sulphide-containing waste waters
Rate.
Specific embodiment
Below in conjunction with attached drawing, the present invention is further described:
A kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization, comprising the following steps:
Step 1, calcium carbide factory's solid waste granularity is reduced by pretreatment, obtains Yu Chu calcium carbide factory solid waste waste residue, calcium carbide factory's solid waste
Waste residue includes MgO, CaO, Al2O3And SiO2；
Step 2, water and pretreated calcium carbide factory's solid waste waste residue are mixed, mixed substance filter and is divided
Separate out maceration extract and filter cake；
Step 3, flue gas desulfurization is carried out respectively to isolated maceration extract and filter cake；
Step 4, the product in collection step 3 after flue gas desulfurization, and it is filtered.
By after the drying of calcium carbide factory's solid waste waste residue in step 1,20 mesh are crushed to hereinafter, obtaining Yu Chu calcium carbide factory solid waste waste residue.
Water is mixed as leaching solvent with Yu Chu calcium carbide factory solid waste waste residue in step 2, and stirring at normal temperature dipping utilizes and filters dress
Suction filtration is set, maceration extract and filter cake are obtained；The calcium carbide factory that the dosage of water and the dosage of Yu Chu calcium carbide factory solid waste waste residue meet every gram is solid
The useless corresponding water that 100mL is added；Room temperature refers to 10~30 DEG C；Dip time is 30min.
Isolated maceration extract carries out flue gas desulfurization in step 3, the specific steps are as follows:
1. maceration extract is pumped into absorption tower after nozzle atomization, flue gas enters absorption tower, flue gas and absorption by air-introduced machine
Liquid counter current contacting, calcium hydroxide in sulfur dioxide and absorbing liquid and magnesium hydroxide in flue gas react；
2. absorb the bottom of the tower is stirred continuously by blender, and blasts air, oxidation step 1. middle desulfurization by air blower
Product after reaction；
3. absorption tower is discharged in the slurries of absorb the bottom of the tower by slurry discharge pump, collect.
Step 1. in, the pH value of absorbing liquid: 10~11.8, step 3. in slurries pH value are as follows: 8.5~10.
Isolated filter cake carries out flue gas desulfurization in step 3, the specific steps are as follows:
1. adding cosolvent in filter cake, stirring at normal temperature impregnates in aqueous solution, the lysigenous aluminium hydroxide of filter cake, hydrogen
Maceration extract is pumped into absorption tower by calcium oxide and magnesium hydroxide maceration extract after nozzle atomization, and flue gas reacts with absorbing liquid；Water
The dosage water that 100mL is added corresponding with the filter cake that the dosage of Yu Chu calcium carbide factory solid waste waste residue meets every gram；Room temperature refers to 10~
30℃；Dip time is 3h；
2. collecting the slurries after oxidation.
Step 1. in, the pH value of absorbing liquid: 8~10, step 2. in slurries pH value are as follows: 5.5~8.
By the slurries collected in step 3 from absorb the bottom of the tower by the way that aluminum sulfate solution, Adlerika and sulphur is obtained by filtration
Adlerika is obtained epsom salt by evaporation and concentration, crystallisation by cooling by sour calcium solid, and aluminum sulfate solution is for further
It is processed into required aluminium compound；Crystallisation by cooling refers in -8~0 DEG C of crystallisation by cooling.
Mechanism of the invention is: the pretreatment of calcium carbide factory's solid waste can remove the extra moisture of solid waste itself, reduce its waste residue grain
Degree, makes it easier to dissolve.Aqueous polar is big, soluble end is wide, economical and easily available, and it is solid that Yu Chu calcium carbide factory is impregnated using water as leaching solvent
It is useless, so that partial oxidation calcium, magnesia in solid waste is hydrolyzed into calcium hydroxide, magnesium hydroxide, maceration extract is obtained after filtering and is consolidated
Useless filter cake.For maceration extract in alkalinity, the absorbing liquid pH value for flue gas desulfurization is 10~11.8.Solid waste filter cake contains a large amount of oxidation
Aluminium and silica add activator in oxidation aluminum water solution, and water solubility increases, formed absorbing liquid pH value for 8.5~
10.Under room temperature, silica and water do not react, and are deposited on serum pot bottom, need to periodically be discharged and prevent blocking.The pH of absorbing liquid
Value is very big on the influence of the absorption rate of sulfur dioxide, and when pH value is 10~11.8, absorption rate has almost been reacted in 3 minutes
Finish.Serum pot, which sets blender, can guarantee the uniform of slurries, prevent slurries from precipitating, and enhance the activation of calcium hydroxide and magnesium hydroxide
Effect.Slurry pool, which sets blender, can prevent slurries precipitating, fouling and blocking, and Adlerika is concentrated by evaporation to solution in gruel shape
Thick liquid when, stop heating, make solution close to saturation, be conducive to crystal be precipitated.
The key reaction formula of dipping is as follows:
CaO+H2O=Ca (OH)2
MgO+H2O=Mg (OH)2
The key reaction formula of maceration extract desulfurization is as follows:
Ca(OH)2+SO2=CaSO3·H2O
CaSO3·H2O+SO2=Ca (HSO3)2
Mg(OH)2+SO2=MgSO3+H2O
CaSO3·H2O+1/2O2+H2O=CaSO4·2H2O
Ca(HSO3)2+O2+2H2O=CaSO4·2H2O+H2SO4
MgSO3+1/2O2=MgSO4
The key reaction formula of solid waste filter cake aqueous solution desulfurization is as follows:
2Al(OH)3+3SO2=Al2(SO3)3+3H2O
Al2(SO3)3+3/2O2=Al2(SO4)3
The present invention carries out flue gas desulfurization using calcium carbide factory's solid waste, under normal temperature condition, smoke desulfurization efficiency up to 90% or more,
Desulfurization rate is basically completed within 3 minutes, realizes the cycling and reutilization of calcium carbide factory's solid waste, and process flow is simple, cost and
Operating cost is extremely low, environmental benefit and economic benefit with highly significant.
The present embodiment is by taking calcium carbide factory's solid waste is used for the boiler smoke disposition of Yulin company operation as an example, to this
Invention is explained.
The X-ray fluorescence spectra analysis result of calcium carbide industry solid waste sample in the present embodiment is as shown in table 1 below:
1 calcium carbide factory's Industrial Solid Waste main component of table and content detection result
As shown in Table 1, calcium carbide factory's solid waste is mainly by Al2O3、CaO、MgO、SiO2Four kinds at being grouped as, wherein MgO with
CaO content accounts for the 43.44% and 30.11% of total content respectively, and the two content summation accounts for about the 73% of total content, therefore, the electricity
Stone factory solid waste aqueous solution is in alkalinity.
Embodiment
After the drying of calcium carbide factory's solid waste waste residue, 20 mesh are crushed to hereinafter, obtaining Yu Chu calcium carbide factory solid waste waste residue.Using water as
Leaching solvent is mixed with Yu Chu calcium carbide factory solid waste waste residue, and at different temperatures, stirring dipping 30min is filtered using Suction filtration device,
Obtain maceration extract and filter cake.Maceration extract is pumped into absorption tower, cigarette between 10 to 11.8 by the pH value of maceration extract after nozzle atomization
Gas enters absorption tower, flue gas and absorbing liquid counter current contacting by air-introduced machine, the hydrogen-oxygen in sulfur dioxide and absorbing liquid in flue gas
Change calcium and magnesium hydroxide reacts.Absorb the bottom of the tower is stirred continuously by blender, and blasts air by air blower.Simultaneously
Absorption tower is discharged in the slurries of absorb the bottom of the tower by slurry discharge pump, is collected.The slurries collected from absorb the bottom of the tower are logical
Magnesium sulfate mixed solution and calcium sulphate solid etc. is obtained by filtration, by mixed solution by be concentrated by evaporation -8 DEG C at a temperature of it is cold
But crystallization obtains epsom salt.
Handle the SO of flue gas2Initial concentration is 3000mg/L, under normal temperature condition, the SO of flue gas after processing2Concentration is 210mg/
L, desulfuration efficiency 93%, desulphurization reaction is basically completed in 3min.
Embodiment of the present invention are not limited by the above embodiments, other any without departing from principle of the invention foundation
The method of calcium carbide factory's solid waste desulfurization recycling of lower implementation utilizes calcium carbide factory's solid waste made by principle of the invention accommodation
The method of desulfurization recycling, all within protection scope of the present invention.
Claims (8)
1. a kind of method of calcium carbide factory's solid waste desulfurization and cycling and reutilization, which comprises the following steps:
Step 1, calcium carbide factory's solid waste granularity is reduced by pretreatment, obtains Yu Chu calcium carbide factory solid waste waste residue, calcium carbide factory's solid waste waste residue
Including MgO, CaO, Al2O3And SiO2；
Step 2, water and pretreated calcium carbide factory's solid waste waste residue are mixed, mixed substance filter and is isolated
Maceration extract and filter cake；
Step 3, flue gas desulfurization is carried out respectively to isolated maceration extract and filter cake；
Step 4, the product in collection step 3 after flue gas desulfurization, and it is filtered.
2. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 1 and cycling and reutilization, which is characterized in that step
By after the drying of calcium carbide factory's solid waste waste residue in 1,20 mesh are crushed to hereinafter, obtaining Yu Chu calcium carbide factory solid waste waste residue.
3. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 1 and cycling and reutilization, which is characterized in that step
Water is mixed as leaching solvent with Yu Chu calcium carbide factory solid waste waste residue in 2, and stirring at normal temperature dipping is filtered using Suction filtration device, obtained
Maceration extract and filter cake；The dosage of water is corresponding with calcium carbide factory's solid waste that the dosage of Yu Chu calcium carbide factory solid waste waste residue meets every gram to be added
The water of 100mL；Room temperature refers to 10~30 DEG C；Dip time is 30min.
4. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 1 and cycling and reutilization, which is characterized in that step
Isolated maceration extract carries out flue gas desulfurization in 3, the specific steps are as follows:
1. maceration extract is pumped into absorption tower after nozzle atomization, flue gas enters absorption tower by air-introduced machine, and flue gas and absorbing liquid are inverse
Stream contact, calcium hydroxide in sulfur dioxide and absorbing liquid and magnesium hydroxide in flue gas react；
2. absorb the bottom of the tower is stirred continuously by blender, and blasts air by air blower, oxidation step 1. in desulphurization reaction
Product afterwards；
3. absorption tower is discharged in the slurries of absorb the bottom of the tower by slurry discharge pump, collect.
5. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 4 and cycling and reutilization, which is characterized in that step
In 1., the pH value of absorbing liquid: 10~11.8, step 3. in slurries pH value are as follows: 8.5~10.
6. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 1 and cycling and reutilization, which is characterized in that step
Isolated filter cake carries out flue gas desulfurization in 3, the specific steps are as follows:
1. adding cosolvent in filter cake, stirring at normal temperature impregnates in aqueous solution, the lysigenous aluminium hydroxide of filter cake, hydroxide
Maceration extract is pumped into absorption tower by calcium and magnesium hydroxide maceration extract after nozzle atomization, and flue gas reacts with absorbing liquid；The use of water
The water of amount addition 100mL corresponding with the filter cake that the dosage of Yu Chu calcium carbide factory solid waste waste residue meets every gram；Room temperature refers to 10-30 DEG C；
Dip time is 3h；
2. collecting the slurries after oxidation.
7. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 6 and cycling and reutilization, which is characterized in that step
In 1., the pH value of absorbing liquid: 8~10, step 2. in slurries pH value are as follows: 5.5~8.
8. the method for a kind of calcium carbide factory's solid waste desulfurization according to claim 4 and cycling and reutilization, which is characterized in that will walk
The slurries collected in rapid 3 from absorb the bottom of the tower are by being obtained by filtration aluminum sulfate solution, Adlerika and calcium sulphate solid, by sulphur
Sour magnesium solution obtains epsom salt by evaporation and concentration, crystallisation by cooling, and aluminum sulfate solution is required for being further processed into
Aluminium compound；Crystallisation by cooling refers in -8~0 DEG C of crystallisation by cooling.
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| CN115138668A (en) * | 2022-06-29 | 2022-10-04 | 中国矿业大学(北京) | Fly ash treatment method |
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