CN105819480A - Semi-dry process flue gas desulfurized ash modification treatment method - Google Patents
Semi-dry process flue gas desulfurized ash modification treatment method Download PDFInfo
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- CN105819480A CN105819480A CN201610155138.8A CN201610155138A CN105819480A CN 105819480 A CN105819480 A CN 105819480A CN 201610155138 A CN201610155138 A CN 201610155138A CN 105819480 A CN105819480 A CN 105819480A
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- desulphurization
- mno
- flue gas
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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
- C01F11/02—Oxides or hydroxides
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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
Abstract
The invention discloses a semi-dry process flue gas desulfurized ash modification treatment method. Flue gas desulfurized ash, which is obtained after a CFB desulfurization technology, is modified by MnO2, water, and an oxidant; during the modification process, flue gas desulfurized ash is continuously oxidized, calcium oxide in flue gas desulfurized ash is converted into calcium hydroxide, calcium sulfite is converted into calcium sulfate, and modified desulfurized ash is obtained. Specifically, the modification treatment comprises the following steps: spraying atomized water, which contains a MnO2 catalyst, on desulfurized ash, stirring for 5 to 10 minutes to uniformly mix desulfurized ash and water; then spraying an oxidant on the desulfurized ash, stirring for 25 to 40 minutes, and evenly mixing so as to fully modify desulfurized ash. According to the modification treatment method, atomized water containing MnO2 and an oxidant are combined to modify desulfurized ash in an enclosed environment; after modification, the water content of desulfurized ash is 15 to 17%, desulfurized ash can be directly entrucked without dehydration or drying, and the energy and time are saved.
Description
Technical field
The present invention relates to the modification processing method of a kind of material, especially relate to the semidry method after a kind of flue gas desulfurization and take off
Sulfur ash modification processing method, be mainly used in apply CFB(circulating fluid bed flue gas desulfurization technique technology) process flue gas environmental protection
In project；Belong to environmental technology field.
Background technology:
Carry out industry environmental protection work the most energetically due to country, industrial smoke process is also one of important course of efforts at environmental protection.
In order to reach the environmental protection index of national requirements, in existing glass industries, using CFB sulfur removal technology technology, smoke gas treatment is changed
Kind, reach national requirements for environmental protection.But the product Desulphurization after flue gas desulfurization is manipulated so for main bugbear, its reason be by
In using the Desulphurization after CFB desulfurization to contain substantial amounts of calcium sulfite, the unstability of calcium sulfite is easily decomposed and is again discharged two
Sulfur oxide, causes secondary pollution；The Desulphurization containing the calcium sulfite technology that there is also limitation in application.Produce to solve desulfurization
CaSO in thing3Instability problem, prior art be mainly by CaSO3Carry out oxidation modification so that it is be transformed into
CaSO4.Such as Chinese patent CN104096707A discloses a kind of semi-dry desulphurization ash resource utilization method, mainly uses
CO2Make calcium oxide be changed into calcium carbonate, then regulate pH value, reoxidize calcium sulfite afterwards and be modified；Chinese patent
CN104150520B also discloses that a kind of dry method, semi-dry desulphurization ash two sections turn round oxygen-enriched heated oxide technique and supporting dress thereof
Put.But these flue gas desulfurization ashes being both for different industries are modified, owing to its desulfurization ash composition of different industries is each
Differ, it is impossible to compatible use, even if modification technology that can be compatible is also required to high cost and reaches modified purpose, simultaneously its
Modified effect need to improve.
And along with the continuous growth of float glass demand, the modification technology demand of Desulphurization is along with desulfurization product
Increase and increasingly highlight increase in demand, its importance increases the most day by day., in order to improve the secondary profit of desulfurization product
With being worth the modification being compatible with again the Desulphurization with heterogeneity composition simultaneously, technological difficulties are had become as.
In order to solve this technological difficulties, my company by research and development, invent a kind of semi-dry desulphurization ash modification technology and
Its process equipment, can solve the CaSO in the Desulphurization for different component composition3Modified problem, simultaneously by this kind of side
The modified Desulphurization of method do not have other influences its again with negative issue.
It is not found to have the patent literature constructed with the present invention by patent retrieval, has certain relation with the present invention
Patent mainly have following:
1, Patent No. CN201310499106.6, entitled " method of modifying of a kind of semidry method sintering flue gas desulfurization ash "
Patent of invention, which discloses the method for modifying of a kind of semidry method sintering flue gas desulfurization ash, by semidry method sintering flue gas desulfurization
Ash is ground, sieve after, impregnated in deionized water modified, then impregnated in 5～20% oxalic acid solution in modified.Specifically
Step is: first ground by semidry method sintering flue gas desulfurization ash, crosses 100 mesh sieves, obtains Desulphurization I；Again the Desulphurization I of gained is impregnated
In deionized water, it is heated to 40～70 DEG C, is incubated 2～4h；Filtering, filtrate is chlorate solution, and filtering residue is Desulphurization II；
Again the Desulphurization II of gained be impregnated in oxalic acid solution, be heated to 60～80 DEG C, insulated and stirred 4～8h, wherein use alkali liquor
Absorb SO2Gas；Filter, take filtering residue and adopt and be washed with deionized water 3～4 times, be dried at 70 DEG C, obtain modified Desulphurization.
2, Patent No. CN201110072276.7, the invention of entitled " preparation method of a kind of modified desulphurized ash "
Patent, which discloses the preparation method of a kind of modified desulphurized ash.In desulfurization ash, first add water be sufficiently mixed, make to take off
The water content of sulfur lime-ash is 20～40wt%；Again desulfurization ash is placed under conditions of room epidemic disaster is 70～100% 20～
40 days, obtaining modified desulphurized ash, in described modified desulphurized ash, the content of free calcium oxide is less than 5%.This invention is first to de-
Sulfur lime-ash carries out pretreatment modification, is applied in manufacture of cement by modified desulfurization ash, eliminates dry row's desulfurization ash
Mix the problem that the cement stability brought in cement is bad, thus the recycling efficiently solving current desulfurization ash is difficult
Topic.
3, Patent No. CN201010509838.5, entitled " a kind of side that Desulphurization modification is used as cement retarder
Method " patent of invention, which disclose a kind of by steel enterprise sintering technique or power-plant flue gas dry method or semidry method flue gas
The Desulphurization produced after desulfurization is modified the method as cement retarder, and its characterization step is: A, employing ball milling or gas
The mode that stream is pulverized carries out miniaturization process to Desulphurization, and the specific surface area making Desulphurization particle diameter is 300～1000 meters 2/ kilogram；
B, the Desulphurization after miniaturization processes is positioned in the hermetic container that temperature is 450-700 DEG C, drum in hermetic container
Enter oxygen or air, react 20～60 minutes, obtain the modified Desulphurization as cement retarder.
Though these patents above-mentioned have been directed to Desulphurization modification, but carefully analyze it appeared that these patents also
Do not have positive true solution determine different component constitute Desulphurization in CaSO3Modified problem, the most still will appear from foregoing one
A little problems, still need to be improved further.
Summary of the invention
Present invention aims in existing glass industries, use flue gas desulfurization after CFB sulfur removal technology technical finesse
Ash deficiency existing for modification, proposes a kind of new flue gas desulfurization ash modification processing method, at this flue gas desulfurization ash modification
Reason method both can improve the secondary value of desulfurization product, is compatible with again the Desulphurization with heterogeneity composition simultaneously
Modification, so that the CaSO in CFB product3Content is reduced to 0.1-5% from more than 25%, obtains stable Desulphurization.
In order to reach this purpose, the invention provides a kind of semi-dry process flue gas desulphurization ash modification processing method, will use
The flue gas desulfurization ash obtained after CFB sulfur removal technology technical finesse, utilizes MnO2Flue gas desulfurization ash is entered together with oxidant with water
Row modification so that flue gas desulfurization ash is the most oxidized in modifying process, wherein the calcium oxide in flue gas desulfurization ash converts
For calcium hydroxide, calcium sulfite is converted into calcium sulfate, thus obtains modified Desulphurization.
Further, described MnO is utilized2With water, flue gas desulfurization ash being modified together with oxidant process is de-
Spray containing MnO on sulfur ash2The atomized water of catalyst, and it is stirred 5-10 minute causing the uniform moisture of Desulphurization；Again will
Oxidant is sprayed onto on Desulphurization and is stirred 25-40 minute, stirs so that Desulphurization is the most modified.
Further, described sprinkling contains MnO2The atomized water of catalyst is to spray into be in Desulphurization with concentration
The MnO of 1.5-2.5%2Atomized water, the 11-15% of the amount that the atomization water yield is Desulphurization of addition, stir.
Further, described MnO2Atomized water is with MnO2With water (H2O) according to weight ratio be 1:45-55 mixing,
Formed through atomising device atomization.
Further, described sprinkling contains MnO2The atomized water of catalyst is carried out in hermetic container, during stirring
Between be about 5-10 minute, regulation rotating speed to uniform moisture (2% moisture content), a portion water and calcium oxide react generate hydroxide
Calcium (containing calcium oxide in Desulphurization is 25%, then consume the moisture content of 8%), and release heat, system temperature can be made to rise to 90-
100℃。
Further, described being sprayed onto on Desulphurization by oxidant is stirred 25-40 minute being to contain in sprinkling
MnO2The atomized water of catalyst, after stirring, sprays into the oxidizing agent solution that concentration is 12-18%, and its oxidizing agent solution amount is de-
The 28-33% of sulfur ash, spray oxidizing agent solution stirs simultaneously, and during this, system temperature is higher than 90 DEG C, and system is steamed because of a small amount of moisture content
Send out, there is small pressure, after having sprayed oxidizing agent solution, continue stir about 25-40 minute.
Further, described oxidizing agent solution is hydrogen peroxide or peracetic acid soln.
Further, described MnO2Granularity is identical with Desulphurization.
Further, described Desulphurization is modified processing all processes and is in closed oxidation unit and carries out,
In modifying process, the calcium oxide contained in Desulphurization reacts according to weight portion 10-25% with atomized water: wherein 7-9% ratio
Going out heat with calcium oxide exothermic heat of reaction, under minute-pressure, in closed oxidation unit, liter high-temperature is to 90-100 DEG C, to ensure revolution
Modified-reaction temperature constant.
Further, described MnO2As catalyst, having Oxidation in the basic conditions, self is reduced into two
Valency, also can be oxidized to tetravalence simultaneously, and in hermetic container, the calcium sulfite in semi-dry desulphurization ash is converted into calcium sulfate,
And in the case of the steam-laden of 100 DEG C, coordinating auxiliary heating, calcium sulphate dihydrate becomes α-half-H 2 O calcium sulphate, sulphuric acid
Calcium need not use high temperature dehydration again.
Further, the described whole technological process of modified Desulphurization is:
1, Desulphurization is weighed；
2, Desulphurization is loaded hermetic container；
3, MnO is chosen according to the weight of Desulphurization2,And by MnO2Crushed into powder, granularity is identical with Desulphurization granularity, typically exists
200-300 mesh；
4, by MnO2Powder is that 1:45-55 mixes with water according to weight ratio, and makes it become by atomising device to contain
MnO2Atomized water；
5, according to MnO2The 11-15% of the amount that amount is Desulphurization of atomized water, on Desulphurization, spray MnO2Atomized water, and
Start hermetic container agitating device, be stirred continuously during spraying, stir the uniform moisture causing Desulphurization for 5-10 minute；?
Whipping process will make calcium oxide in Desulphurization be completely converted into calcium hydroxide, and in course of reaction, reactant self will produce
Heat, and evaporation section moisture, formed minute-pressure (about 0.01-0.1MPa) so that the temperature in container reach 90-100 DEG C of temperature (as
Really Desulphurization reaction produces temperature and does not reaches requirement, and can set up heat tracing pipe in or beyond container increases temperature).
6, at MnO2Atomized water sprayed, and after stirring, then oxidant be sprayed onto on Desulphurization be stirred
25-40 minute, stir so that Desulphurization is the most modified；Spray into the oxidizing agent solution that oxidant concentration is 12-18%, its oxygen
Agent amount of solution is the 25-35% of Desulphurization, and spray oxidant stirs simultaneously；During this system temperature be higher than 90 DEG C, and system because of
A small amount of water evaporates, has small pressure (about 0.01-0.1MPa), continues stir about 25-60 minute, enter after having sprayed oxidant
The abundant modification of row；
7, slowly reduced pressure by pressure regulator valve, to normal pressure；
8, continue stirring, open discharge gate simultaneously, discharge modified Desulphurization to feed bin.
It is an advantage of the current invention that:
The present invention utilizes MnO2Atomized water and oxidant combine, under closed environment, carry out Desulphurization modification, and logical
Cross modified material self-heating so that in modifying process, system temperature is higher than 90 DEG C, the beneficially oxidation of calcium sulfite；Airtight
In space, a small amount of water evaporates, make system have the pressure (about 0.01-0.1MPa) of trace, the beneficially oxidation of calcium sulfite,
It is dispersed in MnO in Desulphurization2Play good catalytic action in the basic conditions, accelerate the oxidation of calcium sulfite；Close
Close container and remain the elemental oxygen that the oxidants such as hydrogen peroxide decompose out, beneficially the oxidation of calcium sulfite；Catalyst MnO2's
Addition is few, makes the color of Desulphurization not change, and will not become other coloured materials, beneficially Desulphurization
Secondary utilizes.Modified Desulphurization water content, can directly entrucking at 15-17%, it is not necessary to dehydrate, has saved the energy, joint
About time.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment one
A kind of semi-dry process flue gas desulphurization ash modification processing method, will use CFB sulfur removal technology technical finesse in Improving Glass Manufacturing Processes
After obtain flue gas desulfurization ash, utilize MnO2It is modified flue gas desulfurization ash processing together with oxidant with water so that flue gas
Desulphurization is the most oxidized in modifying process, and wherein the calcium oxide in flue gas desulfurization ash is converted into calcium hydroxide, calcium sulfite
It is converted into calcium sulfate, thus obtains modified Desulphurization.The described whole technological process of modified Desulphurization is:
1, weigh Desulphurization, Desulphurization is ground into powder, typically at 200-300 mesh；
2, Desulphurization is loaded hermetic container；
3, MnO is chosen according to the weight of Desulphurization2,And by MnO2Crushed into powder, granularity is identical with Desulphurization granularity；
4, by MnO2Powder is that 1:45 mixes with water according to weight ratio, and makes it become MnO by atomising device2's
Atomized water；
5, according to MnO2The amount of atomized water is 11% preparation MnO of the amount of Desulphurization2Atomized water, sprays MnO on Desulphurization2Atomization
Water, and start hermetic container agitating device, it being stirred continuously during spraying, stirring causes the uniform moisture of Desulphurization for 5 minutes；
Calcium oxide in Desulphurization will be made in whipping process to be completely converted into calcium hydroxide, and in course of reaction, reactant self will produce
Heat, and evaporation section moisture, form minute-pressure so that the temperature in container reaches 90-100 DEG C of temperature, if Desulphurization reaction
Producing temperature and do not reach requirement, can set up heat tracing pipe in or beyond container increases temperature.
6, at MnO2Atomized water sprayed, and after stirring, then oxidant be sprayed onto on Desulphurization be stirred
40 minutes, stir so that Desulphurization is the most modified；Spraying into the hydrogen peroxide solution that oxidant concentration is 12%, its dioxygen is water-soluble
Liquid measure is the 35% of Desulphurization, and spray hydrogen peroxide solution stirs simultaneously；During this, system temperature is higher than 90 DEG C, and system is because of a small amount of
Water evaporates, has small pressure (about 0.01-0.1MPa), continues stir about 25 minutes, carry out fully after having sprayed oxidant
Modification；
7, slowly reduced pressure by pressure regulator valve, to normal pressure；
8, continue stirring, open discharge gate simultaneously, discharge modified Desulphurization to feed bin.
Embodiment two
A kind of semi-dry process flue gas desulphurization ash modification processing method, will use CFB sulfur removal technology technical finesse in glass manufacturing process
After obtain flue gas desulfurization ash, utilize MnO2It is modified flue gas desulfurization ash processing together with oxidant with water so that flue gas
Desulphurization is the most oxidized in modifying process, and wherein the calcium oxide in flue gas desulfurization ash is converted into calcium hydroxide, calcium sulfite
It is converted into calcium sulfate, thus obtains modified Desulphurization.The described whole technological process of modified Desulphurization is:
1, Desulphurization is weighed；
2, Desulphurization is loaded hermetic container；
3, MnO is chosen according to the weight of Desulphurization2,And by MnO2Crushed into powder, granularity is identical with Desulphurization granularity, typically exists
200-300 mesh；
4, by MnO2Powder is that 1:55 mixes with water according to weight ratio, and makes it become MnO by atomising device2
Atomized water；
5, according to MnO2Atomized water the amount that amount is Desulphurization 15%, on Desulphurization spray MnO2Atomized water, and start
Hermetic container agitating device, is stirred continuously during spraying, and stirring causes the uniform moisture of Desulphurization for 10 minutes；Stirred
Journey will make calcium oxide in Desulphurization be completely converted into calcium hydroxide, and in course of reaction, reactant self will produce heat, and steam
Send out portion of water, form minute-pressure so that the temperature in container reaches 90-100 DEG C of temperature and (reaches if Desulphurization reaction produces temperature
Less than requiring, can set up heat tracing pipe in or beyond container increases temperature).
6, at MnO2Atomized water sprayed, and after stirring, then oxidant be sprayed onto on Desulphurization be stirred
25 minutes, stir so that Desulphurization is the most modified；Spray into oxidant be concentration be the peroxide acetate aqueous solution of 18%, its mistake
The water-soluble liquid measure of fluoroacetic acid is the 25% of Desulphurization, and spray oxidant stirs simultaneously；During this, system temperature is higher than 90 DEG C, and system
Because of a small amount of water evaporates, there is small pressure (about 0.01-0.1MPa), continue stir about 60 minutes after having sprayed oxidant, enter
The abundant modification of row；
7, slowly reduced pressure by pressure regulator valve, to normal pressure；
8, continue stirring, open discharge gate simultaneously, discharge modified Desulphurization to feed bin.
Embodiment three
A kind of semi-dry process flue gas desulphurization ash modification processing method, will use CFB sulfur removal technology technical finesse in glass manufacturing process
After obtain flue gas desulfurization ash, utilize MnO2It is modified flue gas desulfurization ash processing together with oxidant with water so that flue gas
Desulphurization is the most oxidized in modifying process, and wherein the calcium oxide in flue gas desulfurization ash is converted into calcium hydroxide, calcium sulfite
It is converted into calcium sulfate, thus obtains modified Desulphurization.The described whole technological process of modified Desulphurization is:
1, weighing Desulphurization, ash granularity is 200-300 mesh；
2, Desulphurization is loaded hermetic container；
3, MnO is chosen according to the weight of Desulphurization2,And by MnO2Crushed into powder, granularity is identical with Desulphurization granularity；
4, by MnO2Powder is that 1:50 mixes with water according to weight ratio, and makes it become MnO by atomising device2's
Atomized water；
5, according to MnO2Atomized water the amount that amount is Desulphurization 12%, on Desulphurization spray MnO2Atomized water, and start
Hermetic container agitating device, is stirred continuously during spraying, stirs the uniform moisture causing Desulphurization for 5-10 minute；In stirring
During calcium oxide in Desulphurization will be made to be completely converted into calcium hydroxide, and in course of reaction, reactant self produces heat, and
Evaporation section moisture, forms minute-pressure so that the temperature in container reaches 90-100 DEG C and (reaches not if Desulphurization reaction produces temperature
To requiring, can set up heat tracing pipe in or beyond container increases temperature).
6, at MnO2Atomized water sprayed, and after stirring, then oxidant be sprayed onto on Desulphurization be stirred
30 minutes, stir so that Desulphurization is the most modified；Spray into oxidant be concentration be the hydrogen peroxide solution of 15%, in an amount of from de-
The 30% of sulfur ash, spray oxidant stirs simultaneously；During this, system temperature is higher than 90 degree, and system is because of a small amount of water evaporates, has
Small pressure (about 0.01-0.1MPa), continues stir about 40 minutes after having sprayed oxidant, carries out abundant modification；
7, slowly reduced pressure by pressure regulator valve, to normal pressure；
8, continue stirring, open discharge gate simultaneously, discharge modified Desulphurization to feed bin.
Above-mentioned listed embodiment, simply carries out clear, complete description to technical scheme；Obviously, described
Embodiment be only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this
All other embodiments that field those of ordinary skill is obtained under not making creative work premise, broadly fall into the present invention
The scope of protection.
By above-described embodiment it can be seen that the present invention relates to a kind of semi-dry process flue gas desulphurization ash modification processing method, will
The flue gas desulfurization ash obtained after using CFB sulfur removal technology technical finesse in Improving Glass Manufacturing Processes, utilizes MnO2With water and oxidant
It is modified flue gas desulfurization ash processing so that flue gas desulfurization ash is the most oxidized in modifying process, wherein flue gas desulfurization ash
In calcium oxide be converted into calcium hydroxide, calcium sulfite is converted into calcium sulfate, thus obtains modified Desulphurization.
Further, described MnO is utilized2With water, flue gas desulfurization ash being modified process is to spray to contain on Desulphurization
There is MnO2The atomized water of catalyst, and it is stirred 5-10 minute causing the uniform moisture of Desulphurization；Again oxidant is sprayed onto
It is stirred on Desulphurization 25-40 minute, stirs so that Desulphurization is the most modified.
Further, described sprinkling contains MnO2The atomized water of catalyst is to spray into be in Desulphurization with concentration
The MnO of 1.5-2.5%2Atomized water, the 11-15% of the amount that the atomization water yield is Desulphurization of addition, stir.
Further, described MnO2Atomized water is with MnO2With water (H2O) according to weight ratio be 1:45-55 mixing,
Formed through atomising device atomization.
Further, described sprinkling contains MnO2The atomized water of catalyst is carried out in hermetic container, during stirring
Between be about 5-10 minute, regulation rotating speed to uniform moisture (2% moisture content), a portion water and calcium oxide react generate hydroxide
Calcium (containing calcium oxide in Desulphurization is 25%, then consume the moisture content of 8%), and release heat, system temperature can be made to rise to 90-
100℃。
Further, described being sprayed onto on Desulphurization by oxidant is stirred 25-40 minute being to contain in sprinkling
MnO2The atomized water of catalyst, after stirring, sprays into the oxidizing agent solution that concentration is 12-18%, and its oxidizing agent solution amount is de-
The 28-33% of sulfur ash, spray oxidizing agent solution stirs simultaneously, and during this, system temperature is higher than 90 DEG C, and system is steamed because of a small amount of moisture content
Send out, there is small pressure, after having sprayed oxidizing agent solution, continue stir about 25-40 minute.
Further, described oxidizing agent solution is hydrogen peroxide or peracetic acid soln.
Further, described MnO2Granularity is identical with Desulphurization.
Further, described Desulphurization is modified processing all processes and is in closed oxidation unit and carries out,
In modifying process, the calcium oxide contained in Desulphurization reacts according to weight portion 10-25% with atomized water: wherein 7-9% ratio
Carry out exothermic reaction with calcium oxide, under minute-pressure, closed oxidation unit produces the temperature of 90-100 DEG C, to ensure that revolution changes
Property reaction temperature constant.
Further, described MnO2As catalyst, having Oxidation in the basic conditions, self is reduced into two
Valency, but its not oxidized one-tenth tetravalence must be controlled, and in hermetic container, the calcium oxide in semi-dry desulphurization ash is converted into hydrogen-oxygen
Changing calcium, calcium sulfite is converted into calcium sulfate, and in the case of the steam-laden of 100 DEG C, calcium sulphate dihydrate becomes-half
H 2 O calcium sulphate, calcium sulfate need not use high temperature dehydration again.
It is an advantage of the current invention that:
The present invention utilizes MnO2Atomized water and oxidant combine, under closed environment, carry out Desulphurization modification, and logical
Cross modified material self-heating so that in modifying process, system temperature is higher than 90 DEG C, the beneficially oxidation of calcium sulfite；Airtight
In space, a small amount of water evaporates, make system have the oxidation of the pressure of trace, beneficially calcium sulfite, de-to being dispersed in
MnO in sulfur ash2Play good catalytic action in the basic conditions, accelerate the oxidation of calcium sulfite；Hermetic container remains
The oxidation of the elemental oxygen that the oxidants such as hydrogen peroxide decompose out, beneficially calcium sulfite；Catalyst MnO2Addition few, make to take off
The color of sulfur ash does not changes, and the secondary that will not become other coloured materials, beneficially Desulphurization utilizes.Modified
After Desulphurization water content at 15-17%, can directly entrucking, it is not necessary to dehydrate, saved the energy, saved the time.This
Bright have the beneficial effects that:
1. the present invention is with MnO2As catalyst, improve revolution reaction rate, simultaneously MnO2Catalytic process does not has have face
Color containing manganese material, the most modified Desulphurization by all kinds of means again with.
2. the present invention carries out oxidation revolution reaction in airtight oxidation unit, reduces the atom in the oxidants such as hydrogen peroxide
Oxygen volatilization is escaped, it is ensured that effectively carrying out of modified-reaction, provides certain reaction pressure for modified-reaction simultaneously.
3. the present invention is by the exothermic reaction in modifying process, gives to provide the temperature of 90-100 DEG C, can promote modification
The reaction rate of reaction.
The most modified Desulphurization water content, can directly entrucking at 15-17%, it is not necessary to dehydrate, has saved the energy,
Save the time.
5. after the present invention passes through modified-reaction, so that the CaSO in semi-dry desulphurization ash3Content reduces from more than 25%
To 5% and less, the most modified product can by all kinds of means again with.
6. the present invention is by the various reaction ratios in clear and definite modified-reaction, can give in the modification of various Desulphurizations
Application.
7., in hermetic container, in Desulphurization, spray into the MnO with 2%2Atomized water, the amount of the water of addition is about de-
The 10% of the amount of sulfur ash, stirs, and mixing time is about 5-10 minute, regulation rotating speed to uniform moisture (2% moisture content), Qi Zhongyi
Part water and calcium oxide react generation calcium hydroxide (containing calcium oxide in Desulphurization is 25%, then consume the moisture content of 8%), and release heat
Amount, can make system temperature rise to 90-100 DEG C.Spray into the hydrogen peroxide solution of 15% afterwards, in an amount of from the 30% of Desulphurization, spray
Oxidant stirs simultaneously, continues stir about 30 minutes after having sprayed reagent.During this, system temperature is higher than 90 DEG C, beneficially sulfurous
The oxidation of acid calcium；A small amount of water evaporates, makes system have the oxidation of the pressure of trace, beneficially calcium sulfite；It is dispersed in
MnO in Desulphurization2Play good catalytic action in the basic conditions, accelerate the oxidation of calcium sulfite；Hermetic container retains
Decomposing hydrogen dioxide solution elemental oxygen out, the beneficially oxidation of calcium sulfite；Catalyst MnO2Addition few, make Desulphurization
Color does not changes, and the secondary that will not become other coloured materials, beneficially Desulphurization utilizes.
It is as follows that Desulphurization forms contrast the most afterwards
| CaO% | Ca(OH)2% | CaSO3% | CaSO4% | |
| Scope before modified | 10-25 | 10-30 | 10-25 | 10-40 |
| Example before modified | (20.12) | (24.49) | (21.47) | (24.13) |
| Modified scope | <2 | >20-40 | <5 | >20-60 |
| Modified example | (0.34-0.76) | (44.01-46.05) | (0.58-2057) | (45.01-52.36) |
Claims (10)
1. a semi-dry process flue gas desulphurization ash modification processing method, it is characterised in that after CFB sulfur removal technology technical finesse being used
The flue gas desulfurization ash obtained, utilizes MnO2It is modified flue gas desulfurization ash processing together with oxidant with water so that flue gas takes off
Sulfur ash is the most oxidized in modifying process, and wherein the calcium oxide in flue gas desulfurization ash is converted into calcium hydroxide, and calcium sulfite turns
Turn to calcium sulfate, thus obtain modified Desulphurization.
2. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 1, it is characterised in that described utilizes MnO2
With water, flue gas desulfurization ash being modified process is to spray containing MnO on Desulphurization2The atomized water of catalyst, and be stirred
Within 5-10 minute, cause the uniform moisture of Desulphurization；Being sprayed onto on Desulphurization by oxidant and be stirred 25-40 minute, stirring is all
Even so that Desulphurization is the most modified.
3. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described sprinkling contains
MnO2The atomized water of catalyst is that to spray in Desulphurization with concentration be the MnO of 1.5-2.5%2Atomized water, the atomization of addition
The water yield is the 11-15% of the amount of Desulphurization, stirs.
4. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described MnO2Atomization
Water is with MnO2With water (H2O) according to weight ratio be 1:45-55 mixing, through atomising device atomization and formed.
5. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described sprinkling contains
MnO2The atomized water of catalyst is carried out in hermetic container, and mixing time is about 5-10 minute, and regulation rotating speed is equal to moisture
Even, a portion water and calcium oxide react generation calcium hydroxide, and release heat, and system temperature can be made to rise to 90-100
℃。
6. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described by oxidant
It is sprayed onto on Desulphurization and is stirred 25-40 minute being to spray containing MnO2The atomized water of catalyst, after stirring, sprays into
Concentration is the oxidizing agent solution of 12-18%, and its oxidizing agent solution amount is the 28-33% of Desulphurization, and spray oxidizing agent solution stirs simultaneously,
During this, system temperature is higher than 90 DEG C, and system is because of a small amount of water evaporates, has small pressure, after having sprayed oxidizing agent solution
Continue stir about 25-40 minute.
7. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 6, it is characterised in that described oxidant is molten
Liquid is hydrogen peroxide or peracetic acid soln.
8. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described Desulphurization enters
Row modification all processes is in closed oxidation unit and carries out, in modifying process, and the calcium oxide contained in Desulphurization
Reacting according to weight portion 10-25% with atomized water: wherein 7-9% ratio carries out exothermic reaction, under minute-pressure, closed aoxidizes
Device produces the temperature of 90-100 DEG C, to ensure the temperature constant of revolution modified-reaction.
9. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described MnO2As
Catalyst, has Oxidation in the basic conditions, self is reduced into bivalence, but also can be oxidized to tetravalence, and airtight
Calcium sulfite being converted in container calcium sulfate, and in the case of the steam-laden of 100 DEG C, calcium sulphate dihydrate becomes-
Half-H 2 O calcium sulphate, calcium sulfate need not use high temperature dehydration again.
10. semi-dry process flue gas desulphurization ash modification processing method as claimed in claim 2, it is characterised in that described modification takes off
The sulfur whole technological process of ash is:
Weigh Desulphurization；
Desulphurization is loaded hermetic container；
MnO is chosen according to the weight of Desulphurization2,And by MnO2Crushed into powder, granularity is identical with Desulphurization granularity, typically exists
200-300 mesh；
By MnO2Powder is that 1:45-55 mixes with water according to weight ratio, and makes it become MnO by atomising device2's
Atomized water；
According to MnO2The 11-15% of the amount that amount is Desulphurization of atomized water, on Desulphurization, spray MnO2Atomized water, and start
Hermetic container agitating device, is stirred continuously during spraying, stirs the uniform moisture causing Desulphurization for 5-10 minute；In stirring
During calcium oxide in Desulphurization will be made to be completely converted into calcium hydroxide, and in course of reaction, reactant self produces heat, and
Evaporation section moisture, forms minute-pressure so that the temperature in container reaches 90-100 DEG C of temperature；
At MnO2Atomized water sprayed, and after stirring, then oxidant is sprayed onto on Desulphurization is stirred 25-40 and divides
Clock, stirs so that Desulphurization is the most modified；Spray into the oxidizing agent solution that oxidant concentration is 12-18%, its amount oxidant
Solution is the 25-35% of Desulphurization, and spray oxidant stirs simultaneously；During this, system temperature is higher than 90 DEG C, and system is because of a small amount of water
Part evaporation, has small pressure, continues stir about 25-60 minute, carry out abundant modification after having sprayed oxidant；
Slowly reduced pressure by pressure regulator valve, to normal pressure；
Continue stirring, open discharge gate simultaneously, discharge modified Desulphurization to feed bin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232054A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Method for oxidizing CaSO3 in desulfurized fly ash in alkaline condition |
| CN103803828A (en) * | 2013-12-25 | 2014-05-21 | 武汉武新新型建材有限公司 | Modified desulfurization ash for cement and concrete and preparation method thereof |
| CN104628280A (en) * | 2015-02-04 | 2015-05-20 | 葛洲坝武汉道路材料有限公司 | Desulfurization ash-based activated mineral powder and preparation method and application thereof |
-
2016
- 2016-03-18 CN CN201610155138.8A patent/CN105819480B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232054A (en) * | 2013-05-08 | 2013-08-07 | 武汉钢铁(集团)公司 | Method for oxidizing CaSO3 in desulfurized fly ash in alkaline condition |
| CN103803828A (en) * | 2013-12-25 | 2014-05-21 | 武汉武新新型建材有限公司 | Modified desulfurization ash for cement and concrete and preparation method thereof |
| CN104628280A (en) * | 2015-02-04 | 2015-05-20 | 葛洲坝武汉道路材料有限公司 | Desulfurization ash-based activated mineral powder and preparation method and application thereof |
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| CN109653387A (en) * | 2018-12-14 | 2019-04-19 | 中北大学 | A kind of Desulphurization base polymers insulation board and preparation method thereof and a kind of assembled integrated insulated wall and preparation method thereof |
| CN110844888A (en) * | 2019-10-23 | 2020-02-28 | 江苏沙钢集团有限公司 | Reduction-oxidation two-stage treatment method for desulfurized fly ash |
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