CN108117101A - Sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method - Google Patents
Sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method Download PDFInfo
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- CN108117101A CN108117101A CN201810127997.5A CN201810127997A CN108117101A CN 108117101 A CN108117101 A CN 108117101A CN 201810127997 A CN201810127997 A CN 201810127997A CN 108117101 A CN108117101 A CN 108117101A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
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- B01D2251/602—Oxides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a kind of sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method, it is therefore intended that when solving existing desulfurization leaching manganese Sulphuric acid manganese method for high-concentration sulfur dioxide processing, because slurry pH value is acidity made of electrolytic anode liquid and manganese ore, cause SO in the flue gas after reaction2It is higher while to solve in existing technology pH value in reaction in manganous dithionate formation zone, it is necessary to the problem of being further processed, cause manganous dithionate higher, influence the later use of manganese sulfate product.The present invention is configured to slurries with water, acid solution respectively using manganese ore as desulfurization absorbent, and the manganese ore slurries pump that water is prepared squeezes into rear order reaction group, and the manganese ore slurries that acid solution is configured to, which pump, squeezes into middle order reaction group, and the concentrated sulfuric acid is reached the last order reaction group.Meanwhile slurries are run with flue gas adverse current, so as to fulfill the removing of sulfur dioxide and the extraction of manganese ore.After measured, inventive desulfurization is efficient, reachable more than 99.5%, the SO of outlet drain2Concentration is low, can be less than 100mg/m3；Manganese leaching rate is high, and up to more than 95%, manganous dithionate is low in product, can be less than 5g/L, have remarkable progress.
Description
Technical field
The present invention relates to manganese sulfate preparation field, especially flue gas desulfurization Sulphuric acid manganese field, be specially sub-prime multiple spot into
Material method removing flue gas middle and high concentration SO2Sulphuric acid manganese method.The present invention is essentially SO in a kind of removing flue gas2With extracting sulfuric acid
The method of manganese, with high desulfurization degree and leaching rate, the manganous dithionate containing low content in prepared manganese sulfate solution,
It disclosure satisfy that the electrolysis demand of subsequent sulphuric acid manganese, that is, SO in a kind of removing flue gas be provided2To produce low content manganous dithionate
The method of manganese sulfate solution.
Background technology
Manganese ore has pyrolusite, manganese spar, braunite, psilomelane etc.；Wherein, the main ingredient of manganese spar is MnCO3, brown manganese
The main ingredient of ore deposit is Mn2O3.Traditional leaching manganese method is using manganese ore roasting, the technique of sulfuric acid leaching, for generating electrolytic metal
The manganese products such as manganese, technical grade sulfuric acid manganese.
In recent years, by pyrolusite and water slurrying desulfurization, the SO of discharge can be made2Concentration is less than 100mg/m3It is or even lower.It is soft
The main ingredient of manganese ore is MnO2, MnO2Energy and SO2It reacts, reaction speed is fast and abundant.Therefore, scientific research personnel is to soft manganese
Ore deposit desulfurization has carried out substantial amounts of research.Appoint Min at patent " a kind of new Flue Gas Desulfurization with Pyrolusite Pulp device "（Application number
CN201420660149.8）In, slurries are made come desulfurization using pyrolusite and water, reactor is spray column.
With SO2The research of leaching manganese technology is goed deep into, the SO of high concentration2Desulfurization leaching manganese Sulphuric acid manganese technology is developed.Jiang
Text is lifted " utilizes high concentration SO in patent2Flue gas leaches the process that manganese ore slurry produces manganese product "（Application number
CN201510497919.0）In, slurries are made using electrolytic anode liquid and manganese ore, come desulfurization leaching manganese extracting sulfuric acid manganese, reactor
For spray column.Because electrolytic anode liquid and slurries pH made of manganese ore are relatively low, SO in the flue gas after reaction2It is higher, usually exist
1000mg/m3More than.Therefore, the further desulfurization of the methods of which needs to use activated carbon is to reach discharge standard.
For this purpose, there is an urgent need to a kind of new method, to solve the above problems.
The content of the invention
The goal of the invention of the present invention is：For existing desulfurization leaching manganese Sulphuric acid manganese method at high-concentration sulfur dioxide
During reason, because electrolytic anode liquid and slurry pH value made of manganese ore are relatively low, cause SO in the flue gas after reaction2It is higher, it is necessary into one
The problem of step processing, provides a kind of sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method.The present invention is with manganese
Ore deposit is configured to slurries, the manganese ore slurries pump that water is prepared squeezes into rear order reaction with water, acid solution respectively as desulfurization absorbent
Group, manganese ore slurries that acid solution is configured to pump squeeze into middle order reaction group, and the concentrated sulfuric acid is reached the last order reaction group.Meanwhile slurries
It is run with flue gas adverse current, so as to fulfill the removing of sulfur dioxide and the extraction of manganese ore.After measured, inventive desulfurization is efficient, can
Up to more than 99.5%, the SO of outlet drain2Concentration is low, can be less than 100mg/m3；Manganese leaching rate is high, up to more than 95%, connects in product
Two manganese sulfates are low, can be less than 5g/L, have remarkable progress.
To achieve these goals, the present invention adopts the following technical scheme that：
Sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method, includes the following steps：
（1）Fume treatment
Sulfur dioxide flue gas after dedusting is sequentially sent to after supercharging in preceding order reaction group, middle order reaction group, rear order reaction group
And react with manganese ore slurries therein, manganese sulfate is generated, the sulfur dioxide in flue gas is removed, and reaches discharge standard,
It discharges；
（2）One section of reaction
Manganese mineral powder with water is mixed, is configured to one section of manganese ore reacting slurry, one section of manganese ore reacting slurry is pumped by conveying
One section of reaction is carried out in order reaction group afterwards, reaction temperature is 40 ~ 80 DEG C；
（3）Second-stage reaction
After manganese ore is mixed with acid solution, two sections of manganese ore reacting slurries are configured to, two sections of manganese ore reacting slurries are passed through into conveying
It is pumped into order reaction group and carries out second-stage reaction, reaction temperature is 40 ~ 80 DEG C；
（4）Three sections of reactions
Three sections of reactions are carried out before the concentrated sulfuric acid is sent into order reaction group, to improve the leaching rate of manganese ore, and part is eliminated and connects two sulphur
Sour manganese, reaction temperature are 40 ~ 80 DEG C；
In the step 1, preceding order reaction group, middle order reaction group, rear order reaction group are sequentially connected in series, the middle rank reactive component is other
It is sequentially connected in series using several reactors.
In sulfur dioxide flue gas after dedusting, the content of sulfur dioxide is 20000 ~ 80000mg/m3。
In the step 1, sulfur dioxide flue gas is pre-processed using electric precipitation or bag-type dust.
The prime, middle rank, rear class reactive component not Cai Yong several reactors be in series.
Preferably, the preceding order reaction group, rear class reactive component Cai Yong not single reactors.
The reactor is spray column, the one or more in bubble tower.
The solid content of manganese powder is 10 ~ 25% in one section of manganese ore reacting slurry；Manganese powder in two sections of manganese ore reacting slurries
Solid content be that 5 ~ 20%, pH is 1.5~3.
The acid solution is the concentrated sulfuric acid, the one or more in dilute sulfuric acid, electrolytic anode liquid.
In the step 4, before the concentrated sulfuric acid is sent into order reaction group, the slurry pH value in preceding order reaction group is 0.5 ~ 2.
It waits after the completion of reacting, after the manganese sulfate slurries of generation are carried out purification and impurity removal processing, as electrolytic manganese metal, industry
The raw material of manganese sulfate or high purity manganese sulfate.
In the present invention, Mn in the manganese sulfate slurries of generation2+Content be 20~70g/L.
The slurries of the reaction mechanism requirement reaction of manganese ore leaching are in acidity, and acidity is more strong better, to improve the leaching of manganese ore
Rate；And SO2The reaction mechanism requirement desulfuration solution of removing is for alkalescence or close to neutrality, to reach high desulfuration efficiency and low SO2
Concentration of emission；The two requires opposite working condition.For this purpose, to reach high leaching manganese rate and low SO simultaneously2Concentration of emission carries
High reaction efficiency, applicant are correspondingly improved the prior art.It is due to alkalescence or sharp close to neutral environment in the present invention
In desulfurization, just created in the back segment of system close to neutral slight alkali environment, ensure desulfurization degree height and SO2Qualified discharge；It is and sour
Property environment be beneficial to leaching manganese, in systems front end create sour environment, meet leaching manganese requirement.Meanwhile in leaching process of manganese ore, acid
Property it is stronger, the motive force of system is bigger, and the leaching rate of manganese ore is higher, for this purpose, the present invention system front end add in the concentrated sulfuric acid, improve
Slurries are acid, to further improve the leaching rate of manganese.
In addition, MnO2With SO2Reaction generation manganese sulfate, and by-product manganous dithionate can be generated.Pyrolusite desulfurization technology can produce
The manganous dithionate of raw high level, and higher manganous dithionate amount can seriously affect in electrolysis the upper plate of manganese and yield or
Influence the product quality of technical grade sulfuric acid manganese.At present, the individual program of generally use, to two sulphur of company in generation manganese sulfate slurries
Sour manganese carries out removing processing, time-consuming and laborious.It has been found that with the increase of acid concentration, manganous dithionate resolution ratio can increase,
And the pH value of slurries is adjusted to 1~2, relatively low dithionic acid manganese content can be reached.For this purpose, inventor added in slurries it is dense
Sulfuric acid reduces acidity, so as to effectively reduce the content of manganous dithionate.
Desulfurization cannot be taken into account with the slurrying of electrolytic anode liquid and soak the deficiency of manganese for simple manganese ore and water slurrying with manganese ore,
And the advantages of manganese ore is with water slurrying and manganese ore and electrolytic anode liquid slurrying is absorbed, inventor improves the prior art, by force
Change desulfurization and leaching manganese, propose that a kind of desulfurization leaching manganese rate is all high, desulfurizing agent is few, the manganese ore of manganous dithionate low output removing SO2Side
Method.
As shown in Figure 1, in the present invention, using manganese ore as desulfurization absorbent, slurries are configured to water, acid solution respectively,
The manganese ore slurries pump that water is prepared squeezes into rear order reaction group, and the manganese ore slurries pump that acid solution is configured to squeezes into middle order reaction
Group, the concentrated sulfuric acid are reached the last order reaction group；SO in flue gas2It drives in the wrong direction with slurries, order reaction group, middle order reaction group before being introduced into, with it
In manganese ore react, obtain partial removal, enter back into rear order reaction group, react to obtain sufficiently with manganese ore therein
Removing, after reaching discharge standard, into smoke stack emission；Meanwhile enter intermediate reaction group after the manganese slurry desulfurization of rear order reaction group, in
After the manganese slurry desulfurization of order reaction group and fully leaching manganese, manganese sulfate can obtain；And the concentrated sulfuric acid is added in preceding order reaction group, it can effectively carry
Height leaching manganese rate, and reduce the content of manganous dithionate.Meanwhile provide power, high concentration SO by booster fan2Flue gas successively into
Enter in preceding order reaction group, middle order reaction group, rear order reaction group and react with manganese ore slurries therein and generate manganese sulfate, SO2
It is removed, after flue gas reaches discharge standard, is discharged through chimney.
In the present invention, high concentration SO2Flue gas can derive from the SO that the calcining of high sulfur-bearing electrolytic manganese residues generates2, can be from
In the SO that troilite, sulfuric acid baking burning generate2Gas, SO2Concentration is typically larger than 20000mg/m3.Meanwhile acid solution can be with
It is that water is formulated or dilute sulfuric acid or electrolytic anode liquid or other acid solutions with the concentrated sulfuric acid.Reactor therein can
Think spray column, bubble tower or other patterns.
In the present invention, manganese mineral powder can be the composite ore of pyrolusite, psilomelane, manganese spar, braunite, manganite etc.（I.e.
Manganese ore is to contain MnO2、MnCO3、Mn2O3、Mn3O4Composite ore）, water is with slurry and acid solution is with slurry can be used identical manganese ore
Powder, wherein, water is with slurry to can also be used MnO2The high manganese mineral powder of content, the Mn in the manganese mineral powder of water use with slurry4+Content >=
12%.Wherein, the sieving rate of manganese mineral powder is at least 80% by 200 mesh.Usually manganese mineral powder is thinner, more soaks manganese beneficial to desulfurization.
The present invention can clear up the generation of manganous dithionate by effective control to acid condition.In preceding order reaction group,
The concentrated sulfuric acid is added in, control ph 1 ~ 2 to improve the leaching rate of manganese ore, and eliminates manganous dithionate.Meanwhile one section of manganese ore reaction
Solid content in slurries is 10%~25%；Solid content in two sections of manganese ore reacting slurries is that 5%~20%, pH is 1.5~3；Reaction
Temperature is 40~80 DEG C.
After measured, inventive desulfurization is efficient, reachable more than 99.5%, the SO of outlet drain2Concentration is low, can be less than
100mg/m3；Manganese leaching rate is high, and up to more than 95%, manganous dithionate is low in product, can be less than 5g/L.Meanwhile prime of the present invention
Mn in the manganese sulfate slurries discharged in reaction group2+For 20~70g/L, after the purified removal of impurities processing of manganese sulfate slurries generated,
Raw material of the energy as electrolytic manganese metal, industrial manganic sulfate or high purity manganese sulfate.In addition, the present invention have simple system, investment and
The characteristics of operating cost is relatively low has higher application value and preferable application prospect.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
（1）The concentration of emission of sulfur dioxide of the present invention is low, disclosure satisfy that increasingly stringent SO2Emission request
（2）The leaching rate of manganese greatly improved in the present invention, and manganese ore has higher utilization rate；
（3）Due to the Mn in manganese ore2O3Leach reaction it is slow, reaction needs two steps, and second step needs SO2, for this purpose, the present invention is to anti-
Process is answered to be controlled accordingly, the concentrated sulfuric acid is added in three sections of reactions, is there is SO2Tower in, Mn2O3Reaction is more abundant, effect
Fruit is much better than then individually soaks manganese using depth；
（4）Two sets of pulping systems are provided in the present invention, but raw material is manganese ore, and carrying out depth compared to other desulfurizing agents takes off
Sulphur effectively reduces the species of raw material, and desulfurization product is manganese sulfate, so as to effectively simplify reaction system, reduces plant maintenance
Cost；
（5）The present invention can effectively reduce the content of manganous dithionate in product, using meet product as electrolytic manganese metal raw material and
The requirement of high purity manganese sulfate raw material；
（6）In the present invention, water desulfurization effect with slurry is good, and acid solution leaching manganese effect with slurry is good, by the control to reaction solution,
The adverse effect that manganese ore variation is brought is adapted to, there is extremely strong adaptability and preferable technique effect.
Description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein：
Fig. 1 is the structural diagram of the present invention.
Fig. 2 is the structure diagram of device in embodiment 1.
Fig. 3 is the structure diagram of device in embodiment 2.
It is marked in figure：1st, the first manganese ore powder cabin, the 2, second manganese ore powder cabin, stage reactor after 3, first, the 4, second rear class are anti-
Answer device, stage reactor in 5, first, stage reactor in 6, second, stage reactor before 7, first, 8, first matches somebody with somebody stock tank, and 9, second matches somebody with somebody
Stock tank, stage reactor in the 10, the 3rd.
Specific embodiment
All features or disclosed all methods disclosed in this specification or in the process the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification, unless specifically stated, can be equivalent by other or with similar purpose
Alternative features are replaced.I.e., unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
.
Embodiment 1
As shown in the figure, in the present embodiment, preceding order reaction group, middle order reaction group, rear order reaction group are sequentially connected in series.Wherein, rear class is anti-
It should organize as stage reactor after first, order reaction in stage reactor, the 3rd in stage reactor, second during middle order reaction group uses first
Device is sequentially connected in series, and preceding order reaction group is stage reactor before first.In one section of reaction, using the first manganese ore powder cabin, first
It cooperates with stock tank, prepares one section of manganese ore reacting slurry.In second-stage reaction, stock tank is matched somebody with somebody using the second manganese ore powder cabin, second
It cooperates, prepares two sections of manganese ore reacting slurries.
Its reaction process is as follows.
Flue gas SO after electric precipitation2Content is 60000mg/m3, temperature is 200 DEG C, after being pressurized by a centrifugal blower
Stage reactor, the first rear class in stage reactor, the 3rd in stage reactor, second in stage reactor, first before sequentially entering first
Reactor.Wherein, SO2It reacts with manganese slurry, generates manganese sulfate, SO2It is removed, the SO that rear stage reactor comes out2Concentration≤
100mg/m3, reach discharge standard, from smoke stack emission.
Full Mn contents in first manganese ore powder cabin in manganese powder are 36%, Mn4+Content is 20%；After grinding, manganese powder fineness is
90% passes through 200 mesh.First in stock tank, water is made into the slurries of 15% solid content with manganese mineral powder, and the is squeezed into manganese slurry delivery pump
Stage reactor after one.
Full Mn contents in second manganese ore powder cabin in manganese powder are 35%, Mn4+Content is 11%；After grinding, manganese powder fineness is
90% passes through 200 mesh.Second in stock tank, anolyte is made into the slurries of 8% solid content with manganese mineral powder, is squeezed into manganese slurry delivery pump
Stage reactor in 3rd.
The concentrated sulfuric acid is added in stage reactor before first, improves the acidity of slurries（PH value is adjusted to 1 ~ 2）, to improve leaching manganese
Rate and resolution manganous dithionate.
Manganese slurry is contacted with flue gas adverse current, stage reactor in stage reactor, the 3rd after slurries sequentially enter first, second intermediate
Stage reactor before stage reactor, first in reactor, first；After the slurries of stage reactor are fully reacted with flue gas before first, use
Slurry discharge pump transfers out system, carries out impurity and purification processing, the raw material as electrolytic manganese metal.
In the present embodiment, reactor uses spray column, 60~65 DEG C of tower interior reaction temperature, stage reactor discharge slurry before first
The Mn of liquid2+Concentration is 42g/L.After measured, the desulfurization degree of the present embodiment is 99.8%, and leaching manganese rate 95%, dithionic acid manganese content is low
In 5g/L.
Embodiment 2
As shown in the figure, in the present embodiment, preceding order reaction group, middle order reaction group, rear order reaction group are sequentially connected in series.Wherein, rear class is anti-
It should organize and be in series using stage reactor after stage reactor, second after first, middle order reaction group is stage reactor in first, prime
Reaction group is stage reactor before first.In one section of reaction, cooperated, prepared with stock tank using the first manganese ore powder cabin, first
One section of manganese ore reacting slurry.In second-stage reaction, cooperated using the first manganese ore powder cabin, second with stock tank, prepare two sections of manganese
Ore deposit reacting slurry.
Its reaction process is as follows.
Flue gas SO after electric precipitation2Content is 40000mg/m3, temperature is 250 DEG C, after being pressurized by a centrifugal blower
Stage reactor after stage reactor, second after stage reactor, first in stage reactor, first before sequentially entering first.Wherein, SO2
It reacts with manganese slurry, generates manganese sulfate, SO2It is removed, the SO that rear stage reactor comes out2Concentration≤100mg/m3, reach row
Standard is put, from smoke stack emission.
Full Mn contents are 39%, Mn in manganese powder in first manganese ore powder cabin4+Content is 18%；After grinding, manganese powder fineness is 90%
By 200 mesh, it is levigate after manganese powder be stored in manganese powder feed bin.First in stock tank, water is made into 20% solid content with manganese mineral powder
Slurries, stage reactor after squeezing into second with manganese slurry delivery pump.
Second in stock tank, dilute sulfuric acid is made into the slurries of 20% solid content with manganese mineral powder, and first is squeezed into manganese slurry delivery pump
Middle stage reactor.In addition, before first in stage reactor, the concentrated sulfuric acid is added in, adjusts pH value to 1 ~ 2.
Manganese slurry is contacted with flue gas adverse current, and stage reactor, the first middle rank are anti-after stage reactor, first after second successively for slurries
Device is answered into stage reactor before first, after the slurries of stage reactor are fully reacted with flue gas before first, is conveyed with slurry discharge pump
Go out system, carry out impurity and purification processing, the raw material as industrial manganic sulfate processed.
In the present embodiment, reactor uses bubble tower, 65~75 DEG C of tower interior reaction temperature, stage reactor discharge slurry before first
The Mn of liquid2+Concentration is 70g/L.After measured, the desulfurization degree of the present embodiment is 99.8%, and leaching manganese rate 93%, dithionic acid manganese content is low
In 5g/L.
The invention is not limited in foregoing specific embodiments.The present invention, which expands to, any in the present specification to be disclosed
The step of new feature or any new combination and any new method or process disclosed or any new combination.
Claims (10)
1. sub-prime multiple feed method removing flue gas middle and high concentration SO2Sulphuric acid manganese method, which is characterized in that include the following steps：
（1）Fume treatment
Sulfur dioxide flue gas after dedusting is sequentially sent to after supercharging in preceding order reaction group, middle order reaction group, rear order reaction group
And react with manganese ore slurries therein, manganese sulfate is generated, the sulfur dioxide in flue gas is removed, and reaches discharge standard,
It discharges；
（2）One section of reaction
Manganese mineral powder with water is mixed, is configured to one section of manganese ore reacting slurry, one section of manganese ore reacting slurry is pumped by conveying
One section of reaction is carried out in order reaction group afterwards, reaction temperature is 40 ~ 80 DEG C；
（3）Second-stage reaction
After manganese ore is mixed with acid solution, two sections of manganese ore reacting slurries are configured to, two sections of manganese ore reacting slurries are passed through into conveying
It is pumped into order reaction group and carries out second-stage reaction, reaction temperature is 40 ~ 80 DEG C；
（4）Three sections of reactions
Three sections of reactions are carried out before the concentrated sulfuric acid is sent into order reaction group, to improve the leaching rate of manganese ore, and part is eliminated and connects two sulphur
Sour manganese, reaction temperature are 40 ~ 80 DEG C；
In the step 1, preceding order reaction group, middle order reaction group, rear order reaction group are sequentially connected in series, the middle rank reactive component is other
It is sequentially connected in series using several reactors.
2. according to the method described in claim 1, it is characterized in that, in sulfur dioxide flue gas after dedusting, sulfur dioxide
Content is 20000 ~ 80000mg/m3。
3. according to the method described in claim 1, it is characterized in that, in the step 1, using electric precipitation or bag-type dust to two
Sulfur oxide flue gas is pre-processed.
4. according to the method described in claim 1, it is characterized in that, in the step 1, middle order reaction group is using 1 ~ 5 reaction
Device is in series.
5. if according to the method described in claim 4, it is characterized in that, the preceding order reaction group, rear class reactive component Cai Yong not
A dry reactor is in series.
6. according to the method described in claim 1, it is characterized in that, the reactor for spray column, one kind in bubble tower or
It is a variety of.
7. according to the method described in claim 1, it is characterized in that, the solid content of manganese powder is in one section of manganese ore reacting slurry
10~25%；The solid content of manganese powder is that 5 ~ 20%, pH is 1.5 ~ 3 in two sections of manganese ore reacting slurries.
8. according to the method described in claim 1, it is characterized in that, the acid solution is the concentrated sulfuric acid, dilute sulfuric acid, electrolytic anode
One or more in liquid.
9. according to claim 1-8 any one of them methods, which is characterized in that in the step 4, the concentrated sulfuric acid is sent into prime
In reaction group, the slurry pH value in preceding order reaction group is 0.5 ~ 2.
10. according to claim 1-9 any one of them methods, which is characterized in that wait after the completion of reacting, by the manganese sulfate of generation
After slurries carry out purification and impurity removal processing, the raw material as electrolytic manganese metal, industrial manganic sulfate or high purity manganese sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502650A (en) * | 2018-12-27 | 2019-03-22 | 四川大学 | A kind of method that manganese oxide ore desulfurization prepares the manganese sulfate mother liquor of low manganous dithionate |
| CN111111419A (en) * | 2020-01-02 | 2020-05-08 | 四川大学 | Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution |
| CN112777642A (en) * | 2021-01-26 | 2021-05-11 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
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| CN101456597A (en) * | 2009-01-08 | 2009-06-17 | 四川大学 | Method for preparing manganese sulfate solution by using sulphur dioxide gas leach manganese dioxide ore |
| CN204193781U (en) * | 2014-11-06 | 2015-03-11 | 四川恒泰环境技术有限责任公司 | A kind of novel Flue Gas Desulfurization with Pyrolusite Pulp device |
| CN105198000A (en) * | 2015-08-13 | 2015-12-30 | 四川大学 | Process method for manufacturing manganese products through high-concentration SO2 smoke leaching manganese ore pulp |
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| CN1537811A (en) * | 2003-09-24 | 2004-10-20 | 贵州工业大学 | Method of preparing manganese sulphate using gray manganese ore and dialozite to adsorb sulfur dioxide waste gas |
| CN101456597A (en) * | 2009-01-08 | 2009-06-17 | 四川大学 | Method for preparing manganese sulfate solution by using sulphur dioxide gas leach manganese dioxide ore |
| CN204193781U (en) * | 2014-11-06 | 2015-03-11 | 四川恒泰环境技术有限责任公司 | A kind of novel Flue Gas Desulfurization with Pyrolusite Pulp device |
| CN105198000A (en) * | 2015-08-13 | 2015-12-30 | 四川大学 | Process method for manufacturing manganese products through high-concentration SO2 smoke leaching manganese ore pulp |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502650A (en) * | 2018-12-27 | 2019-03-22 | 四川大学 | A kind of method that manganese oxide ore desulfurization prepares the manganese sulfate mother liquor of low manganous dithionate |
| CN111111419A (en) * | 2020-01-02 | 2020-05-08 | 四川大学 | Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution |
| CN111111419B (en) * | 2020-01-02 | 2021-03-23 | 四川大学 | Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution |
| CN112777642A (en) * | 2021-01-26 | 2021-05-11 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
| CN112777642B (en) * | 2021-01-26 | 2023-03-14 | 广西埃索凯新材料科技有限公司 | Method for preparing high-purity manganese sulfate by reducing and leaching pyrolusite by using rotary kiln slag |
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