CN104645815A - Cycling separation method for manganous dithionate in desulfurized liquid - Google Patents
Cycling separation method for manganous dithionate in desulfurized liquid Download PDFInfo
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- CN104645815A CN104645815A CN201510038008.1A CN201510038008A CN104645815A CN 104645815 A CN104645815 A CN 104645815A CN 201510038008 A CN201510038008 A CN 201510038008A CN 104645815 A CN104645815 A CN 104645815A
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Abstract
The invention provides a cycling separation method for manganous dithionate in desulfurized liquid. The method comprises the following steps: (1) desulfurization: carrying out multi-stage countercurrent gas-liquid reaction between slurry containing manganese dioxide ore and ammonium sulfate with flue gas containing sulphur, and carrying out pressure filtration and separation; (2) sulfuration and acidification: introducing a filtrate obtained in step (1) into a hydrogen sulfide gas for sulfuration reaction, carrying out pressure filtration and separation, and acidifying a filter cake to obtain hydrogen sulfide and manganese sulfate products; (3) aftertreatment cycling working procedure: neutralizing the filtrate obtained in step (2) by sulfuration and acidification to reach pH of 7-7.0, carrying out pressure filtration and separation, returning the filtrate to prepare slurry by desulfurization for recycling, and using filter residue for preparing a building material. The method can separate 99.95%-99.96% of manganous dithionate in a manganese sulfate solution.
Description
Technical field
The present invention relates to purification separation technical field, particularly relate to the circulating and separating method of manganous dithionate in a kind of sulfur-containing smoke gas doctor solution.
Background technology
Burning smoke boiler particularly station boiler adopts traditional calcium method desulfurization to be difficult to reach new discharge standard, the desulfurization of acidic oxidation manganese can stable operation control sulfur dioxide in flue gas and be less than 400 milligrams/every cubic metre, but can manganous dithionate be produced when adopting manganese dioxide to carry out flue gas desulfurization, great negative effect can be brought to electrolysis procedure.The more processing method of current report carries out resolution process to manganous dithionate, but process costs is higher.
Manganous dithionate is carried out resolution process by prior art, and to alleviate the impact of manganous dithionate, but process costs is higher.The present invention adopt manganese is formed that solid the method be separated from system solve manganous dithionate affect problem.
The following detailed description of the circulating and separating method of manganous dithionate in inventive desulfurization liquid, to set forth the feature of the method applied in the present invention and to prove effect of the present invention.
Shown in composition graphs 1, the circulating and separating method of manganous dithionate in a kind of doctor solution, the method comprises:
(1) desulfurization
Will by weight percentage, Fe content is the slip that the mining ammonium sulfate of manganese dioxide of 15-45% (being preferably 20-45%) is made into that solid content is 20-30% (being preferably 25%) by weight percentage, this slip and sulfur-containing smoke gas are carried out multi-stage countercurrent gas liquid reaction, MnO to slip
2weight percentage be less than for 2% (being preferably less than 1.5%); Reaction terminates rear use a small amount of lime, and slip to be neutralized to pH be 6-6.5, and press filtration is separated, and gained filtrate enters next step operation; Press filtration is separated the residual washing-out obtained, wash water is for preparing manganese dioxide slip, and boiler smoke water evaporation amount is comparatively large, and wash water can balance.
In this sweetening process, maintain ammonium sulfate concentrations and be greater than 150g/L.
Described multi-stage countercurrent gas liquid reaction is preferably three stage countercurrent gas liquid reactions, mainly improves the utilization ratio of sulfur dioxide.Three stage countercurrent gas liquid reactions are specially: first in the first order of adverse current gas-liquid reaction apparatus, pass into sulfur-containing smoke gas, and control gas speed≤1.5m/sec, gas liquid ratio controls at 8-12L/m
3then in the third level of gas-liquid reaction apparatus, add manganese dioxide slip, and control it and do reverse flow relative to sulfur-containing smoke gas, three grades of these three grades of gas-liquid reaction apparatus are carried out self-loopa respectively simultaneously, namely first order reaction slurry constantly supplements from the second level, and the third level constantly supplements slip to the second level, and the manganese dioxide slip of new preparation constantly supplements to the third level, reaction terminates rear slip and enters separation circuit from the first order, and the third level of the flue gas autoreaction device after desulfurization is discharged.Discharge≤the 400mg/m of sulfur dioxide after three stage countercurrent gas liquid reactions
3.
Conventional dioxide ore for manganese all can be used for the present invention, and the present invention uses commercial manganese dioxide breeze.Due to the speed of particle size influences desulphurization reaction and the rate of recovery of manganese of manganese dioxide breeze, the preferred manganese dioxide breeze of the present invention be wherein 90% can by 100 mesh sieves.Described manganese dioxide breeze adopts Tyler screen to carry out sieving and obtain, and the particle diameter that namely 100 orders are corresponding is 147 μm.
In manganese dioxide breeze, by weight percentage, Fe content is 15-45%.In addition, the solution of preparation manganese dioxide slip can be ammonium sulfate, also can be manganese metal slag washing water.Preferably sulfuric acid ammonium salt solution preparation manganese dioxide slip of the present invention.
The sulfur-containing smoke gas that the present invention uses can be coal-fired tail gas of converter, boiler exhaust gas or other is containing SO
2tail gas.
It not is limit separation that the press filtration that the present invention uses is separated, and just illustrate separation method, the separation method of this area routine all can be used for the present invention.
The present invention realizes adverse current gas-liquid reaction apparatus that multi-stage countercurrent gas liquid reaction the uses normal experiment device that is this area, uses it for the present invention, is intended to make full use of raw material, save cost, improve reaction efficiency, and reaction is carried out continuously.It is emphasized that the device that other can realize adverse current gas liquid reaction all can be used for the present invention, such as secondary or multi-stage countercurrent gas-liquid reaction apparatus, preferably, the present invention uses three stage countercurrent gas-liquid reaction apparatus.
The reaction equation of this step is:
MnO
2+SO
2+H
2O＝MnSO
4+H
2O
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains is passed into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5-5.0, press filtration is separated, and gained filtrate enters next step operation, filter cake is first used the running water agitator treating 2h of 60-65 DEG C, material water weight ratio is 1:1-2 (preferred 1:1), then squeeze press filtration, filtrate is for preparing manganese dioxide slip, and filter cake sulfuric acid is by filter cake acidifying, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is for the production of manganese product.
Certainly; use other inorganic acid; such as nitric acid, hydrochloric acid or the manganese metal electrolyte mother liquor containing sulfuric acid are that those skilled in the art easily expect as souring soln acidifying filter cake, and also within protection scope of the present invention, the manganese product salt obtained like this can also be manganese nitrate, manganese chloride etc.Preferably sulfuric acid of the present invention.
In desulfurized step, control the concentration of ammonium sulfate mainly for vulcanization reaction provides buffer system, have enough nertralizers when ensureing that hydrogen sulfide and manganese sulfate vulcanization reaction carry out, the hydrogen ion that vulcanization reaction produces and ammonium sulfate react and generate ammonium hydrogen sulfate.
Do not need the concentration controlling manganese in solution in sulfidation, manganese can recycle;
Containing manganese sulfide in filter cake after squeezing press filtration.Adopt sulfuric acid or the manganese metal electrolyte mother liquor acidifying containing sulfuric acid, the manganese sulfide in filter cake is converted into solvable manganese salt, i.e. manganese sulfate, thus produces for manganese product.
Similarly, the squeezing press filtration that the present invention uses not is limit separation, and just illustrate separation method, the separation method of this area routine all can be used for the present invention.
The reaction equation of this step is:
(NH
4)
2SO
4+H
2S＝NH
4SO
4+NH
4HS
MnSO
4+NH
4HS＝MnS↓+NH
4HSO
4
MnS+H
2SO
4＝MnSO
4+H
2S↑
(3) post processing circulating process
Filtrate limestone vegetation step (2) sulfuration, acidifying obtained is 7.0-7.5 to pH, and press filtration is separated, and filtrate recycles for preparing manganese dioxide slip, and filter residue gypsum is for the preparation of building materials;
The reaction equation of this step is:
NH
4HSO
4+CaO＝CaSO
4↓+NH
4OH。
SO
2+O
2+2NH
4OH＝(NH
4)
2SO
4+H
2O
Below, enumerate embodiment and the present invention is further described, but the present invention is not limited to following embodiment.
Summary of the invention
The technical problem that the present invention solves is the circulating and separating method providing manganous dithionate in a kind of doctor solution, solves the product quality impact that manganese method flue gas desulfurization manganous dithionate causes.Specifically, first dioxide ore for manganese is made slip by the present invention, adverse current gas liquid reaction is carried out with sulfur-containing smoke gas, press filtration after reaction, gained filtrate passes into hydrogen sulfide gas and carries out vulcanization reaction, press filtration is separated, and the hydrogen sulfide produced during filter cake acidifying is back to vulcanization reaction manganese sulfate for the production of manganese product, and the filtrate obtained after press filtration carries out post processing circulating process.In the manganese sulfate product that the method obtains, in the separative efficiency of manganous dithionate, achieve unforeseeable beneficial effect.
Specifically, the technical solution used in the present invention is, the circulating and separating method of manganous dithionate in a kind of doctor solution, the method comprises the steps:
(1) desulfurization
By dioxide ore for manganese process to 90% breeze by 100 mesh sieves, then the mining ammonium sulfate of manganese dioxide is made into solid content is the slip of 20-30% by weight percentage, this slip and sulfur-containing smoke gas is carried out multi-stage countercurrent gas liquid reaction, MnO to slip
2weight percentage be less than 2%; After reaction terminates, slip being neutralized to pH is 6-6.5, and press filtration is separated, and gained filtrate enters next step operation;
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains is passed into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5-5.0, and press filtration is separated, gained filtrate enters next step operation, by filter cake acidifying, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is for the production of manganese product;
(3) post processing circulating process
It is 7.0-7.5 that the filtrate that step (2) sulfuration, acidifying obtain is neutralized to pH, and press filtration is separated, and filtrate is back to that desulfurization is with slurry to be recycled, and filter residue is for the preparation of building materials.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in the sweetening process of described step (1), maintains ammonium sulfate concentrations and is greater than 150g/L, be preferably greater than 200g/L.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), is made into the slip that solid content is 25% by weight percentage by dioxide ore for manganese.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described dioxide ore for manganese, by weight percentage, Fe content is 15-45%, and preferred Fe content is 20-45%.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), reacts MnO to slip
2weight percentage be less than 1.5%.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), multi-stage countercurrent gas liquid reaction is three stage countercurrent gas liquid reactions, be specially: first in the first order of adverse current gas-liquid reaction apparatus, pass into sulfur-containing smoke gas, control gas speed≤1.5m/sec, gas liquid ratio controls at 8-12L/m
3then in the third level of gas-liquid reaction apparatus, add manganese dioxide slip, and control it and do reverse flow relative to sulfur-containing smoke gas, three grades of these three grades of gas-liquid reaction apparatus are carried out self-loopa respectively simultaneously, namely first order reaction slurry constantly supplements from the second level, and the third level constantly supplements slip to the second level, and the manganese dioxide slip of new preparation constantly supplements to the third level, reaction terminates rear slip and enters separation circuit from the first order, and the third level of the flue gas autoreaction device after desulfurization is discharged
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (2), press filtration is separated the running water agitator treating 2h that the filter cake obtained first uses 60-65 DEG C, and material water weight ratio is 1:1-2, and preferred 1:1, then squeezes press filtration.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, the residual washing-out obtained after step (1) press filtration being separated, wash water can be used for preparation dioxide ore for manganese slip.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (2), with sulfuric acid by filter cake acidifying.
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), sulfur-containing smoke gas is coal-fired tail gas of converter, boiler exhaust gas or other is containing SO
2tail gas.
Adopt above-mentioned technical scheme, at least there is following beneficial effect:
Adopt desulfurization-sulfuration-circulation technology, make manganese form solid being separated from system, what solve manganous dithionate in manganese sulfate solution affects problem, reduces process costs.
Accompanying drawing explanation
Fig. 1 is technical process figure of the present invention.
Detailed description of the invention
Embodiment
Embodiment 1
(1) desulfurization
90% commercial particle diameter is less than 147 μm (cross 100 mesh sieves), by weight percentage, Fe content be 20% manganese dioxide breeze ammonium sulfate be made into the slip that solid content is 25% by weight percentage, this slip and sulfur-containing smoke gas are carried out three stage countercurrent gas liquid reactions, and the gas speed≤1.5m/sec, the gas liquid ratio that control sulfur-containing smoke gas are 8L/m
3, carry out gas liquid reaction, MnO to slip
2weight percentage be less than 2%; Reaction terminates rear use a small amount of lime, and slip to be neutralized to pH be 6.0, and press filtration is separated, and gained filtrate enters next step operation.Press filtration is separated the residual washing-out obtained, wash water is for preparing manganese dioxide slip.In this sweetening process, maintain ammonium sulfate concentrations and be greater than 150g/L.
Sulfur-containing smoke gas adopts technical grade brium carbonate carbon reduction rotary kiln tail gas, and average sulfur dioxide content is 13400mg/m
3, three stage countercurrent reaction outlet contents of sulfur dioxide are at 220-389mg/m
3.
In doctor solution, the concentration of manganese sulfate is 131.5g/L, and wherein the concentration of manganous dithionate is 16.7g/L.
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains is passed into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5, and press filtration is separated, and gained filtrate enters next step operation; Filter cake is first used the running water agitator treating 2h of 60 DEG C, material water weight ratio is 1:2, then squeezes press filtration, and filtrate is for preparing manganese dioxide slip, and filter cake sulfuric acid acidation, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is for the production of manganese sulfate sample 1#.
(3) post processing circulating process
Filtrate limestone vegetation step (2) sulfuration, acidifying obtained is 7.0 to pH, and press filtration is separated, and filtrate recycles for preparing manganese dioxide slip, and filter residue gypsum is for the preparation of building materials.
Embodiment 2
(1) desulfurization
90% commercial particle diameter is less than 147 μm (cross 100 mesh sieves), by weight percentage, Fe content be 45% manganese dioxide breeze ammonium sulfate be made into the slip that solid content is 30% by weight percentage, this slip and sulfur-containing smoke gas are carried out three stage countercurrent gas liquid reactions, and the gas speed≤1.5m/sec, the gas liquid ratio that control sulfur-containing smoke gas are 12L/m
3, carry out gas liquid reaction, MnO to slip
2weight percentage be less than 1.5%; Reaction terminates rear use a small amount of lime, and slip to be neutralized to pH be 6.5, and press filtration is separated, and gained filtrate enters next step operation.Press filtration is separated the residual washing-out obtained, wash water is for preparing manganese dioxide slip.In this sweetening process, maintain ammonium sulfate concentrations and be greater than 200g/L.
Sulfur-containing smoke gas adopts coal-fired boiler tail gas, and average sulfur dioxide content is 4800mg/m
3, three stage countercurrent reaction outlet contents of sulfur dioxide are at 75-155mg/m
3.
In doctor solution, the concentration of manganese sulfate is 143.3g/L, and wherein the concentration of manganous dithionate is 18.9g/L.
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains is passed into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 5.0, and press filtration is separated, and gained filtrate enters next step operation; Filter cake is first used the running water agitator treating 2h of 65 DEG C, material water weight ratio is 1:1, then squeezes press filtration, and filtrate is for preparing manganese dioxide slip, and filter cake sulfuric acid acidation, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is for the production of manganese sulfate sample 2#.
(3) post processing circulating process
Filtrate limestone vegetation step (2) sulfuration, acidifying obtained is 7.5 to pH, and press filtration is separated, and filtrate recycles for preparing manganese dioxide slip, and filter residue gypsum is for the preparation of building materials.
In embodiment 1-2 gained manganese sulfate sample the concentration of manganese sulfate and the concentration parameter of manganous dithionate wherein as shown in table 1.
The content of table 1 embodiment 1-2 gained sample and composition analysis result
| Project | 1# | 2# |
| Manganese sulfate concentration (g/L) | 455.0 | 437.6 |
| Manganous dithionate concentration (g/L) | 0.023 | 0.026 |
| Separative efficiency (%) | 99.96 | 99.95 |
As can be seen from the data in above-mentioned table 1, in the manganese sulfate sample that embodiment 1-2 obtains, the separative efficiency of manganous dithionate is respectively 99.96% and 99.95%.As can be seen here, what the present invention solved manganous dithionate in manganese sulfate solution by desulfurization-sulfuration-circulation technology affects problem.
Claims (10)
1. the circulating and separating method of manganous dithionate in doctor solution, the method comprises the steps:
(1) desulfurization
By dioxide ore for manganese process to 90% breeze by 100 mesh sieves, being then made into solid content with ammonium sulfate is the slip of 20-30% by weight percentage, this slip and sulfur-containing smoke gas is carried out multi-stage countercurrent gas liquid reaction, MnO to slip
2weight percentage be less than 2%; After reaction terminates, slip being neutralized to pH is 6-6.5, and press filtration is separated, and gained filtrate enters next step operation;
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains is passed into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5-5.0, and press filtration is separated, gained filtrate enters next step operation, by filter cake acidifying, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is for the production of manganese product;
(3) post processing circulating process
It is 7.0-7.5 that the filtrate that step (2) sulfuration, acidifying obtain is neutralized to pH, and press filtration is separated, and filtrate is back to that desulfurization is with slurry to be recycled, and filter residue is for the preparation of building materials.
2. the circulating and separating method of manganous dithionate in doctor solution according to claim 1, is characterized in that, in the sweetening process of described step (1), maintains ammonium sulfate concentrations and is greater than 150g/L, be preferably greater than 200g/L.
3. the circulating and separating method of manganous dithionate in doctor solution according to claim 1 and 2, is characterized in that, in described step (1), dioxide ore for manganese is made into the slip that solid content is 25% by weight percentage.
4. in the doctor solution according to any one of claim 1-3, the circulating and separating method of manganous dithionate, is characterized in that, in described dioxide ore for manganese, by weight percentage, Fe content is 15-45%, and preferred Fe content is 20-45%.
5. in the doctor solution according to any one of claim 1-4, the circulating and separating method of manganous dithionate, is characterized in that, in described step (1), reacts MnO to slip
2weight percentage be less than 1.5%.
6. the circulating and separating method of manganous dithionate in the doctor solution according to any one of claim 1-5, it is characterized in that, in described step (1), multi-stage countercurrent gas liquid reaction is three stage countercurrent gas liquid reactions, be specially: first in the first order of adverse current gas-liquid reaction apparatus, pass into sulfur-containing smoke gas, control gas speed≤1.5m/sec, gas liquid ratio controls at 8-12L/m
3then in the third level of gas-liquid reaction apparatus, add manganese dioxide slip, and control it and do reverse flow relative to sulfur-containing smoke gas, three grades of these three grades of gas-liquid reaction apparatus are carried out self-loopa respectively simultaneously, namely first order reaction slurry constantly supplements from the second level, and the third level constantly supplements slip to the second level, and the manganese dioxide slip of new preparation constantly supplements to the third level, reaction terminates rear slip and enters separation circuit from the first order, and the third level of the flue gas autoreaction device after desulfurization is discharged.
7. the circulating and separating method of manganous dithionate in the doctor solution according to any one of claim 1-6, it is characterized in that, in described step (2), press filtration is separated the running water agitator treating 2h that the filter cake obtained first uses 60-65 DEG C, material water weight ratio is 1:1-2, preferred 1:1, then squeezes press filtration.
8. in the doctor solution according to any one of claim 1-7, the circulating and separating method of manganous dithionate, is characterized in that, the residual washing-out obtained after step (1) press filtration being separated, and wash water can be used for preparation dioxide ore for manganese slip.
9. in the doctor solution according to any one of claim 1-8, the circulating and separating method of manganous dithionate, is characterized in that, in described step (2), with sulfuric acid or manganese metal electrolyte mother liquor by filter cake acidifying.
10. in the doctor solution according to any one of claim 1-9, the circulating and separating method of manganous dithionate, is characterized in that, in described step (1), sulfur-containing smoke gas is coal-fired tail gas of converter, boiler exhaust gas or other is containing SO
2tail gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946890A (en) * | 2015-07-15 | 2015-09-30 | 贵州红星发展大龙锰业有限责任公司 | Method for synchronously recycling ammonia and manganese in manganese metal chemical combination slag |
| CN115571919A (en) * | 2022-09-29 | 2023-01-06 | 广西汇元锰业有限责任公司 | Method for removing calcium and magnesium ions in production of high-purity manganese sulfate |
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| US4230603A (en) * | 1979-04-02 | 1980-10-28 | United States Steel Corporation | Desulfurizing pellet of manganese oxide and aluminum oxide and process for producing said pellet |
| CN1052260A (en) * | 1989-12-09 | 1991-06-19 | 成都环保建设工程技术设备公司 | The sulfur method of sulfur-containing smoke gas or tail gas |
| CN101619388A (en) * | 2009-08-10 | 2010-01-06 | 四川大学 | Method for restraining generation of manganous dithionate in process of leaching sulfur dioxide gas out of pyrolusite |
| CN101898798A (en) * | 2010-03-19 | 2010-12-01 | 深圳市东江环保股份有限公司 | Method for preparing manganese sulfate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230603A (en) * | 1979-04-02 | 1980-10-28 | United States Steel Corporation | Desulfurizing pellet of manganese oxide and aluminum oxide and process for producing said pellet |
| CN1052260A (en) * | 1989-12-09 | 1991-06-19 | 成都环保建设工程技术设备公司 | The sulfur method of sulfur-containing smoke gas or tail gas |
| CN101619388A (en) * | 2009-08-10 | 2010-01-06 | 四川大学 | Method for restraining generation of manganous dithionate in process of leaching sulfur dioxide gas out of pyrolusite |
| CN101898798A (en) * | 2010-03-19 | 2010-12-01 | 深圳市东江环保股份有限公司 | Method for preparing manganese sulfate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946890A (en) * | 2015-07-15 | 2015-09-30 | 贵州红星发展大龙锰业有限责任公司 | Method for synchronously recycling ammonia and manganese in manganese metal chemical combination slag |
| CN115571919A (en) * | 2022-09-29 | 2023-01-06 | 广西汇元锰业有限责任公司 | Method for removing calcium and magnesium ions in production of high-purity manganese sulfate |
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|---|---|
| CN104645815B (en) | 2016-06-22 |
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