CN104645815B - A kind of preparation method of manganese sulfate - Google Patents
A kind of preparation method of manganese sulfate Download PDFInfo
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- CN104645815B CN104645815B CN201510038008.1A CN201510038008A CN104645815B CN 104645815 B CN104645815 B CN 104645815B CN 201510038008 A CN201510038008 A CN 201510038008A CN 104645815 B CN104645815 B CN 104645815B
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Abstract
The present invention provides the circulating and separating method of manganous dithionate in a kind of doctor solution, and the method comprises the steps: (1) desulfurization: the slip containing dioxide ore for manganese and ammonium sulfate and sulfur-containing smoke gas are carried out multi-stage countercurrent gas liquid reaction, and filter pressing separates；(2) sulfuration, acidifying: the filtrate that just step (1) obtains passes into hydrogen sulfide gas and carries out vulcanization reaction, filter pressing separates, and filter cake acidifying obtains hydrogen sulfide and manganese sulfate product；(3) post processing circulating process: step (2) vulcanized, to be neutralized to pH be 7-7.0 to the filtrate that obtains of acidifying, and filter pressing separates, filtrate is back to that desulfurization is with slurry is circulated use, and filtering residue is used for preparing building materials。The manganous dithionate of 99.95-99.96% in the separable manganese sulfate solution of the method。
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 extremely difficult to new discharge standard, acidic oxidation manganese desulfurization can stable operation control sulfur dioxide in flue gas less than 400 milligrams/every cubic metre, but adopt manganese dioxide can produce manganous dithionate when carrying out flue gas desulfurization, great negative effect can be brought to electrolysis procedure。Report that more processing method is that manganous dithionate is carried out resolution process at present, but process costs is higher。
Summary of the invention
Present invention solves the technical problem that and be in that to provide the circulating and separating method of manganous dithionate in a kind of doctor solution, solve 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, filter pressing after reaction, gained filtrate passes into hydrogen sulfide gas and carries out vulcanization reaction, filter pressing separates, and the hydrogen sulfide produced during by filter cake acidifying is back to vulcanization reaction manganese sulfate and is used for producing manganese product, and the filtrate obtained after filter pressing carries out post processing circulating process。In the manganese sulfate product that the method obtains, in the separation 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
Being processed by dioxide ore for manganese to 90% breeze by 100 mesh sieves, then the mining ammonium sulfate of manganese dioxide is made into the slip that solid content is 20-30% by weight percentage, this slip and sulfur-containing smoke gas is carried out multi-stage countercurrent gas liquid reaction, MnO to slip2Weight percentage less than 2%；It is 6-6.5 that slip is neutralized to pH after terminating by reaction, and filter pressing separates, and gained filtrate enters next step operation；
(2) sulfuration, acidifying
The filtrate that step (1) desulfurization obtains passing into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5-5.0, and filter pressing separates, 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 used for producing manganese product；
(3) post processing circulating process
Step (2) vulcanized, to be neutralized to pH be 7.0-7.5 to the filtrate that obtains of acidifying, and filter pressing separates, and filtrate is back to that desulfurization is with slurry is circulated use, and filtering residue is used for preparing 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 more than 150g/L, it is preferable that more than 200g/L。
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), it is the slip of 25% by weight percentage that dioxide ore for manganese is made into solid content。
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%, it is preferable that Fe content is 20-45%。
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (1), reacts to MnO in slip2Weight percentage 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, particularly as follows: first pass into sulfur-containing smoke gas in the first order of adverse current gas-liquid reaction apparatus, controlling gas speed≤1.5m/sec, gas liquid ratio controls at 8-12L/m3In the third level of gas-liquid reaction apparatus, then 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 carry 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), filter pressing separates the filter cake obtained and first uses the tap water agitator treating 2h of 60-65 DEG C, and material water weight ratio is 1:1-2, it is preferable that 1:1, then squeezes filter pressing。
The circulating and separating method of manganous dithionate in aforesaid doctor solution, the residual washing-out obtained after step (1) filter pressing being separated, wash water can be used for preparing dioxide ore for manganese slip。
The circulating and separating method of manganous dithionate in aforesaid doctor solution, in described step (2), with sulphuric 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 SO2Tail gas。
Adopt above-mentioned technical scheme, at least have the advantages that
Adopting desulfurization-sulfuration-circulation technology, make manganese form solid and separate from system, what solve manganous dithionate in manganese sulfate solution affects problem, reduces process costs。
Accompanying drawing explanation
Fig. 1 is the technical process figure of the present invention。
Detailed description of the invention
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 adopts and manganese is formed solid and the method that separates from system solves manganous dithionate affects 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 the effect of the present invention。
Shown in Fig. 1, the circulating and separating method of manganous dithionate in a kind of doctor solution, the method includes:
(1) desulfurization
Will by weight percentage, the mining ammonium sulfate of manganese dioxide that Fe content is 15-45% (being preferably 20-45%) is made into solid content by weight percentage for the slip of 20-30% (being preferably 25%), this slip and sulfur-containing smoke gas are carried out multi-stage countercurrent gas liquid reaction, MnO to slip2Weight percentage less than 2% (being preferably smaller than 1.5%)；It is 6-6.5 that slip is neutralized to pH with a small amount of Calx after terminating by reaction, and filter pressing separates, and gained filtrate enters next step operation；Filter pressing separates the residual washing-out obtained, and wash water is used for preparing manganese dioxide slip, and boiler smoke water evaporation amount is relatively big, and wash water can balance。
In this sweetening process, maintain ammonium sulfate concentrations more 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, particularly as follows: first pass into sulfur-containing smoke gas in the first order of adverse current gas-liquid reaction apparatus, control gas speed≤1.5m/sec, and gas liquid ratio controls at 8-12L/m3In the third level of gas-liquid reaction apparatus, then 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 carry 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 reactions3。
Conventional dioxide ore for manganese is used equally to the present invention, and the present invention uses commercial manganese dioxide breeze。Due to the response rate of the speed of particle size influences desulphurization reaction of manganese dioxide breeze and manganese, currently preferred manganese dioxide breeze is therein 90% can pass through 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%。It addition, the solution of preparation manganese dioxide slip can be ammonium sulfate, it is possible to for manganese metal slag washing water。Preferably sulfuric acid ammonium salt solution of the present invention preparation manganese dioxide slip。
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 SO2Tail gas。
It not is that separation is limited that the filter pressing that the present invention uses separates, and is merely illustrative separation method, and the separation method of this area routine is used equally to the present invention。
The present invention realizes the normal experiment device that adverse current gas-liquid reaction apparatus is this area that multi-stage countercurrent gas liquid reaction uses, and uses it for the present invention, it is intended that make full use of raw material, saves cost, improves reaction efficiency, and makes reaction continuously perform。It is emphasized that other device being capable of adverse current gas liquid reaction is used equally to the present invention, for instance two grades or multi-stage countercurrent gas-liquid reaction apparatus, it is preferred that the present invention uses three stage countercurrent gas-liquid reaction apparatus。
The reaction equation of this step is:
MnO2+SO2+H2O=MnSO4+H2O
(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, filter pressing separates, and gained filtrate enters next step operation, by filter cake first with the tap water agitator treating 2h of 60-65 DEG C, material water weight ratio is 1:1-2 (preferred 1:1), then squeezing filter pressing, filtrate is used for preparing manganese dioxide slip, and filter cake sulphuric acid is by filter cake acidifying, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is used for producing manganese product。
Certainly; use other mineral acid; such as nitric acid, hydrochloric acid or the manganese metal electrolyte mother solution containing sulphuric acid are that those skilled in the art are readily apparent that as souring soln acidifying filter cake, and also within protection scope of the present invention, the manganese product salt so obtained can also is that manganese nitrate, manganese chloride etc.。Preferably sulfuric acid of the present invention。
The concentration controlling ammonium sulfate in desulfurized step provides buffer system principally for vulcanization reaction, it is ensured that hydrogen sulfide and manganese sulfate vulcanization reaction have enough nertralizers when carrying out, and the hydrion that vulcanization reaction produces and ammonium sulfate react generation ammonium hydrogen sulfate。
Need not controlling the concentration of manganese in solution in sulfidation, manganese can recycle；
Containing Manganese monosulfide. in filter cake after squeezing filter pressing。Adopting sulphuric acid or the manganese metal electrolyte mother solution acidifying containing sulphuric acid, the Manganese monosulfide. in filter cake is converted into solvable manganese salt, i.e. manganese sulfate, thus producing for manganese product。
Similarly, the squeezing filter pressing that the present invention uses not is that separation is limited, and is merely illustrative separation method, and the separation method of this area routine is used equally to the present invention。
The reaction equation of this step is:
(NH4)2SO4+H2S=NH4SO4+NH4HS
MnSO4+NH4HS=MnS ↓+NH4HSO4
MnS+H2SO4=MnSO4+H2S↑
(3) post processing circulating process
The filtrate Calx that step (2) sulfuration, acidifying obtain is neutralized to pH is 7.0-7.5, and filter pressing separates, and filtrate is used for preparing manganese dioxide slip and is circulated use, and filtering residue Gypsum Fibrosum is used for preparing building materials；
The reaction equation of this step is:
NH4HSO4+ CaO=CaSO4↓+NH4OH。
SO2+O2+2NH4OH=(NH4)2SO4+H2O
Below, enumerate embodiment and the present invention is further described, but the present invention is not limited to following embodiment。
Embodiment
Embodiment 1
(1) desulfurization
By 90% commercial particle diameter less than 147 μm (cross 100 mesh sieves), by weight percentage, Fe content be 20% manganese dioxide breeze ammonium sulfate to be made into solid content be the slip of 25% by weight percentage, this slip and sulfur-containing smoke gas carry out three stage countercurrent gas liquid reactions, and the control gas speed≤1.5m/sec of sulfur-containing smoke gas, gas liquid ratio are 8L/m3, carry out gas liquid reaction, MnO to slip2Weight percentage less than 2%；It is 6.0 that slip is neutralized to pH with a small amount of Calx after terminating by reaction, and filter pressing separates, and gained filtrate enters next step operation。Filter pressing separates the residual washing-out obtained, and wash water is used for preparing manganese dioxide slip。In this sweetening process, maintain ammonium sulfate concentrations more 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/m3, three stage countercurrent reaction outlet contents of sulfur dioxide are at 220-389mg/m3。
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 passing into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 4.5, and filter pressing separates, and gained filtrate enters next step operation；By filter cake first with the tap water agitator treating 2h of 60 DEG C, material water weight ratio is 1:2, then squeezes filter pressing, and filtrate is used for preparing manganese dioxide slip, filter cake sulfuric acid acidation, and the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is used for producing manganese sulfate sample 1#。
(3) post processing circulating process
The filtrate Calx that step (2) sulfuration, acidifying obtain is neutralized to pH is 7.0, and filter pressing separates, and filtrate is used for preparing manganese dioxide slip and is circulated use, and filtering residue Gypsum Fibrosum is used for preparing building materials。
Embodiment 2
(1) desulfurization
By 90% commercial particle diameter less than 147 μm (cross 100 mesh sieves), by weight percentage, Fe content be 45% manganese dioxide breeze ammonium sulfate to be made into solid content be the slip of 30% by weight percentage, this slip and sulfur-containing smoke gas carry out three stage countercurrent gas liquid reactions, and the control gas speed≤1.5m/sec of sulfur-containing smoke gas, gas liquid ratio are 12L/m3, carry out gas liquid reaction, MnO to slip2Weight percentage less than 1.5%；It is 6.5 that slip is neutralized to pH with a small amount of Calx after terminating by reaction, and filter pressing separates, and gained filtrate enters next step operation。Filter pressing separates the residual washing-out obtained, and wash water is used for preparing manganese dioxide slip。In this sweetening process, maintain ammonium sulfate concentrations more than 200g/L。
Sulfur-containing smoke gas adopts coal-fired boiler tail gas, and average sulfur dioxide content is 4800mg/m3, three stage countercurrent reaction outlet contents of sulfur dioxide are at 75-155mg/m3。
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 passing into hydrogen sulfide gas and carries out vulcanization reaction, the pH controlling reaction end is 5.0, and filter pressing separates, and gained filtrate enters next step operation；By filter cake first with the tap water agitator treating 2h of 65 DEG C, material water weight ratio is 1:1, then squeezes filter pressing, and filtrate is used for preparing manganese dioxide slip, filter cake sulfuric acid acidation, and the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and manganese sulfate is used for producing manganese sulfate sample 2#。
(3) post processing circulating process
The filtrate Calx that step (2) sulfuration, acidifying obtain is neutralized to pH is 7.5, and filter pressing separates, and filtrate is used for preparing manganese dioxide slip and is circulated use, and filtering residue Gypsum Fibrosum is used for preparing building materials。
In embodiment 1-2 gained manganese sulfate sample, the concentration of manganese sulfate and the concentration parameter of manganous dithionate therein are 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 |
| Separation efficiency (%) | 99.96 | 99.95 |
By the data in above-mentioned table 1 it can be seen that in the obtained manganese sulfate sample of embodiment 1-2, the separation efficiency of manganous dithionate respectively 99.96% and 99.95%。As can be seen here, the present invention affects problem by what desulfurization-sulfuration-circulation technology solved manganous dithionate in manganese sulfate solution。
Claims (13)
1. being capable of in doctor solution a preparation method for the manganese sulfate of manganous dithionate multi-cycle separation, the method comprises the steps:
(1) desulfurization
Using manganese dioxide breeze as raw material, in this manganese dioxide breeze 90% can pass through 100 mesh sieves, with ammonium sulfate, this manganese dioxide breeze is made into the slip that solid content is 20-30% by weight percentage, this slip and sulfur-containing smoke gas is carried out multi-stage countercurrent gas liquid reaction, MnO to slip2Weight percentage less than 2%；It is 6-6.5 that slip is neutralized to pH after terminating by reaction, and filter pressing separates, 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, filter pressing separates, gained filtrate enters next step operation, by filter cake acidifying, the hydrogen sulfide that acidifying produces is back to vulcanization reaction, and the manganese sulfate solution that acidifying produces is used for producing manganese sulfate product；
(3) post processing circulating process
The filtrate that step (2) sulfuration, acidifying obtain is neutralized to pH is 7.0-7.5, and filter pressing separates, and filtrate returns step (1) for manganese dioxide breeze is made into slip, and filtering residue is used for preparing building materials。
2. the preparation method of manganese sulfate according to claim 1, it is characterised in that in the sweetening process of described step (1), maintains ammonium sulfate concentrations more than 150g/L。
3. the preparation method of manganese sulfate according to claim 2, it is characterised in that in the sweetening process of described step (1), maintains ammonium sulfate concentrations more than 200g/L。
4. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described step (1), it is the slip of 25% by weight percentage that dioxide ore for manganese is made into solid content。
5. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described dioxide ore for manganese, by weight percentage, Fe content is 15-45%。
6. the preparation method of manganese sulfate according to claim 5, it is characterised in that in described dioxide ore for manganese, by weight percentage, Fe content is 20-45%。
7. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described step (1), reacts to MnO in slip2Weight percentage less than 1.5%。
8. the preparation method of the manganese sulfate 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, particularly as follows: first pass into sulfur-containing smoke gas in the first order of adverse current gas-liquid reaction apparatus, controlling gas speed≤1.5m/sec, gas liquid ratio controls at 8-12L/m3In the third level of adverse current gas-liquid reaction apparatus, then add manganese dioxide slip, and control it and do reverse flow relative to sulfur-containing smoke gas, three grades of this three stage countercurrents gas-liquid reaction apparatus carry 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。
9. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described step (2), filter pressing separates the filter cake obtained and first uses the tap water agitator treating 2h of 60-65 DEG C, and material water weight ratio is 1:1-2, then squeezes filter pressing。
10. the preparation method of manganese sulfate according to claim 9, it is characterised in that in described step (2), filter pressing separates the filter cake obtained and first uses the tap water agitator treating 2h of 60-65 DEG C, and material water weight ratio is 1:1, then squeezes filter pressing。
11. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that the residual washing-out obtained after step (1) filter pressing being separated, wash water can be used for preparing dioxide ore for manganese slip。
12. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described step (2), with sulphuric acid or containing the manganese metal electrolyte mother solution of sulphuric acid by filter cake acidifying。
13. the preparation method of the manganese sulfate according to any one of claim 1-3, it is characterised in that in described step (1), sulfur-containing smoke gas is coal-fired tail gas of converter, boiler exhaust gas or other is containing SO2Tail gas。
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| 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 |
| CN101619388B (en) * | 2009-08-10 | 2010-12-01 | 四川大学 | Method for restraining generation of manganous dithionate in process of leaching sulfur dioxide gas out of pyrolusite |
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