CN102249333A - Method for preparing manganese sulfate, manganese nitrate and calcium sulfate - Google Patents
Method for preparing manganese sulfate, manganese nitrate and calcium sulfate Download PDFInfo
- Publication number
- CN102249333A CN102249333A CN2010105979195A CN201010597919A CN102249333A CN 102249333 A CN102249333 A CN 102249333A CN 2010105979195 A CN2010105979195 A CN 2010105979195A CN 201010597919 A CN201010597919 A CN 201010597919A CN 102249333 A CN102249333 A CN 102249333A
- Authority
- CN
- China
- Prior art keywords
- sulfate
- manganese
- manganous
- nitrate
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention provides a method for preparing manganese sulfate, manganese nitrate and calcium sulfate, and the method comprises: grinding manganosite into coarse powder, soaking the coarse powder in a waste liquid generated in titanium white production utilizing a sulfuric acid method at the temperature of 60-80 DEG C for 8-10 hours, carrying out suction-filtering to obtain a clarified filtrate, and adding manganese hydroxide to remove impurities and obtain a pure manganese sulfate solution; distilling the pure manganese sulfate solution while decompressing to obtain a manganese sulfate saturated solution, cooling and precipitating manganese sulfate crystals containing crystal water, then drying and crushing to obtain a manganese sulfate crystal product; reacting the pure manganese sulfate solution with a calcium nitrate solution under stirring, filtering the reaction product to obtain a calcium sulfate filter cake and a manganese nitrate filtrate, distilling the manganese nitrate filtrate while decompressing to obtain a manganese nitrate supersaturated solution, cooling and crystallizing to obtain manganese nitrate crystals, drying and crushing to obtain a manganese nitrate powder product; and washing the calcium sulfate filter cake, drying and crushing to obtain a calcium sulfate dihydrate product.
Description
Technical field
The present invention relates to the improvement of the inorganic chemical industry three wastes and utilize technical field, relate in particular to a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, its raw material is for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore.
Background technology
Titanium White Production By Sulfuric Acid Process is that the titanium-iron powder and the vitriol oil are carried out acidolysis reaction production titanous sulfate, generates metatitanic acid through hydrolysis, promptly obtains the titanium dioxide product through calcination, pulverizing again, and its chemical principle is:
、 Fe
2O
3+3H
2SO
4＝＝Fe
2(SO
4)
3+3H
2O
TiO
2+2H
2SO
4＝＝Ti(SO
4)
2+2H
2O
Fe+Fe
2(SO
4)
3＝＝3FeSO
4
Ti(SO
4)
2+3H
2O＝＝H
2TiO
3↓+2H
2SO
4，
H
2TiO
3＝TiO
2+H
2O.
Titanium White Production By Sulfuric Acid Process, the main component that industrial residue contained of its generation is a sulfuric acid, not only quantity discharged is big but also emission concentration is also very high.The waste residue that it is 10-25% that titanium dioxide of every production is discharged 10 tons of sulfuric acid mass percentage concentration approximately, these waste residues can be taked to concentrate circulation technology originally and make the vitriol oil, but, it is high to exist power consumption, used material requires harsh, ferrous sulfate separation difficulty and fatal problem such as impurity enriched when reclaiming.At present also there is not ideal method to solve the waste acid treatment of titanium dioxide and the problem of utilization as yet.
Summary of the invention
The main component that is contained in the Titanium White Production By Sulfuric Acid Process gained waste liquid is sulfuric acid and ferrous sulfate, and wherein, the vitriolic mass content is 10-20%.In order to make full use of this waste liquid, the invention provides a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, its raw material is for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore, this method is with the simple processing treatment of Titanium White Production By Sulfuric Acid Process gained waste liquid process, extract and utilization sulfuric acid wherein, made full use of the potential value of Titanium White Production By Sulfuric Acid Process gained waste liquid, and do not produced secondary pollution, being one turns waste into wealth, economic and practical method.
Technical scheme of the present invention is as follows: a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, and its raw material comprises following concrete steps for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore:
Steps A: square manganese stone mill is become 100-150 purpose meal, drop into the steeping tank (1) with heating unit together with Titanium White Production By Sulfuric Acid Process gained waste liquid, soaked 8-10 hour, soaking temperature is 60-80 ℃, through suction filtration machine (2) suction filtration soak solution, obtain clarifying filtrate and filter residue;
Step B: add the manganous hydroxide removal of impurities in the clarifying filtrate, filter, obtain purified manganese sulfate solution;
Step C: it is the manganous sulfate saturated solution that purified manganese sulfate solution is sent into one (3) the middle underpressure distillation of underpressure distillation device, cooling, separate out the manganous sulfate crystal that contains crystal water, manganous sulfate crystal product (7) is pulverized, obtained to the manganous sulfate crystal that contains crystal water through washing machine one (4) washing, moisture eliminator one (5), pulverizer one (6) again;
Step D: purified manganese sulfate solution is dropped into corrosion-resistant reactor (8) with the ratio 1 of ca nitrate soln with the molar content of the pure substance of manganous sulfate and nitrocalcite: 0.8-1.2, carry out chemical reaction under stirring, obtain containing the mixture of manganous nitrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and manganous nitrate filtrate;
Step e: manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device be the manganous nitrate supersaturated solution, crystallisation by cooling obtains anhydrous nitric acid manganese crystal, and anhydrous nitric acid manganese crystal is pulverized and obtained manganous nitrate powder product (13) through moisture eliminator two (11), pulverizer two (12);
Step F: two H 2 O calcium sulphate products (17) are pulverized, obtained to the calcium sulfate filter cake through washing machine two (14) washings, moisture eliminator three (15), pulverizer three (16).
The method for preparing manganous sulfate, manganous nitrate and calcium sulfate of the present invention, its chemical principle is:
MnO+H
2SO
4＝＝＝＝＝MnSO
4+H
2O
MnSO
4+Ca(NO
3)
2+2H
2O＝＝＝＝＝Mn(NO
3)
2+CaSO
4·2H
2O
Beneficial effect of the present invention is: the method for preparing manganous sulfate, manganous nitrate and calcium sulfate of the present invention, and make full use of the potential value of Titanium White Production By Sulfuric Acid Process gained waste liquid, and do not produced secondary pollution, being one turns waste into wealth, economic and practical method.This method is simple to operate, and facility investment is few, is worthy of popularization.
Description of drawings
Fig. 1 is the process flow sheet for preparing the method for manganous sulfate, manganous nitrate and calcium sulfate of the present invention, wherein, (1) steeping tank, (2) suction filtration machine, (3) underpressure distillation device one, (4) washing machine one, (5) moisture eliminator one, (6) pulverizer one, (7) manganous sulfate crystal product, (8) corrosion-resistant reactor, (9) strainer two, (10) underpressure distillation device two, (11) moisture eliminator two, (12) pulverizer two, (13) manganous nitrate powder product, (14) washing machine two, (15) moisture eliminator three, (16) pulverizer three, (17) two H 2 O calcium sulphate products.
Embodiment
Embodiment 1:
With reference to Fig. 1, a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, its raw material comprises following concrete steps for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore:
Steps A: get 500kg Titanium White Production By Sulfuric Acid Process gained waste liquid, adjusting the vitriolic mass concentration that wherein contains is 18%, square manganese stone mill is become 100 purpose meal, drop into steeping tank (1) together with Titanium White Production By Sulfuric Acid Process gained waste liquid with heating unit, soaked 8 hours, soaking temperature is 60 ℃, through suction filtration machine (2) suction filtration soak solution, obtains clarifying filtrate and filter residue;
Step B: add the manganous hydroxide removal of impurities in the clarifying filtrate, filter, obtain purified manganese sulfate solution;
Step C: it is the manganous sulfate saturated solution that purified manganese sulfate solution is sent into one (3) the middle underpressure distillation of underpressure distillation device, cooling, separate out the manganous sulfate crystal that contains crystal water, the manganous sulfate crystal that contains crystal water, pulverize, obtain manganous sulfate crystal product (7) through washing machine one (4) washing, moisture eliminator one (5), pulverizer one (6) again, the quality of the pure substance of the manganous sulfate that it contains is 138.67kg;
Step D: with purified manganese sulfate solution and ca nitrate soln with the pure substance of manganous sulfate and nitrocalcite the ratio of molar content drop into corrosion-resistant reactor (8) at 1: 0.8, carry out chemical reaction under stirring, obtain containing the mixture of manganous nitrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and manganous nitrate filtrate;
Step e: manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device be the manganous nitrate supersaturated solution, crystallisation by cooling obtains anhydrous nitric acid manganese crystal, anhydrous nitric acid manganese crystal is pulverized and is obtained manganous nitrate powder product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the manganous nitrate that it contains is 131.51kg;
Step F: two H 2 O calcium sulphate products (17) are pulverized, obtained to the calcium sulfate filter cake through washing machine two (14) washings, moisture eliminator three (15), pulverizer three (16), and the quality of the pure substance of two H 2 O calcium sulphates that it contains is 126.37kg.
Embodiment 2:
With reference to Fig. 1, a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, its raw material comprises following concrete steps for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore:
Steps A: get 500kg Titanium White Production By Sulfuric Acid Process gained waste liquid, adjusting the vitriolic mass concentration that wherein contains is 20%, square manganese stone mill is become 120 purpose meal, drop into steeping tank (1) together with Titanium White Production By Sulfuric Acid Process gained waste liquid with heating unit, soaked 90 hours, soaking temperature is 70 ℃, through suction filtration machine (2) suction filtration soak solution, obtains clarifying filtrate and filter residue;
Step B: add the manganous hydroxide removal of impurities in the clarifying filtrate, filter, obtain purified manganese sulfate solution;
Step C: it is the manganous sulfate saturated solution that purified manganese sulfate solution is sent into one (3) the middle underpressure distillation of underpressure distillation device, cooling, separate out the manganous sulfate crystal that contains crystal water, the manganous sulfate crystal that contains crystal water, pulverize, obtain manganous sulfate crystal product (7) through washing machine one (4) washing, moisture eliminator one (5), pulverizer one (6) again, the amount of the pure substance of the manganous sulfate that it contains is 154.08kg;
Step D: with purified manganese sulfate solution and ca nitrate soln with the pure substance of manganous sulfate and nitrocalcite the ratio of molar content drop into corrosion-resistant reactor (8) at 1: 1, carry out chemical reaction under stirring, obtain containing the mixture of manganous nitrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and manganous nitrate filtrate;
Step e: manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device be the manganous nitrate supersaturated solution, crystallisation by cooling obtains anhydrous nitric acid manganese crystal, anhydrous nitric acid manganese crystal is pulverized and is obtained manganous nitrate powder product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the manganous nitrate that it contains is 182.65kg;
Step F: two H 2 O calcium sulphate products (17) are pulverized, obtained to the calcium sulfate filter cake through washing machine two (14) washings, moisture eliminator three (15), pulverizer three (16), and the quality of the pure substance of two H 2 O calcium sulphates that it contains is 175.51kg.
Embodiment 3:
With reference to Fig. 1, a kind of method for preparing manganous sulfate, manganous nitrate and calcium sulfate, its raw material comprises following concrete steps for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore:
Steps A: get 500kg Titanium White Production By Sulfuric Acid Process gained waste liquid, adjusting the vitriolic mass concentration that wherein contains is 30%, square manganese stone mill is become 150 purpose meal, drop into steeping tank (1) together with Titanium White Production By Sulfuric Acid Process gained waste liquid with heating unit, soaked 10 hours, soaking temperature is 80 ℃, through suction filtration machine (2) suction filtration soak solution, obtains clarifying filtrate and filter residue;
Step B: add the manganous hydroxide removal of impurities in the clarifying filtrate, filter, obtain purified manganese sulfate solution;
Step C: it is the manganous sulfate saturated solution that purified manganese sulfate solution is sent into one (3) the middle underpressure distillation of underpressure distillation device, cooling, separate out the manganous sulfate crystal that contains crystal water, the manganous sulfate crystal that contains crystal water, pulverize, obtain manganous sulfate crystal product (7) through washing machine one (4) washing, moisture eliminator one (5), pulverizer one (6) again, the amount of the pure substance of the manganous sulfate that it contains is 231.12kg;
Step D: with purified manganese sulfate solution and ca nitrate soln with the pure substance of manganous sulfate and nitrocalcite the ratio of molar content drop into corrosion-resistant reactor (8) at 1: 1.2, carry out chemical reaction under stirring, obtain containing the mixture of manganous nitrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and manganous nitrate filtrate;
Step e: manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device be the manganous nitrate supersaturated solution, crystallisation by cooling obtains anhydrous nitric acid manganese crystal, anhydrous nitric acid manganese crystal is pulverized and is obtained manganous nitrate powder product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the manganous nitrate that it contains is 273.98kg;
Step F: two H 2 O calcium sulphate products (17) are pulverized, obtained to the calcium sulfate filter cake through washing machine two (14) washings, moisture eliminator three (15), pulverizer three (16), and the quality of the pure substance of two H 2 O calcium sulphates that it contains is 263.27kg.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries product.Just make some simple deduction or replace, all should be considered as belonging to the scope of patent protection that the present invention is determined by claims of being submitted to.
Claims (1)
1. a method for preparing manganous sulfate, manganous nitrate and calcium sulfate is characterized in that, and is raw materials used for using Titanium White Production By Sulfuric Acid Process gained waste liquid and manganese ore, comprises following concrete steps:
Steps A: square manganese stone mill is become 100-150 purpose meal, drop into the steeping tank (1) with heating unit together with Titanium White Production By Sulfuric Acid Process gained waste liquid, soaked 8-10 hour, soaking temperature is 60-80 ℃, through suction filtration machine (2) suction filtration soak solution, obtain clarifying filtrate and filter residue;
Step B: add the manganous hydroxide removal of impurities in the clarifying filtrate, filter, obtain purified manganese sulfate solution;
Step C: it is the manganous sulfate saturated solution that purified manganese sulfate solution is sent into one (3) the middle underpressure distillation of underpressure distillation device, cooling, separate out the manganous sulfate crystal that contains crystal water, manganous sulfate crystal product (7) is pulverized, obtained to the manganous sulfate crystal that contains crystal water through washing machine one (4) washing, moisture eliminator one (5), pulverizer one (6) again;
Step D: purified manganese sulfate solution is dropped into corrosion-resistant reactor (8) with the ratio 1 of ca nitrate soln with the molar content of the pure substance of manganous sulfate and nitrocalcite: 0.8-1.2, carry out chemical reaction under stirring, obtain containing the mixture of manganous nitrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and manganous nitrate filtrate;
Step e: manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device be the manganous nitrate supersaturated solution, crystallisation by cooling obtains anhydrous nitric acid manganese crystal, and anhydrous nitric acid manganese crystal is pulverized and obtained manganous nitrate powder product (13) through moisture eliminator two (11), pulverizer two (12);
Step F: two H 2 O calcium sulphate products (17) are pulverized, obtained to the calcium sulfate filter cake through washing machine two (14) washings, moisture eliminator three (15), pulverizer three (16).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105979195A CN102249333A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganese nitrate and calcium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105979195A CN102249333A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganese nitrate and calcium sulfate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102249333A true CN102249333A (en) | 2011-11-23 |
Family
ID=44976969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105979195A Pending CN102249333A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganese nitrate and calcium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102249333A (en) |
-
2010
- 2010-12-21 CN CN2010105979195A patent/CN102249333A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100424203C (en) | Method for producing titanium pigment using blast-furnace slag capable of recovering other resources | |
| CN102557128A (en) | Novel production process of titanium dioxide powder | |
| CN103572058B (en) | A kind of method of enrichment rare earth rare elements and the white gypsum of preparation from sulfate process titanium dioxide waste liquid | |
| CN103993178A (en) | Method for recycling germanium from optical fiber wastes containing germanium | |
| CN102249334A (en) | Method for preparing manganese sulfate, manganese hydroxide and potassium sulfate | |
| CN102249340A (en) | Method for preparing manganese sulfate, manganese phosphate and calcium sulfate | |
| CN102166452B (en) | Method for filtration-assisted purification of acidolysis solution obtained in the process of decomposing phosphorite by using nitric acid | |
| CN102166453B (en) | Method for purification of acidolysis solution obtained in the process of decomposing phosphorite by using nitric acid | |
| CN105858700A (en) | Novel production technique for preparing calcium chloride from carbide slag | |
| CN103265056B (en) | Method for extracting industrial slat from salt mixture | |
| CN102259930A (en) | Method for preparing manganese sulfate, anhydrous manganese chloride and calcium sulfate | |
| CN102249336A (en) | Method for preparing manganese sulfate, manganese carbonate and calcium sulfate | |
| CN102249339A (en) | Method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate | |
| CN102115207B (en) | Method for producing ferrous carbonate and ammonium sulfate by using waste acid obtained during production of titanium pigment by adopting sulfuric acid process | |
| CN102249333A (en) | Method for preparing manganese sulfate, manganese nitrate and calcium sulfate | |
| CN101823730A (en) | Method for simultaneously producing sodium thiocyanate and ammonium carbonate | |
| CN101913656A (en) | Method for preparing iron oxide yellow pigment by using titanium white by-product of ferrous sulfate | |
| CN102115209B (en) | Method for producing ferrous nitrate and barium sulfate by using waste acid obtained by producing titanium white by sulfuric acid method | |
| CN102133495A (en) | Method for purifying acidolysis solution by filter aid and polyacrylamide | |
| CN102249338A (en) | Method for preparing manganese sulfate, manganous nitrate and calcium sulfate | |
| CN102249337A (en) | Method for preparing manganese sulfate, manganous nitrate and calcium sulfate | |
| CN102115087A (en) | Method for producing silicon dioxide and calcium silicate by phosphorus residue | |
| CN102249335A (en) | Method for preparing manganese sulfate, manganese hydroxide and calcium sulfate | |
| CN102249314A (en) | Method for preparing chromic hydroxide, lead chloride and sodium nitrate by chromium-containing mirabilite | |
| CN102249329A (en) | Method for preparing chromic hydroxide, sodium chloride and nitric acid utilizing sodium sulfate containing chromium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111123 |