CN102249337A - Method for preparing manganese sulfate, manganous nitrate and calcium sulfate - Google Patents
Method for preparing manganese sulfate, manganous nitrate and calcium sulfate Download PDFInfo
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- CN102249337A CN102249337A CN2010105979636A CN201010597963A CN102249337A CN 102249337 A CN102249337 A CN 102249337A CN 2010105979636 A CN2010105979636 A CN 2010105979636A CN 201010597963 A CN201010597963 A CN 201010597963A CN 102249337 A CN102249337 A CN 102249337A
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- sulfate
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Abstract
The invention provides a method for preparing manganese sulfate, manganous nitrate and calcium sulfate. The method comprises the steps of: grinding manganosite into coarse powder, dipping the coarse powder and the waste liquor from titanium white production by sulfuric acid method in a soaking tank at a temperature of 60-80DEG C for 8-10 hours, conducting pumping filtration so as to obtain clarified filtrate, then adding manganese hydroxide for impurity removal, thus obtaining a purified manganese sulfate solution; conducting reduced pressure distillation to the purified manganese sulfate solution so as to obtain a saturated solution of manganese sulfate, cooling the saturated solution so as to separate out a manganese sulfate crystal containing crystal water, drying and crushing the crystal, thus obtaining a manganese sulfate crystal product; reacting the purified manganese sulfate solution with a calcium nitrate solution under stirring, filtering the reaction product so as to obtain a calcium sulfate filter cake and manganous nitrate filtrate which is subjected to reduced pressure distillation to form a manganous nitrate solution at a concentration of 30-50%, cooling and crystallizing the manganous nitrate solution, thus obtaining a manganous nitrate hydrate, i.e. a liquid manganous nitrate product; washing, drying and crushing the calcium sulfate filter cake, thus obtaining a dihydrate calcium sulfate 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: it is the manganese nitrate solution of 30-50% for concentration that manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device, and crystallisation by cooling is separated out the manganous nitrate hydrate, is manganous nitrate liquid product (13);
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, and (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, (13) manganous nitrate liquid 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 ratio 1: the 0.8 input corrosion-resistant reactor (8) of ca nitrate soln with the molar content of the pure substance of manganous sulfate and nitrocalcite, 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: it is 30% manganese nitrate solution for concentration that manganous nitrate filtrate is sent to underpressure distillation device two (10) distillation, and crystallisation by cooling is separated out the manganous nitrate hydrate, is manganous nitrate liquid product (13), 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 ratio 1: the 1 input corrosion-resistant reactor (8) of ca nitrate soln with the molar content of the pure substance of manganous sulfate and nitrocalcite, 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: it is 40% manganese nitrate solution for concentration that manganous nitrate filtrate is sent to underpressure distillation device two (10) distillation, and crystallisation by cooling is separated out the manganous nitrate hydrate, is manganous nitrate liquid product (13), 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 ratio 1: the 1.2 input corrosion-resistant reactor (8) of ca nitrate soln with the molar content of the pure substance of manganous sulfate and nitrocalcite, 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: it is 50% manganese nitrate solution for concentration that manganous nitrate filtrate is sent to underpressure distillation device two (10) distillation, and crystallisation by cooling is separated out the manganous nitrate hydrate, is manganous nitrate liquid product (13), 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: it is the manganese nitrate solution of 30-50% for concentration that manganous nitrate filtrate is sent to two (10) distillations of underpressure distillation device, and crystallisation by cooling is separated out the manganous nitrate hydrate, is manganous nitrate liquid product (13);
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).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105979636A CN102249337A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganous nitrate and calcium sulfate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105979636A CN102249337A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganous nitrate and calcium sulfate |
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| Publication Number | Publication Date |
|---|---|
| CN102249337A true CN102249337A (en) | 2011-11-23 |
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ID=44976973
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|---|---|---|---|
| CN2010105979636A Pending CN102249337A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, manganous nitrate and calcium sulfate |
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| Country | Link |
|---|---|
| CN (1) | CN102249337A (en) |
-
2010
- 2010-12-21 CN CN2010105979636A patent/CN102249337A/en active Pending
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Application publication date: 20111123 |