CN102249339A - Method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate - Google Patents
Method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate Download PDFInfo
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- CN102249339A CN102249339A CN2010105981602A CN201010598160A CN102249339A CN 102249339 A CN102249339 A CN 102249339A CN 2010105981602 A CN2010105981602 A CN 2010105981602A CN 201010598160 A CN201010598160 A CN 201010598160A CN 102249339 A CN102249339 A CN 102249339A
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- sulfate
- manganese
- manganous
- chloride
- tetrahydrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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Abstract
The invention provides a method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate. The method comprises the following steps of: grinding manganosite into coarse powder, soaking titanium pigment produced by using a sulfuric acid method at a temperature between 60 DEG C and 80 DEG C for 8-10 hours, performing suction filtration to obtain a clear filtrate, and adding manganese hydroxide for removing impurities to obtain a pure manganese sulfate solution; distilling the pure manganese sulfate solution into a manganese sulfate saturated solution under reduced pressure, cooling, precipitating manganese sulfate crystals containing crystal water out, drying and smashing to obtain a manganese sulfate crystal product; reacting the pure manganese sulfate solution with a calcium chloride solution under stirring, filtering a reaction product to obtain a calcium sulfate filter cake and a manganese chloride filtrate, distilling the manganese chloride filtrate into a manganese chloride saturated solution under reduced pressure, cooling and crystalizing to obtain a manganese chloride hydrate, drying and smashing to obtain a tetrahydrate manganese chloride crystal product; and washing the calcium sulfate filter cake, drying and smashing to obtain 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, tetrahydrate manganese chloride 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 titanium-iron powder and the vitriol oil to be carried out acidolysis reaction produce titanous sulfate, generates metatitanic acid through hydrolysis, again through calcination, pulverize and promptly obtain the titanium dioxide product, 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, tetrahydrate manganese chloride 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, tetrahydrate manganese chloride 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 calcium chloride solution with the molar content of the pure substance of manganous sulfate and calcium chloride: 0.8-1.2, carry out chemical reaction under stirring, obtain containing the mixture of Manganous chloride tetrahydrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and Manganous chloride tetrahydrate filtrate;
Step e: Manganous chloride tetrahydrate filtrate is sent to two (10) distillations of underpressure distillation device be the Manganous chloride tetrahydrate saturated solution, crystallisation by cooling obtains the Manganous chloride tetrahydrate hydrate, and the Manganous chloride tetrahydrate hydrate is pulverized and obtained tetrahydrate manganese chloride crystal 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, tetrahydrate manganese chloride and calcium sulfate of the present invention, its chemical principle is:
MnO+H
2SO
4＝＝＝＝＝MnSO
4+H
2O
MnSO
4+CaCl
2+6H
2O＝＝＝＝＝MnCl
2·4H
2O+CaSO
4·2H
2O
Beneficial effect of the present invention is: the method for preparing manganous sulfate, tetrahydrate manganese chloride and calcium sulfate of the present invention, made full use of the potential value of Titanium White Production By Sulfuric Acid Process gained waste liquid, and do not produce 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 chloride tetrahydrate 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) tetrahydrate manganese chloride crystal 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, tetrahydrate manganese chloride 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 calcium chloride solution with the molar content of the pure substance of manganous sulfate and calcium chloride, carry out chemical reaction under stirring, obtain containing the mixture of Manganous chloride tetrahydrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and Manganous chloride tetrahydrate filtrate;
Step e: Manganous chloride tetrahydrate filtrate is sent to two (10) distillations of underpressure distillation device be the Manganous chloride tetrahydrate saturated solution, crystallisation by cooling obtains the Manganous chloride tetrahydrate hydrate, the Manganous chloride tetrahydrate hydrate is pulverized and is obtained tetrahydrate manganese chloride crystal product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the tetrahydrate manganese chloride that it contains is 145.47kg;
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, tetrahydrate manganese chloride 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 9 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 calcium chloride solution with the molar content of the pure substance of manganous sulfate and calcium chloride, carry out chemical reaction under stirring, obtain containing the mixture of Manganous chloride tetrahydrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and Manganous chloride tetrahydrate filtrate;
Step e: Manganous chloride tetrahydrate filtrate is sent to two (10) distillations of underpressure distillation device be the Manganous chloride tetrahydrate saturated solution, crystallisation by cooling obtains the Manganous chloride tetrahydrate hydrate, the Manganous chloride tetrahydrate hydrate is pulverized and is obtained tetrahydrate manganese chloride crystal product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the tetrahydrate manganese chloride that it contains is 202.04kg;
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, tetrahydrate manganese chloride 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 monobutyltin trichloride calcium solution with the molar content of manganous sulfate and monobutyltin trichloride calcium, carry out chemical reaction under stirring, obtain containing the mixture of chlorination Manganous chloride tetrahydrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and monobutyltin trichloride manganese filtrate;
Step e: monobutyltin trichloride manganese filtrate is sent to two (10) distillations of underpressure distillation device be monobutyltin trichloride manganese saturated solution, crystallisation by cooling obtains monobutyltin trichloride manganese hydrate, chlorination nitre Manganous chloride tetrahydrate hydrate is pulverized and is obtained tetrahydrate manganese chloride crystal product (13) through moisture eliminator two (11), pulverizer two (12), and the quality of the pure substance of the tetrahydrate manganese chloride that it contains is 303.06kg;
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, tetrahydrate manganese chloride 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 calcium chloride solution with the molar content of the pure substance of manganous sulfate and calcium chloride: 0.8-1.2, carry out chemical reaction under stirring, obtain containing the mixture of Manganous chloride tetrahydrate and calcium sulfate, filter through filter two (9), obtain calcium sulfate filter cake and Manganous chloride tetrahydrate filtrate;
Step e: Manganous chloride tetrahydrate filtrate is sent to two (10) distillations of underpressure distillation device be the Manganous chloride tetrahydrate saturated solution, crystallisation by cooling obtains the Manganous chloride tetrahydrate hydrate, and the Manganous chloride tetrahydrate hydrate is pulverized and obtained tetrahydrate manganese chloride crystal 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 |
|---|---|---|---|
| CN2010105981602A CN102249339A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate |
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|---|---|---|---|
| CN2010105981602A CN102249339A (en) | 2010-12-21 | 2010-12-21 | Method for preparing manganese sulfate, tetrahydrate manganese chloride and calcium sulfate |
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|---|---|
| CN102249339A true CN102249339A (en) | 2011-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447283A (en) * | 2013-08-30 | 2013-12-18 | 漯河兴茂钛业股份有限公司 | Safe disposal method for waste residue produced by production of titanium tetrachloride by using titanium dioxide by chlorination process |
-
2010
- 2010-12-21 CN CN2010105981602A patent/CN102249339A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103447283A (en) * | 2013-08-30 | 2013-12-18 | 漯河兴茂钛业股份有限公司 | Safe disposal method for waste residue produced by production of titanium tetrachloride by using titanium dioxide by chlorination process |
| CN103447283B (en) * | 2013-08-30 | 2017-06-09 | 漯河兴茂钛业股份有限公司 | The Safe disposal method of waste residue produced by Titanium Dioxide Produced by Chloride Procedure production titanium tetrachloride |
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Application publication date: 20111123 |