CN102390867A - Diatomite purification and impurity removal method for manganese sulfate solution - Google Patents
Diatomite purification and impurity removal method for manganese sulfate solution Download PDFInfo
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- CN102390867A CN102390867A CN2011102116085A CN201110211608A CN102390867A CN 102390867 A CN102390867 A CN 102390867A CN 2011102116085 A CN2011102116085 A CN 2011102116085A CN 201110211608 A CN201110211608 A CN 201110211608A CN 102390867 A CN102390867 A CN 102390867A
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Abstract
The invention provides a new diatomite purification and impurity removal method for manganese sulfate solution, and belongs to the field of deep processing of a mineral product. Suspended matters in the manganese sulfate solution are completely removed after the manganese sulfate solution is subjected to purification and impurity removal of the diatomite, so that the purity of manganese sulfate is effectively improved, and the purification and impurity removal efficiency is increased. The method has the characteristics of easiness for operation, high purification efficiency, low cost and the like.
Description
Technical field
The present invention relates to a kind of zeyssatite purifying and impurity-removing method of manganese sulfate solution, improved its manganous sulfate purity greatly, belong to mineral products deep processing field.
Background technology
Manganous sulfate is a kind of important basic chemical industry raw material, is widely used in chemical field such as medicine, papermaking, catalyzer, fodder additives and produces field of metallurgy such as electrolytic manganese and produce other manganese salt etc.Along with manganese is that product is more and more wider in international and domestic purposes, its throughput enlarges rapidly, and with regard to China, the development of electrolytic manganese is very fast, and throughput has reached more than 2,300,000 tons/year.Many manganese products such as manganous sulfate, electrolytic manganese will use the material of bivalent manganese to be raw material, like manganous carbonate or manganese monoxide.The ore consumption is big, and corresponding subsidiary material and power consumption be also along with increase, thereby causes the rising of cost straight line, brings great existence crisis to manufacturing enterprise.Therefore it is extremely urgent to inquire for new substitution of resources manganese carbonate ore, also is a kind of effective way of keeping the existence of manganese enterprise production.
The pyrolusite of occurring in nature tetravalence manganese (mainly being Manganse Dioxide) ore deposit amount is more, and manganese content is high, and price is low.But the Manganse Dioxide in the pyrolusite is insoluble to sulfuric acid, must be reduced into manganese monoxide (MnO) ability and sulfuric acid reaction generation manganous sulfate to it through reduction reaction.Publication number is that the Chinese patent of CN101837959A has been introduced a kind of method of in fluidizing furnace, utilizing the sulphur reducing pyrolusite and co-producing sulfuric acid, and burning sulphur is as thermal source and reductive agent, and the temperature that provides the Manganse Dioxide reduction to need has been saved fuel greatly.Pyrolusite is because of containing metallic elements such as calcium, iron, aluminium; Can generate vitriol with sulfuric acid, add various inorganic or organic floculants, generate insoluble substances such as cupric sulfide; After passing through filtered through gauze again; Find that its manganese sulfate solution still contains some fine particulate matter, very big to subsequent technique influence, even directly have influence on the purity of manganous sulfate.But in fluidizing furnace discharge manganese monoxide, contain part sulphur, sulphur has very big influence to utilizing manganese sulfate solution to produce electrolytic manganese.
Diatomaceous color is white, pearl, grey and terra brown etc., owing to have characteristics such as exquisiteness, loose, light weight, porous, suction and perviousness are strong, and have the particular structural structure to make it have many special technique and physicals; Like aerated density is 0.3-0.5g/cm3, and Mohs' hardness is 1-1.5 (diatom bone particulate is 4.5-5 μ m), and porosity reaches 80-90%; Can absorb itself weight 1.5-4 water doubly, be the poor conductor of heat, electricity, sound, fusing point 1650-1750 ℃; Chemicalstability is high; Except that being dissolved in hydrofluoric acid, being insoluble to any strong acid, and can reaching more than 98% the specific absorption of sulphur.Therefore be very suitable for the manganese sulfate solution removal of impurities.
Summary of the invention
The objective of the invention is in to the pyrolusite course of processing, impurity and sulfuric acid form the solution suspended substance, still contain the molecule suspended substance through solution behind the membrane filtration, directly carry out the purity that crystallization will influence manganous sulfate.In order thoroughly to remove suspended substance in the manganese sulfate solution, a kind of novel method of zeyssatite purification and impurity removal of manganese sulfate solution is provided.Manganse Dioxide directly enters manganese monoxide pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leaches manganous sulfate after sulphur is reduced into manganese monoxide, and this solution is purified through zeyssatite, realizes thoroughly removing suspended substance in the solution, improves the purity of manganous sulfate.
Technical scheme of the present invention is:
(1) with sulphur and pyrolusite in proportion blending send in the fluidizing furnace;
(2) blast air at the fluidizing furnace hypomere, boiling in fluidizing furnace, burning, the control fluidized layer temperature is about 500～1000 ℃;
The manganese monoxide of (3) discharging from the fluidizing furnace discharge port secluding air cooling that falls into the water prevents that manganese monoxide is oxidized to Manganse Dioxide, also can manganese monoxide directly be entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leach manganous sulfate;
(4) adopt zeyssatite that manganese sulfate solution is carried out the purification and impurity removal process;
(5) carry out manganous sulfate crystallization recrystallization to filtering back solution, solid, to its open wide heat manganese sulphate powder.
The concrete purification and impurity removal process of diatomite filter in step 4: connect the import and export pipeline.Adopt suitable 60 ℃ of left and right sides of washings hot water earlier with the complete cleaning of entire machine, close all valves after cleaning up; Add the circulation bucket to zeyssatite and add (general 1 kilogram/square metre in right amount in 5.; Machine such as 15 square metres of filtration areas; Earlier add about 8～10 kilograms) C535RV/C545RV (slightly) zeyssatite, open the charging valve 2., valve 2 4., 7. 10. valve 3 (14), valve 4 reach vent valve.Start transferpump and begin diatomaceous circulation precoating; Treat to close feed valve 2. when entire machine is full of 25 ℃ manganese sulfate solution; Circulated about 8～10 minutes, add again C503RV (in) the about 3-4 kilogram of zeyssatite, continuing circulation 5～10 minutes (needs to add C512RV (carefully) or STD zeyssatite 2-3 kilogram again according to filter criteria; As do not need fine earth, can add thick, middle soil).Vent valve is in time closed after 7. air being drained.9. observe and 6. take a sample from the outlet visor by sampling valve; Then can begin formal filtration like conformance with standard: both hands steadily open outlet valve 5
simultaneously and feed valve 2.; And valve-off 2 4. with valve 4 10.; Note tensimeter variation 8.; Reduce tensimeter fluctuation 8., in order to avoid the zeyssatite precoated layer is damaged as far as possible.Like manganous sulfate concentration when higher, when the beginning normal filtration, in jar, add 5～10 kilograms of composite soils (8: 2, C535RV, C503RV and C512RV can add fine earth sometimes).8. be increased to 0.3MPa and flow like tensimeter and be reduced to when almost not having, promptly will stop to filter and cleaning; After filtering end, open surplus liquid valve, left standstill about 30 minutes, to be filtered jar of interior zeyssatite natural sedimentation opened the liquid valve that is left, the liquid in the emptying hay tank behind the bottom.Connect clean water; Open the charging valve 2. and residual cake valve
start transferpump and begin to carry out the filtering direction flushing earlier; About 5 seconds (mainly washing down impurity in the pipe); Valve-off 3
is opened valve 6
beginning and is cleaned (open shutdown in 5～10 seconds, continue start then) in the other direction then.Advise filter stick
once being cleaned to guarantee filtration efficiency fully in every 3-6 month: the alkaline soak with 5 ‰ 12 hours; Do not bleed off buck; Open the top end socket, the liquid outlet that uses pressurized air (5～8 kilograms of air pressure) to aim at every filter bar is blown to get final product in 2～3 minutes and (is annotated: must after cleaning up in pipeline and the transferpump, carry out earlier during back flushing! ).Solid arrow is a filtering direction among Fig. 2, and dotted arrow is the back flushing direction.
In one embodiment, adopt the zeyssatite purification and impurity removal in the step 4, in order to prevent the influence to the zeyssatite characteristic, the temperature of manganese sulfate solution is preferably about 25 ℃.
In another embodiment, when manganese sulfate solution in the step 4 was passed through diatomite filter, through the controlled liq flow velocity, the peak pressure of preferred diatomite filter was no more than 0.3Mpa.
In another embodiment, big again through the small-particle diatomite filtration when passing through the zeyssatite purification and impurity removal in the step 4 earlier through the oversized particles diatomite filtration, filter generally about twice.
The temperature of also in another embodiment, opening wide heat solid in the step 5 is preferably about 250 ℃.
Description of drawings
The present invention will further specify with following diagram, wherein:
Fig. 1 is a fluidizing furnace structural representation according to the invention.
Fig. 2 is that manganese sulfate solution according to the invention is through zeyssatite purification and impurity removal synoptic diagram; 1. manganous sulfate qualifying liquid; 2. charging valve; 3. tap water; 4. valve 2; 5. zeyssatite adds bucket; 6. sampling valve; 7. vent valve; 8. 9. tensimeter exports visor, and 10. valve 4;
valve 5;
valve 6,
valve 3,
valve 3;
residual cake valve,
filter stick.
Technique effect
1, adopt the zeyssatite purifying and impurity-removing method can improve the purity of manganese sulfate product effectively.
2, the zeyssatite purifying and impurity-removing method can reuse, and has practiced thrift resource, reduces production costs.
Embodiment
Following examples have been merely and have further specified the present invention, do not limit content of the present invention, and affiliated technical field can also take other concrete mode to implement.Therefore, embodiment can not be interpreted as the only embodiment of the present invention.
Embodiment 1
500kg sulphur and 250kg pyrolusite (1: 0.5 in proportion) blending are sent in the fluidizing furnace; Blast air at the fluidizing furnace hypomere; Make material under the strength effect of furnace bottom air-flow and furnace roof negative pressure; Boiling in fluidizing furnace, burning, the control fluidized layer temperature is reduced to manganese monoxide with the Manganse Dioxide in the pyrolusite about 850～950 ℃; Manganese monoxide is directly entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leaches manganous sulfate, adopt GB GB1622-86 redox titration to determine the content of manganous sulfate.To zeyssatite add the circulation bucket 5. in adding an amount of 10 kilograms of C535RV/C545RV (slightly) zeyssatite, open the charging valve 2., valve 2 4., 7. 10. valve 3 (14), valve 4 reach vent valve.Start transferpump and begin diatomaceous circulation precoating; Treat to close feed valve 2. when entire machine is full of 25 ℃ manganese sulfate solution; Circulated about 8～10 minutes, add again C503RV (in) the about 3-4 kilogram of zeyssatite, continue circulation 5～10 minutes; Add C512RV (carefully) or STD zeyssatite 2-3 kilogram again, continue circulation 5～10 minutes.Vent valve is in time closed after 7. air being drained.9. observe and 6. take a sample from the outlet visor by sampling valve; Beginning is formal after the conformance with standard filters: both hands steadily open outlet valve 5
simultaneously and feed valve 2.; And valve-off 2 4. with valve 4 10.; Carry out the diatomite filtration manganese sulfate solution; Note tensimeter variation 8., reduce tensimeter fluctuation 8., as far as possible in order to avoid the zeyssatite precoated layer is damaged.Be reduced to when almost not having when 8. tensimeter is increased to 0.3MPa and flow, promptly will stop to filter and cleaning.Adopt this filtering and impurity removing process can obtain purer manganese sulfate solution, crystallization and recrystallization get aqueous sulfuric acid manganese solid, open wide to be heated to 250 ℃ and to obtain the anhydrous manganous sulfate solid, detect through GB GB1622-86 redox titration, and manganous sulfate purity is 98.8%.
Control Example:
500kg sulphur and 250kg pyrolusite (1: 0.5 in proportion) blending are sent in the fluidizing furnace; Blast air at the fluidizing furnace hypomere, make material under the strength effect of furnace bottom air-flow and furnace roof negative pressure, boiling in fluidizing furnace, burning; The control fluidized layer temperature is about 850～950 ℃; Manganse Dioxide in the pyrolusite is reduced to manganese monoxide, manganese monoxide is directly entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leaches manganous sulfate, adopt ordinary method to determine the content of manganous sulfate.Through the removal of impurities of gauze filtration, purification, obtain purer manganese sulfate solution, crystallization obtains the manganous sulfate solid, detects through aforesaid method, and manganous sulfate purity is 88.8%.
Embodiment 2: the something in common with embodiment 1 is no longer narrated, and difference is:
400kg sulphur and 800kg pyrolusite (1: 2 in proportion) blending are sent in the fluidizing furnace 750～850 ℃ of control fluidized layer temperatures, 800～850 ℃ of fluidizing furnace temperature outs.Manganse Dioxide in the pyrolusite is reduced to manganese monoxide, manganese monoxide is directly entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leaches manganous sulfate, adopt GB GB1622-86 redox titration to determine the content of manganous sulfate.Through diatomite filtration removal of impurities process, obtain purer manganese sulfate solution, adopt the high temperature crystallization method to obtain the manganous sulfate solid, detect through aforesaid method, manganous sulfate purity is 99.3%.
Embodiment 3: with embodiment 1, something in common is no longer narrated, and difference is:
400kg sulphur and 1600kg pyrolusite (1: 4 in proportion) blending are sent in the fluidizing furnace 600～700 ℃ of control fluidized layer temperatures, 700～800 ℃ of fluidizing furnace temperature outs.Manganse Dioxide in the pyrolusite is reduced to manganese monoxide, manganese monoxide is directly entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leaches manganous sulfate, adopt GB GB1622-86 redox titration to determine the content of manganous sulfate.Through diatomite filtration removal of impurities process, obtain purer manganese sulfate solution, adopt the high temperature crystallization method to obtain the manganous sulfate solid, detect through aforesaid method, manganous sulfate purity is 98.6%.
Claims (5)
1. the present invention provides a kind of novel method of zeyssatite purification and impurity removal of manganese sulfate solution, and step comprises:
(1) with sulphur and pyrolusite in proportion blending send in the fluidizing furnace;
(2) blast air at the fluidizing furnace hypomere, boiling in fluidizing furnace, burning, the control fluidized layer temperature is about 500～1000 ℃;
The manganese monoxide of (3) discharging from the fluidizing furnace discharge port secluding air cooling that falls into the water prevents that manganese monoxide is oxidized to Manganse Dioxide, also can manganese monoxide directly be entered pulp in the sulphuric acid soln (or electrolytic manganese anolyte), leach manganous sulfate;
(4) adopt zeyssatite that manganese sulfate solution is carried out the purification and impurity removal process;
(5) carry out manganous sulfate crystallization recrystallization to filtering back solution, solid, to its open wide heat manganese sulphate powder.
2. when the process of claim 1 wherein in the step 4 through the zeyssatite purification and impurity removal, manganese sulfate solution carries out under 25 ℃ of conditions.
3. according to the method for claim 1 or 2, wherein in the step 4 during through the zeyssatite purification and impurity removal, manganese sulfate solution during through diatomite filter peak pressure be no more than 0.3Mpa.
4. according to the method for claim 1 or 2, big again through the small-particle diatomite filtration earlier through the oversized particles diatomite filtration when wherein passing through the zeyssatite purification and impurity removal in the step 4, filter generally about twice.
5. according to the method for claim 1 or 2, the temperature of wherein opening wide heat solid in the step 5 is about 250 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102116085A CN102390867A (en) | 2011-07-27 | 2011-07-27 | Diatomite purification and impurity removal method for manganese sulfate solution |
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|---|---|---|---|
| CN2011102116085A CN102390867A (en) | 2011-07-27 | 2011-07-27 | Diatomite purification and impurity removal method for manganese sulfate solution |
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| CN102390867A true CN102390867A (en) | 2012-03-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072788A (en) * | 2022-08-03 | 2022-09-20 | 贵州金瑞新材料有限责任公司 | Preparation method for purifying and decontaminating manganese sulfate solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN102039118A (en) * | 2009-10-16 | 2011-05-04 | 中国矿业大学(北京) | Preparation method of loaded nano TiO2 photocatalytic material with diatomite filter aid as carrier |
-
2011
- 2011-07-27 CN CN2011102116085A patent/CN102390867A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| CN102039118A (en) * | 2009-10-16 | 2011-05-04 | 中国矿业大学(北京) | Preparation method of loaded nano TiO2 photocatalytic material with diatomite filter aid as carrier |
| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072788A (en) * | 2022-08-03 | 2022-09-20 | 贵州金瑞新材料有限责任公司 | Preparation method for purifying and decontaminating manganese sulfate solution |
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Application publication date: 20120328 |