CN101982419A - Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite - Google Patents
Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite Download PDFInfo
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- CN101982419A CN101982419A CN 201010517663 CN201010517663A CN101982419A CN 101982419 A CN101982419 A CN 101982419A CN 201010517663 CN201010517663 CN 201010517663 CN 201010517663 A CN201010517663 A CN 201010517663A CN 101982419 A CN101982419 A CN 101982419A
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- pyrolusite
- oxides
- nitrogen gas
- nitrate solution
- manganese nitrate
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Abstract
The invention discloses a method for preparing a manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite, which mainly comprises the following steps: (1) pyrolusite powder, water or/and a tailing cleaning solution and a metal chelating agent are prepared into ore pulp with the solid-liquid weight ratio of 1 to (1-5); (2) the prepared pyrolusite pulp and the oxynitride gas are continuously sent to an absorption reactor, so that the oxynitride gas contact with the ore pulp directly to carry out absorption reaction; and the absorption reaction is carried out at the positive pressure of 5000 to 10000Pa; and (3) an impurity removing agent is added to the absorption tail liquid for removing impurities and purifying, and the manganous nitrate solution is prepared through solid-liquid separation. In the technique of the invention, the ore pulp is continuously sent to and taken out of the absorption reactor so as to realize stable and continuous production; and the method has the advantages of high utilization rate of the oxynitride, high leaching rate of manganese, discharge standard achievement of tail gas, less secondary pollution, comprehensive utilization additional value enhancement of the pyrolusite, obvious economic benefits and the like.
Description
Technical field
What the present invention relates to is a kind of with oxides of nitrogen gas (NO
2, NO) the leaching pyrolusite produces the processing method of manganese nitrate solution.Belong to metallurgical, environmental technology field.
Background technology
At present, the main method that hydrometallurgy leaching pyrolusite is produced manganese nitrate solution is a reduction-pickling process, adopts reduction methods such as roasting, microwave with MnO in the pyrolusite earlier
2Be reduced to MnO, with the pyrolusite after the nitric acid leaching reduction, make MnO and nitric acid reaction generate manganese nitrate solution again, make manganese nitrate solution through purification and impurity removal then.
Oxynitride can be directly in liquid phase and the Manganse Dioxide generation redox reaction in the pyrolusite, the main manganous nitrate that generates, this technology need not consume sulfuric acid or nitric acid, do not need the ore pulp heating, not need pyrolusite is carried out the preroasting reduction, therefore leach pyrolusite with oxides of nitrogen gas as reductive agent, can shorten the technical process of above-mentioned traditional soft leaching manganese ore greatly, reform traditional pyrolusite leaching technology.
About producing manganese nitrate solution with oxides of nitrogen gas leaching pyrolusite, do not see the patent documentation report at present both at home and abroad as yet, domestic have the bright clear grade of dragon to study the method that absorbs low-concentration nitrogen oxide gas in the waste gas with pyrolusite pulp, confirmed the thermodynamics feasibility of this method, but do not seen that this studies the report of further industrial application.The present inventor discovers, pyrolusite pulp absorbs nitrogen oxides of exhaust gas gas and can not use in industry, this mainly is because extract technology and lectotype selection exist the common problem of following two keys still unresolved: the equipment that (1) is adopted can not be realized the successive reaction operation, under the rhythmic reaction condition, ore pulp once adds, since no fresh ore pulp mend into, according to stoichiometric ratio, the absorption rate of oxides of nitrogen gas and the leaching yield of manganese are inversely proportional to, carrying out along with reaction, the leaching yield of manganese is more and more higher, and the absorption rate of oxides of nitrogen gas is more and more lower, this oxides of nitrogen gas severe overweight that will cause discharging discharges, and produces the serious environmental pollution problem; (2) the solubleness concentration in water of the NO in the oxynitride is lower, therefore, need take measures to improve the specific absorption of NO.
Summary of the invention
Purpose of the present invention is intended to propose a kind ofly can realize steady and continuous production, oxynitride utilising efficiency height, and manganese leaching yield height, but tail gas qualified discharge, secondary pollution is few, and the leaching pyrolusite method of remarkable in economical benefits is to improve pyrolusite comprehensive utilization added value.
Purpose of the present invention realizes by the technical scheme that is made of following measure:
(1) in the ore pulp dispensing containers, with powder pyrolusite, water or/and tailings washings, metal chelator are mixed with the solid-liquid mass ratio is 1: the ore pulp of (1～5), wherein the metal chelator mass content is 0.1%～1% of a pyrolusite mass content;
(2) pyrolusite pulp and the oxides of nitrogen gas that prepare are sent into absorption reactor thermally constantly, oxides of nitrogen gas directly contacts with ore pulp and carries out absorption reaction, generation contains the absorption tail washings of manganous nitrate, behind abundant absorption reaction, gas back up to standard discharging, the absorption reaction tail washings enters next process, and absorption reaction is operated under malleation 5000～10000Pa, and the flow of ore pulp is determined according to the oxides of nitrogen gas flow Manganse Dioxide stoichiometric ratio required with it;
(3) absorb tail washings and enter the purification and impurity removal pond, add cleaner and make impurity separate out precipitation, promptly obtain the manganese nitrate solution that will prepare through solid-liquid separation again.
In such scheme, oxides of nitrogen gas preferably becomes air bubble-shaped to enter ore pulp through gas distributor, realize with ore pulp in Manganse Dioxide directly contact and carry out absorption reaction, the generation manganous nitrate; Described absorption reactor thermally preferably adopts the absorption reactor thermally that is provided with mechanical stirring device and jet blistering device; The mechanical stirring device of absorption reactor thermally preferably is not less than 5kW/m by power of agitator
3The ore pulp configuration.
Said oxides of nitrogen gas is to contain nitrogen protoxide or/and the gas of nitrogen peroxide in the such scheme, the source of oxides of nitrogen gas, can utilize the industrial gaseous waste of nitrogen-containing oxide gas, or directly buy commercial oxides of nitrogen gas, also can at high temperature produce with air voluntarily with oxygen reaction.
Said powder pyrolusite in the such scheme, to its grade, promptly its contained Manganse Dioxide ratio has no special requirements, and is not more than 100 orders but require to pulverize.
Said metal chelator in the such scheme, be meant and with multiple polyvalent metal ions such as calcium, magnesium, lead, zinc, iron in the pyrolusite infusion solution (0.01～7.5) in quite wide pH value scope sequestering action take place, form the various inorganicss of more stable water soluble complex and in the organism one or more, as poly-phosphate, poly carboxylic acid (polyacrylic acid, polymethyl acrylic acid, hydrolytic polymaleic anhydride, fumaric acid (FUMARIC ACID TECH GRADE)-propene sulfonic acid interpolymer etc.), hydroxycarboxylic acid (citric acid, tartrate) etc.), EDTA etc.
Said absorption tail washings adds the cleaner purification and impurity removal in the such scheme, the cleaner kind that is added and pyrolusite impurities kind, manganese nitrate solution following process specification of quality are relevant, the impurities kind is different with the following process specification of quality, and the cleaner kind of adding is also just different.Become manganous nitrate as the manganese nitrate solution following process, under the quality situation that requires usually, when the pyrolusite impurities is Fe
2+, Al
3+, Cu
2+, Pb
2+, Co
2+, Ni
2+Deng impurity, can take in tail washings, to add earlier MnO
2Oxygenant is with contained Fe
2+Oxidation of impurities is Fe
3+, add liming (or ammoniacal liquor) again, by regulating the pH value of tail washings, make the Fe in the tail washings
3+, Al
3+Ion precipitation is removed, and adds barium sulphide (or vulcanizing ammonia, Tong Shiji) afterwards again and make heavy metal ion Cu in tail washings
2+, Pb
2+, Co
2+, Ni
2+Precipitated removal.
The manganese nitrate solution that such scheme is produced can as producing manganous nitrate through the purification and impurity removal evaporative crystallization, be produced electrolytic manganese or Manganse Dioxide etc. through the purification and impurity removal electrolysis by producing all kinds of manganese products after the further deep processing.
The present invention discloses leaches pyrolusite with oxides of nitrogen gas and produces the method for manganese nitrate solution and have following very outstanding advantageous effect:
(1) starting material pyrolusite used in the present invention is a natural crystal, and reserves are abundant, and low price, grade requirement not high (containing manganese 20～25% gets final product) only need Mechanical Crushing to 100 order to get final product during use.
(2) adopt mechanical stirring jet blistering reactor, can effectively reduce the gas phase diffusion resistance, promote the dissolving of oxynitride in ore pulp to absorb.
(3) adopt all kinds of metal ions that generate in interpolation metal chelator and the pyrolusite leaching process to form stable complex compound, further promote network and the absorption of indissoluble oxynitride NO.
(4) whole system positive-pressure closing operation, oxynitride utilization ratio height can be realized qualified discharge.
(5) technical process of the present invention is a kind of continuous absorption reaction process flow process, and total system only needs an absorption reactor thermally, does not need blocked operation, and ore pulp is back to back, and can realize the continous-stable high efficiency production, but the tail gas qualified discharge.
Four, description of drawings
Fig. 1 is the process flow diagram of one embodiment of the present invention.
In the accompanying drawings, the connotation of each shown by reference numeral is as follows: 1 is the oxides of nitrogen gas generation systems; 2 is flue; 3 is the oxides of nitrogen gas gas blower; 4 is the jet blistering reactor; 5 for joining stock tank; 6 is ore slurry pipeline; 7 is blowdown stack; 8 is the purification and impurity removal pond; 9 is filter separator; 10 leave standstill the pond; 11 is crystallizer; 12 is centrifuge separator; 13 is moisture eliminator.
Embodiment
The present invention is described in further detail below in conjunction with process flow sheet and by embodiment, but content of the present invention is not limited only to content related among the embodiment.
Embodiment 1:
The sulfur dioxide gas of present embodiment comes from nitric acid production tail gas, and the oxides of nitrogen gas generation is 5000Nm
3/ h, earlier pyrolusite, water and metal chelator are mixed with liquid-solid ratio (mass ratio) and are 2: 1 ore pulp in the pulp tank 5 that agitator is housed, squeeze in the absorption reaction 4 by the ore pulp pump, after oxides of nitrogen gas is lowered the temperature through heat exchange, be pressed into the reactor 4 that is provided with mechanical stirring and jet blistering device by gas blower, in reactor 4, enter in the ore pulp and be absorbed by gas dispersion jet blistering device.Oxides of nitrogen gas through absorb up to standard after by blowdown stack 7 discharging.The denitration that contains manganous nitrate, slag and water absorbs tail washings discharges from the ore pulp outlet of absorption reactor thermally and is sent to purification and impurity removal pond 8, at first adds MnO in slurries
2Oxygenant is with contained Fe
2+Oxidation of impurities is Fe
3+, add liming (or ammoniacal liquor) again, the pH value of solution value is adjusted to about 6.0, make the Fe in the solution
3+, Al
3+Precipitated removal; In solution, add barium sulphide (or vulcanizing ammonia, Tong Shiji) again and make heavy metal ion Cu
2+, Pb
2+, Co
2+, Ni
2+Precipitated removal; Adopt filtering separation device 9 to carry out solid-liquid separation behind the purification and impurity removal, parting liquid is the manganese nitrate solution that will prepare, and separates slag through the washing discharging, and washings turns back to tankman's preface preparation ore pulp.
Connect the technical process of embodiment 1, the manganese nitrate solution for preparing is sent into left standstill pond 10, leave standstill about 24 hours, remove Ca in the manganese nitrate solution with precipitation
2+Obtain more purified manganese nitrate solution through after the above-mentioned processing, enter cooling crystallizer 11 again, obtain manganous nitrate through the crystallisation by cooling reaction, adopt 12 pairs of crystal dehydrations of centrifuge separator, obtain the manganous nitrate crystal, adopt 13 pairs of manganous nitrates of lyophilizer to carry out under 0 ℃～10 ℃ the condition can obtaining the product manganous nitrate in dry two hours.
Claims (10)
1. produce the method for manganese nitrate solution with oxides of nitrogen gas leaching pyrolusite for one kind, it is characterized in that mainly comprising following processing step:
(1) in the ore pulp dispensing containers, with powder pyrolusite, water or/and tailings washings, metal chelator are mixed with the solid-liquid mass ratio is 1: the ore pulp of (1～5), wherein the metal chelator mass content is 0.1%～1% of a pyrolusite mass content;
(2) pyrolusite pulp and the oxides of nitrogen gas that prepare are sent into absorption reactor thermally constantly, oxides of nitrogen gas directly contacts with ore pulp and carries out absorption reaction, generation contains the absorption tail washings of manganous nitrate, behind abundant absorption reaction, gas back up to standard discharging, the absorption reaction tail washings enters next process, and absorption reaction is operated under malleation 5000～10000Pa, and the flow of ore pulp is determined according to the oxides of nitrogen gas flow Manganse Dioxide stoichiometric ratio required with it;
(3) absorb tail washings and enter the purification and impurity removal pond, add cleaner and make impurity separate out precipitation, promptly obtain the manganese nitrate solution that will prepare through solid-liquid separation again.
2. according to claim 1ly produce the method for manganese nitrate solution, it is characterized in that oxides of nitrogen gas becomes air bubble-shaped to enter ore pulp through gas distributor with oxides of nitrogen gas leaching pyrolusite.
3. according to claim 2ly produce the method for manganese nitrate solution, it is characterized in that described absorption reactor thermally is the absorption reactor thermally that is provided with mechanical stirring device and jet blistering device with oxides of nitrogen gas leaching pyrolusite.
4. according to claim 3ly produce the method for manganese nitrate solution, it is characterized in that being not less than 5kW/m at the power of agitator of absorption reactor thermally mechanical stirring device with oxides of nitrogen gas leaching pyrolusite
3Ore pulp.
5. describedly produce the method for manganese nitrate solution according to claim 1 or 2 or 3 or 4, it is characterized in that described oxides of nitrogen gas is to contain nitrogen protoxide or/and the gas of nitrogen peroxide with oxides of nitrogen gas leaching pyrolusite.
6. describedly produce the method for manganese nitrate solution according to claim 1 or 2 or 3 or 4, it is characterized in that the powder of powder pyrolusite is not more than 100 orders with oxides of nitrogen gas leaching pyrolusite.
7. according to claim 1 or 2 or the 3 or 4 described methods of producing manganese nitrate solution with oxides of nitrogen gas leaching pyrolusite, it is characterized in that described metal chelator for sequestering action taking place with polyvalent metal ion in the pyrolusite infusion solution in pH value 0.01～7.5 scope, at least a inorganics that forms more stable water soluble complex is or/and organism.
8. according to claim 7ly produce the method for manganese nitrate solution, it is characterized in that described metal chelator is selected from poly-phosphate, poly carboxylic acid, hydroxycarboxylic acid and EDTA with oxides of nitrogen gas leaching pyrolusite.
9. according to claim 5ly produce the method for manganese nitrate solution, it is characterized in that described metal chelator is selected from poly-phosphate, poly carboxylic acid, hydroxycarboxylic acid and EDTA with oxides of nitrogen gas leaching pyrolusite.
10. according to claim 6ly produce the method for manganese nitrate solution, it is characterized in that described metal chelator is selected from poly-phosphate, poly carboxylic acid, hydroxycarboxylic acid and EDTA with oxides of nitrogen gas leaching pyrolusite.
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| CN 201010517663 CN101982419A (en) | 2010-10-25 | 2010-10-25 | Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite |
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| CN 201010517663 CN101982419A (en) | 2010-10-25 | 2010-10-25 | Method for preparing manganous nitrate solution by utilizing oxynitride gas to leach pyrolusite |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435103A (en) * | 2013-08-15 | 2013-12-11 | 贵州红星发展股份有限公司 | High-purity manganous nitrate and preparation method thereof |
| CN103754940A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for preparing manganous nitrate solution |
| CN103754942A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for preparing manganous nitrate solution |
| CN110589891A (en) * | 2019-10-22 | 2019-12-20 | 成都市科隆化学品有限公司 | Method for producing high-purity manganese nitrate |
| CN112574047A (en) * | 2020-12-25 | 2021-03-30 | 湖州展望药业有限公司 | Production process of low-lead bulk drug esmolol hydrochloride |
| CN116177608A (en) * | 2023-02-07 | 2023-05-30 | 成都合众新能源科技有限公司 | Battery-grade manganese iron nitrate based on recycling of nitrogen oxides and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574617A (en) * | 2009-06-12 | 2009-11-11 | 四川大学 | Synchronous desulphrization and denitration method of flue gas pyrolusite pulp for reclamation |
-
2010
- 2010-10-25 CN CN 201010517663 patent/CN101982419A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574617A (en) * | 2009-06-12 | 2009-11-11 | 四川大学 | Synchronous desulphrization and denitration method of flue gas pyrolusite pulp for reclamation |
Non-Patent Citations (1)
| Title |
|---|
| 《环境工程》 20030228 朱晓帆等 喷射鼓泡反应器在软锰矿烟气脱硫中的应用 1-10 第21卷, 第1期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435103A (en) * | 2013-08-15 | 2013-12-11 | 贵州红星发展股份有限公司 | High-purity manganous nitrate and preparation method thereof |
| CN103435103B (en) * | 2013-08-15 | 2016-01-20 | 贵州红星发展股份有限公司 | High pure nitric acid manganese and preparation method thereof |
| CN103754940A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for preparing manganous nitrate solution |
| CN103754942A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for preparing manganous nitrate solution |
| CN110589891A (en) * | 2019-10-22 | 2019-12-20 | 成都市科隆化学品有限公司 | Method for producing high-purity manganese nitrate |
| CN112574047A (en) * | 2020-12-25 | 2021-03-30 | 湖州展望药业有限公司 | Production process of low-lead bulk drug esmolol hydrochloride |
| CN116177608A (en) * | 2023-02-07 | 2023-05-30 | 成都合众新能源科技有限公司 | Battery-grade manganese iron nitrate based on recycling of nitrogen oxides and preparation method thereof |
| CN116177608B (en) * | 2023-02-07 | 2023-12-12 | 成都合众新能源科技有限公司 | Battery-grade manganese iron nitrate based on recycling of nitrogen oxides and preparation method thereof |
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Application publication date: 20110302 |