CN101886168B - Extraction technology of semi-manganese oxide ore - Google Patents
Extraction technology of semi-manganese oxide ore Download PDFInfo
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- CN101886168B CN101886168B CN2010102262265A CN201010226226A CN101886168B CN 101886168 B CN101886168 B CN 101886168B CN 2010102262265 A CN2010102262265 A CN 2010102262265A CN 201010226226 A CN201010226226 A CN 201010226226A CN 101886168 B CN101886168 B CN 101886168B
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Abstract
The invention provides a new method for extracting a semi-manganese oxide ore to prepare a manganese sulfate solution, belonging to the technical field of manganese ore extraction. The method comprises the following steps: crushing the semi-manganese oxide ore; adding cassava alcohol waste water in a reactor, then adding the semi-manganese oxide ore and sulfuric acid, and adjusting the ore pulp liquid-to-solid ratio to be 3:1-5:1 with water; and stirring at 70-98 DEG C for reaction for 1-6h to obtain the reaction lixivium, wherein the leaching rate of manganese is more than 90%. In the invention, the trade waste, i.e. cassava alcohol waste water is taken as a reducing agent, so that the method changes waste into treasures, has double benefits of environmental protection and economy, and has mild process condition and simple edulcoration process.
Description
Technical field:
The present invention relates to a kind of extract technology of semi-manganese oxide ore, particularly in sulfuric acid medium, make the method that reductive agent leaches semi-manganese oxide ore with cassava alcohol waste water.
Background technology:
Cassava has that output is big, starch content is high, and drought-enduring, impoverishment tolerant, characteristics such as plantation saving of labor, less investment, and China's alcohol output 1/3 is a raw material production with the cassava.Cassava alcohol waste water is to utilize cassava mash after fermenting to distill out alcohol at primary tower, the waste water that after filtering out vinasse, discharges.Every production 1t cassava alcohol produces 7～15t waste water approximately, and such waste water contains a large amount of organism and suspended substance, and is acid, belongs to high-concentration acid organic wastewater.If this waste water is not added processing and directly enters water body, will cause very serious pollution to environment.The pollution and the recycling that solve waste liquid are problems anxious to be solved.In pollution treatment, recycle the useful component in the waste water, turn waste into wealth, increase economic benefit, be the development trend of wastewater comprehensive treatment.
Semi-manganese oxide ore is rhodochrosite (MnCO
3) part is oxidized to Manganse Dioxide (MnO
2) mineral, be present in a large number in the transition ore bed of pyrolusite and rhodochrosite.MnCO
3Can directly leach with sulphuric acid soln, and MnO
2Be insoluble to sulfuric acid.Therefore, the manganese leaching yield of the direct acidleach of semi-manganese oxide ore is lower.In leaching process, add reductive agent, can be through redox reaction MnO
2Be reduced into Mn
2+And leached Mn
2+Combine to generate manganous sulfate with sulfuric acid.Manganous sulfate is the main raw material of manganese products such as preparation industrial manganic sulfate, manganous carbonate, Manganse Dioxide, trimanganese tetroxide and electrolytic manganese.
In order to obtain a kind of reductive agent preferably, people have found out many methods, have reported some relevant documents like open source literature, and we take passages as follows through retrieval:
1. the novel process of [application (patent) number] CN91102845.5 [title] wet producing manganese sulfate from two kinds of mine [application (patent right) people] No. 44 [summary] these methods in guest road, lake, Huangshi, Huangshi Power Source Comprehensive Scientific and Technical Inst. [address] 435000 Hubei Province with poor, bad, give up contain MnO
2Manganese ore powder and troilite powder add sulphuric acid soln, generate manganese sulfate solution after the reacting by heating, remove the iron ion in the solution with feeding compressed-air actuated method again.
2. [application (patent) number] CN87102046 [title] is reductive agent with the sulfurous iron ore with method [applying for (patent right) people] this method of cypress village, Guiyang County outskirts of a town township, Electrolytic Manganese Factory, Guiyang County [address] Hunan Province [summary] of producing manganous sulphate solution from manganese dioxide ore; Directly soak fine-graded dioxide ore for manganese with sulphuric acid soln, its reaction formula is: FeS
2+ MnO
2+ 2H
2SO
4=MnSO
4+ FeSO
4+ 2H
2O+2S, when temperature of reaction is 85～100 ℃, in 2～4 hours reaction times, reaction end pH value is 6.8～7 o'clock, the leaching rate of Manganse Dioxide is greater than 90%.
3. the Chinese manganese industry of [autograph] hydrocarbon polymer wet processing manganese-silver ore applied research [author] surplus beautiful show of Sun Yaguang [mechanism] Zhengzhou mineral products comprehensive utilizating research institute [periodical name] .2004; 22 (1): 1-14 [digest] has studied hydrocarbon polymer and has soaked manganese-cyaniding silver leaching process principle, condition and application; Utilize hydrocarbon polymer and Manganse Dioxide reactions such as starch, sucrose; When control manganese leaching yield 96%, leaching rate of loss＜2% of silver; Soak the manganese slag and adopt the cyanide process desilver, when NaCN consumption 1kg/t slag, extraction time 3h, silver leaching rate 94.15%; Soak two steps of manganese-cyaniding and leach the silver-colored recovery greater than 92.27%.
4. the working method of [application (patent) number] a kind of manganous sulfate of CN89105118.X [title] [application (patent right) people] Shujiatun District chemical industry technical service station, Chemical Technique Service Centre of Sujiatun District Shenyang City [address] ShenYang, Liaoning Province city [summary] employing manganese content is put into reaction tank after mixing greater than 8% manganese ore and rice skin; Add dilute sulphuric acid, carry out thermopositive reaction at normal temperatures.Each raw material proportioning by weight is: 15～20 parts of manganese ores, 2～3 parts of rice skins, 20～30 parts of dilute sulphuric acids.When pH value of reactants equals 5, take out with manganese sulfate solution and isolate unreacted intact ore and mud.Filter cake after mud filters with filter, adverse current is drained after repeatedly washing, and the high dope that provides is processed through deironing, evaporation, crystallization, drying, crushing packing.
5. [autograph] chaff-sulfuric acid directly soaks flat Song of preparation of manganese condition research [author] Yang Ming and pays chemical institute of Li Guobin [mechanism] University Of Science and Technology Of Hunan [periodical name] inorganic chemicals industry; 2005; 02 [digest] is raw material with rice bran and western Hunan pyrolusite, rice bran-sulfuric acid directly soaked the processing condition that manganese prepares manganous sulfate study.The result shows that the optimum process condition that rice bran-sulfuric acid process is soaked manganese is: soak 250 ℃ of manganese temperature, sulfuric acid massfraction 50% soaks manganese time 75min, and the rice bran consumption is 20% of a pyrolusite powder quality, and the sulfuric acid consumption is 110% of its theoretical consumption.Soak manganese by these processing condition, the leaching yield of manganese can reach more than 95%.
What 6. [autograph] pure plant powder-sulfuric acid process directly leached pyrolusite puts into practice chemical institute of flat Huang Kelong [mechanism] Central South University of [author] poplar children [periodical name] Chinese Mining Industry; 2001,10 (5): 54-56 [digest] has studied with pure plant powder-vitriol oil method and has directly leached the new process of pyrolusite.Test-results shows: the leaching yield of manganese receives the influence of factors such as pyrolusite consumption, pure plant powder consumption, vitriol oil consumption, extraction temperature and extraction time in the pyrolusite.This method is under preferable processing condition, and the leaching yield of manganese can reach more than 95%.Directly leach in the new process of pyrolusite at pure plant powder-sulfuric acid; The leaching yield of manganese receives having the greatest impact of vitriol oil consumption in the pyrolusite, and its optimum process condition is: sour ore deposit ratio is that 2～3: 1 (mL: g), pyrolusite/pure plant powder ratio is 2.0～3.3: 1; Liquid-solid ratio is 3: 1; Extraction temperature is 90～95 ℃, and extraction time is 3h, and the leaching yield of manganese can reach more than 95% in the pyrolusite at this moment.
7. technical study [author] the grain Hai Fengli of [autograph] sulfuric acid-molasses alcohol waste liquid leaching manganese ore restrains chemical institutes of [mechanism] Guangxi University such as pure Wen Yanxuan [periodical name] colleges and universities' chemical engineering journal; 2008; 22 (5): it is reductive agent that 779-783 [digest] adopts molasses alcohol waste liquid, has studied the novel process that in sulfuric acid medium, directly leaches Mn in the manganese ore.The factors such as molasses alcohol waste liquid consumption, sulfuric acid concentration, temperature of reaction, extraction time and manganese ore globule size of having investigated are to Mn, the influence of Fe and Al leaching yield.Be 2.2mL/g, H at molasses alcohol waste liquid and manganese ore ratio
2SO
4Concentration 2.35mol/L, 90 ℃, 120min, the manganese ore granularity is＜condition of 0.147mm under, the leaching yield of Mn reaches 94.9%.
Recognize from above-mentioned result for retrieval, the open source literature introduction mainly be: 1. and 2. document is to use wet producing manganese sulfate from two kinds of mine, and production technology is ripe, and production cost is lower.But exist the quantity of slag big aborning, it is many to bring impurity into, the problem of filtering and impurity removing difficulty.3. document uses hydrocarbon polymers such as starch, sucrose to make reductive agent, because of hydrocarbon polymers such as starch, sucrose do not contain inorganics basically, so it is few to bring impurity into, and the more purified manganese sulfate solution of easy acquisition.But, can cause the rising of production cost because of hydrocarbon polymer prices such as starch, sucrose are high.4., 5. and 6. document uses pure plant powder to make reductive agent, and its advantage is to utilize local various pure plant powder resource, and reductive agent is cheap and easy to get.But there is pure plant powder hydrolysis saccharogenesis difficulty, needs higher temperature of reaction to reach the more problem of polyacid.7. document uses molasses alcohol waste liquid to make reductive agent, and its advantage is to utilize trade waste, turns waste into wealth, and has environmental protection and economic double benefit.But, can increase product removal of impurities and cost for wastewater treatment because pigment concentration is bigger in the molasses alcohol waste liquid.
In sum, at present the reductive agent that adopted of wet reducing extract technology is desirable not enough.
Summary of the invention:
The purpose of this invention is to provide the extract technology of semi-manganese oxide ore that a kind of raw material sources are easy, cheap, manufacturing requirements is lower; It is characterized in that utilizing cassava alcohol waste water to make reductive agent, the leaching semi-manganese oxide ore prepares the method for manganese sulfate solution in sulfuric acid medium.
Above-mentioned said cassava alcohol waste water is to utilize grain distillery cassava mash behind biochemical fermentation to distill out alcohol at primary tower, the waste water that after filtering out vinasse, discharges.This waste water COD concentration is high, contains a large amount of organic cpds and suspended substance, is mainly starch biochemical degradation product, robust fibre, protein, organic acid, pigment, VITAMINs etc., is acid, belongs to high-concentration acid organic wastewater.Contain in the waste water: COD 2 * 10
4～6 * 10
4Mg/L, BOD
51 * 10
4～2 * 10
4Materials such as mg/L.
Above-mentioned said semi-manganese oxide ore is meant rhodochrosite (MnCO
3) part is oxidized to Manganse Dioxide (MnO
2) mineral, total Mn content is greater than 12%, wherein MnO
2Content greater than 8%.
The present invention realizes like this; Semi-manganese oxide ore was crushed to 60～400 mesh sieves; The cassava alcohol waste water that in reactor drum, adds 2.0～3.5 times of semi-manganese oxide ore quality; Add semi-manganese oxide ore, add 0.8～1.5 times of concentration of semi-manganese oxide ore quality then and be 93～98% sulfuric acid, it is 3: 1～5: 1 that water modulation ore pulp causes liquid-solid ratio; Stirring reaction obtained reacting leach liquor in 1～6 hour under 70～98 ℃ of temperature; It is 5.0～6.0 that the reaction leach liquor uses lime or Wingdale to be neutralized to the pH value, removes impurity such as heavy metal ion and calcium in the solution, magnesium, silicon then through the method for known chemical subtraction.Filtration obtains the purified manganese sulfate solution, and the leaching yield of manganese is greater than 90%.
The present invention compares with existing manganese ore leaching-out technique, and its outstanding substantive distinguishing features and obvious improvement is:
(1) employed reductive agent cassava alcohol waste water is a kind of trade effluent of need handling, the useful component in this technology utilization waste water, under acidic conditions with MnO
2Reduction is leached.Simultaneously, the complicated organic macromolecule in the waste water is converted into simple small molecules, has reduced the COD value of waste water effectively, and improves the biodegradability of waste water, has environmental protection and economic double benefit.
(2) compare as reductive agent with adopting pure plant powder, reaction conditions is gentle, and speed of response is fast, and leaching process waste residue amount is few, filters easily, and the yield of Mn can improve more than 10%.
(3) compare as reductive agent with adopting molasses alcohol waste liquid, pigment concentration is low in the cassava alcohol waste water, and the purification of follow-up leach liquor is simplified greatly, and quality product is easy to guarantee.
Embodiment:
Embodiment 1
Semi-manganese oxide ore was crushed to 100 mesh sieves (forming as shown in table 1); The cassava alcohol waste water (forming as shown in table 2) that in reactor drum, adds 2.5 times of semi-manganese oxide ore quality; Add semi-manganese oxide ore; Add 1.1 times of concentration of semi-manganese oxide ore quality then and be 98% sulfuric acid, it is 4: 1 that water modulation ore pulp causes liquid-solid ratio; Stirring reaction obtained reacting leach liquor in 3 hours under 95 ℃ of temperature, and the Mn leaching yield of semi-manganese oxide ore reaches 95%.
The composition analysis of table 1 semi-manganese oxide ore
| Composition | Total Mn | MnCO 3 | MnO 2 | Fe | SiO 2 | Al 2O 3 | CaO | MgO | S | P |
| Content (%) | 18.37 | 18.40 | 14.52 | 8.41 | 24.48 | 5.23 | 4.36 | 1.39 | 0.01 | 0.05 |
Table 2 cassava alcohol waste water composition
| Composition | COD | BOD 5 | SS | TN | TP | pH |
| Content (mg/L) | 35650 | 13270 | 23910 | 648 | 134 | 4.2 |
Embodiment 2
Semi-manganese oxide ore was crushed to 200 mesh sieves (forming as shown in table 1); The cassava alcohol waste water (forming as shown in table 2) that in reactor drum, adds 1.5 times of semi-manganese oxide ore quality; Add semi-manganese oxide ore; Add 1.5 times of concentration of semi-manganese oxide ore quality then and be 93% sulfuric acid, it is 3: 1 that water modulation ore pulp causes liquid-solid ratio; Stirring reaction obtained reacting leach liquor in 1 hour under 90 ℃ of temperature, and the Mn leaching yield of semi-manganese oxide ore reaches 91%.
Embodiment 3
Semi-manganese oxide ore was crushed to 400 mesh sieves (forming as shown in table 1); The cassava alcohol waste water (forming as shown in table 2) that in reactor drum, adds 2.5 times of semi-manganese oxide ore quality; Add semi-manganese oxide ore; Add 1.2 times of concentration of semi-manganese oxide ore quality then and be 98% sulfuric acid, it is 4: 1 that water modulation ore pulp causes liquid-solid ratio; Stirring reaction obtained reacting leach liquor in 6 hours under 70 ℃ of temperature, and the Mn leaching yield of semi-manganese oxide ore reaches 92%.
Embodiment 4
Semi-manganese oxide ore was crushed to 60 mesh sieves (forming as shown in table 1); The cassava alcohol waste water (forming as shown in table 2) that in reactor drum, adds 3.5 times of semi-manganese oxide ore quality; Add semi-manganese oxide ore; Add 0.8 times of concentration of semi-manganese oxide ore quality then and be 98% sulfuric acid, it is 5: 1 that water modulation ore pulp causes liquid-solid ratio; Stirring reaction obtained reacting leach liquor in 3 hours under 98 ℃ of temperature, and the Mn leaching yield of semi-manganese oxide ore reaches 90%.
Claims (1)
1. extract technology of semi-manganese oxide ore; It is characterized in that making reductive agent with 2.0～3.5 times cassava alcohol waste water of semi-manganese oxide ore quality; 0.8～1.5 times of concentration of use semi-manganese oxide ore quality is 98% sulfuric acid; Under 70～98 ℃ of temperature, leach semi-manganese oxide ore, stirring reaction obtained manganese sulfate solution in 1～6 hour; Said cassava alcohol waste water is to utilize grain distillery cassava mash behind biochemical fermentation to distill out alcohol at primary tower, and through filtering out the waste water that discharges behind the vinasse slag, be to contain: COD 2 * 10
4～6 * 10
4Mg/L, BOD
51 * 10
4～2 * 10
4The material of mg/L is mainly starch biochemical degradation product, robust fibre, protein, organic acid, pigment, VITAMINs, is acid.
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|---|---|---|---|
| CN2010102262265A CN101886168B (en) | 2010-07-14 | 2010-07-14 | Extraction technology of semi-manganese oxide ore |
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| CN101886168B true CN101886168B (en) | 2012-05-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757250A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757222B (en) * | 2013-12-29 | 2016-02-24 | 四川师范大学 | The leaching method of pyrolusite |
| CN103757248A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching manganese carbonate ore |
| CN103789542B (en) * | 2014-01-20 | 2015-10-07 | 中南大学 | A kind of wet reducing leaching method of manganese oxide mineral |
| CN103937999B (en) * | 2014-04-23 | 2015-09-23 | 北京科技大学 | A kind of vacuum distilling ferromanganese extracts method and the device of manganese metal |
| CN104131182A (en) * | 2014-07-28 | 2014-11-05 | 东北大学 | Reduction leaching method for separating manganese and silver in manganese silver concentrate |
| CN104962761A (en) * | 2015-07-14 | 2015-10-07 | 广西大学 | Method for resource utilization of watermelon peel |
| CN104962760A (en) * | 2015-07-14 | 2015-10-07 | 广西大学 | Method for resource utilization of banana peel |
| CN104962745A (en) * | 2015-07-14 | 2015-10-07 | 广西大学 | Method for resource utilization of banana stem and leaf and electrolytic manganese anode slime |
| CN104962734A (en) * | 2015-07-14 | 2015-10-07 | 广西大学 | Method for resource utilization of pineapple peel and electrolytic manganese anode slime |
| CN108251663A (en) * | 2017-12-05 | 2018-07-06 | 中信大锰矿业有限责任公司大新锰矿分公司 | Utilize the method for tapioca reducing leaching manganese oxide ore |
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| CN100451139C (en) * | 2006-09-21 | 2009-01-14 | 广西大学 | Gray manganese ore leaching out process |
| CN101439878A (en) * | 2008-12-26 | 2009-05-27 | 桂林市孟泰矿产技术开发有限责任公司 | Method for preparing manganese sulfate by biomass self-heating reduction of low grade manganese oxide ore |
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