CN105331800A - Reducing roasting process for low-grade high-iron manganese ore - Google Patents
Reducing roasting process for low-grade high-iron manganese ore Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The invention discloses a reducing roasting process for low-grade high-iron manganese ore and relates to the technical field of reduction production of iron manganese ore. The reducing roasting process comprises the following steps of (1) crushing of raw materials, (2) burdening, (3) feeding of the raw materials into a kiln, (4) high-temperature reduction, (5) discharging and (6) cooling. The reducing roasting process has the characteristics of being good in production continuity, high in reduction rate, low in energy consumption, little in pollution, capable of reducing MnO2 in the low-grade high-iron manganese ore into MnO and Fe2O3 into Fe3O4, and the like; the low-grade high-iron manganese ore can be directly used as an ore source and is reduced into raw materials for preparing manganese sulfate, electrolytic manganese dioxide and electrolytic manganese through the large rotary kiln, and iron contained in the low-grade high-iron manganese ore is recycled through magnetic separation of leaching residues.
Description
Technical field
The present invention relates to Ferromanganese Ore reduction production technical field, particularly a kind of low-grade ferric manganese ore reducing roasting technique.
Background technology
The manganese ore of China is main mainly with lean ore, mainly exists with manganous carbonate and manganese oxide form, and manganese oxide in manganese oxide ore and ferric oxide symbiosis, and iron level is high, belongs to low-grade ferric manganese ore, is mainly used in blast fumance Mn-rich slag, the pig iron.At present, domesticly in low-grade ferric manganese ore comprehensive development and utilization, be still in the lower development phase, exist the rate of recovery low, pollute large, high in cost of production weak point.Using the low-grade ferrous manganese ore containing manganese 15 ~ 25%, iron 10 ~ 20% as mineral resources, produce manganous sulfate, electrolytic metal Mn, electrolytic manganese dioxide there is no large-scale industrial production.
The requirement of the new technology of R&D and promotion (accelerating reducing process technology and equipment that research and development take low-grade manganese dioxide ore as raw material) is encouraged according to Chinese Ministry of Environmental Protection's " electrolytic manganese industry pollution prevention technique policy ", scientific research institutions and manufacturing enterprise propose various solution, wherein rotary kiln low-grade ferrous manganese ore reducing roasting technique thinks one of most proven technique, and early have report, but because former technique exists investment, iron leaching yield in sulphuric acid soln of ring formation, roasted ore is high greatly, easily, the defects such as deironing difficulty, are difficult to be applied on a large scale.
Chinese patent (application number is 201310129267.6) disclosed " production method of electrolytic manganese dioxide ", comprises the steps: that its top feed mouth being transported to the reduction furnace vertically placed after a) manganese oxide powder and coal mixing being dried from up to down moves; B) by coal gas through being arranged on the heating agent gas burner spray combustion below reduction furnace, burning produce high-temperature flue gas in the furnace chamber of reduction furnace, rotate rising; C) the high temperature manganese monoxide after reduction by after cooling through drawing mechanism discharging, obtained manganese monoxide mineral powder; D) manganese monoxide mineral powder and sulfuric acid are carried out leaching combination reaction, obtain rough manganese sulfate solution through solid-liquid separation; E) purification and impurity removal is carried out to described rough manganese sulfate solution, after the manganese sulfate solution after purification is injected electrolyzer electrolysis, obtain electrolytic manganese dioxide product.Another Chinese patent (application number is 201410503359.0) disclosed " utilizing discarded Manganse Dioxide to produce the method for manganese monoxide ", for raw material with low-grade manganese dioxide powder and popular smokeless coal dust, through utilizing, waste heat exchanges pre-heat extraction moisture, the induction of intermediate frequency magnetic wave is tentatively rapidly heated roasting successively, hot water radiation wire zone heating roasting reduction, insulation continuity reduction, waste heat close exchange cooling, water quick cooling cooling, after discharging enters storage bin step, obtained energy-efficient cheap manganese monoxide roasting powder; The method and low-grade, low cost Manganse Dioxide, as raw materials for production, achieve the recycling of discarded Manganse Dioxide.Also has Chinese patent (application number is 200910060533.8) disclosed " a kind of fluidized reduction method of powdery manganese dioxide ore ", it comprises the steps: 1) granularity is less than the first preheating of powdery manganese dioxide ore of 1.0mm, then suspended state, temperature be 750-950 DEG C, reducing atmosphere, solid-gas ratio be 0.6-1.0KG/NM
3react 5-10 second under condition, obtain calcining matter; Described reducing atmosphere is containing CO, the volume content 4.5-6.5% of CO in gas in gas; 2) by calcining matter through low intensity magnetic separation, separating ferrum concentrate byproduct, obtains manganese monoxide also original product.
Summary of the invention
The object of the present invention is to provide and a kind ofly Manganse Dioxide in low-grade ferric manganese ore can be reduced into MnO, ferric oxide is reduced into Fe
3o
4sinter process, and there is the features such as continuous production is good, reduction ratio is high, energy consumption is low, pollution is few.
For achieving the above object, the technical measures that the present invention takes are a kind of low-grade ferric manganese ore reducing roasting technique of invention, and it is as follows in technological process:
(1), raw material pulverizing: low-grade ferric manganese ore and bituminous coal are ground into respectively the particulate being less than 5mm He being less than 3mm;
(2), prepare burden: low-grade ferric manganese ore particulate and bituminous coal particulate are mixed according to the part by weight of 1:0.06-0.1, becomes into kiln material;
(3), enter kiln: kiln material will be entered and send in revolution roasting kiln by lock wind discharge valve from kiln tail; Enter the exhaust gas flow direction of kiln material backheating in revolution roasting kiln and move, from kiln Caudad kiln hood direction successively by drying zone and drying zone, entering into the high temperature reduction district formed by coal gas segmentation anoxycausis in kiln;
(4), high temperature reduction: in high temperature reduction district, enter the MnO in kiln material
2and Fe
2o
3there is reduction reaction with the C in bituminous coal and the CO in coal gas respectively, generate MnO and Fe
3o
4;
In high temperature reduction process, the temperature in high temperature reduction district controls at 620-780 DEG C, and roasting time controls at 50-60 minute, and the oxygen concentration in tail gas controls at 0.6-1%, and kiln hood pressure-controlling is at the pressure-fired of 5-15Pa;
, discharging: the material after roasting, continue to kiln hood direction motion, enter cooling kiln at kiln hood by dumping device;
(6), cooling: enter the material in cooling kiln, under the environment of isolated air, moved by cooling kiln kiln Caudad cooling kiln kiln hood, be cooled to gradually, within 100 DEG C, become containing MnO and Fe
3o
4roasting material, drawn off by cooling kiln kiln hood.
Enter kiln step (3) described in coal gas can be the purification coal gas that gas station provides, also can be the hot addle coal gas prepared by gas furnace, described coal gas is incorporated in high temperature reduction district by kiln hood gas burner incomplete combustion, mainly provides thermal source and build reducing atmosphere.
Enter kiln step (3) described in the operational throughput of coal gas regulate according to kiln tail oxygen concentration, when kiln tail oxygen concentration is less than 0.6%, reduces coal gas operational throughput or strengthen into kiln air quantity, in order to avoid cause energy dissipation and atmospheric pollution; When kiln tail oxygen concentration is greater than 1%, increases coal gas operational throughput or reduce into kiln air quantity, keeping causing reducing atmosphere.
High temperature reduction step (4) in, the temperature section in high temperature reduction district controls as follows: the temperature of high temperature reduction district kiln hood section is about 710 DEG C; The temperature of high temperature reduction district interlude controls to be about 780 DEG C, and the temperature of high temperature reduction district initial section is about 620 DEG C.
High temperature reduction district kiln hood section in described high temperature reduction district, high temperature reduction district interlude and high temperature reduction district initial section, be respectively arranged with the combustion-supporting air-blast device of gas burner, middle combustion-supporting air-blast device and the combustion-supporting air-blast device of initial section; Each combustion-supporting air-blast device is the temperature according to Zhong Geduan monitoring point, high temperature reduction district, carries out combustion-supporting air blast, makes coal gas and bituminous coal volatile matter sectional combustion; When the temperature of monitoring point is lower than design temperature, increase combustion-supporting air blast; When the temperature of monitoring point is higher than design temperature, reduce combustion-supporting air blast.
High temperature reduction step (4) described in high temperature reduction process in, roasting time controlled at 55 minutes.
Reduction step (4) described in reduction process in, kiln hood pressure-controlling is at the pressure-fired of 10Pa.
Discharging step (5) described in dumping device be stock column sealing discharge tube.
Cooling step (6) described in cooling kiln be showering cooling kiln.
Above-mentioned containing MnO and Fe
3o
4roasting material in the process of producing manganous sulfate, electrolytic manganese dioxide, electrolytic manganese further, by control leach acid concentration, leach endpoint pH, suppress Fe
3o
4and sulfuric acid reaction, the leaching yield of iron can be reduced.Its filter residue again through magnetic separation, recyclable iron wherein.
Low-grade ferric manganese ore reducing roasting technique of the present invention, owing to being provided with multiple combustion-supporting air-blast device on roasting kiln, by coal gas segmentation and anoxycausis, extend firing section, make the temperature of high-temperature zone in kiln more even, there will not be the phenomenon that regional area is too high, and then ring formation phenomenon in kiln can be avoided to occur; Meanwhile, by combustion-supporting air blast, control the reduction temperature of high-temperature zone, iron protoxide can be reduced generate while the reduction ratio improving manganese; In addition, also controlled the operational throughput of coal gas by monitoring kiln tail oxygen concentration, and then control the reducing atmosphere of manganese, iron, improve the reduction ratio of manganese.
Low-grade ferric manganese ore reducing roasting technique of the present invention, by large-sized rotary kiln production test more than a year, continuous production is good, without ring formation in kiln, production capacity is large, and manganese reduction ratio is greater than 93%, iron leaching yield is less than 10%, ton ore deposit reduction coal consumption 75Kg, gasification coal consumption 50Kg, change mark coal 110Kg into, power consumption 10 KWhs/ton of ore deposits, than domestic at Wiring technology at present, energy efficient more than 30%.This technique is arranged outward without waste water, and waste gas is through dedusting, desulfurization qualified discharge, and environmental pollution is little.
The product that application the present invention produces; when producing manganous sulfate, electrolytic manganese dioxide, electrolytic manganese; by suitable adjustment production technique, there is not deironing difficulty situation phenomenon, to the comprehensive utilization of low-grade ferric manganese ore, reduce energy consumption and environment protection plays a good role.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.Explanation is below the mode exemplified, but protection scope of the present invention is not limited thereto.
One of the present invention low-grade ferric manganese ore reducing roasting technique, it is as follows in technological process:
(1), raw material pulverizing: the particulate low-grade ferric manganese ore (containing manganese 15 ~ 25%, iron 10 ~ 20%) and bituminous coal (volatile matter 30%, ash content 12%, sulphur 0.6%) being ground into respectively 1-3mm and 1-2mm;
(2), prepare burden: low-grade ferric manganese ore particulate and bituminous coal particulate are mixed according to the part by weight of 1:0.075, becomes into kiln material;
(3), enter kiln: kiln material will be entered and send in revolution roasting kiln by lock wind discharge valve from kiln tail; Enter the exhaust gas flow direction of kiln material backheating in revolution roasting kiln and move, from kiln Caudad kiln hood direction successively by drying zone and drying zone, entering into the high temperature reduction district formed by coal gas segmentation anoxycausis in kiln;
Coal gas used is the water-gas prepared by gas furnace, is to be incorporated in high temperature reduction district by kiln hood gas burner incomplete combustion, mainly provides thermal source and builds reducing atmosphere.
The operational throughput of coal gas regulates according to kiln tail oxygen concentration, when kiln tail oxygen concentration is less than 0.6%, reduces coal gas operational throughput or strengthens into kiln air quantity, in order to avoid cause energy dissipation and atmospheric pollution; When kiln tail oxygen concentration is greater than 1%, increases coal gas operational throughput or reduce into kiln air quantity, keeping causing reducing atmosphere;
(4), high temperature reduction: in high temperature reduction district, enter the MnO in kiln material
2and Fe
2o
3there is reduction reaction with the C in bituminous coal and the CO in coal gas respectively, generate MnO and Fe
3o
4, its chemical reaction is as follows:
MnO
2+C＝MnO+CO
MnO
2+CO＝MnO+CO
2
3Fe
2O
3+C＝2Fe
3O
4+CO
3Fe
2O
3+CO＝2Fe
3O
4+CO
2；
High temperature reduction zoning is divided into three sections (about 10 meters is one section), that is: high temperature reduction district kiln hood section, high temperature reduction district interlude and high temperature reduction district initial section, and be respectively arranged with the combustion-supporting air-blast device of gas burner (being arranged on burner place), middle combustion-supporting air-blast device and initial combustion-supporting air-blast device (each combustion-supporting air-blast device is mainly used in extending firing section, avoids localized hyperthermia);
In high temperature reduction process, the temperature section in high temperature reduction district controls as follows:
In high temperature reduction district kiln hood section, the air that coal gas and the combustion-supporting air-blast device of gas burner provide is carried out anoxycausis and (that is: controls the input of air by burner, make its incomplete combustion, the remaining coal gas of institute is supplied to the interlude burning of high temperature reduction district), form the temperature (that is: the temperature of high temperature reduction district kiln hood section exit point) of 710 DEG C;
At high temperature reduction district interlude, the air blast that after being burnt by high temperature reduction district kiln hood section, more than institute, the part in coal gas and the combustion-supporting air-blast device of a part and centre in bituminous coal volatile matter provide again is carried out anoxycausis and (that is: is controlled blast volume, make its incomplete combustion, the remaining coal gas of institute and bituminous coal volatile matter continue to be supplied to the initial section burning of high temperature reduction district), form the temperature (that is: apart from the temperature at kiln hood 10 meters of, high temperature reduction district) of 780 DEG C;
In high temperature reduction district initial section, remaining coal gas and bituminous coal volatile matter again burn with the air blast that initial combustion-supporting air-blast device provides, form the temperature (that is: the temperature at distance kiln hood 20 meters of, high temperature reduction district) of 620 DEG C.
The control method of each section of temperature is as follows: the high temperature reduction district kiln hood section in high temperature reduction district, high temperature reduction district interlude and high temperature reduction district initial section be mounting temperature sensor respectively, each group of combustion-supporting air-blast device, according to the temperature of each section of temperature sensor monitors in high temperature reduction district, carries out combustion-supporting air blast; When the temperature of monitoring point is lower than design temperature, increase combustion-supporting air blast; When the temperature of monitoring point is higher than design temperature, reduce combustion-supporting air blast (above-mentioned all air-blast devices are by frequency conversion switch-mode regulation air force).
Specifically, when the temperature of high temperature reduction district kiln hood section is lower than 710 DEG C, then strengthen gas burner combustion air volume (that is: the combustion-supporting air-blast device of gas burner increases blast volume), make the many burnings of coal gas some, to improve temperature; When the temperature of high temperature reduction district kiln hood section is higher than 710 DEG C, then reduces the combustion-supporting blast volume of gas burner (that is: the combustion-supporting air-blast device of gas burner reduces blast volume), coal gas is burnt less, to reduce temperature;
When the temperature of high temperature reduction district interlude is lower than 780 DEG C, then strengthen blast volume by the combustion-supporting air-blast device in centre, make the many burnings of unburn coal gas some, to improve temperature (if temperature still can not improve, then strengthening coal gas operational throughput); When the temperature of high temperature reduction district interlude is higher than 780 DEG C, then the blast volume (if temperature still can not reduce, then reducing coal gas operational throughput) of combustion-supporting air-blast device in the middle of reducing, to reduce temperature;
When the temperature of high temperature reduction district initial section is lower than 620 DEG C, then strengthens blast volume by initial combustion-supporting air-blast device, make coal gas Thorough combustion, to improve temperature (if temperature still can not improve, then strengthening coal gas operational throughput); When the temperature of high temperature reduction district initial section is higher than 620 DEG C, then reduces the blast volume (if temperature still can not reduce, then reducing coal gas operational throughput) of initial combustion-supporting air-blast device, gas-fired amount is reduced, to reduce temperature.
In whole reduction process, roasting time (that is: temperature is this section of 620-780 DEG C) controls at 55 minutes, and the oxygen concentration in tail gas controls 0.8%, and kiln hood pressure-controlling is at the pressure-fired of 10Pa, avoid kiln outer air to enter, prevent material to be oxidized once again;
(5), discharging: the material after roasting, continue to move to kiln hood direction, seal discharge tube (that is: utilize the material stored in discharge tube to form sealing, and automatically open discharging by the gravity of material) at kiln hood by stock column and enter showering cooling kiln kiln tail;
(6), cool: enter the material in cooling kiln, under the environment of isolated air (avoiding the material reduced to be oxidized once again), moved by cooling kiln kiln Caudad cooling kiln kiln hood, the appearance of cooling kiln adopts showering cooling, the material in cooling kiln is allowed to be cooled to gradually, within 100 DEG C, become containing MnO and Fe
3o
4roasting material, drawn off by cooling kiln kiln hood.
Low-grade ferrous manganese ore reducing roasting technique of the present invention, can directly using low-grade ferric manganese ore as mineral resources, large-sized rotary kiln is utilized to be reduced into raw material as preparing manganous sulfate, electrolytic manganese dioxide, electrolytic manganese, and by leaching filter residue magnetic separation, the iron contained by recovery.
Claims (8)
1. a low-grade ferric manganese ore reducing roasting technique, is characterized in that technological process is as follows:
(1), raw material pulverizing: low-grade ferric manganese ore and bituminous coal are ground into respectively the particulate being less than 5mm He being less than 3mm;
(2), prepare burden: low-grade ferric manganese ore particulate and bituminous coal particulate are mixed according to the part by weight of 1:0.06-0.1, becomes into kiln material;
(3), enter kiln: kiln material will be entered and send in revolution roasting kiln by lock wind discharge valve from kiln tail; Enter the exhaust gas flow direction of kiln material backheating in revolution roasting kiln and move, from kiln Caudad kiln hood direction successively by drying zone and drying zone, entering into the high temperature reduction district formed by coal gas sectional combustion in kiln;
(4), high temperature reduction: in high temperature reduction district, enter the MnO in kiln material
2and Fe
2o
3there is reduction reaction with the C in bituminous coal and the CO in coal gas respectively, generate MnO and Fe
3o
4;
In high temperature reduction process, the temperature in high temperature reduction district controls at 620-780 DEG C, and roasting time controls at 50-60 minute, and the oxygen concentration in tail gas controls at 0.6-1%, and kiln hood pressure-controlling is at the pressure-fired of 5-15Pa;
, discharging: the material after roasting, continue to kiln hood direction motion, enter cooling kiln at kiln hood by dumping device;
(6), cooling: enter the material in cooling kiln, under the environment of isolated air, moved by cooling kiln kiln Caudad cooling kiln kiln hood, be cooled to gradually, within 100 DEG C, become containing MnO and Fe
3o
4roasting material, drawn off by cooling kiln kiln hood.
2. low-grade ferric manganese ore reducing roasting technique according to claim 1, it is characterized in that: enter kiln step (3) described in the operational throughput of coal gas regulate according to kiln tail oxygen concentration, when kiln tail oxygen concentration is less than 0.6%, reduces coal gas operational throughput or strengthen into kiln air quantity; When kiln tail oxygen concentration is greater than 1%, increases coal gas operational throughput or reduce into kiln air quantity, to keep causing reducing atmosphere.
3. low-grade ferric manganese ore reducing roasting technique according to claim 1, is characterized in that: high temperature reduction step (4) in, the temperature section in high temperature reduction district controls as follows: the temperature of high temperature reduction district kiln hood section is about 710 DEG C; The temperature of high temperature reduction district interlude controls to be about 780 DEG C, and the temperature of high temperature reduction district initial section is about 620 DEG C.
4. low-grade ferric manganese ore reducing roasting technique according to claim 1, it is characterized in that: the high temperature reduction district kiln hood section in described high temperature reduction district, high temperature reduction district interlude and high temperature reduction district initial section, be respectively arranged with the combustion-supporting air-blast device of gas burner, middle combustion-supporting air-blast device and the combustion-supporting air-blast device of initial section; Each combustion-supporting air-blast device is the temperature according to Zhong Geduan monitoring point, high temperature reduction district, carries out combustion-supporting air blast, makes coal gas and bituminous coal volatile matter sectional combustion; When the temperature of monitoring point is lower than design temperature, increase combustion-supporting air blast; When the temperature of monitoring point is higher than design temperature, reduce combustion-supporting air blast.
5. low-grade ferric manganese ore reducing roasting technique according to claim 4, is characterized in that: high temperature reduction step (4) described in high temperature reduction process in, roasting time controlled at 55 minutes.
6. low-grade ferric manganese ore reducing roasting technique according to claim 1, is characterized in that: reduction step (4) described in reduction process in, kiln hood pressure-controlling is at the pressure-fired of 10Pa.
7. low-grade ferric manganese ore reducing roasting technique according to claim 1, is characterized in that: discharging step (5) described in dumping device be stock column sealing discharge tube.
8. low-grade ferric manganese ore reducing roasting technique according to claim 1, is characterized in that: cooling step (6) described in cooling kiln be showering cooling kiln.
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|---|---|---|---|
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Cited By (5)
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| CN107523684A (en) * | 2017-07-19 | 2017-12-29 | 东北大学 | A kind of suspension roasting ferromanganese method for separating and processing containing Ferromanganese Ore |
| CN107697896A (en) * | 2017-11-28 | 2018-02-16 | 中南大学 | A kind of method that high-purity phosphoric acid iron is prepared using ferric manganese ore as raw material |
| CN108251646A (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 | The method for producing manganese monoxide using activated carbon adsorption slag reduction roasting manganese oxide ore |
| CN111921536A (en) * | 2020-08-12 | 2020-11-13 | 中南大学 | Novel catalytic adsorption material prepared based on natural minerals and biomass |
| CN114908248A (en) * | 2022-06-09 | 2022-08-16 | 沈阳鑫博工业技术股份有限公司 | Iron-manganese separation and mineral separation method for refractory low-grade high-iron-manganese paragenetic ore |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107523684A (en) * | 2017-07-19 | 2017-12-29 | 东北大学 | A kind of suspension roasting ferromanganese method for separating and processing containing Ferromanganese Ore |
| CN107697896A (en) * | 2017-11-28 | 2018-02-16 | 中南大学 | A kind of method that high-purity phosphoric acid iron is prepared using ferric manganese ore as raw material |
| CN108251646A (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 | The method for producing manganese monoxide using activated carbon adsorption slag reduction roasting manganese oxide ore |
| CN111921536A (en) * | 2020-08-12 | 2020-11-13 | 中南大学 | Novel catalytic adsorption material prepared based on natural minerals and biomass |
| CN114908248A (en) * | 2022-06-09 | 2022-08-16 | 沈阳鑫博工业技术股份有限公司 | Iron-manganese separation and mineral separation method for refractory low-grade high-iron-manganese paragenetic ore |
| CN114908248B (en) * | 2022-06-09 | 2024-05-17 | 沈阳鑫博工业技术股份有限公司 | Refractory low-grade high-iron-manganese continuous ore iron-manganese separation beneficiation method |
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