CN101921908B - Molybdenum concentrate self-heating roasting method and device thereof - Google Patents
Molybdenum concentrate self-heating roasting method and device thereof Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 84
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- 239000007789 gas Substances 0.000 claims description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
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- 238000007599 discharging Methods 0.000 abstract description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 4
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
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- 229910052702 rhenium Inorganic materials 0.000 description 4
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Abstract
The invention relates to the technical field of producing industrial molybdenum oxide from molybdenum sulfide concentrates, mainly providing a molybdenum concentrate self-heating roasting method and a device thereof. In the invention, a rotary kiln with a kiln body heat exchanger is utilized to roast molybdenum concentrates to produce the industrial molybdenum oxide; in the roasting process, the heat released by the roasting reaction of the molybdenum concentrates is utilized to preheat air entering from the kiln body heat exchanger, the preheated air is fed into the rotary kiln from the discharge end of a kiln head so as to be subject to roasting reaction together with the molybdenum concentrates, heat is supplemented to materials in a residual sulphur removal region at the rear segment of the rotary kiln, and the temperature of a reaction high-temperature region at the middle segment of the rotary kiln is reduced; and after the starting up process, the molybdenum concentrate roasting process is completed under the state of no external heat supply. The invention solves the problems of overheat during the roasting main reaction period of the molybdenum concentrates and insufficient heat in the later period of desulfuration and the difficulty of feeding cooling air and discharging hot air for a high temperature rotary shell; and the device is simple, heat allocation is reasonable, temperature adjustment of each segment in the kiln is flexible, no external heat source is needed, the product quality is high, and the equipment yield is large.
Description
Technical field
The present invention relates to moly-sulfide concentrate manufacture molybdenum oxide technical field, mainly propose a kind of molybdenum concentrate self-heating roasting method and device thereof.
Background technology
At present, all moly-sulfide concentrate of domestic and international application have 96% at first will change into industrial molybdenum oxide through roasting approximately, and the further molybdenum salt of extraction solubility, and then smelting becomes molybdenum or its alloy, and major part is used for ferrous metallurgy.Calcining molybdenum ore concentrate when oxygen is not enough, MoS
2Generate brown MoO with oxygen reaction
2, and emit heat; When oxygen is sufficient, generate faint yellow MoO
3, emit heat simultaneously.The reaction heat chemical equation is following:
MoS
2+3O
2→MoO
2+2SO
2+817kJ
MoO
2+0.5O
2→MoO
3+111kJ
MoS
2+3.5O
2→MoO
3+2SO
2+928kJ
It is thus clear that the aerial roasting of concentrated molybdenum ore is significant exothermal reaction process, can self-heating accomplish fully, roasting process need not consume heat energy and should not generate low concentration SO
2Flue gas.But in the roasting process of the production of calcining molybdenum concentrate, be early stage easy reverberatory furnace roasting, or the rotary kiln baking of present widespread use, multiple hearth furnace roasting even comprise the flash stove roasting of the industrial application that is unrealized and add auxiliary agent roasting etc. and all need adopt outer thermal source to provide the roasting heat to carry out to guarantee successful reaction.The roasting heat is generally provided by outer thermals source such as coal, oil, various coal gas, Sweet natural gas, electricity.
At present; Domestic part peanut still adopts reverberatory furnace explained hereafter molybdenum oxide; Reinforced, discharging during calcining molybdenum concentrate and the stirring of furnace charge all are manual operations, and the roasting heat is supplied with by coal, heavy oil or gas-fired, and combines the switch of fire door to control maturing temperature.The advantage of reverberatory furnace sinter process is that facility investment is few, the construction period is short, but discharges from same flue because of fuel flue gas and technology flue gas in the roasting process, causes and discharges flue dust complicated component in the flue gas, bad recovery of the rhenium of association and SO
2Concentration low excessively (generally being merely 0.44～0.6%) and bad processing are prone to cause the severe contamination of environment.In addition, the heat utilization efficiency of reverberatory furnace is low, has shortcomings such as energy consumption is big, working condition is poor, labour intensity is big, and energy consumption 1t industry molybdenum oxide consumes coal up to the 480kg standard coal equivalent, so this technology day by day is eliminated.
Domestic large and medium-sized enterprise adopts the multiple hearth furnace calcining molybdenum concentrate more.The general 8-16 layer of multiple hearth furnace siege constitutes; Concentrated molybdenum ore feeds from the 1st layer, and the 1st layer is heated with Sweet natural gas with the 2nd layer of siege, carries out preheating and removes the flotation oil (like vapor oil or kerosene etc.) in the concentrated molybdenum ore; Concentrated molybdenum ore rotates the 3rd layer to the 5th layer of people then; Lean on concentrated molybdenum ore thermopositive reaction generation oxidation at these 3 layers, molybdenum dioxide that is oxidized to afterwards and molybdic oxide fall into the 3rd layer, continue oxidation through outer heating; Continuous oxidation of molybdenum dioxide this moment and major part are converted into molybdic oxide, and last two-layer people's oxygen or the oxygen-rich air of will filling usually strengthened the unoxidized molybdenum dioxide of oxidation and a small amount of unoxidized molybdenumdisulphide.And make desulfurization complete gradually.The industrial molybdenum oxide roasting recovery of present most multiple hearth furnace outputs is about 98%, and higher reaches 99%, desulfurization degree＞99.8%, and containing S is 0.05-0.07%, it is 30-50m that energy consumption 1t industry molybdenum oxide consumes Sweet natural gas
3, be individually 100m
3(chemical composition, granularity and the flotation oil content that are decided by people's stove concentrated molybdenum ore).But the multiple hearth furnace structure is complicated, and movable part is more in the body of heater.And each layer burner hearth exothermic heat of reaction is uneven.As the bad MoO that surpasses of temperature control
3Sublimation temperature (795 ℃) time, be prone to cause MoO
3The distillation loss, but also can cause the furnace charge sintering, cause feed opening to stop up, regularly prepurging has not only increased labour intensity, also influences ordinary production.Efflux the SO in the tail gas during multiple hearth furnace roasting
2Concentration lower (about 1.5%), relieving haperacidity is uneconomical, is prone to cause SO
2Pollution, form social effects of pollution.
In China, medium-sized and small enterprises mostly adopt rotary kiln baking technology.Material is under the rotation and tilting action of kiln body during roasting, and by the motion of kiln Caudad kiln hood, molybdenum glance begins to carry out oxidizing reaction thereupon.The chemical reaction that in kiln, takes place according to concentrated molybdenum ore and the heat effect of process furnace can be divided into three sections in the kiln, every section position changes with the difference of feed rate, concentrate rerum natura and chemical ingredients.The preheating and drying band is positioned at the kiln afterbody, and temperature is between 250～450 ℃, and material is at this preheating and drying, remove deoil, water; Reaction zone is in the kiln middle part, and temperature is between 500～700 ℃, and concentrated molybdenum ore reaches burning-point in this section; Lean on the chemical reaction heat of itself to carry out oxidizing reaction, generate molybdenum oxide, when the residual sulphur of material reduces to 3.5% when following; Can not lean on autoignition reaction to continue desulfurization; High temperature or high-temperature flue gas that this moment, outer heating source was supplied with make residual sulphur continue to take off, and this section furnace temperature is 350～650 ℃, and the good material of roasting is in this section discharging.
The heat-supplying mode of rotary kiln has electrically heated, heavy oil heating, coal gas heating, coal heating, and energy consumption 1t industry molybdenum oxide consumes coal up to the 275kg standard coal equivalent.Material is in stove and stirs state continuously in the rotary kiln baking technology, and roasting is abundant, and the sulfur-bearing rate is less in the product; SO in the tail gas
2The height of concentration ratio reverberatory furnace sinter process is about 1.5%, but still does not reach the concentration conditions of unstable state relieving haperacidity needed 2～4%, unsuitable relieving haperacidity.
It is thus clear that; The not only remarkable consume fuel of the sinter process of the concentrated molybdenum ore of widespread use at present or other energy, and, cause the baking flue gas volumetric expansion because of the oxygen deprivation flue gas replacement air that produces with fuel combustion provides oxygenant to the roasting reaction; Form dilution effect, made SO in the baking flue gas
2On the whole volumetric concentration has only about 1%, and this concentration is obvious low excessively, does not reach the concentration requirement of relieving haperacidity, is not easy to recycling, and directly discharging can cause the waste of resource and the severe contamination of environment again.Simultaneously, in the concentrated molybdenum ore the more valuable resource rare elements rhenium of association along with low concentration SO
2Flue gas almost is exposed to light accidentally, and has only few producer reclaiming rhenium, and simultaneously, concentrated molybdenum ore has 3% loss approximately in roasting process, and wherein about 2/3rds for containing molybdenum powder dirt with a large amount of flue gas emptyings.
In the actual production, at first advance people's drying and preheating phase after general concentrated molybdenum ore is gone into stove, the main fume afterheat that relies on just can reach required preheating temperature in common adverse current roasting; Interim in main reaction; Exothermic heat of reaction significantly and the fusing point and the boiling point of product molybdenum oxide are all low especially; Consider that these situation just avoid high temperature as far as possible, therefore need timely heat extraction-rely on usually furnace high-temperature district to be blended into cold wind even water spray again and utilize water jacket to conduct heat and realize that these measures are suppressed response intensity; Reaction process prolongs, and the reaction heat loss increases; Desulfurization later stage of key (be in the stove back segment take off residual sulphur section); Although residual sulphur relative quantity descends rapidly; But absolute desulfurization rate is more and more little, therefore also will give the material concurrent heating that is about to become product-utilize above-mentioned heat extraction or fume afterheat can't satisfy this requirement usually conversely and needs to rely on ad hoc burning or electric heating device.So get into after the main reaction phase, turn to the process of discharge port to see along the molybdenum-containing material material, the important measures of existing roasting are first heat extraction, back concurrent heating.This thermal technology's measure of adopting heats up with the dependence fuel combustion, relies on the air draught spray cooling, and the flue gas weight of multiple hearth furnace, reverberatory furnace and most of rotary kilns just constantly expands, and fluidizing furnace also is like this, wherein SO
2And dust constantly " dilution ", formed dilution effect, make common concentration, comprehensive utilization and relieving haperacidity all become very difficulty and cost sharp increase.
Summary of the invention
To above problem; The present invention provides a kind of molybdenum concentrate self-heating roasting method and device thereof; Its objective is needs outer thermal source that heat is provided when existing calcining molybdenum ore concentrate technology of solution and equipment carry out roasting to concentrated molybdenum ore, main reaction phase heat is superfluous, and desulfurization later stage heat is in short supply; And the baking flue gas amount is excessive, baking flue gas SO
2The problem that concentration is low.
The object of the invention is realized through following technical scheme: a kind of molybdenum concentrate self-heating roasting method; Utilization has the rotary kiln baking concentrated molybdenum ore of kiln body heat-exchanger rig with the manufacture molybdenum oxide; The air that roasting process utilizes the preheating of calcining molybdenum ore concentrate reaction liberated heat to be got into by kiln body heat-exchanger rig; Air after the preheating is infeeded in the rotary kiln by the discharge end of kiln hood, reacts with concentrated molybdenum ore generation roasting, and takes off the material additional heat in residual sulphur district for the rotary kiln back segment; Reduce the temperature of reaction high-temperature zone, rotary kiln stage casing, the calcining molybdenum ore concentrate process behind the stove of opening is fully need not the completion down of the state of outside heat supply.
A kind of molybdenum concentrate self-heating roasting method, its process step is:
1) before production; The effect of fume recovery system air inducing makes and keeps certain negative pressure in the rotary kiln; Utilizing outer thermal source that even preheating is carried out in rotary kiln inside, reach more than 400 ℃ at the rotary kiln draught animals, when kiln tail mouth reaches the preheating temperature more than 150 ℃, is after dried, crushed granularity that 80～200 purpose concentrated molybdenum ore raw materials are sent in the rotary kiln afterbody; Raw material is being stirred to kiln hood by the kiln afterbody and to be moved under rotary kiln body rotation and tilting action; Keep rotary kiln draught animals temperature more than 400 ℃;
2) the concentrated molybdenum ore raw material is moving to the rotary kiln stage casing, when temperature reaches more than 380 ℃, begins to carry out oxidizing reaction; The flue gas that utilizes outer thermal source to produce provides oxidizing reaction required oxygenant, through being arranged on gas blower on the kiln body through the heat-exchanger rig that rotary kiln is provided with, natural air is provided simultaneously; And the volume(tric)fraction of oxygen in the rotary kiln maintained 5～8%; Utilize natural air that heat exchange is carried out in the material main reaction high-temperature zone in rotary kiln stage casing, reduce the temperature of main reaction high-temperature zone, the natural air after the heat exchange gets into rotary kiln through the rotary kiln draught animals; Oxidizing roasting supplemental oxidant for concentrated molybdenum ore; The part heat is provided simultaneously,, promotes the carrying out of desulphurization reaction to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section;
3) negative pressure state in the control rotary kiln; Strengthen gradually by gas blower and supply with natural air amount in the rotary kiln; Keep the interior gas flow rate of kiln at 5～11m/s; The sulfur dioxide gas that the certain negative pressure effect produces reaction in the rotary kiln detaches rotary kiln with other flue dust from the kiln tail, gets into the flue dust recovery system, and is drawn into the air through the interchanger preheating in the rotary kiln continuously;
4) coordinate control rotary kiln body rotating speed and the speed of supplying with the rotary kiln raw material; The bed thickness of keeping material in the rotary kiln is 3～15cm; In rotary kiln, form three warm areas, i.e. the dry materials preheating zone of rotary kiln leading portion is in the rotary kiln stage casing; Material main reaction high-temperature zone between other two warm areas again is at the residual sulphur section of taking off of rotary kiln back segment; Said dry materials preheating zone is 200～500 ℃ by kiln tail mouth to the TR of material main reaction high-temperature zone; It is said that to take off residual sulphur section be 400～830 ℃ by the kiln hood mouth to the TR of material main reaction high-temperature zone; Said material main reaction high-temperature zone is 940～500 ℃ by the center to the TR of dry materials preheating zone, and said material main reaction high-temperature zone is 940～830 ℃ by the center to the TR of taking off residual sulphur section; Stop outside heat supply, increasing feeds natural air amount in the rotary kiln, and the volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, and keeping the interior gas flow rate of kiln is 10～20m/s;
5) concentrated molybdenum ore in kiln through the rolling kiln discharge draught animals of stirring after the abundant oxidizing roasting in 7～12 hours, finished product kiln discharge;
6) after dried, crushed the concentrated molybdenum ore raw material send in the rotary kiln afterbody oxidizing roasting in kiln, finished product kiln discharge continuously; Open and promptly in rotary kiln, form above-mentioned steps 4 behind the stove) behind said three warm areas; The whole technological process that just stops after the outside heat supply is all carried out under the outside heat supply state stopping; The heat that opens the whole technological process behind the stove is provided by calcining molybdenum ore concentrate reaction liberated heat fully, promptly utilizes calcining molybdenum ore concentrate reaction liberated heat to accomplish roasting process fully; Open in the whole technological process behind the stove, through the natural air that the heat-exchanger rig of rotary kiln setting is introduced, the volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, keeps in the kiln gas flow rate at 10～20m/s.
A kind of molybdenum concentrate self-heating roasting method; Make the natural air that gets into by the frequency conversion type gas blower carry out heat exchange through the first kiln body of heat-exchanger rig with material main reaction high-temperature zone; Make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone, carried out heat exchange with the kiln body that rotary kiln material takes off residual sulphur section again by the air of high-temperature zone kiln body heating; Air with certain temperature gets into the rotary kiln inner chamber again; To the roasting reaction required oxygen is provided, the part heat is provided simultaneously,, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in material main reaction high-temperature zone to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section.
In the above-mentioned process step, each section temperature realizes through regulating feeding quantity and frequency conversion gas blower wind supply quantity and induced draft fan draft in the rotary kiln.
Said a kind of molybdenum concentrate self-heating roasting method, before production, the outer thermal source that rotary kiln inside is carried out even preheating can be coal furnace or fuel oil, fuel burner nozzle or fuel wood.
A kind of molybdenum concentrate self-heating roasting device, it comprises that gradient is 1～5%, and by the rotary kiln of supporting-point roller, back supporting-point roller, gear pair support before the rotary kiln shell, rotary kiln outermost layer housing is a metal cylinder; The leading portion of said rotary kiln body is that the dry materials preheating section of kiln tail is made up of the single or multiple lift thermal insulation layer and the outer field housing of internal layer; The stage casing of said rotary kiln body is that material main reaction high-temperature zone is refractory masses, outside interchanger (air passageways) and housing from inside to outside, and the back segment of said rotary kiln body promptly takes off residual sulphur section and is inboard interchanger (air passageways), thermal insulation layer and housing from inside to outside; On the said rotary kiln shell leading portion gas blower is installed; Said rotary kiln end is that discharge end is provided with exhaust outlet; The heat-exchanger rig that said rotary kiln is introduced natural air is made up of outside interchanger, inboard interchanger, and the stage casing that said outside interchanger is arranged on the rotary kiln body is material main reaction high-temperature zone; The back segment that said inboard interchanger is arranged on the rotary kiln body promptly takes off residual sulphur section; The frequency conversion type gas blower is communicated with outside interchanger on the rotary kiln through the air intake connecting pipeline, and said inboard interchanger communicates with outside interchanger and exhaust outlet respectively, and the said rotary kiln end that is arranged on is that the exhaust outlet of discharge end communicates with the rotary kiln inner chamber; The stage casing that outside interchanger is arranged on the rotary kiln body is material main reaction high-temperature zone; Outside interchanger is communicated with frequency conversion type gas blower, inboard interchanger respectively; The natural air that is got into by the frequency conversion type gas blower is introduced in the interchanger of the outside; Because the stage casing that outside interchanger is arranged on the rotary kiln body is that kiln body main reaction section is the high-temperature zone, make the natural air that gets in the interchanger of the outside and the kiln body of main reaction high temperature section carry out heat exchange, make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone; By the inboard interchanger of the air admission of high-temperature zone kiln body heating, the kiln body that takes off residual sulphur section with rotary kiln material carries out heat exchange; Air with certain temperature is the exhaust outlet entering rotary kiln inner chamber of discharge end by rotary kiln end through inboard interchanger again; To the roasting reaction required oxygen is provided, the part heat is provided simultaneously,, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in the high-temperature zone to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section.
The rational allocation and flexibly control of the present invention in order to realize rotary kiln temperature; Said outside interchanger and inboard interchanger all adopt sealed structure; Promptly outside interchanger and inboard interchanger are the air-cooled structure of jacketed type; It is a plurality of parallel air communication channel that the floor of the usefulness some amount that on the rotary kiln body, is provided with is split to form; The outside a plurality of parallel air communication channel that interchanger and inboard interchanger had, described a plurality of parallel air communication channel make air ring week evenly get into outside interchanger along the circle distribution of rotary kiln body; And make along a plurality of parallel air communication channel and get into the air of outside interchanger and the kiln body of rotary kiln high-temperature zone fully, evenly carries out heat exchange; Make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone, evenly got into inboard interchanger by the air ring week of high-temperature zone kiln body heating, the kiln body that takes off residual sulphur section with rotary kiln fully, evenly carries out heat exchange; Air with certain temperature evenly gets into the rotary kiln inner chamber through inboard interchanger along the air communication channel of rotary kiln body circle distribution; To the roasting reaction required oxygen is provided; The part heat is provided simultaneously; To keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in the high-temperature zone.
In the said apparatus, adopt slip ring power supply device to realize the gas blower power supply.
Gas blower described in the said apparatus is the frequency conversion gas blower, on its inlet pipeline regulated valve is housed.
The invention has the beneficial effects as follows:
Because the big calorimetric that technology of the present invention makes calcining molybdenum ore concentrate lean on the autoxidation reaction to be discharged is fully accomplished; Roasting concentrated molybdenum ore per ton can save the energy requirement that the at present domestic best about 275kg of capability of energy dissipation marks coal; Coals will be marked for country practice thrift at least 3.85 ten thousand tons in China's year processing concentrated molybdenum ore 14～160,000 ton like this.
Because it is more sufficient that technology of the present invention is the calcining molybdenum ore concentrate oxygen supply, make the concentrated molybdenum ore oxidizing reaction sooner, more abundant, cause the product sweetening effectiveness better, the product sulfur-bearing is about 0.05%, well below the standard of international sulphur content 0.1%; Product production improves about 20% than existing processes state of the art; Molybdic oxide content in the product improves about 20% than existing processes state of the art, and this will reduce greatly smelts the molybdenum-iron cost.
Because technology of the present invention is lowered the temperature to concentrated molybdenum ore main reaction high-temperature zone, causes the distillation degree that has reduced molybdic oxide, has reduced the loss of valuable molybdenum.
Because it is that the calcining molybdenum ore concentrate reaction provides oxygenant that the present invention adopts air to replace the fuel combustion flue gas, effectively less flue gas volume, thus increased baking flue gas SO
2The dust concentration that contains molybdenum and rhenium in concentration and the flue gas is for the comprehensive utilization of baking flue gas provides favourable condition.
The product temperature of output is low, the material state is loose, sulphur smoke smell that nonirritant is very strong again, and this can improve workman's work situation and reduction labor strength greatly.
Description of drawings
Fig. 1 is the tooling system schematic that has local section of an embodiment of technology of the present invention.
Fig. 2 is the A-A cross-sectional schematic of Fig. 1.
Fig. 3 is the B-B cross-sectional schematic of Fig. 1.
Among the figure, 1, the rotary flashing drying shredding unit, 2, the kiln tail sealing device, 3, the rotary kiln feeding device, 4, rotary kiln; 5, gas blower, 6, outside interchanger, 7, inboard interchanger, 8, kiln hood sealing and finished product hopper device, 9, the solid fuel high temperature hot-blast furnace; 10, preceding supporting-point roller, 11, gear pair, 12, speed reduction unit, 13, adjustable speed motor, 14, the back supporting-point roller; 15, fume recovery system, 16, bagroom, 17, scatterer, 18, cyclone.
Embodiment
In conjunction with accompanying drawing and embodiment the present invention is further specified.
In Fig. 1, this rotary kiln 4 has the kiln body of long 30m, diameter 2m; Its afterbody is high, head is low, and the angle of inclination is 1 °; It is supported by preceding supporting-point roller 10 and back supporting-point roller 14; It is driven through speed reduction unit 12 speed changes by adjustable speed motor 13, and the gear pair 11 that drive is connected with rotary kiln body middle part orders about it and rotates.Before production, through the draft of regulating induced draft fan in the fume recovery system keep being in the rotary kiln micro-vacuum state (300～-800Pa), utilize in 9 pairs of rotary kilns 4 of solid fuel high temperature hot-blast furnace and carry out even preheating; Reach more than 400 ℃ at rotary kiln 4 kiln hood mouths, when kiln tail mouth reaches the preheating temperature more than 150 ℃, be the granularity after 1 oven dry of rotary flashing drying shredding unit, pulverizing that 80～200 purpose concentrated molybdenum ore raw materials are sent in rotary kiln 4 afterbodys, raw material is under the rotation and tilting action of rotary kiln 4; Stirring to the kiln hood mouth by the kiln afterbody and to move, through in the rotary kiln, the material delivering plate that is provided with of back segment, the spreading mode of material delivering plate is to rotate with cylindrical shell; Material is taken up, reach the slope of repose of material self after, material is evenly shed along the material delivering plate ramp gradually; Surpass the position of cylindrical shell vertex up to being taken up to; Shed just completion basically of process, form material curtain uniformly like this on each section of material, with the contact area increase of warm air; Improve thermo-efficiency, reduced power consumption; Solid fuel high temperature hot-blast furnace 9 continues heat supply, keeps kiln hood mouth temperature more than 400 ℃.Stage casing in the concentrated molybdenum ore raw material gets into rotary kiln 4 when temperature of charge reaches more than 380 ℃, begins to carry out oxidizing reaction, and the flue gas that solid fuel high temperature hot-blast furnace 9 produces is as oxygenant; Unlatching is installed in the gas blower 5 apart from the about 12m of kiln tail mouth place; The natural air that is drawn into, feed and to be installed on the rotary kiln 4 apart from the outside interchanger 6 of kiln tail mouth 12～23m, long 11m and to be installed on the rotary kiln 4 inboard interchanger 7 apart from kiln tail mouth 23～30m, long 7m; Described inboard interchanger 7 one ends are positioned at kiln hood mouth position and the exhaust outlet through the kiln hood mouth communicates with the rotary kiln inner chamber; Among this embodiment, the length of inboard interchanger 7 is 7m, and described inboard interchanger 7 one ends are communicated with outside interchanger 6, and described outside interchanger 6 length are 11m; Described outside interchanger 6 is positioned on the rotary kiln body of rotary kiln material main reaction high-temperature zone, between internal layer refractory masses and outer casing; Described inboard interchanger 7 is positioned on the rotary kiln body that rotary kiln takes off residual sulphur district, is positioned at the innermost layer of rotary kiln body, and sets gradually adiabator layer, housing at its skin; Get into the natural air of rotary kiln, and make under the certain suction function that produces in the rotary kiln 4 in fume recovery system 15 air inducing effects, pour in the rotary kiln 4 from the kiln hood mouth, the volume(tric)fraction of only keeping oxygen in the rotary kiln 4 interior atmosphere is 5～8%.Negative pressure in the control rotary kiln 4; Keep rotary kiln 4 interior gas flow rates about 5～11m/s; When concentrated molybdenum ore raw material in the rotary kiln 4 reaches oxidizing reaction temperature more than 380 ℃ the time; Raw material and gas blower 5 begin to carry out sufficient oxidizing reaction through the natural air that outside interchanger 6 and inboard interchanger 7 infeed in the rotary kiln 4, and fume recovery system 15 produces the SO that certain suction function produces reaction in rotary kiln 4
2Gas detaches rotary kiln 4 with other flue dust from the kiln afterbody; Successively through cyclone 18 gather dust, after scatterer 17 heat radiation is gathered dust, bag filter 16 gathers dust; Get into the acid exhaust system, and be drawn into the natural air of gas blower 5 supplies continuously in the rotary kiln 4.Coordinate the rotating speed of control adjustable speed motor 13 and speed and the rotating speed of frequency conversion gas blower 5 and the draft of induced draft fan that rotary kiln feeding device 3 is supplied with rotary kiln 4 raw materials; The bed thickness of keeping material in the rotary kiln 4 is 3～15cm; In rotary kiln 4, form three warm areas, i.e. the dry materials preheating zone of rotary kiln leading portion is in the rotary kiln stage casing; Material main reaction high-temperature zone between other two warm areas again is at the residual sulphur section of taking off of rotary kiln back segment; Said dry materials preheating zone is raise by the temperature of kiln tail mouth to material main reaction high-temperature zone gradually, and TR is 200～500 ℃; Saidly take off residual sulphur section and raise gradually by the temperature of kiln hood mouth to material main reaction high-temperature zone; TR is 400～830 ℃, and said material main reaction high-temperature zone is 940～500 ℃ by the center to the TR of dry materials preheating zone, and said material main reaction high-temperature zone is 940～830 ℃ by the center to the TR of taking off residual sulphur section; Stop 9 heat supplies of solid fuel high temperature hot-blast furnace; Increase the air quantity of gas blower 5, infeed more natural air through heat-exchanger rig, the volume(tric)fraction of keeping oxygen in the rotary kiln 4 is 8～18%; And negative pressure in the control rotary kiln 4, keep rotary kiln 4 interior gas flow rates about 10～20m/s.The concentrated molybdenum ore raw material through the motion kiln discharge draught animals of stirring after the abundant oxidizing roasting, gets in kiln hood sealing and the finished product hopper device 8 the finished product kiln discharge in rotary kiln.After dried, crushed the concentrated molybdenum ore raw material send in the rotary kiln afterbody oxidizing roasting in kiln, the continuous kiln discharge of finished product continuously; Open promptly in rotary kiln, form said three warm areas in top behind the stove after; The whole technological process that just stops after the outside heat supply is all carried out under the outside heat supply state stopping; The heat that opens the whole technological process behind the stove is provided by calcining molybdenum ore concentrate reaction liberated heat fully, promptly utilizes calcining molybdenum ore concentrate reaction liberated heat to accomplish roasting process fully; Open in the whole technological process behind the stove, through the natural air that the heat-exchanger rig of rotary kiln setting is introduced, the volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, keeps in the kiln gas flow rate at 10～20m.
As shown in Figure 1; And with reference to Fig. 2, Fig. 3; The leading portion of said rotary kiln body is that the dry materials preheating section of kiln tail is made up of the single or multiple lift thermal insulation layer and the outer field housing of internal layer; The stage casing of said rotary kiln body is that material main reaction high-temperature zone is refractory masses, outside interchanger (air passageways) and housing from inside to outside, and the back segment of said rotary kiln body promptly takes off residual sulphur section and is inboard interchanger (air passageways), thermal insulation layer and housing from inside to outside; On the said rotary kiln shell leading portion gas blower 5 is installed, gas blower adopts slip ring power supply device to realize power supply; Said gas blower is the frequency conversion gas blower, on its inlet pipeline regulated valve is housed; Said rotary kiln end is that discharge end is provided with exhaust outlet, and the heat-exchanger rig that said rotary kiln is introduced natural air is made up of outside interchanger 6, inboard interchanger 7, and the stage casing that said outside interchanger 6 is arranged on the rotary kiln body is material main reaction high-temperature zone; The back segment that said inboard interchanger is arranged on the rotary kiln body promptly takes off residual sulphur section; Frequency conversion type gas blower 5 is communicated with outside interchanger 6 on the rotary kiln through the air intake connecting pipeline, and said inboard interchanger 7 communicates with outside interchanger 6 and exhaust outlet respectively, and the said rotary kiln end that is arranged on is that the exhaust outlet of discharge end communicates with the rotary kiln inner chamber; The stage casing that outside interchanger is arranged on the rotary kiln body is material main reaction high-temperature zone; Make outside interchanger 6 be communicated with 7 with frequency conversion type gas blower 5, inboard interchanger respectively; The natural air that is got into by the frequency conversion type gas blower is introduced in the interchanger 6 of the outside; Because it is that kiln body main reaction section is the high-temperature zone that outside interchanger is arranged on the stage casing of rotary kiln body; Make the natural air that gets in the interchanger of the outside carry out heat exchange, make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone, the air admission inboard interchanger that is heated by high-temperature zone kiln body with the kiln body of main reaction high temperature section; The kiln body that takes off residual sulphur section with rotary kiln material carries out heat exchange, and the temperature of rotary kiln material being taken off residual sulphur section once promotes; Air with certain temperature is the exhaust outlet entering rotary kiln inner chamber of discharge end by rotary kiln end through inboard interchanger 7 again; To the roasting reaction required oxygen is provided, the part heat is provided simultaneously,, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in the high-temperature zone to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section.
Said outside interchanger 6 all adopts sealed structure with inboard interchanger 7; Promptly outside interchanger 6 and inboard interchanger 7 are the air-cooled structure of jacketed type; It is a plurality of parallel air communication channel that the floor of the usefulness some amount that on the rotary kiln body, is provided with is split to form; The outside a plurality of parallel air communication channel that interchanger and inboard interchanger had; Described a plurality of parallel air communication channel makes air ring week evenly get into outside interchanger along the circle distribution of rotary kiln body, and makes along a plurality of parallel air communication channel and get into the air of outside interchanger and the kiln body of rotary kiln high-temperature zone fully, evenly carries out heat exchange; Make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone; Air ring week by the heating of high-temperature zone kiln body evenly gets into inboard interchanger, and the kiln body that takes off residual sulphur section with rotary kiln fully, evenly carries out heat exchange, and the temperature of rotary kiln material being taken off residual sulphur section once promotes; Air with certain temperature evenly gets into the rotary kiln inner chamber through inboard interchanger along the air communication channel of rotary kiln body circle distribution; To the roasting reaction required oxygen is provided; The part heat is provided simultaneously; To keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in the high-temperature zone.
Claims (9)
1. molybdenum concentrate self-heating roasting method; It is characterized in that: utilize the rotary kiln baking concentrated molybdenum ore that has kiln body heat-exchanger rig with the manufacture molybdenum oxide; The air that roasting process utilizes the preheating of calcining molybdenum ore concentrate reaction liberated heat to be got into by kiln body heat-exchanger rig through being arranged on gas blower (5) on the kiln body through the heat-exchanger rig that rotary kiln is provided with, provides natural air; Utilize natural air that heat exchange is carried out in the material main reaction high-temperature zone in rotary kiln stage casing; Air after the heat exchange is infeeded in the rotary kiln by the discharge end of kiln hood, with concentrated molybdenum ore generation roasting reaction, is the oxidizing roasting supplemental oxidant of concentrated molybdenum ore; And the material additional heat of taking off residual sulphur district for the rotary kiln back segment, reduce the temperature of reaction high-temperature zone, rotary kiln stage casing; The volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, and keeping the interior gas flow rate of kiln is 10～20m/s; The calcining molybdenum ore concentrate process that opens behind the stove need not be accomplished under the state of outside heat supply fully.
2. according to the described molybdenum concentrate self-heating roasting method of claim 1, it is characterized in that: the process step of said self-heating roasting method is:
1) before production; Keep certain negative pressure in the rotary kiln, utilize outer thermal source that even preheating is carried out in rotary kiln inside, reach more than 400 ℃ at the rotary kiln draught animals, when kiln tail mouth reaches the preheating temperature more than 150 ℃; Is granularity after dried, crushed that 80～200 purpose concentrated molybdenum ore raw materials are sent in the rotary kiln afterbody; Raw material is being stirred to kiln hood by the kiln afterbody and to be moved under rotary kiln body rotation and tilting action, and maintenance rotary kiln draught animals temperature is more than 400 ℃;
2) the concentrated molybdenum ore raw material is moving to the rotary kiln stage casing, when temperature reaches more than 380 ℃, begins to carry out oxidizing reaction; The flue gas that utilizes outer thermal source to produce provides oxidizing reaction required oxygenant, through being arranged on gas blower (5) on the kiln body through the heat-exchanger rig that rotary kiln is provided with, natural air is provided simultaneously; And the volume(tric)fraction of oxygen in the rotary kiln maintained 5～8%; Utilize natural air that heat exchange is carried out in the material main reaction high-temperature zone in rotary kiln stage casing, reduce the temperature of main reaction high-temperature zone, the natural air after the heat exchange gets into rotary kiln through the rotary kiln draught animals; Oxidizing roasting supplemental oxidant for concentrated molybdenum ore; The part heat is provided simultaneously,, promotes the carrying out of desulphurization reaction to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section;
3) negative pressure state in the control rotary kiln; Strengthen gradually by gas blower and supply with natural air amount in the rotary kiln; Keep the interior gas flow rate of kiln at 5～11m/s; The sulfur dioxide gas that the certain negative pressure effect produces reaction in the rotary kiln detaches rotary kiln with other flue dust from the kiln tail, gets into the flue dust recovery system, and is drawn into the air through the heat-exchanger rig preheating in the rotary kiln continuously;
4) coordinate control rotary kiln body rotating speed and the speed of supplying with the rotary kiln raw material; The bed thickness of keeping material in the rotary kiln is 3～15cm; In rotary kiln, form three warm areas, i.e. the dry materials preheating zone of rotary kiln leading portion is in the rotary kiln stage casing; Material main reaction high-temperature zone between other two warm areas again is at the residual sulphur section of taking off of rotary kiln back segment; Said dry materials preheating zone is 200～500 ℃ by kiln tail mouth to the TR of material main reaction high-temperature zone; It is said that to take off residual sulphur section be 400～830 ℃ by the kiln hood mouth to the TR of material main reaction high-temperature zone; Said material main reaction high-temperature zone is 940～500 ℃ by the center to the TR of dry materials preheating zone, and said material main reaction high-temperature zone is 940～830 ℃ by the center to the TR of taking off residual sulphur section; Stop outside heat supply, increasing feeds natural air amount in the rotary kiln, and the volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, and keeping the interior gas flow rate of kiln is 10～20m/s;
5) concentrated molybdenum ore in kiln through the rolling kiln discharge draught animals of stirring after the abundant oxidizing roasting, finished product kiln discharge;
6) after dried, crushed the concentrated molybdenum ore raw material send in the rotary kiln afterbody oxidizing roasting in kiln, the continuous kiln discharge of finished product continuously; Open and promptly in rotary kiln, form above-mentioned steps 4 behind the stove) behind said three warm areas; The whole technological process that just stops after the outside heat supply is all carried out under the outside heat supply state stopping; The heat that opens the whole technological process behind the stove is provided by calcining molybdenum ore concentrate reaction liberated heat fully, promptly utilizes calcining molybdenum ore concentrate reaction liberated heat to accomplish roasting process fully; Open in the whole technological process behind the stove, through the natural air that the heat-exchanger rig of rotary kiln setting is introduced, the volume(tric)fraction of keeping oxygen in the kiln atmosphere is 8～18%, and negative pressure in the control rotary kiln, keeps in the kiln gas flow rate at 10～20m/s.
3. molybdenum concentrate self-heating roasting method according to claim 1 and 2; It is characterized in that: make the natural air that gets into by the frequency conversion type gas blower carry out heat exchange through the first kiln body of heat-exchanger rig with material main reaction high-temperature zone; Make the cooling of once being lowered the temperature of the kiln body of rotary kiln high-temperature zone; Carried out heat exchange with the kiln body that rotary kiln material takes off residual sulphur section again by the air of high-temperature zone kiln body heating, the temperature of rotary kiln material being taken off residual sulphur section once promotes; Air with certain temperature gets into the rotary kiln inner chamber again; To the roasting reaction required oxygen is provided, the part heat is provided simultaneously,, promote the carrying out of desulphurization reaction, and the reducing temperature twice cooling is carried out in material main reaction high-temperature zone to keep the temperature that the rotary kiln back segment promptly takes off residual sulphur section.
4. molybdenum concentrate self-heating roasting method according to claim 1 and 2 is characterized in that: each section temperature realizes through regulating feeding quantity and frequency conversion gas blower wind supply quantity and induced draft fan draft in the said rotary kiln.
5. molybdenum concentrate self-heating roasting device; It is characterized in that: it comprises that gradient is 1～5%; And by the rotary kiln (4) of supporting-point roller before the rotary kiln shell (10), back supporting-point roller (14), gear pair (14) support, it is characterized in that: described rotary kiln is provided with air heat-exchanging device and gas blower (5) is installed on the rotary kiln shell leading portion; Described air heat-exchanging device is made up of outside interchanger (6), inboard interchanger (7), and the stage casing that said outside interchanger (6) is arranged on the rotary kiln body is material main reaction high-temperature zone; The back segment that said inboard interchanger (7) is arranged on the rotary kiln body promptly takes off residual sulphur section; Gas blower (5) is communicated with outside interchanger (6) on the rotary kiln through the air intake connecting pipeline, and said inboard interchanger (7) is that the exhaust outlet of discharge end communicates with outside interchanger (6), rotary kiln end respectively; The said rotary kiln end that is arranged on is that the exhaust outlet of discharge end communicates with the rotary kiln inner chamber; The stage casing that outside interchanger (6) is arranged on the rotary kiln body is material main reaction high-temperature zone; Outside interchanger (6) is communicated with gas blower (5), inboard interchanger (7) respectively; The natural air that is got into by gas blower is introduced in the outside interchanger (6); Carrying out heat exchange with the kiln body of main reaction high temperature section, by the inboard interchanger (7) of the air admission of high-temperature zone kiln body heating, is the exhaust outlet entering rotary kiln inner chamber of discharge end by rotary kiln end through inboard interchanger again.
6. molybdenum concentrate self-heating roasting device according to claim 5; It is characterized in that: said outside interchanger (6) and inboard interchanger (7) all adopt sealed structure; Promptly outside interchanger (6) and inboard interchanger (7) are the air-cooled structure of jacketed type; It is a plurality of parallel air communication channel that the floor of the usefulness some amount that on housing, is provided with is split to form; Outside interchanger (6) and inboard interchanger (7) have a plurality of parallel air communication channel; Described a plurality of parallel air communication channel makes air pass through gas blower (5) ring week evenly to get into outside interchanger (6) along the circle distribution of rotary kiln body, and makes along a plurality of parallel air communication channel and get into the air of outside interchanger and the kiln body of rotary kiln high-temperature zone fully, evenly carries out heat exchange; Evenly got into inboard interchanger (7) by the air ring of high-temperature zone kiln body heating week, the air with certain temperature evenly gets into the rotary kiln inner chamber through inboard interchanger (7) along the air communication channel of rotary kiln body circle distribution.
7. molybdenum concentrate self-heating roasting device according to claim 5 is characterized in that: the said outside interchanger (6) that is positioned on the kiln body of rotary kiln material main reaction high-temperature zone, between internal layer refractory masses and outer casing; The said rotary kiln that is positioned at takes off the inboard interchanger (7) on the residual sulphur district kiln body, is positioned at the innermost layer of rotary kiln body, and sets gradually adiabator layer, housing at its skin.
8. molybdenum concentrate self-heating roasting device according to claim 5 is characterized in that: adopt slip ring power supply device to realize gas blower (5) power supply.
9. molybdenum concentrate self-heating roasting device according to claim 5 is characterized in that: described gas blower (5) is the frequency conversion gas blower, on its inlet pipeline regulated valve is housed.
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| CN114804186A (en) * | 2022-05-16 | 2022-07-29 | 吴江市威士达铜业科技有限公司 | Production method and production device of copper oxide |
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| CN1176230C (en) * | 2002-06-28 | 2004-11-17 | 锦州市沈宏实业股份有限公司 | Process for calcining molybdenum ore concentrate |
| CN101008045B (en) * | 2006-01-24 | 2010-10-13 | 洛阳栾川钼业集团冶炼有限责任公司 | Rotary flash distillation direct combustion heat-supply type rotary kiln baking apparatus and process for molybdenum concentrate |
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