CN102874850B - Roasting system and roasting method for lithium-ore acidification by using externally-heated type rotary furnace - Google Patents
Roasting system and roasting method for lithium-ore acidification by using externally-heated type rotary furnace Download PDFInfo
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- CN102874850B CN102874850B CN201210414399.9A CN201210414399A CN102874850B CN 102874850 B CN102874850 B CN 102874850B CN 201210414399 A CN201210414399 A CN 201210414399A CN 102874850 B CN102874850 B CN 102874850B
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Abstract
The invention discloses a roasting system and a roasting method for lithium-ore acidification by using an externally-heated type rotary furnace, which comprises the following steps of: generating acidifying grog through acidifying roasting after mixing beta lithium ores and sulfuric acid by using the externally-heated type rotary furnace as the core equipment of acidifying roasting reaction, and sending the acidifying grog which is generated after acidifying roasting into a subsequent working procedure after cooling the acidifying grog, wherein the sulfuric acid for acidifying roasting is used after the concentration of an acid liquor after tail gas is washed is adjusted through fuming sulfuric acid and can also be directly prepared from concentrated sulfuric acid or fuming acid or by mixing the two acids; the tail gas which is generated in the process of acidifying roasting is discharged with reaching standards after acid washing and alkali washing, and most of the acidic gas in the tail gas returns to the roasting system along with the washing acid to be reutilized during acid washing. The invention overcomes the defects of large tail-gas quantity, serious pollution and the like of a traditional internally-heated type acidifying-roasting process and provides a good method for the extraction of metallic lithium in the lithium ores, the self-heating of the reaction is fully utilized, energy does not need to be additionally consumed after the self reaction temperature is reached, and the energy-saving effect is remarkable.
Description
Technical field
The invention belongs to lithium salts production technical field, relate to and a kind ofly with external heat type rotary furnace, carry out the acidizing fired system and method for lithium ore, the system and method that the external heat type rotary furnace of take specifically carries out the sulfurization roasting of lithium ore as nucleus equipment.
Background technology
The method of carrying lithium from lithium ore is a lot, but sulfuric acid process is still the lithium method of putting forward the most widely in the world at present, this technique of the current extensively employing of domestic and international most of lithium salts producer, it is little that sulfuric acid process has streams flux, production efficiency is high, energy consumption is low, and metal recovery rate is high waits outstanding advantages, thus the lithium salts of producing in this way to account for the ratio of world's lithium salts ultimate production high.
Take triphane as example, acidizing fired principle be with sulfuric acid make beta spodumene temperature be 250～300 ℃ by following reacting thiourea hydrochlorate:
Li
2O.Al
2O
3.4SiO
2+H
2SO
4→Li
2SO
4+H
2O.Al
2O
3.4SiO
2
Also there is following side reaction simultaneously:
Na
2O.Al
2O
3.4SiO
2+H
2SO
4→Na
2SO
4+H
2O.Al
2O
3.4SiO
2
K
2O.Al
2O
3.4SiO
2+H
2SO
4→K
2SO
4+H
2O.Al
2O
3.4SiO
2
MgO.Al
2O
3.4SiO
2+H
2SO
4→MgSO
4+H
2O.Al
2O
3.4SiO
2
CaO.Al
2O
3.4SiO
2+H
2SO
4→CaSO
4+H
2O.Al
2O
3.4SiO
2
2FeO+4H
2SO
4→Fe
2(SO
4)
3+SO
2+4H
2O …
When sulphating, between the manosil AS salt core of beta spodumene and sulfuric acid, there is ion-exchange, the result of exchange makes the lithium in triphane be replaced by hydrogen, and in fact mineral structure does not destroy.
Lithium salts both domestic and external producer adopts internal heat type revolution sulfating roaster (kiln) to realize this process more, the shortcomings such as sulfuric acid consumption is large, tail is large-minded, seriously polluted, equipment corrosion is serious have been produced, a large amount of waste heat and reaction heat are taken away with tail gas, be difficult to realize effective utilization, energy consumption is relatively large.
Summary of the invention
The object of this invention is to provide a kind of method of carrying out the acidizing fired system of lithium ore and roasting with external heat type rotary furnace, the present invention greatly reduces the fume amount producing in acidization, has improved economic benefit, has effectively realized environmental protection; Reduced the quantity discharged of waste gas, part heat is recycled utilization, and energy-saving effect is remarkable; Heat exchange efficiency is high, good operational environment, heat-eliminating medium are easy to realize heat recuperation after heat exchange.
The object of the invention is to realize by following technical proposals.
A kind of external heat type rotary furnace that utilizes carries out the acidizing fired system of lithium ore, comprise feed bin, and the metering outfit being connected with feed bin, described metering outfit connects mixing equipment, described mixing equipment is connected with external heat type rotary furnace, and external heat type rotary furnace connects respectively pickling installation and cooling apparatus; The air outlet of described pickling installation connects alkali cleaning equipment, and the discharge port of pickling installation connects nitration mixture equipment, and the opening for feed of pickling installation connects vitriol oil storage tank; Described nitration mixture equipment connection has oleum storage tank; Described alkali cleaning equipment is connected with respectively lye vat and chimney.
Further, in system of the present invention:
Described external heat type rotary furnace comprises the body of heater supporting by rotary kiln bracing or strutting arrangement, and described body of heater comprises that successively connected shaft leading portion, rotating cylinder heating zone, rotating cylinder are from hot arc and discharge end; Described shaft leading portion is connected with the rotary kiln feed end of carrying by motor, and shaft leading portion is provided with rotary kiln transmission mechanism;
Described rotating cylinder heating zone is provided with heating jacket, establishes heating agent or Heating element in heating jacket; Described heating agent or Heating element comprise hot flue gas heating, electrically heated or directly flame heating; Described rotating cylinder heating zone top is provided with thermal source outlet, and bottom is provided with thermal source import; Described shaft leading portion body of heater roof is provided with air outlet.
Described cooling apparatus comprises the cylindrical shell supporting by water cooler bracing or strutting arrangement, and described cylinder lumen is provided with heat exchanging pipe, by the cavity between cylinder body outer wall and heat exchanging pipe, forms water cooler shell side; Described barrel front end is provided with water cooler feed end, and cylindrical shell tail end is provided with water cooler discharge end, and water cooler discharge end connects heat-eliminating medium entrance by swivel joint; On described cylindrical shell, be provided with water cooler transmission mechanism; On described swivel joint, be provided with heat-eliminating medium outlet.
Described mixing equipment is intermittent type or continous way mixing equipment, and mixing equipment is coulter type mixer, agravic formula mixing machine or bipyramid screw mixer.
Correspondingly, the present invention gives a kind of external heat type rotary furnace that utilizes and carries out the acidizing fired method of lithium ore, comprises the steps:
1) lithium ore is sent into lithium ore storage bunker, and the lithium ore in feed bin, after metering outfit metering, is sent into mixing equipment;
2), in pickling installation, use after the vitriol oil washing acidifying baking tail gases from vitriol oil storage tank simultaneously, with oleum its concentration of Mixed adjustment in nitration mixture equipment from oleum storage tank, send into mixing equipment; Or directly by the vitriol oil or fuming acid or two kinds of acid, be mixed, send into mixing equipment;
3) lithium ore powder is sent into external heat type rotary furnace after fully mixing in mixing equipment with nitration mixture, carries out acidification reaction under certain condition;
4) from external heat type rotary furnace discharge end acidifying grog out, sending into water cooler is cooled to certain temperature and discharges and send into subsequent handling;
5) sour gas of drawing from external-heating revolving furnace outlet duct is used the vitriol oil absorption portion sour gas from vitriol oil storage tank pickling installation, all the other sour gas are used the alkali liquid washing from alkali lye storage tank again in alkali cleaning equipment, remove after remaining sour gas by chimney qualified discharge.
Further, in the inventive method:
In described step 1), lithium ore powder refers to the beta spodumene that α triphane forms after high temperature roasting transition, or lithionite etc. obtains corresponding concentrate containing lithium minerals matter and through ore dressing, or other is containing silicate, phosphoric acid salt, borate, the fluorochemical ore of lithium, or other is containing waste, the by product of lithium.
Described sulfuric acid concentration is 93%～98.3%, and oleum concentration is for containing free SO
30%～60% sulfuric acid, in nitration mixture equipment more than its concentration to 93% of Mixed adjustment.
In described step 3), lithium ore powder mixes than the ratio that is 2～6:1 according to mass ratio with sulphur material acid acid, carries out acidification reaction.
In described step 3), acidification reaction temperature is 200～300 ℃; Pressure is ± micro-positive/negative-pressure of 500Pa; The transformation efficiency of acidification reaction is 90%～100%.
In described step 4), water cooler cooling temperature is 50 ~ 150 ℃.
Innovation point of the present invention:
1) adopt external-heating revolving acidifying stove, substitute original internal heat type acidifying stove, greatly reduce the exhaust gas volumn and the Dust Capacity that in acidization, produce.Solved sulfuric acid in internal heat type acidifying furnace exhaust, the irretrievable problem of dust, improved economic benefit, stopped the discharge of waste gas, waste water, environment-friendly advantage is obvious.
For the feature of the acidizing fired reaction of lithium ore, external heat type rotary furnace only can be realized needs hot spot that external heat chuck is set to equipment, and heat release is spontaneous carries out in subsequent reactions utilization reaction self, does not need extra consumed energy, and energy-saving effect is remarkable.
2) adopt vitriol oil washing high-temp waste gas, not only can absorb the acid gas (being mainly water vapour, sulfuric acid acid gas, sulfurous gas etc.) in acidifying furnace exhaust, reduce the quantity discharged of waste gas, can also improve into sour temperature, reclaim a part of heat.
3) only to equipment, need hot spot that external heat chuck is set, heat release is spontaneous carries out in subsequent reactions utilization reaction self, does not need extra consumed energy, and energy-saving effect is remarkable.
4) adopt shell and tube revolution water cooler to carry out the cooling of acidifying grog, heat exchange efficiency is high, good operational environment, heat-eliminating medium are easy to realize heat recuperation after heat exchange.
Accompanying drawing explanation
Fig. 1 is the technological process of production of the present invention.
Fig. 2 is nucleus equipment external heat type rotary furnace schematic diagram of the present invention.
Fig. 3 is the cooling apparatus schematic diagram that the present invention creates.
In figure: 1, chimney, 2, lye vat, 3, alkali cleaning equipment, 4, pickling installation, 5, nitration mixture equipment, 6, cooling apparatus, 6-1, heat-eliminating medium entrance, 6-2, swivel joint, 6-3, water cooler shell side, 6-4, heat exchanging pipe, 6-5, water cooler feed end, 6-6, water cooler transmission mechanism, 6-7, water cooler bracing or strutting arrangement, 6-8, water cooler discharge end, 6-9, heat-eliminating medium outlet, 7, external heat type rotary furnace, 7-1, rotary kiln feed end, 7-2, air outlet, 7-3, thermal source outlet, 7-4, heating jacket, 7-5, rotating cylinder heating zone, 7-6, rotating cylinder is from hot arc, 7-7, rotary kiln discharge end, 7-8, thermal source import, 7-9, rotary kiln bracing or strutting arrangement, 7-10, rotary kiln transmission mechanism, 8, mixing equipment, 9, metering outfit, 10, feed bin, 11, vitriol oil storage tank, 12, oleum storage tank.
Embodiment
A kind of external heat type rotary furnace that utilizes of the present invention carries out the acidizing fired system of lithium ore as shown in Figure 1, comprise feed bin 10, and the metering outfit 9 being connected with feed bin 10, metering outfit 9 connects mixing equipment 8, wherein: mixing equipment 8 is connected with external heat type rotary furnace 7, external heat type rotary furnace 7 connects respectively pickling installation 4 and cooling apparatus 6; The air outlet of pickling installation 4 connects alkali cleaning equipment 3, and the discharge port of pickling installation 4 connects nitration mixture equipment 5, and the opening for feed of pickling installation 4 connects vitriol oil storage tank 11; Nitration mixture equipment 5 is connected with oleum storage tank 12; Alkali cleaning equipment 3 is connected with respectively lye vat 2 and chimney 1.
As shown in Figure 2, external heat type rotary furnace 7 comprises the body of heater supporting by rotary kiln bracing or strutting arrangement 7-9, and described body of heater comprises that successively connected shaft leading portion, rotating cylinder heating zone 7-5, rotating cylinder are from hot arc 7-6 and rotary kiln discharge end 7-7; Described shaft leading portion is connected with the rotary kiln feed end 7-1 carrying by motor, and shaft leading portion is provided with rotary kiln transmission mechanism 7-10; Rotating cylinder heating zone 7-5 is provided with heating jacket 7-4, establishes heating agent or Heating element in heating jacket 7-4; Described heating agent or Heating element comprise hot flue gas heating, electrically heated or directly flame heating; Rotating cylinder heating zone 7-5 top is provided with thermal source outlet 7-3, and bottom is provided with thermal source import 7-8; Described shaft leading portion body of heater roof is provided with air outlet 7-2.
As shown in Figure 3, cooling apparatus 6 comprises the cylindrical shell supporting by water cooler bracing or strutting arrangement 6-7, and cylinder lumen is provided with heat exchanging pipe 6-4, by the cavity between cylinder body outer wall and heat exchanging pipe 6-4, forms water cooler shell side 6-3; Barrel front end is provided with water cooler feed end 6-5, and cylindrical shell tail end is provided with water cooler discharge end 6-8, and water cooler discharge end 6-8 connects heat-eliminating medium entrance 6-1 by swivel joint 6-2; On cylindrical shell, be provided with water cooler transmission mechanism 6-6; On described swivel joint 6-2, be provided with heat-eliminating medium outlet 6-9.
Wherein, mixing equipment is intermittent type or continous way mixing equipment, and mixing equipment is coulter type mixer, agravic formula mixing machine or bipyramid screw mixer.
The embodiment of method comprises:
1) lithium ore is sent into lithium ore storage bunker 10, and the lithium ore in feed bin 10, after metering outfit 9 meterings, is sent into mixing equipment 8.For lithium ore, the present invention is not particularly limited, the beta spodumene that can select α triphane to form after high temperature roasting transition, or lithionite etc. obtains corresponding concentrate containing lithium minerals matter and through ore dressing, or other is containing silicate, phosphoric acid salt, borate, the fluorochemical ore of lithium, or other waste containing lithium, by product etc.Preferably, the beta spodumene that uses α triphane to form after high temperature roasting transition.For handling equipment, the present invention is not particularly limited, and can select the methods well known in the art such as rotary conveyor, chapelet, bucket conveyer.Preferably, use chapelet.For metering outfit, the present invention is not particularly limited, and can select weighing belt, helix balance, Weightlessness balance etc., preferred, uses helix balance.
2) simultaneously, in pickling installation 4, use after the vitriol oil washing acidifying baking tail gases from vitriol oil storage tank 11, with oleum its concentration of Mixed adjustment in nitration mixture equipment 5 from oleum storage tank 12, in nitration mixture equipment 5, more than its concentration to 93% of Mixed adjustment, send into mixing equipment 8; Or directly by the vitriol oil or fuming acid or two kinds of acid, be mixed, send into mixing equipment 8.For vitriol oil concentration, the present invention is not particularly limited, preferred, the vitriol oil that working concentration is 98.3%; For oleum concentration, the present invention is not particularly limited, preferred, uses free SO
3concentration is that 20%(conversion sulfuric acid concentration is 104.5%) oleum.
3) lithium ore powder is sent into external heat type rotary furnace 7 after fully mixing in mixing equipment 8 with nitration mixture, carries out acidification reaction.Lithium ore is with the material acid of sulfuric acid than being 2～6:1, and preferred, material acid is than being 4:1; For mixing equipment, the present invention is not particularly limited, and can select the methods well known in the art such as coulter type mixer, agravic formula mixing machine, bipyramid screw mixer, Double shaft stirring blender, preferred, uses agravic formula mixing machine.
External heat type rotary furnace barrel body rotation required drive of the present invention is provided by transmission mechanism 7-10 by external connection power, and pickling installation 4 is derived and sent into the gas that acidizing fired process produces by pneumatic outlet 7-2; Heating agent or the Heating element of rotating cylinder heating zone 7-5 institute heat requirement in external heat chuck 7-4 provides, and rotating cylinder continues to be warming up to acidizing fired final temperature from hot arc 7-6 by exothermic heat of reaction; For the type of heating of external heat type rotary furnace, the present invention is not particularly limited, and can select the methods well known in the art such as hot flue gas heating, electrically heated, direct flame heating, preferred, uses cycling hot flue gas heating; For the temperature of acidizing fired reaction, the present invention is not particularly limited, and preferred, temperature of reaction is 200～300 ℃; For the pressure of acidizing fired reaction, the present invention is not particularly limited, preferred, under micro-positive/negative-pressure of ± 500Pa, carries out.
4) from external heat type rotary furnace 7 discharge end 7-7 acidifying grog out, send into water cooler 6 and be cooled to certain temperature.The temperature that need be cooled to for acidifying grog, the present invention is not particularly limited, and can be cooled to 50～150 ℃, is preferably cooled to 80 ℃; For cooling apparatus, the present invention is not particularly limited, and can select the methods well known in the art such as rotary cooler, chain-plate type water cooler, preferred, uses rotary cooler, preferred, uses shell and tube revolution water cooler.Cooling shell and tube revolution water cooler, the high temperature acidified grog coming from external heat type rotary furnace is sent into water cooler 6 by feed end 6-5, enter water cooler shell side 6-3, with cooler cylinder rotation, to discharge end 6-8, move and discharge thus water cooler and send into subsequent handling, heat-eliminating medium enters swivel joint 6-2 by heat-eliminating medium entrance 6-1, by swivel joint, enter heat exchanging pipe 6-4, and by heat-eliminating medium outlet 6-9, drawn after high temperature acidified grog heat exchange in water cooler shell side 6-3; Rotating cylinder is supported by bracing or strutting arrangement 6-7, and barrel body rotation required drive is provided by transmission mechanism 6-6 by external connection power.Adopt shell and tube revolution water cooler to carry out the cooling of acidifying grog, heat exchange efficiency is high, good operational environment, heat-eliminating medium are easy to realize heat recuperation after heat exchange.
5) sour gas of drawing from external heat type rotary furnace 7 airways is used the vitriol oil absorption portion sour gas from vitriol oil storage tank 11 pickling installation 4, in alkali cleaning equipment 3, use again the alkali liquid washing from alkali lye storage tank 2, remove after remaining sour gas by chimney 1 qualified discharge.For absorption acid concentration, the present invention is not particularly limited, preferred, the vitriol oil that working concentration is 98.3%; For alkali cleaning alkali kind, the present invention is not particularly limited, and can select the methods well known in the art such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, preferred, uses sodium hydroxide; For alkali cleaning concentration of lye, the present invention is not particularly limited, and preferred, working concentration is 10%; For tail gas absorption equipment, the present invention is not particularly limited, preferred, uses tower equipment, preferred, uses the packing tower of anti-corrosion material.
Fig. 1 is pyrolytic process schema of the present invention, after lithium ore in feed bin 10 mixes in mixing equipment 8 with sulfuric acid after metering outfit 9 meterings, in external heat type rotary furnace 7, through acidizing fired generation acidifying grog, acidifying grog is cooled to temperature required through cooling apparatus 6; Acidizing fired sulfuric acid used is used after oleum is adjusted concentration in nitration mixture equipment 5 by the acid solution of washing after tail gas, also can be directly by the vitriol oil or fuming acid or two kinds of acid, be mixed; The tail gas that acidizing fired process produces in pickling installation 4 through overpickling, in alkali cleaning equipment 3 after alkali cleaning by chimney 1 qualified discharge, the major part when pickling of the sour gas in tail gas is returned to roasting system recycling with washing acid.
Fig. 2 is nucleus equipment external heat type rotary furnace schematic diagram of the present invention, rotating cylinder heating zone 7-5, rotating cylinder, from hot arc 7-6, external heat chuck 7-4, feed end 7-1, discharge end 7-7, thermal source import 7-8, thermal source outlet 7-3, pneumatic outlet 7-2, bracing or strutting arrangement 7-9, transmission mechanism 7-10, consists of.Rotating cylinder heating zone 7-5 institute heat requirement is provided by external heat chuck 7-4, and rotating cylinder continues to be warming up to acidizing fired final temperature from hot arc 7-6 by exothermic heat of reaction; External thermal source is introduced by thermal source import 7-8, and after conducting heat to rotating cylinder heating zone 7-5, by thermal source outlet, 7-3 draws; Rotating cylinder is supported by bracing or strutting arrangement 7-9, and barrel body rotation required drive is provided by transmission mechanism 7-10 by external connection power, and pickling installation 4 is derived and sent into the gas that acidizing fired process produces by pneumatic outlet 7-2.
Embodiment 1
1), through roasting high temperature transition and send into triphane feed bin to 200 object beta spodumenes by chapelet through cooling, levigate, material composition sees the following form:
| Component | Li 2O | SiO 2 | Al 2O 3 | P 2O 5 | K 2O | Na 2O | FeO | MgO | CaO | MnO | F | Scaling loss |
| Content % | 6.00 | 62.21 | 28.42 | - | 0.15 | 0.14 | 0.12 | 0.13 | 0.11 | - | - | - |
Illustrate: "-" is test item not, and its content counts in other impurity.
The discharge of triphane feed bin uses Pneumatic floating system and bulkhead rocking equipment.Triphane in feed bin, by after screw feeder Weighing, enters plough coulter type blender;
2) vitriol oil that simultaneously, the sulfuric acid of acidizing fired use is 98.3% by concentration and free SO
3be 20% the oleum composition that is mixed, after two kinds of acid are adjusted concentration to 100% ± 2% in nitration mixture groove, send into plough coulter type blender 8.
3) by the triphane powder after weighing device accurate weighing, fully mixing in plough coulter type blender with the nitration mixture from nitration mixture groove, beta spodumene is 3.5:1 with the material acid ratio of sulfuric acid, mixed material is by acidifying stove feed auger, enter external heat type rotary furnace and carry out roasting, acidifying stove chuck is designed to two sections, leading portion reacts required heat to be provided by converter external jacket interior heat wind, hot blast is burnt and provides in roasting kiln by producer gas generator coal gas and air, back segment carries out spontaneous thermopositive reaction, 250 ℃ of material final temperatures, under micro-positive/negative-pressure that acidification reaction is ± 500Pa at pressure, carry out, the transformation efficiency of acidification reaction is 90%～100%.
4) from external heat type rotary furnace 7 stove tails acidifying material out, by discharging spiral, send into revolution water cooler 6 and be cooled to 65 ℃, use recirculated water is heat-eliminating medium, 31 ℃ of inflow temperatures, and 36 ℃ of return water temperatures, backwater is sent into after water cooling tower is cooled to 31 ℃ and is recycled; By embedded scraper transporter, sent into down and leached together operation subsequently, in acidifying grog, the leaching yield of Lithium Sulphate is 98.5%.In acidization, producing high temperature acid gas is derived and to be sent into exhaust gas recovery system and process by burner airway.
5) the high temperature acid gas of drawing from external heat type rotary furnace burner airway, the sulphur trioxide of the part sulfurous gas that the water vapour that main component is volatilization, sulfuric acid vapor, reaction produce, the generation of sulfuric acid decomposed, a small amount of dust and the micro-air of the system of bleeding.Through sulfuric acid absorption part water vapour and SO for pickling tower
3, then the sodium hydroxide solution that is 6% through concentration in soda-wash tower washing, remove remaining sour gas up to standard rear emptying.
Embodiment 2
1) extraneous next beta spodumene raw material is sent into triphane feed bin, and material composition sees the following form:
| Component | Li 2O | SiO 2 | Al 2O 3 | P 2O 5 | K 2O | Na 2O | FeO | MgO | CaO | MnO | F | Scaling loss |
| Content % | 6.00 | 62.21 | 28.42 | - | 0.15 | 0.14 | 0.12 | 0.13 | 0.11 | - | - | - |
Illustrate: "-" is test item not, and its content counts in other impurity.
Broken arch spiral is set in feed bin, after the triphane in feed bin measures by belt balance weighing, enters after agravic mixer mixes with sulfuric acid and send into and turn round acidifying stove.Single-machine dust remover is equipped with at feed bin top, removes triphane and enters the dust that feed bin dropping process produces.
2) simultaneously, the vitriol oil that the sulfuric acid of acidizing fired use is 93% by concentration is delivered to sulfuric acid absorption tower, and free SO
3concentration is that 60% oleum is sent into nitration mixture groove, and the sulfuric acid of coming with the sulfuric acid scrubbing tower composition that is mixed, sends into agravic mixing equipment 8 after two kinds of acid are adjusted concentration to 100% ± 2% in nitration mixture groove.
3) by the triphane after weighing device accurate weighing, fully mix in agravic mixer with the nitration mixture from nitration mixture groove, beta spodumene is 4:1 with the material acid ratio of sulfuric acid, mixed material is by acidifying stove feed auger, enter external heat type rotary furnace and carry out roasting, acidifying stove chuck is designed to two sections, leading portion reacts required heat to be provided by the electrothermal part in converter external jacket, back segment carries out spontaneous thermopositive reaction, 280 ℃ of material final temperatures, carry out under micro-positive/negative-pressure that acidification reaction is ± 500Pa at pressure; The transformation efficiency of acidification reaction is 90%～100%.
4) from external heat type rotary furnace 7 stove tails acidifying grog out, by discharging spiral, send into revolution water cooler 6 and be cooled to 50 ℃, use de-salted water is heat-eliminating medium, 20 ℃ of inflow temperatures, 65 ℃ of leaving water temperature(LWT)s, boiler is sent in water outlet, cooled acidifying grog is sent into down and is leached together operation, and the leaching yield of Lithium Sulphate reaches more than 99%.
5) the high temperature acid gas of drawing from external heat type rotary furnace burner airway, the sulphur trioxide of the part sulfurous gas that the water vapour that main component is volatilization, sulfuric acid vapor, reaction produce, the generation of sulfuric acid decomposed, a small amount of dust and the micro-air of the system of bleeding.Through pickling tower more than 90% sour gas of sulfuric acid absorption, then the sodium hydroxide solution that is 8% through concentration in soda-wash tower washing, remove remaining sour gas up to standard rear emptying.
Embodiment 3
1) extraneous next beta spodumene raw material is sent into triphane feed bin, and material composition sees the following form:
| Component | Li 2O | SiO 2 | Al 2O 3 | P 2O 5 | K 2O | Na 2O | FeO | MgO | CaO | MnO | F | Scaling loss |
| Content % | 6.00 | 64.76 | 27.72 | - | - | 0.22 | 0.32 | 0.16 | - | - | - | - |
Illustrate: "-" is test item not, and its content counts in other impurity.
Broken arch spiral is set in feed bin, after the triphane in feed bin measures by belt balance weighing, enters after agravic mixer mixes with sulfuric acid and send into and turn round acidifying stove.
2) simultaneously, concentration is that 98% sulfuric acid is delivered to sulfuric acid absorption tower, concentration is that 20% oleum is sent into the sulfuric acid that nitration mixture groove comes with sulfuric acid scrubbing tower and mixed, and as the acid that feeds intake of mixer, after two kinds of acid are adjusted concentration to 100% ± 2% in nitration mixture groove, sends into agravic mixing equipment 8.
3) by the triphane after weighing device accurate weighing, fully mix in agravic mixer with the nitration mixture from nitration mixture groove, beta spodumene is 2:1 with the material acid ratio of sulfuric acid, mixed material is by acidifying stove feed auger, enter external heat type rotary furnace and carry out roasting, acidifying stove chuck is designed to two sections, leading portion reacts required heat from the cycling hot flue gas in converter external jacket, hot flue gas is burnt and provides in roasting kiln by Sweet natural gas and air, back segment carries out spontaneous thermopositive reaction, 300 ℃ of material final temperatures, under micro-positive/negative-pressure that acidification reaction is ± 500Pa at pressure, carry out, the transformation efficiency of acidification reaction is 90%～100%.
4) from stove tail acidifying material out, by discharging spiral, send into revolution water cooler 6, be cooled to 150 ℃.Use soft water is heat-eliminating medium, 20 ℃ of inflow temperatures, and 65 ℃ of leaving water temperature(LWT)s, boiler is sent in water outlet; Cooled acidifying grog is sent into down and is leached together operation, and the leaching yield of Lithium Sulphate reaches more than 99%.
5) the high temperature acid gas of drawing from external heat type rotary furnace burner airway, the sulphur trioxide of the part sulfurous gas that the water vapour that main component is volatilization, sulfuric acid vapor, reaction produce, the generation of sulfuric acid decomposed, a small amount of dust and the micro-air of the system of bleeding.Through sulfuric acid absorption part water vapour and SO for pickling tower
3, then the sodium hydroxide solution that is 6% through concentration in soda-wash tower absorption, remove remaining sour gas up to standard rear emptying.
Embodiment 4
1) extraneous come through pyroprocessing and levigately to 200 object lithionite concentrate, send into lithionite feed bin, material composition sees the following form:
| Component | Li 2O | Rb 2O | Cs 2O | Na 2O | K 2O | F - | CaO | MgO | MnO | Al 2O 3 | SiO 2 | Fe 2O 3 |
| Content % | 3.98 | 1.88 | 0.76 | 1.61 | 8.68 | 5.83 | 0.04 | 0.18 | 0.01 | 24.30 | 51.80 | 0.04 |
Lithionite in feed bin, after helix balance continuous measurement, is sent into agravic formula mixer.
2) simultaneously, concentration is that 98.3% sulfuric acid is delivered to pickling tower, in pickling tower, use after the vitriol oil washing acidifying baking tail gases from vitriol oil storage tank, with the oleum that is 20% from oleum storage tank concentration its concentration of Mixed adjustment in nitration mixture groove, after adjusting concentration to 100% ± 2% in nitration mixture groove, two kinds of acid send into agravic formula mixer.
3) lithionite powder is sent into external heat type rotary furnace after fully mixing in agravic formula mixer with sulfuric acid, and lithionite is 2:1 with the material acid ratio of sulfuric acid, mixed material enters external heat type rotary furnace and carries out roasting, acidifying stove chuck is designed to two sections, leading portion reacts required heat to be provided by converter external jacket interior heat wind, hot blast is burnt and provides in roasting kiln by producer gas generator coal gas and air, back segment carries out spontaneous thermopositive reaction, 480 ℃ of hot gas approach temperature, 350 ℃ of hot exhanst gas outlet temperature, 45% hot flue gas returns to the mixed wind that hot flue gas that Coalhotairfurnace and burning produce forms 480 ℃ and sends into hot flue gas chuck, 200 ℃ of material final temperatures, acidizing fired institute heat requirement is provided by the hot flue gas chuck of external heat type rotary furnace outside, hot flue gas in chuck is burnt and provides in Coalhotairfurnace by hard coal and air, under micro-positive/negative-pressure that acidification reaction is ± 500Pa at pressure, carry out, the transformation efficiency of acidification reaction is 90%～100%.
4) from external heat type rotary furnace 7 discharge ends acidifying grog out, send into shell and tube revolution water cooler 6 and be cooled to 80 ℃, material rotates and constantly to discharge end, moves with water cooler at water cooler shell side, heat-eliminating medium in water cooler tubulation with hot acidifying grog indirect heat exchange, use recirculated water is heat-eliminating medium, 31 ℃ of inflow temperatures, 37 ℃ of return water temperatures, backwater is sent into after water cooling tower is cooled to 31 ℃ and is recycled, and the loss of recirculated water is supplemented by service water.By embedded scraper transporter, sent into down and leached together operation subsequently, in gained acidifying grog, the leaching yield of Lithium Sulphate reaches more than 98.7%.In acidization, producing high temperature acid gas is derived and to be sent into exhaust gas recovery system and process by burner airway.
5) vitriol oil that it is 98.3% that the sour gas of drawing from external heat type rotary furnace burner airway is used from vitriol oil storage tank concentration pickling tower absorbs more than 90% sour gas, the sodium hydroxide solution that is 8% by concentration in soda-wash tower again washing, removes after remaining sour gas by chimney qualified discharge.
Embodiment 5
1) extraneous next beta spodumene raw material is sent into triphane feed bin, and material composition sees the following form:
| Component | Li 2O | SiO 2 | Al 2O 3 | P 2O 5 | K 2O | Na 2O | FeO | MgO | CaO | MnO | F | Scaling loss |
| Content % | 6.00 | 64.76 | 27.72 | - | - | 0.22 | 0.32 | 0.16 | - | - | - | - |
Illustrate: "-" is test item not, and its content counts in other impurity.
Feed bin outer wall arranges concussion feeding device, after the triphane in feed bin measures by belt balance weighing, enters after bipyramid screw mixer mixes with sulfuric acid and sends into and turn round acidifying stove.
2), use after the vitriol oil washing acidifying baking tail gases from vitriol oil storage tank 11 in pickling installation 4, the vitriol oil that the sulfuric acid of acidizing fired use is 98.3% by concentration is sent into bipyramid spiral mixing equipment 8 in nitration mixture groove simultaneously.
3) by the triphane powder after weighing device accurate weighing, fully mixing in bipyramid screw mixer with the nitration mixture from nitration mixture groove, beta spodumene is 4:1 with the material acid ratio of sulfuric acid, mixed material is by acidifying stove feed auger, enter external heat type rotary furnace and carry out roasting, acidifying stove chuck is designed to two sections, leading portion reacts required heat to be provided by converter external jacket interior heat wind, hot blast is burnt and provides in roasting kiln by producer gas generator coal gas and air, back segment carries out spontaneous thermopositive reaction, hot flue gas in chuck is burnt and provides in hotblast stove by two stage type gas generating furnace cooled coal gas and air, 520 ℃ of hot gas approach temperature, 380 ℃ of hot exhanst gas outlet temperature, 65% hot flue gas returns to the mixed wind that hot flue gas that Coalhotairfurnace and burning produce forms 520 ℃ and sends into hot flue gas chuck, 270 ℃ of material final temperatures, under micro-positive/negative-pressure that acidification reaction is ± 500Pa at pressure, carry out, the transformation efficiency of acidification reaction is 90%～100%.
4) from external heat type rotary furnace 7 discharge ends acidifying grog out, send into shell and tube revolution water cooler and be cooled to 100 ℃, material rotates and constantly to discharge end, moves with water cooler at water cooler shell side, heat-eliminating medium in water cooler tubulation with hot acidifying grog indirect heat exchange, use de-salted water is heat-eliminating medium, 25 ℃ of inflow temperatures, 75 ℃ of leaving water temperature(LWT)s, water outlet is sent into boiler and is produced steam.In gained acidifying grog, the leaching yield of Lithium Sulphate reaches more than 98.7%.
5) vitriol oil washing absorption that it is 98.3% that the sour gas of drawing from external heat type rotary furnace airway is used from vitriol oil storage tank concentration pickling tower, the washing of sodium hydroxide solution that gas after washing is 8% by concentration again in soda-wash tower, removes after remaining sour gas by chimney qualified discharge.
It should be noted that: the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein replaced on an equal basis.
All within spirit of the present invention, principle and aim, in the ken that one skilled in the relevant art possesses, any modification of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. one kind is utilized external heat type rotary furnace to carry out the acidizing fired system of lithium ore, comprise feed bin (10), and the metering outfit (9) being connected with feed bin (10), described metering outfit connects mixing equipment (8), it is characterized in that: described mixing equipment (8) is connected with external heat type rotary furnace (7), external heat type rotary furnace (7) connects respectively pickling installation (4) and cooling apparatus (6); The air outlet of described pickling installation (4) connects alkali cleaning equipment (3), and the discharge port of pickling installation (4) connects nitration mixture equipment (5), and the opening for feed of pickling installation (4) connects vitriol oil storage tank (11); Described nitration mixture equipment (5) is connected with oleum storage tank (12); Described alkali cleaning equipment (3) is connected with respectively lye vat (2) and chimney (1).
2. a kind of external heat type rotary furnace that utilizes according to claim 1 carries out the acidizing fired system of lithium ore, it is characterized in that: described external heat type rotary furnace (7) comprises the body of heater supporting by rotary kiln bracing or strutting arrangement (7-9), and described body of heater comprises that successively connected shaft leading portion, rotating cylinder heating zone (7-5), rotating cylinder are from hot arc (7-6) and rotary kiln discharge end (7-7); Described shaft leading portion is connected with the rotary kiln feed end (7-1) of carrying by motor, and shaft leading portion is provided with rotary kiln transmission mechanism (7-10);
Described rotating cylinder heating zone (7-5) is provided with heating jacket (7-4), in heating jacket (7-4), establishes heating agent or Heating element; Described heating agent or Heating element comprise hot flue gas heating, electrically heated or directly flame heating;
Described rotating cylinder heating zone (7-5) top is provided with thermal source outlet (7-3), and bottom is provided with thermal source import (7-8); Described shaft leading portion body of heater roof is provided with air outlet (7-2).
3. a kind of external heat type rotary furnace that utilizes according to claim 1 carries out the acidizing fired system of lithium ore, it is characterized in that: described cooling apparatus (6) comprises the cylindrical shell supporting by water cooler bracing or strutting arrangement (6-7), described cylinder lumen is provided with heat exchanging pipe (6-4), by the cavity between cylinder body outer wall and heat exchanging pipe (6-4), forms water cooler shell side (6-3); Described barrel front end is provided with water cooler feed end (6-5), and cylindrical shell tail end is provided with water cooler discharge end (6-8), and water cooler discharge end (6-8) connects heat-eliminating medium entrance (6-1) by swivel joint (6-2); On described cylindrical shell, be provided with water cooler transmission mechanism (6-6);
On described swivel joint (6-2), be provided with heat-eliminating medium outlet (6-9).
4. a kind of external heat type rotary furnace that utilizes according to claim 1 carries out the acidizing fired system of lithium ore, it is characterized in that: described mixing equipment is intermittent type or continous way mixing equipment, mixing equipment is coulter type mixer, agravic formula mixing machine or bipyramid screw mixer.
5. utilize external heat type rotary furnace to carry out the acidizing fired method of lithium ore, it is characterized in that, the method comprises the steps:
1) lithium ore is sent into lithium ore storage bunker (10), and the lithium ore in feed bin (10), after metering outfit (9) metering, is sent into mixing equipment (8);
2), in pickling installation (4), use after the vitriol oil washing acidifying baking tail gases from vitriol oil storage tank (11) simultaneously, with oleum its concentration of Mixed adjustment in nitration mixture equipment (5) from oleum storage tank (12), send into mixing equipment (8); Or directly by the vitriol oil or fuming acid or two kinds of acid, be mixed, send into mixing equipment (8);
3) lithium ore powder is sent into external heat type rotary furnace (7) after fully mixing in mixing equipment (8) with nitration mixture, carries out acidification reaction;
4) from external heat type rotary furnace (7) discharge end (7-7) acidifying grog out, sending into cooling apparatus (6) is cooled to certain temperature and discharges and send into subsequent handling;
5) sour gas of drawing from external heat type rotary furnace (7) escape pipe is used the vitriol oil absorption portion sour gas from vitriol oil storage tank (11) pickling installation (4), all the other sour gas are used the alkali liquid washing from lye vat (2) again in alkali cleaning equipment (3), remove after remaining sour gas by chimney (1) qualified discharge;
Described sulfuric acid concentration is 93%～98.3%, and oleum concentration is for containing free SO
30%～60% sulfuric acid, in nitration mixture equipment (5) more than its concentration to 93% of Mixed adjustment;
In described step 3), lithium ore powder mixes than the ratio that is 2～6:1 according to mass ratio with the material acid of mixing acid, carries out acidification reaction;
In described step 3), acidification reaction temperature is 200～300 ℃; Pressure is ± micro-positive/negative-pressure of 500Pa; The transformation efficiency of acidification reaction is 90%～100%;
Cooling apparatus in described step 4) (6) cooling temperature is 50-150 ℃.
6. a kind of external heat type rotary furnace that utilizes according to claim 5 carries out the acidizing fired method of lithium ore, it is characterized in that, in described step 1), lithium ore powder refers to beta spodumene or the lithionite concentrate that α triphane forms after high temperature roasting transition.
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| CN103162528A (en) * | 2013-03-19 | 2013-06-19 | 江西本源新材料科技有限公司 | Lepidolite mixed acid heating device |
| CN103160301B (en) * | 2013-03-21 | 2014-04-16 | 何建祥 | Low-temperature carbonization apparatus and method for oil sand, oil sludge, oil shale and biomass |
| CN103204510B (en) * | 2013-04-24 | 2015-04-15 | 成都正远机电设备有限公司 | Spodumene roasting transformation method |
| KR102445712B1 (en) * | 2013-10-23 | 2022-09-20 | 네마스카 리튬 인코포레이션 | Processes for preparing lithium carbonate |
| CN104596294B (en) * | 2015-02-15 | 2016-06-01 | 江西铜业股份有限公司 | A kind of Pt Pd concentrate calciner |
| CN108557847A (en) * | 2018-04-11 | 2018-09-21 | 宜春市鼎鑫高能科技有限公司 | A kind of sour mine hybrid system in lithium carbonate preparation process |
| CN110331280A (en) * | 2019-08-19 | 2019-10-15 | 四川卡森科技有限公司 | A kind of amblygonite roasting acidification system and its roasting acidization tool |
| CN111411219A (en) * | 2020-04-23 | 2020-07-14 | 西安三瑞实业有限公司 | Rare earth concentrate low-temperature acidizing roasting method and device |
| CN111363914A (en) * | 2020-04-23 | 2020-07-03 | 西安三瑞实业有限公司 | System and method for acidizing and roasting rare earth concentrate by using multi-section external heating rotary furnace |
| CN113136485A (en) * | 2021-04-13 | 2021-07-20 | 西安三瑞非常规能源开发有限公司 | Method and device for sulfating and low-temperature roasting of vanadium-containing mineral |
| CN113860337B (en) * | 2021-10-14 | 2023-06-27 | 天齐锂业(射洪)有限公司 | Comprehensive treatment process method for tail gas produced by sulfuric acid method lithium salt |
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