CN105331803A - Roasting defluorination device and technology - Google Patents
Roasting defluorination device and technology Download PDFInfo
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- CN105331803A CN105331803A CN201510705513.7A CN201510705513A CN105331803A CN 105331803 A CN105331803 A CN 105331803A CN 201510705513 A CN201510705513 A CN 201510705513A CN 105331803 A CN105331803 A CN 105331803A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/10—Roasting processes in fluidised form
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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Abstract
The invention provides a roasting defluorination device and technology. The roasting defluorination device comprises a feeding system, a mineral powder preheating system, a fluidized-bed roasting system and a vapor preheating system. The fluidized-bed roasting system comprises a fluidized-bed roasting furnace. The feeding system is connected with the mineral powder preheating system. The mineral powder preheating system and the vapor preheating system are connected with the fluidized-bed roasting system. Optionally, the device further comprises a gas absorption system, a cooling system and an air guiding system, the gas absorbing system and the cooling system are connected with the fluidized-bed roasting system, and the air guiding system and the gas absorbing system are connected. The defluorination rate of the roasting defluorination device reaches more than 85%. A solid fluorine fixing agent is used for absorbing fluorine containing tail gas to recycle fluorine resources. Water of a vapor boiler is preheated by heat generated in the high-temperature defluorination tail gas and defluorination material cooling process to generate high-temperature vapor, the heat utilization rate is high, and vapor consumption is low. The roasting process is good in economical efficiency, and the roasting defluorination device and technology are suitable for large-scale continuous industrial production.
Description
Technical field
The invention belongs to the treatment process technical field of mineral raw material, relate to a kind of New Method for Processing of fluorine-containing mineral defluorinate, particularly relate to a kind of roasting defluorinate device and technique.
Background technology
Elemental lithium be described as be 21 century can source element.Lithium and compound thereof are widely used in the industrial circles such as lithium cell, pottery, glass, aluminum smelting technology, medicine.In recent years, along with lithium ion battery is in the widespread use in portable electric appts, electromobile, space technology and national defense industry field, the demand of lithium is increased day by day.There is abundant reason mica resource in China, its Li
2o content is generally at 4-5%.Therefore, how economic, development and utilization lithionite ore efficiently, significant to China's lithium industry.
At present, the industrial lime-roasting method that generally adopts extracts lithium from lepidolite ore, by Wingdale and lithionite by the part by weight of 3:1 in ball mill ball milling, mix, then through 800 ~ 900 DEG C of high-temperature roasting ripe materials, grog obtains leach liquor and residue through shrend, fine grinding, leaching, filtration or centrifugation again, and leach liquor obtains monohydrate lithium hydroxide through evaporation, crystallization and centrifugation.Lime-roasting method technique is simple, low in raw material price, but has that lithium content in leach liquor is low, evaporation energy consumption is high, the rate of recovery of lithium is low and the shortcoming such as Wingdale proportioning is high.People successively develop chlorinating roasting (ThermochimicaActa, 2000,362,25-35), sulfuric acid process (inorganic chemicals industry, 2004,4,30-31), sulphate process (MineralsEngineering, 2010,23,563-566) and pressure cooking method (non-ferrous metal [Smelting Part], 2001,5,19-21) etc. novel process from lepidolite ore, extract lithium.
Lithium in lepidolite ore exists with the complicated form of fluorine aluminosilicate, and mineral structure is very fine and close, causes the leaching yield of ore grinding difficulty and lithium low.Except chlorination process, all the other techniques all need to carry out high-temperature vapor roasting transition to lithionite in advance, defluorinate process makes the valuable elements such as lithium, potassium, rubidium and the caesium be combined with fluorine change respective oxide compound into.Its short texture after defluorinate process, grindability index are good, and are conducive to the leaching yield improving lithium.Therefore, the processing treatment such as follow-up ore grinding, leaching lithium of roasting defluorinate pre-treatment to lithionite of lithionite has vital role.
Lepidolite ore defluorinate process water partial vapor pressure and maturing temperature water in lithionite roasting defluorination reaction plays two key players.Document (the research of Yichun lithia mica roasting process, Mineral Engineering, 1994,93, roasting process under 56-58) compared for air and having water vapour to exist, finds that water vapour can significantly improve defluorinate efficiency under existing, and thinks that high-temperature vapor is when the lithionite surface of red heat, first absorption, on mineral surface, is then dissociated into H
+and OH
–, and overflow with HF form; Water vapour-lithionite reaction system, mainly by the impact of Thermodynamics (partial potential) and lithionite structure (physical factor), is conducive to removing of fluorine in lithionite under a large amount of steam partial pressure and high temperature; And water vapour to the diffusion of lithionite internal structure or lithium-containing compound to external migration are all the keys affecting water vapour defluorinate efficiency.Therefore, water vapour and lithionite breeze fully contact and reaction is the important factor affecting defluorinate efficiency.
Prior art such as CN201410247471.2, CN201310239742.5, CN201310062852.9, CN201210379229.1, CN201210052443.6 etc. generally adopt the defluorinate of rotary kiln baking lepidolite ore.But, in rotary kiln, water vapour contacts insufficient with lithionite material, inhibit the absorption of water vapour on lithionite surface, to internal diffusion or the migration containing lithium material, cause its defluorinate rate low, the ring formation problem of furnace charge under high temperature is there is time serious, affect the normal operation of equipment, roasting defluorinate is carried out as adopted stainless steel reacting in rotary kiln device in CN201210052443.6, water vapour defluorination reaction 80min is carried out under the high temperature of 860 DEG C, in its defluorinate ore deposit, F content is still up to 2.0wt%, and defluorinate rate only has 40%; Particularly, due to the existence of low melting point in lithionite, make, when rotary kiln processing treatment lithionite, inevitably to occur the melting ring formation problem of the furnace charge under high temperature, thus have a strong impact on the normal running of rotary kiln technology; If the too low defluorinate efficiency that can affect again lithionite of maturing temperature; In addition, the unfavorable factor that energy consumption is high, steam consumption is greatly also restriction rotary kiln baking defluorinate industrial applications and popularization.
On the other hand, in lithionite defluorinate roasting process, fluorine mainly with the effusion of HF form, is directly discharged in air if do not process, will works the mischief to environment.Therefore, the fluorine how recycled in lithionite is lithionite defluorinate sinter process problems faced.CN102530874A discloses the method preparing HF and fluorochemical from lithionite defluorinate tail gas, alkaline solution (sodium hydroxide, milk of lime or ammoniacal liquor) is mainly adopted to absorb HF, drying dehydration obtains corresponding villiaumite, then can prepare HF through dense sulfuric acid treatment.This technique is simple, technology maturation, but the method is owing to adopting wet method alkali liquor absorption, cannot utilize the energy of high-temperature tail gas.
Summary of the invention
For prior art Problems existing, the object of the present invention is to provide a kind of roasting defluorinate device and technique, it is high that described roasting defluorinate device has defluorinate efficiency, and steam consumption is low, the advantage of roasting process good economy performance, is applicable to extensive continuous industry and produces.
For reaching this object, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of roasting defluorinate device, described device comprises feed system, breeze pre-heating system, water vapour pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system comprises fluidized-solids roaster, feed system is connected with breeze pre-heating system, and breeze pre-heating system and water vapour pre-heating system are connected with fluiddized-bed roasting system;
Optionally, described device also comprises gas absorption system, cooling system and induced draught system, and gas absorption system is connected with fluiddized-bed roasting system with cooling system, and induced draught system is connected with gas absorption system.
Described fluiddized-bed roasting system comprises feed valve, fluidized-solids roaster, stoving oven separator and bleeder valve, the opening for feed of described fluidized-solids roaster is connected with feed system by feed valve, the discharge port of fluidized-solids roaster is connected with cooling system by bleeder valve, the inlet mouth of stoving oven separator is connected with the air outlet of fluidized-solids roaster, and the air outlet of stoving oven separator is connected with gas absorption system.
Preferably, described fluidized-solids roaster is 3-7 level fluidized-bed reactor, is preferably 3-5 level fluidized-bed reactor.
Preferably, the fluidisation section of described fluidized-solids roaster is provided with vertical inner member.
Preferably, described gas distribution grid perforate direction is tangential direction circumferentially.
Described breeze pre-heating system comprises coal-fired fluidized bed, coal-fired fluidized bed separator, cyclone preheater and cyclonic separator, coal-fired fluidized bed air outlet is connected with the inlet mouth of coal-fired fluidized bed separator, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator, and the raw meal inlet of cyclone preheater is connected with feed system.
Preferably, described cyclone preheater is 3-6 level cyclone preheater.
Preferably, the discharge port of described cyclonic separator is connected with the raw meal inlet of cyclone preheater, and the air outlet of cyclonic separator is connected with bagroom.
Preferably, described bagroom is connected with feed system through blanking machine.
Described water vapour pre-heating system comprises steam boiler and combustion chamber, and the water outlet of steam boiler is connected with the inlet mouth of combustion chamber, and the water vapour air outlet of combustion chamber is connected with fluiddized-bed roasting system.
Preferably, the flue gas air outlet of combustion chamber is connected with the inlet mouth of steam boiler.
Described feed system comprises hopper and screw feeder, and the discharge port of described hopper is connected with the opening for feed of screw feeder, and the discharge port of described screw feeder is connected with breeze pre-heating system.
Described gas absorption system comprises gas absorbing device and gas-solid separator, and the inlet mouth of gas absorbing device is connected with fluiddized-bed roasting system, and the air outlet of gas absorbing device is connected with the inlet mouth of gas-solid separator.
Preferably, the air outlet of described gas-solid separator is connected with induced draught system by water vapour pre-heating system, and the discharge port of gas-solid separator is connected with gas absorbing device.
Preferably, described gas absorbing device is fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed.
Preferably, fluorine fixing material is filled with in described gas absorbing device.
Preferably, described fluorine fixing material is the combination of any one or at least two kinds in alkalimetal oxide, alkaline earth metal oxide, alkali metal hydroxide or alkaline earth metal hydroxides.
Preferably, described cooling system comprises cooling bed and cooling bed separator, and the opening for feed of cooling bed is connected with fluiddized-bed roasting system, and the air outlet of cooling bed is connected with the inlet mouth of cooling bed separator.
Preferably, the air outlet of described cooling bed separator is connected with water vapour pre-heating system, and the discharge port of cooling bed separator is connected with cooling bed.
Preferably, described induced draught system comprises induced draft fan.
As preferred technical scheme, described device comprises feed system, breeze pre-heating system, fluiddized-bed roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system;
Feed system comprises hopper and screw feeder; Breeze pre-heating system comprises coal-fired fluidized bed, coal-fired fluidized bed separator, cyclone preheater and cyclonic separator; Fluiddized-bed roasting system comprises feed valve, fluidized-solids roaster, stoving oven separator and bleeder valve; Water vapour pre-heating system comprises steam boiler and combustion chamber; Gas absorption system comprises gas absorbing device and gas-solid separator; Cooling system comprises cooling bed and cooling bed separator; Induced draught system comprises induced draft fan;
The discharge port of hopper is connected with the opening for feed of screw feeder, and the discharge port of screw feeder is connected with the raw meal inlet of cyclone preheater; Coal-fired fluidized bed air outlet is connected with the inlet mouth of coal-fired fluidized bed separator, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator, and the discharge port of cyclone preheater is connected with the opening for feed of fluidized-solids roaster by feed valve;
The water outlet of steam boiler is connected with the inlet mouth of combustion chamber, and the water vapour air outlet of combustion chamber is connected with the inlet mouth of fluidized-solids roaster, and the flue gas air outlet of combustion chamber is connected with the inlet mouth of steam boiler, and the air outlet of steam boiler is connected with induced draft fan;
The discharge port of fluidized-solids roaster is connected with the opening for feed of cooling bed by bleeder valve, the air outlet of cooling bed is connected with the inlet mouth of cooling bed separator, and the air outlet of cooling bed separator is connected with the inlet mouth of combustion chamber with the inlet mouth of steam boiler;
The air outlet of fluidized-solids roaster is connected with the inlet mouth of gas absorbing device, and the air outlet of gas absorbing device is connected with the inlet mouth of gas-solid separator, and the air outlet of gas-solid separator is connected with the inlet mouth of steam boiler.
Two of object of the present invention is to provide a kind of technique utilizing device as above to carry out defluorinate, and described technique comprises the steps:
(1) treat that defluorinate material flows into breeze pre-heating system from feed system, carry out preheating, obtain treating defluorinate material after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;
(2) water vapour after defluorinate material and preheating after preheating enters fluidized-solids roaster and carries out defluorination reaction, obtains defluorinate material and fluoro-gas;
Optionally, carry out step (3): the cooling of defluorinate material reclaimed, and purified by fluoro-gas.
Treat described in step (1) that defluorinate material is containing lithium minerals, potassium-bearing mineral or the combination containing a kind of in cesium mineral or at least two kinds, be preferably lepidolite ore;
Preferably, the particle diameter treating defluorinate material described in step (1) is 50-500 μm.
Preferably, the temperature treating defluorinate material after step (2) described preheating is 800-850 DEG C.
Preferably, the temperature of the water vapour after step (2) described preheating is 900-1000 DEG C.
Preferably, the content > 30v% of the water in vapor steam after step (2) described preheating.
Preferably, the temperature of step (2) described defluorination reaction is 820-860 DEG C.
Preferably, treat that the residence time of defluorinate material in fluidized-solids roaster is 30-120min in step (2) after preheating.
The heat produced in step (3) described defluorinate material process of cooling is for the water vapour pre-heating system in step (1).
Preferably, step (3) adopts the combination purification fluoro-gas of a kind of in alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxides or at least two kinds.
Preferably, step (3) adopts K
2o, Na
2the combination purification fluoro-gas of a kind of in O, CaO or MgO or at least two kinds.
Compared with prior art, beneficial effect of the present invention is:
(1) roasting defluorinate device provided by the invention can make water vapour and treat that defluorinate material fully contacts in fluidized-solids roaster, and prevents the sintering ring formation in lepidolite ore roasting defluorinate process;
(2) the defluorinate efficiency of roasting defluorinate device provided by the invention is high, high-temperature vapor defluorinate under employing subnormal ambient, and add the dividing potential drop of water vapour, facilitate the Transport And Transformation of F in lithionite, defluorinate rate reaches more than 85%;
(3) heat utilization ratio of roasting defluorinate device provided by the invention is high, solid adsorbent is adopted to absorb the tail gas of fluiddized-bed roasting system outflow and reclaim F (fluorine) resource, the water that high-temperature gas after purification is used for preheating steam boiler produces high-temperature vapor, has reclaimed the sensible heat of reaction end gas.
Accompanying drawing explanation
Fig. 1 is the lepidolite ore defluorinate device schematic diagram that embodiment 1 provides.
Wherein: 1, hopper; 2, screw feeder; 3-1, first step cyclone preheater; 3-2, second stage cyclone preheater; 3-3, third stage cyclone preheater; 3-4, fourth stage cyclone preheater; 4, feed valve; 5, fluidized-solids roaster; 5-1, stoving oven separator; 6, bleeder valve; 7, cooling bed; 7-1, cooling bed separator; 8, combustion chamber; 9, steam boiler; 10, gas absorbing device; 10-1, gas-solid separator; 11, induced draft fan; 12, coal-fired fluidized bed; 12-1, coal-fired fluidized bed separator; 13, cyclonic separator; 14, bagroom; 15, blanking machine.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
The invention provides a kind of roasting defluorinate device, described device comprises feed system, breeze pre-heating system, fluiddized-bed roasting system and water vapour pre-heating system; Fluiddized-bed roasting system comprises fluidized-solids roaster 5, and feed system is connected with breeze pre-heating system, and breeze pre-heating system and water vapour pre-heating system are connected with fluiddized-bed roasting system;
Optionally, described device also comprises gas absorption system, cooling system and induced draught system, and gas absorption system is connected with fluiddized-bed roasting system with cooling system, and induced draught system is connected with gas absorption system.
Described feed system is used for treating that defluorinate mass transport is to breeze pre-heating system;
Described breeze pre-heating system is used for preheating and treats defluorinate material, makes its temperature reach 800-850 DEG C, and will treat that defluorinate mass transport is to fluiddized-bed roasting system after preheating;
High-temperature vapor for generation of high-temperature vapor (900-1000 DEG C), and is transported to fluiddized-bed roasting system by described water vapour pre-heating system;
Described fluiddized-bed roasting system is used for treating that defluorinate material and high-temperature vapor carry out defluorination reaction after preheating, produces defluorinate material and fluoro-gas after reaction;
Purified gas for absorbing the fluorine in fluoro-gas, and is discharged by described gas absorption system;
Described cooling system, for cooling defluorinate material, is convenient to it and is discharged, collects.
Described induced draught system is connected with fluiddized-bed roasting system by gas absorption system, fluidized-solids roaster 5 is made to form subnormal ambient, enhance the boiling fluidized state of lepidolite ore, can prevent from treating the sintering ring formation in defluorinate material roasting defluorinate process, facilitate water vapour defluorination reaction.
Described fluiddized-bed roasting system comprises feed valve 4, fluidized-solids roaster 5, stoving oven separator 5-1 and bleeder valve 6, the opening for feed of described fluidized-solids roaster 5 is connected with feed system by feed valve 4, the discharge port of fluidized-solids roaster 5 is connected with cooling system by bleeder valve 6, the inlet mouth of stoving oven separator 5-1 is connected with the air outlet of fluidized-solids roaster 5, and the air outlet of stoving oven separator 5-1 is connected with gas absorption system.
Preferably, described fluidized-solids roaster 5 is 3-7 level fluidized-bed reactor, as 3 grades, 4 grades, 5 grades, 6 grades or 7 grades of fluidized-bed reactors, is preferably 3-5 level fluidized-bed reactor.
Preferably, the fluidisation section of described fluidized-solids roaster 5 is provided with vertical inner member.
Preferably, described gas distribution grid perforate direction is tangential direction circumferentially, make lepidolite ore in fluidized-solids roaster 5 fluidisation in a rotative pattern, increase the residence time of lepidolite ore in fluidized-solids roaster 5, make lepidolite ore and water vapour fully contact and defluorination reaction occurs.
Described breeze pre-heating system comprises coal-fired fluidized bed 12, coal-fired fluidized bed separator 12-1, cyclone preheater and cyclonic separator 13, the air outlet of coal-fired fluidized bed 12 is connected with the inlet mouth of coal-fired fluidized bed separator 12-1, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator 12-1, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator 13, and the raw meal inlet of cyclone preheater is connected with feed system.
Preferably, described cyclone preheater is 3-6 level cyclone preheater, as 3 grades of cyclone preheaters, 4 grades of cyclone preheaters, 5 grades of cyclone preheaters or 6 grades of cyclone preheaters etc.
Preferably, the described discharge port of cyclonic separator 13 is connected with the raw meal inlet of cyclone preheater, and the air outlet of cyclonic separator 13 is connected with bagroom 14.
Preferably, described bagroom 14 is connected with feed system through blanking machine 15.
Described water vapour pre-heating system comprises steam boiler 9 and combustion chamber 8, and the water outlet of steam boiler 9 is connected with the inlet mouth of combustion chamber 8, and the water vapour air outlet of combustion chamber 8 is connected with fluiddized-bed roasting system.
Preferably, the flue gas air outlet of combustion chamber 8 is connected with the inlet mouth of steam boiler 9.The high-temperature flue gas flowed out from combustion chamber 8 enters steam boiler 9 preheating water steam, improves the utilising efficiency of waste heat, is conducive to save energy.
Described feed system comprises hopper 1 and screw feeder 2, and the discharge port of described hopper 1 is connected with the opening for feed of screw feeder 2, and the discharge port of described screw feeder 2 is connected with breeze pre-heating system.
Described gas absorption system comprises gas absorbing device 10 and gas-solid separator 10-1, and the inlet mouth of gas absorbing device 10 is connected with fluiddized-bed roasting system, and the air outlet of gas absorbing device 10 is connected with the inlet mouth of gas-solid separator 10-1.
Preferably, the air outlet of described gas-solid separator 10-1 is connected with induced draught system by water vapour pre-heating system, and the discharge port of gas-solid separator 10-1 is connected with gas absorbing device 10.
Preferably, described gas absorbing device 10 is fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed.
Preferably, fluorine fixing material is filled with in described gas absorbing device 10.
Preferably, described fluorine fixing material is the combination of any one or at least two kinds in alkalimetal oxide, alkaline earth metal oxide, alkali metal hydroxide or alkaline earth metal hydroxides.
Adopt solid matter can avoid purifying the waste of waste heat in fluoro-gas process as fluorine fixing material.
Preferably, described cooling system comprises cooling bed 7 and cooling bed separator 7-1, and the opening for feed of cooling bed 7 is connected with fluiddized-bed roasting system, and the air outlet of cooling bed 7 is connected with the inlet mouth of cooling bed separator 7-1.
Preferably, the air outlet of described cooling bed separator 7-1 is connected with water vapour pre-heating system, and the discharge port of cooling bed separator 7-1 is connected with cooling bed 7.
Preferably, described induced draught system comprises induced draft fan 11.
As preferred technical scheme, described device comprises feed system, breeze pre-heating system, fluiddized-bed roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system;
Feed system comprises hopper 1 and screw feeder 2; Breeze pre-heating system comprises coal-fired fluidized bed 12, coal-fired fluidized bed separator 12-1, cyclone preheater and cyclonic separator 13; Fluiddized-bed roasting system comprises feed valve 4, fluidized-solids roaster 5, stoving oven separator 5-1 and bleeder valve 6; Water vapour pre-heating system comprises steam boiler 9 and combustion chamber 8; Gas absorption system comprises gas absorbing device 10 and gas-solid separator 10-1; Cooling system comprises cooling bed 7 and cooling bed separator 7-1; Induced draught system comprises induced draft fan 11;
The discharge port of hopper 1 is connected with the opening for feed of screw feeder 2, and the discharge port of screw feeder 2 is connected with the raw meal inlet of cyclone preheater; The air outlet of coal-fired fluidized bed 12 is connected with the inlet mouth of coal-fired fluidized bed separator 12-1, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator 12-1, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator 13, and the discharge port of cyclone preheater is connected with the opening for feed of fluidized-solids roaster 5 by feed valve 4;
The water outlet of steam boiler 9 is connected with the inlet mouth of combustion chamber 8, the water vapour air outlet of combustion chamber 8 is connected with the inlet mouth of fluidized-solids roaster 5, the flue gas air outlet of combustion chamber 8 is connected with the inlet mouth of steam boiler 9, and the air outlet of steam boiler 9 is connected with induced draft fan 11;
The discharge port of fluidized-solids roaster 5 is connected with the opening for feed of cooling bed 7 by bleeder valve 6, the air outlet of cooling bed 7 is connected with the inlet mouth of cooling bed separator 7-1, and the air outlet of cooling bed separator 7-1 is connected with the inlet mouth of combustion chamber 8 with the inlet mouth of steam boiler 9;
The air outlet of fluidized-solids roaster 5 is connected with the inlet mouth of gas absorbing device 10, and the air outlet of gas absorbing device 10 is connected with the inlet mouth of gas-solid separator 10-1, and the air outlet of gas-solid separator 10-1 is connected with the inlet mouth of steam boiler 9.
Present invention also offers a kind of technique utilizing device as above to carry out roasting defluorinate, described technique comprises the steps:
(1) treat that defluorinate material flows into breeze pre-heating system from feed system, carry out preheating, obtain treating defluorinate material after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;
(2) water vapour after defluorinate material and preheating after preheating enters fluidized-solids roaster 5 and carries out defluorination reaction, obtains defluorinate material and fluoro-gas;
Optionally, carry out step (3): the cooling of defluorinate material reclaimed, and purified by fluoro-gas.
Treat described in step (1) that defluorinate material is containing lithium minerals, potassium-bearing mineral or the combination containing a kind of in cesium mineral or at least two kinds, be preferably lepidolite ore.
Preferably, treat described in step (1) that the particle diameter of defluorinate material is 50-500 μm, as 55 μm, 60 μm, 80 μm, 100 μm, 200 μm, 300 μm, 400 μm or 450 μm etc.
Preferably, the temperature treating defluorinate material after step (2) described preheating is 800-850 DEG C, as 810 DEG C, 820 DEG C, 830 DEG C, 840 DEG C or 850 DEG C etc.
Preferably, the temperature of the water vapour after step (2) described preheating is 900-1000 DEG C, as 910 DEG C, 920 DEG C, 930 DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 970 DEG C, 980 DEG C or 990 DEG C etc.
Preferably, the content > 30v% (" v% " all represents percent by volume if no special instructions) of the water in vapor steam after step (2) described preheating, as 35v%, 40v%, 50v%, 60v%, 70v%, 80v%, 90v% or 95v% etc.
Preferably, the temperature of step (2) described defluorination reaction is 820-860 DEG C, as 830 DEG C, 840 DEG C, 850 DEG C or 855 DEG C etc.
Preferably, treat that the residence time of defluorinate material in fluidized-solids roaster 5 is 30-120min, as 40min, 50min, 70min, 80min, 90min, 100min or 110min etc. in step (2) after preheating.
The heat produced in step (3) described defluorinate material process of cooling is for the water vapour pre-heating system in step (1).
Preferably, step (3) adopts alkalimetal oxide, alkali metal hydroxide, the combination purification fluoro-gas of a kind of in alkaline earth metal oxide or alkaline earth metal hydroxides or at least two kinds, typical but non-limitingly to be combined as: alkalimetal oxide and alkali metal hydroxide, alkaline earth metal oxide and alkaline earth metal hydroxides, alkalimetal oxide and alkaline earth metal oxide, alkalimetal oxide, alkali metal hydroxide and alkaline earth metal oxide, alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide and alkaline earth metal hydroxides etc.
Preferably, step (3) adopts K
2o, Na
2the combination purification fluoro-gas of a kind of in O, CaO or MgO or at least two kinds, is typical but non-limitingly combined as K
2o and Na
2o, CaO and MgO, K
2o and CaO, K
2o, Na
2o and CaO, K
2o, Na
2o, CaO and MgO etc.
Embodiment 1
Fig. 1 provides a kind of structural representation of lepidolite ore fluiddized-bed roasting defluorinate device, and described device comprises: feed system, breeze pre-heating system, fluosolids roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system.
Feed system is used for lithionite breeze to be transported to breeze pre-heating system, comprises hopper 1, screw feeder 2;
Breeze pre-heating system is used for preheating lepidolite ore, its temperature is made to reach 800-850 DEG C, comprise coal-fired fluidized bed 12, coal-fired fluidized bed separator 12-1, Category Four cyclone preheater and cyclonic separator 13, Category Four cyclone preheater comprise be connected successively first step cyclone preheater 3-1, second stage cyclone preheater 3-2, third stage cyclone preheater 3-3 and fourth stage cyclone preheater 3-4;
Fluosolids roasting system is the place of lithionite breeze and water vapour reaction, comprise feed valve 4, fluidized-solids roaster 5, stoving oven separator 5-1 and bleeder valve 6, fluidized-solids roaster 5 is multistage fluidized bed reactor, be preferably 3-7 level, more preferably 3-5 level, the fluidisation section of fluidized-solids roaster 5 is provided with vertical inner member, and gas distribution grid perforate direction is tangential direction circumferentially;
Water vapour pre-heating system is used for preheating water steam, makes the temperature of water vapour reach 900-1000 DEG C, by the moisture vapor transport after preheating to fluiddized-bed roasting system, comprises steam boiler 9 and combustion chamber 8;
The fluoro-gas that gas absorption system produces for purifying fluiddized-bed roasting system, absorbs HF and SiF comprised in fluoro-gas
4, reclaim F resource, the high-temperature gas after purification is transported to water vapour pre-heating system simultaneously and is used for preheating water steam, comprise gas absorbing device 10 and gas-solid separator 10-1, gas absorbing device 10 can be fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed;
Cooling system is used for the defluorinate material that cooling bed 7 roasting system produces, and the sensible heat in cooling defluorinate material process is used for the preheating of water vapour simultaneously, comprises cooling bed 7 and cooling bed separator 7-1;
Induced draught system is used for making fluidized-solids roaster 5 form subnormal ambient, make to treat that defluorinate material increases the dividing potential drop of water vapour in fluiddized-bed roasting system in boiling fluidized state in fluidized-solids roaster 5, promote the Transport And Transformation treating F in defluorinate material, promote water vapour defluorination reaction, comprise induced draft fan 11;
The mode of connection of described feed system, breeze pre-heating system, fluosolids roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system is as follows:
The discharge port of hopper 1 is connected by the opening for feed of pipeline with screw feeder 2, and the discharge port of screw feeder 2 is connected by the opening for feed of pipeline with first step cyclone preheater 3-1;
The air outlet of coal-fired fluidized bed 12 is connected with the inlet mouth of coal-fired fluidized bed separator 12-1, the air outlet of coal-fired fluidized bed separator 12-1 is communicated with the inlet mouth of fourth stage cyclone preheater 3-4, the air outlet of first step cyclone preheater 3-13-1 is connected by the inlet mouth of pipeline with cyclonic separator 13, and the air outlet of cyclonic separator 13 is connected by the inlet mouth of pipeline with bagroom 14; The breeze that bagroom 14 is collected is back to hopper 1 through blanking machine 15; The discharge port of fourth stage cyclone preheater 3-4 is connected with feed valve 4 by pipeline;
The water outlet of steam boiler 9 is connected with the inlet mouth of combustion chamber 8, and the water vapour air outlet of combustion chamber 8 is connected with the inlet mouth of fluidized-solids roaster 5, and the flue gas air outlet of combustion chamber 8 is connected with the inlet mouth of steam boiler 9;
The opening for feed of fluidized-solids roaster 5 is communicated with the discharge port of fourth stage cyclone preheater 3-4, inlet mouth bottom fluidized-solids roaster 5 is connected by the air outlet of pipeline with combustion chamber 8, the air outlet at fluidized-solids roaster 5 top is connected with stoving oven separator 5-1 inlet mouth by pipeline, the discharge port of stoving oven separator 5-1 is connected with fluidized-solids roaster 5 by pipeline, and the air outlet of stoving oven separator 5-1 is connected by the inlet mouth of pipeline with gas absorbing device 10; The discharge port on fluidized-solids roaster 5 top is connected by the opening for feed of pipeline with bleeder valve 6, and the discharge port of bleeder valve 6 is connected by the opening for feed of pipeline with cooling bed 7 bottom;
The inlet mouth of gas absorbing device 10 is connected with the air outlet of stoving oven separator 5-1, the air outlet of gas absorbing device 10 is connected with the inlet mouth of gas-solid separator 10-1, the air outlet of gas-solid separator 10-1 is connected with the inlet mouth of steam boiler 9, and the discharge port of gas-solid separator 10-1 is connected with gas absorbing device 10;
Inlet mouth bottom cooling bed 7 is connected with air line by pipeline, the air outlet at cooling bed 7 top is communicated with by the inlet mouth of pipeline with cooling bed separator 7-1, the air outlet of cooling bed separator 7-1 is connected with the inlet mouth of combustion chamber 8 and the inlet mouth of steam boiler 9 by pipeline, cooling bed 7 bottom is provided with discharge port, discharges after the cooling of defluorinate material from discharge port;
Induced draft fan 11 is connected with the air outlet of steam boiler 9.
The technique adopting described roasting defluorinate device to treat the defluorinate of defluorinate material is as follows:
In coal-fired fluidized bed 12, coal dust and air fully contact and combustion reactions occurs produce high-temperature hot flue gas, the high-temperature hot flue gas produced is sent in fourth stage cyclone preheater 3-4 after separator is separated, and treat defluorinate material by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 preheating successively, make its temperature reach 800-850 DEG C; The rear cinder of reaction is discharged from the bottom discharge mouth of coal-fired fluidized bed 12;
The cold water passed into from the water-in of steam boiler 9 and the high-temperature gas heat exchange from gas-solid separator 10-1, combustion chamber 8 and cooling bed separator 7-1, the water vapour of discharging from the water outlet of steam boiler 9 enters combustion chamber 8 and improves temperature further, makes the temperature of water vapour reach 900-1000 DEG C;
The lithionite breeze of 800-850 DEG C enters fluidized-solids roaster 5 by feed valve 4 and contacts with the water vapour from the 900-1000 bottom fluidized-solids roaster 5 DEG C and react, and produces defluorinate material and fluoro-gas;
The defluorinate material that fluidized-solids roaster 5 produces enters cooling bed 7 by bleeder valve 6, discharges through cooled defluorinate material, and the high-temperature gas produced in process of cooling is used as the thermal source of steam boiler 9 and combustion chamber 8;
The fluoro-gas that fluidized-solids roaster 5 produces is separated through stoving oven separator 5-1, the solid particulate being separated generation returns fluidized-solids roaster 5 and proceeds calcination, be separated the gas produced and enter gas absorbing device 10, the high temperature purification gas produced after fluorine fixing material defluorinate enters steam boiler 9, as the thermal source of preheating water steam;
Induced draft fan 11 is connected with the air outlet of steam boiler 9, produces subnormal ambient for making fluidized-solids roaster 5.
Embodiment 2
The device utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 800 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (900 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 5 grades of fluidized-bed reactors, lithionite breeze median size 50 μm, feeding rate is 300kg/h, maturing temperature 850 DEG C, water vapour content is 99.9v%, fluidizing gas velocity is 0.1m/s, residence time of material is 120min, defluorination reaction removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed,
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is CaO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification in preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 88.3%.
Comparative example 1
The device utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and in Category Four cyclone preheater, carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 800 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (900 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 1 grade of fluidized-bed reactor, lithionite breeze median size 50 μm, feeding rate is 300kg/h, maturing temperature 850 DEG C, water vapour content is 99.9v%, fluidizing gas velocity 0.1m/s, residence time of material is 25min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is CaO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification for preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 69.5%.
Embodiment 3
The device utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 850 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (1000 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 3 grades of fluidized-bed reactors, lithionite breeze median size 100 μm, feeding rate is 300kg/h, maturing temperature 860 DEG C, water vapour content 30v%, fluidizing gas velocity 0.1m/s, residence time of material 30min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is MgO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification in preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 86.5%.
Embodiment 4
The fluiddized-bed roasting defluorinate system utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 850 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (950 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 4 grades of fluidized-bed reactors, lithionite breeze median size 180 μm, feeding rate is 300kg/h, maturing temperature is 850 DEG C, water vapour content 50v%, fluidizing gas velocity 0.1m/s, residence time of material 90min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is CaO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification in preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 87.8%.
Embodiment 5
The fluiddized-bed roasting defluorinate system utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 860 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (800 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 4 grades of fluidized-bed reactors, lithionite breeze median size 300 μm, feeding rate is 300kg/h, maturing temperature 820 DEG C, water vapour content 40v%, fluidizing gas velocity 0.1m/s, residence time of material 60min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is NaOH, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification in preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 85.3%.
Embodiment 6
The fluiddized-bed roasting defluorinate system utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 840 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (890 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 3 grades of fluidized-bed reactors, lithionite breeze median size 450 μm, and feeding rate is 300kg/h, maturing temperature 820 DEG C, water vapour content 40v%, fluidizing gas velocity 0.1m/s, residence time of material 45min; Remove the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is CaO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification in preheating steam boiler 9 water produce high-temperature vapor;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 85.9%.
Embodiment 7
The fluiddized-bed roasting defluorinate system utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 820 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (860 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 4 grades of fluidized-bed reactors, lithionite breeze median size 100 μm, feeding rate is 300kg/h, maturing temperature 820 DEG C, water vapour content 85v%, fluidizing gas velocity 0.1m/s, residence time of material 75min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is K
2o, Na
2o and CaO, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification produces high-temperature vapor for the water in preheating steam boiler 9;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 85.1%.
Embodiment 8
The fluiddized-bed roasting defluorinate system utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 810 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (860 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 4 grades of fluidized-bed reactors, lithionite breeze median size 50 μm, feeding rate is 300kg/h, maturing temperature 830 DEG C, water vapour content 70v%, fluidizing gas velocity 0.1m/s, residence time of material 100min, removes the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is K
2o and Na
2o, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification produces high-temperature vapor for the water in preheating steam boiler 9;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 86.9%.
Embodiment 9
The device utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:
(1) lithionite breeze is added in hopper 1, deliver to fourth stage cyclone preheater 3-4 through screw feeder 2, and carry out heat exchange by third stage cyclone preheater 3-3, second stage cyclone preheater 3-2 and first step cyclone preheater 3-1 and the high-temperature hot flue gas from coal-fired fluidized bed 12 successively; Meanwhile, steam boiler 9 and combustion chamber 8 produce high-temperature vapor;
(2) the lithionite breeze temperature after preheating rises to 860 DEG C, be admitted to fluidized-solids roaster 5, fully contact with the high-temperature vapor (900 DEG C) from combustion chamber 8 and carry out roasting defluorination reaction, its calcination condition is: fluidized-solids roaster 5 is 6 grades of fluidized-bed reactors, lithionite breeze median size 500 μm, and feeding rate is 300kg/h, maturing temperature 860 DEG C, water vapour content 33v%, fluidizing gas velocity 0.1m/s, residence time of material 90min; Remove the F be combined with valuable elements such as Li, and lepidolite ore phase structure is changed;
(3) that discharges from fluidized-solids roaster 5 contains HF and SiH
4gas be admitted in gas absorbing device 10 reclaim, the fluorine fixing material in gas absorbing device is K
2o, the high-temperature tail gas (defluorinate rate is greater than 98%) after purification produces high-temperature vapor for the water in preheating steam boiler 9;
(4) breeze after calcination is admitted in cooling bed 7 and cools, and obtains defluorinate ore deposit, and the heat produced in defluorinate process produces high-temperature vapor for the water in preheating steam boiler 9 and combustion chamber 8.
In the present embodiment, the defluorinate rate of lithionite breeze is 85.5%.
Applicant states; the foregoing is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; person of ordinary skill in the field should understand; anyly belong to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all drop within protection scope of the present invention and open scope.
Claims (10)
1. a roasting defluorinate device, it is characterized in that, described roasting defluorinate device comprises feed system, breeze pre-heating system, water vapour pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system comprises fluidized-solids roaster (5), feed system is connected with breeze pre-heating system, and breeze pre-heating system and water vapour pre-heating system are connected with fluiddized-bed roasting system;
Optionally, described device also comprises gas absorption system, cooling system and induced draught system, and gas absorption system is connected with fluiddized-bed roasting system with cooling system, and induced draught system is connected with gas absorption system.
2. device according to claim 1, it is characterized in that, described fluiddized-bed roasting system comprises feed valve (4), fluidized-solids roaster (5), stoving oven separator (5-1) and bleeder valve (6), the opening for feed of described fluidized-solids roaster (5) is connected with feed system by feed valve (4), the discharge port of fluidized-solids roaster (5) is connected with cooling system by bleeder valve (6), the inlet mouth of stoving oven separator (5-1) is connected with the air outlet of fluidized-solids roaster (5), the air outlet of stoving oven separator (5-1) is connected with gas absorption system,
Preferably, described fluidized-solids roaster (5) is 3-7 level fluidized-bed reactor, is preferably 3-5 level fluidized-bed reactor;
Preferably, the fluidisation section of described fluidized-solids roaster (5) is provided with vertical inner member;
Preferably, described gas distribution grid perforate direction is tangential direction circumferentially.
3. device according to claim 1 and 2, it is characterized in that, described breeze pre-heating system comprises coal-fired fluidized bed (12), coal-fired fluidized bed separator (12-1), cyclone preheater and cyclonic separator (13), the air outlet of coal-fired fluidized bed (12) is connected with the inlet mouth of coal-fired fluidized bed separator (12-1), the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator (12-1), the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator (13), the raw meal inlet of cyclone preheater is connected with feed system,
Preferably, described cyclone preheater is 3-6 level cyclone preheater;
Preferably, the discharge port of described cyclonic separator (13) is connected with the raw meal inlet of cyclone preheater, and the air outlet of cyclonic separator (13) is connected with bagroom (14);
Preferably, described bagroom (13) is connected with feed system through blanking machine (15).
4. according to the device one of claim 1-3 Suo Shu, it is characterized in that, described water vapour pre-heating system comprises steam boiler (9) and combustion chamber (8), the water outlet of steam boiler (9) is connected with the inlet mouth of combustion chamber (8), and the water vapour air outlet of combustion chamber (8) is connected with fluiddized-bed roasting system;
Preferably, the flue gas air outlet of combustion chamber (8) is connected with the inlet mouth of steam boiler (9).
5. according to the device one of claim 1-4 Suo Shu, it is characterized in that, described feed system comprises hopper (1) and screw feeder (2), the discharge port of described hopper (1) is connected with the opening for feed of screw feeder (2), and the discharge port of described screw feeder (2) is connected with breeze pre-heating system.
6. according to the device one of claim 1-5 Suo Shu, it is characterized in that, described gas absorption system comprises gas absorbing device (10) and gas-solid separator (10-1), the inlet mouth of gas absorbing device (10) is connected with fluiddized-bed roasting system, and the air outlet of gas absorbing device (10) is connected with the inlet mouth of gas-solid separator (10-1);
Preferably, the air outlet of described gas-solid separator (10-1) is connected with induced draught system by water vapour pre-heating system, and the discharge port of gas-solid separator (10-1) is connected with gas absorbing device (10);
Preferably, described gas absorbing device (10) is fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed;
Preferably, fluorine fixing material is filled with in described gas absorbing device (10);
Preferably, described fluorine fixing material is the combination of any one or at least two kinds in alkalimetal oxide, alkaline earth metal oxide, alkali metal hydroxide or alkaline earth metal hydroxides;
Preferably, described cooling system comprises cooling bed (7) and cooling bed separator (7-1), the opening for feed of cooling bed (7) is connected with fluiddized-bed roasting system, and the air outlet of cooling bed (7) is connected with the inlet mouth of cooling bed separator (7-1);
Preferably, the air outlet of described cooling bed separator (7-1) is connected with water vapour pre-heating system, and the discharge port of cooling bed separator (7-1) is connected with cooling bed (7);
Preferably, described induced draught system comprises induced draft fan (11).
7. according to the device one of claim 1-6 Suo Shu, it is characterized in that, described device comprises feed system, breeze pre-heating system, fluiddized-bed roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system;
Feed system comprises hopper (1) and screw feeder (2); Breeze pre-heating system comprises coal-fired fluidized bed (12), coal-fired fluidized bed separator (12-1), cyclone preheater and cyclonic separator (13); Fluiddized-bed roasting system comprises feed valve (4), fluidized-solids roaster (5), stoving oven separator (5-1) and bleeder valve (6); Water vapour pre-heating system comprises steam boiler (9) and combustion chamber (8); Gas absorption system comprises gas absorbing device (10) and gas-solid separator (10-1); Cooling system comprises cooling bed (7) and cooling bed separator (7-1); Induced draught system comprises induced draft fan (11);
The discharge port of hopper (1) is connected with the opening for feed of screw feeder (2), and the discharge port of screw feeder (2) is connected with the raw meal inlet of cyclone preheater; The air outlet of coal-fired fluidized bed (12) is connected with the inlet mouth of coal-fired fluidized bed separator (12-1), the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator (12-1), the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator (13), and the discharge port of cyclone preheater is connected with the opening for feed of fluidized-solids roaster (5) by feed valve (4);
The water outlet of steam boiler (9) is connected with the inlet mouth of combustion chamber (8), the water vapour air outlet of combustion chamber (8) is connected with the inlet mouth of fluidized-solids roaster (5), the flue gas air outlet of combustion chamber (8) is connected with the inlet mouth of steam boiler (9), and the air outlet of steam boiler (9) is connected with induced draft fan (11);
The discharge port of fluidized-solids roaster (5) is connected with the opening for feed of cooling bed (7) by bleeder valve (6), the air outlet of cooling bed (7) is connected with the inlet mouth of cooling bed separator (7-1), and the air outlet of cooling bed separator (7-1) is connected with the inlet mouth of combustion chamber (8) with the inlet mouth of steam boiler (9);
The air outlet of fluidized-solids roaster (5) is connected with the inlet mouth of gas absorbing device (10), the air outlet of gas absorbing device (10) is connected with the inlet mouth of gas-solid separator (10-1), and the air outlet of gas-solid separator (10-1) is connected with the inlet mouth of steam boiler (9).
8. utilize the described device of one of claim 1-7 to carry out the technique of defluorinate, it is characterized in that, described technique comprises the steps:
(1) treat that defluorinate material flows into breeze pre-heating system from feed system, carry out preheating, obtain treating defluorinate material after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;
(2) water vapour after defluorinate material and preheating after preheating enters fluidized-solids roaster and carries out defluorination reaction, obtains defluorinate material and fluoro-gas;
Optionally, carry out step (3): the cooling of defluorinate material reclaimed, and purified by fluoro-gas.
9. technique according to claim 8, is characterized in that, treats that defluorinate material is containing lithium minerals, potassium-bearing mineral or the combination containing a kind of in cesium mineral or at least two kinds, be preferably lepidolite ore described in step (1);
Preferably, treat described in step (1) that the particle diameter of defluorinate material is 50-500 μm;
Preferably, the temperature treating defluorinate material after step (2) described preheating is 800-850 DEG C;
Preferably, the temperature of the water vapour after step (2) described preheating is 900-1000 DEG C;
Preferably, the content > 30v% of the water in vapor steam after step (2) described preheating;
Preferably, the temperature of step (2) described defluorination reaction is 820-860 DEG C;
Preferably, treat that the residence time of defluorinate material in fluidized-solids roaster is 30-120min in step (2) after preheating.
10. technique according to claim 8 or claim 9, it is characterized in that, the heat produced in step (3) described defluorinate material process of cooling is for the water vapour pre-heating system in step (1);
Preferably, step (3) adopts the combination purification fluoro-gas of a kind of in alkalimetal oxide, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxides or at least two kinds;
Preferably, step (3) adopts K
2o, Na
2the combination purification fluoro-gas of a kind of in O, CaO or MgO or at least two kinds.
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| CN109827426A (en) * | 2019-03-07 | 2019-05-31 | 北京航化节能环保技术有限公司 | A kind of anticorrosive roasting system and method |
| CN110316748A (en) * | 2019-08-22 | 2019-10-11 | 中国科学院过程工程研究所 | A kind of roasting system and the method for producing Alpha-alumina |
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