CN105385844A

CN105385844A - Roasting defluorination device and process

Info

Publication number: CN105385844A
Application number: CN201510705630.3A
Authority: CN
Inventors: 朱庆山; 李军; 孔景; 李洪钟
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2015-10-27
Filing date: 2015-10-27
Publication date: 2016-03-09
Anticipated expiration: 2035-10-27
Also published as: CN105385844B

Abstract

The invention provides a roasting defluorination device and a process. The roasting defluorination device comprises a material mixing system, a mixture preheating system, a water vapor preheating system and a fluidized-bed roasting system. The fluidized-bed roasting system comprises a fluidized-bed roaster. The material mixing system is connected with the mixture preheating system. The mixture preheating system and the water vapor preheating system are connected with the fluidized-bed roasting system. Optionally, the device further comprises a gas absorbing system, a cooling system and an induced draught system. The gas absorbing system and the cooling system are connected with the fluidized-bed roasting system, and the induced draught system is connected with the gas absorbing system. According to the device, in-situ defluorination can be achieved, the fluorine removal rate reaches 95% or above, and the defluorination rate reaches 90% or above. High-temperature water vapor is produced through high-temperature defluorination tail gas, high-temperature smoke generated by a combustion chamber and heat generated during defluorination material cooling, and the heat utilization rate is high. Water vapor consumption is low, the roasting process is good in economical efficiency, and the roasting defluorination device and the process are suitable for large-scale continuous industrial production.

Description

A kind of roasting defluorinate device and technique

Technical field

The invention belongs to the treatment process technical field of mineral raw material, relate to a kind of roasting defluorinate device and technique, particularly relate to a kind of lepidolite ore fluiddized-bed roasting defluorinate device and technique.

Background technology

Lithium and compound thereof are the important foundation raw materials of lithium electricity new energy materials.The mainly mode of depositing of occurring in nature lithium resource is salt lake brine and pegmatite ore.Wherein, lithionite generally only originates in pegmatite ore, is one of two kinds of topmost industrial lithium mineral.In order to effectively lithionite can be utilized, domestic and international scientific worker has carried out a large amount of research work, achieve many experiences of producing lithium salts from lithionite, but since U.S.'s potash and San Antonio lithium factory of chemical company stopped production in 1966, not yet there is extensive process lithionite to produce the factory of lithium salts in the world.There is abundant reason mica resource in China, its Li ₂how efficiently, economic this part lithium resource of development and utilization O content is generally at 4-5%, significant to China's lithium industry.

At present, lepidolite extracted lithium method mainly comprises lime burning method, chlorinating roasting, sulfuric acid process, sulphate process and pressure cooking method.Industrial, from lepidolite ore, extract lithium generally adopt lime burning method, by Wingdale and lithionite by the part by weight of 3:1 in ball mill ball milling, mix; Through 800 ~ 900 DEG C of high-temperature roastings, then obtain leach liquor and residue through shrend, fine grinding, leaching, filtration or centrifugation, leach liquor obtains monohydrate lithium hydroxide through evaporation, crystallization and centrifugation.It is simple that lime burning method has technique, the advantages such as low in raw material price, but have that Wingdale proportioning is high, the rate of recovery of lithium is low, the shortcoming such as the low and evaporation energy consumption of lithium content is high in leach liquor.Sulfatizing roasting method is usually used in processing silicate minerals, but when extracting lithium for lithionite, leaches through batching, pelletizing, roasting, dilute sulphuric acid, and leach liquor obtains Quilonum Retard through purification, precipitation.Sulfuric acid process process lepidolite ore needs the roasting of water vapour defluorinate in advance, then adds sulfuric acid baking dissolving.Chlorinating roasting adopts chlorizating agent to make the lithium in lithionite and other valuable metals be converted into muriate.Compared with lime burning method, sulfuric acid process, pressure cooking method and chlorinating roasting energy consumption leaching yield that is low, lithium are high, have the trend replacing limestone-based process.

Due to lepidolite ore compact structure, lithium exists with the complicated form of fluorine aluminosilicate, makes the leaching of ore grinding and lithium very difficult.In order to improve the leaching yield of lithium, need to carry out high-temperature vapor defluorinate process to lithionite in advance, its short texture after defluorinate process, grindability index are good, are conducive to the leaching yield improving lithium.In lithionite roasting defluorinate process, steam partial pressure and maturing temperature are principal elements.Document (research of Yichun lithia mica roasting process, Mineral Engineering, 1994,93,56-58) result shows, and water vapour can significantly improve defluorinate efficiency under existing.Think 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.In water vapour-lithionite reaction system, mainly by the impact of Thermodynamics (partial potential) and lithionite structure (physical factor) two aspects, under a large amount of steam partial pressure and high temperature, be conducive to removing of fluorine in lithionite.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.

But existing lithionite defluorinate roasting method (as CN201410247471.2, CN201310239742.5, CN201310062852.9, CN201210379229.1 and CN201210052443.6 etc.) still adopts rotary kiln baking technique.The subject matter of rotary kiln technology has:

(1) water vapour contacts insufficient with lithionite material, is unfavorable for the absorption of water vapour on lithionite surface, to internal diffusion or containing the migration of lithium material, thus causes its defluorinate rate low.As adopted stainless steel reacting in rotary kiln device to carry out roasting defluorinate in CN201210052443.6 patent, carry out water vapour defluorination reaction 80min under 860 DEG C of high temperature, in its defluorinate ore deposit, F content is still up to 2.0wt%, and defluorinate rate only has 40%.

(2) problem such as ring formation of furnace charge under high temperature: due to the existence of low melting point in lithionite, make when rotary kiln processing treatment lithionite, when maturing temperature is too high, inevitably occurs that furnace charge is at furnace wall melting ring formation, 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.

(3) utilization ratio of high temperature defluorinate tail gas is low, there is the shortcoming that energy consumption is high, steam consumption quantity is large and less economical, is also the unfavorable factor of restriction rotary kiln baking defluorinate industrial applications and popularization.

(4) fluorine resource recycling is unreasonable, and 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, adopts alkaline solution (sodium hydroxide, milk of lime or ammoniacal liquor) to absorb HF, and 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, described roasting defluorinate device can realize the solid fluorine of original position, Gu fluorine rate reaches more than 95%, desorption rate reaches more than 90%, and water vapour consumption is low, 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 Component Mixing System, preheating of mixed material system, water vapour pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system comprises fluidized-solids roaster, Component Mixing System is connected with preheating of mixed material system, and preheating of mixed material 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 Component Mixing 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 preheating of mixed material 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 Component Mixing 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 Component Mixing 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 described combustion chamber is connected with the inlet mouth of preheating of mixed material system or steam boiler.

Preferably, the air outlet of described steam boiler is connected with induced draught system.

Described Component Mixing System comprises hopper, screw feeder and mixing bunker, and the discharge port of mixing bunker is connected with the opening for feed of hopper, and 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 preheating of mixed material 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 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 or compressor.

Preferably, described induced draught system is connected with gas absorption system by water vapour pre-heating system.

As preferred technical scheme, described roasting defluorinate device comprises Component Mixing System, preheating of mixed material system, fluiddized-bed roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system;

Component Mixing System comprises mixing bunker, hopper and screw feeder; Preheating of mixed material 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 or compressor;

The discharge port of mixing bunker is connected with the opening for feed of hopper, and 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 that providing a kind of utilizes described roasting defluorinate device to carry out the technique of defluorinate, and described technique comprises the steps:

(1) after defluorinate material mixes with defluorinating agent in mixing bunker, enter preheating of mixed material system and carry out preheating, obtain the mixture after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;

(2) mixture after preheating and the water vapour after preheating enter fluidized-solids roaster and carry out defluorination reaction, obtain defluorinate thing, solid fluoride and fluoro-gas;

Optionally, carry out step (3): the cooling of defluorinate ore deposit reclaimed, and purified by fluoro-gas.

Treat 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 described in step (1).

Preferably, the particle diameter treating defluorinate material described in step (1) is 50-500 μm.

Preferably, step (1) described defluorinating agent is the mixture of a kind of in the oxide compound of Na, K, Ca or Mg, oxyhydroxide, vitriol or carbonate or at least two kinds.

Preferably, the particle diameter of step (1) described defluorinating agent is 100-600 μm.

Preferably, the stoichiometry of resultant after reacting according to defluorinating agent and F, the excessive 10-90% of usage quantity of step (1) described defluorinating agent.

The temperature of the mixture 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 > 10v% of the water in vapor steam after step (2) described preheating.

Preferably, the temperature of step (2) described defluorination reaction is 830-860 DEG C.

Preferably, the residence time of mixture in fluidized-solids roaster in step (2) after preheating is 30-120min.

Preferably, the solid fluoride in step (2) obtains HF gas through dissolving.

Preferably, the heat produced in the process of cooling of step (3) described defluorinate ore deposit is for the water vapour pre-heating system in step (1).

Preferably, the 10-90v% of Purge gas that obtains of step (3) is for the water vapour preheating 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 carries out defluorination reaction owing to adopting fluidized-solids roaster, water vapour can be made and treat that defluorinate material fully contacts in fluidized-solids roaster, improve defluorinate efficiency (more than 90%), prevent the sintering ring formation in roasting defluorinate process, thus facilitating the Transport And Transformation of F in lithionite, defluorinate rate reaches more than 90%;

(2) roasting defluorinate device provided by the invention can realize original position defluorinate, the solid fluorine rate of defluorinating agent is up to more than 95%, the solid fluoride obtained after defluorinating agent and fluoro-gas react can be converted into high-purity HF gas, prevent the effusion of HF gas in reaction process, decrease the corrosion of HF gas to follow up device and the pollution of environment;

(3) the defluorinate efficiency of roasting defluorinate device provided by the invention is high, defluorinate rate reaches more than 90%, fluorine fixing material and defluorinating agent is adopted to carry out double defluorinate, defluorinate tail gas can return fluidized-solids roaster to be continued to participate in defluorination reaction, improve water vapour utilization ratio, reduce water vapour consumption, good economy performance;

(4) heat utilization ratio of roasting defluorinate device provided by the invention is high, the heat produced in high temperature defluorinate tail gas, combustion chamber heat flue gas and cooling defluorinate material process is utilized to produce high-temperature vapor, reclaim the sensible heat in reaction end gas and defluorinate ore deposit, reduce energy consumption.

Accompanying drawing explanation

Fig. 1 is the lepidolite ore defluorinate device schematic diagram that embodiment 1 provides.

Fig. 2 is the structural representation of the lepidolite ore fluiddized-bed roasting defluorinate device that embodiment 2 provides.

Wherein: 1, mixing bunker; 2, hopper; 3, screw feeder; 4-1, first step cyclone preheater; 4-2, first step cyclone preheater; 4-3, third stage cyclone preheater; 4-4, fourth stage cyclone preheater; 5, feed valve; 6, fluidized-solids roaster; 6-1, stoving oven separator; 7, bleeder valve; 8, cooling bed; 8-1, cooling bed separator; 9, combustion chamber; 10, steam boiler; 11, gas absorbing device; 11-1, gas-solid separator; 12, induced draft fan; 13, coal-fired fluidized bed; 13-1, coal-fired fluidized bed separator; 14, cyclonic separator; 15, bagroom; 16, blanking machine; 17, compressor.

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 Component Mixing System, preheating of mixed material system, water vapour pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system comprises fluidized-solids roaster 6, Component Mixing System is connected with preheating of mixed material system, and preheating of mixed material system and water vapour pre-heating system are connected with fluiddized-bed roasting system;

Described Component Mixing System is used for treating defluorinate material and defluorinating agent mixing, and mixture is transported to preheating of mixed material system;

Described preheating of mixed material system is used for the mixture that defluorinate material and defluorinating agent are treated in preheating, makes its temperature reach 800-860 DEG C, and the mixture after preheating is transported to fluiddized-bed roasting system;

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;

Mixture after described fluiddized-bed roasting system is used for preheating and high-temperature vapor carry out defluorination reaction, defluorinate ore deposit, solid fluoride and fluoro-gas is produced after reaction, defluorinating agent can be caught rapidly water vapour and be treated the HF gas that defluorinate material reaction produces, generate solid fluoride, thus realize original position defluorinate, therefore, the concentration of the HF gas in fluoro-gas is very low;

Purified gas for absorbing the fluorine in fluoro-gas, and is discharged by described gas absorption system;

Described cooling system, for cooling defluorinate ore deposit, is convenient to defluorinate ore deposit and is discharged, collects.

Described induced draught system is used for making fluidized-solids roaster 6 form subnormal ambient, and the boiling fluidized state of defluorinate material is treated in strengthening, prevents from treating the sintering ring formation of defluorinate material in roasting defluorinate process, promotes water vapour defluorination reaction.

Described fluiddized-bed roasting system comprises feed valve 5, fluidized-solids roaster 6, stoving oven separator 6-1 and bleeder valve 7, the opening for feed of described fluidized-solids roaster 6 is connected with Component Mixing System by feed valve 5, the discharge port of fluidized-solids roaster 6 is connected with cooling system by bleeder valve 7, the inlet mouth of stoving oven separator 6-1 is connected with the air outlet of fluidized-solids roaster 6, and the air outlet of stoving oven separator 6-1 is connected with gas absorption system.

Preferably, described fluidized-solids roaster 6 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 6 is provided with vertical inner member.

Preferably, described gas distribution grid perforate direction is tangential direction circumferentially, make lepidolite ore in fluidized-solids roaster 6 fluidisation in a rotative pattern, increase the residence time of lepidolite ore in fluidized-solids roaster 6, make lepidolite ore and water vapour fully contact and defluorination reaction occurs.

Described preheating of mixed material system comprises coal-fired fluidized bed 13, coal-fired fluidized bed separation 13-1, cyclone preheater and cyclonic separator 14, the air outlet of coal-fired fluidized bed 13 is connected with the inlet mouth of coal-fired fluidized bed separator 13-1, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator 13-1, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator 14, and the raw meal inlet of cyclone preheater is connected with Component Mixing System.

Preferably, described cyclone preheater is 3-6 level cyclone preheater, as being 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 14 is connected with the raw meal inlet of cyclone preheater, and the air outlet of cyclonic separator 14 is connected with bagroom 15.

Preferably, described bagroom 15 is connected with Component Mixing System through blanking machine 16.

Described water vapour pre-heating system comprises steam boiler 10 and combustion chamber 9, and the water outlet of steam boiler 10 is connected with the inlet mouth of combustion chamber 9, and the water vapour air outlet of combustion chamber 9 is connected with fluiddized-bed roasting system.

Preferably, the flue gas air outlet of described combustion chamber 9 is connected with the inlet mouth of preheating of mixed material system or steam boiler 10.

Preferably, the air outlet of described steam boiler 10 is connected with induced draught system.

Described Component Mixing System comprises hopper 2, screw feeder 3 and mixing bunker 1, the discharge port of mixing bunker 1 is connected with the opening for feed of hopper 2, the discharge port of hopper 2 is connected with the opening for feed of screw feeder 3, and the discharge port of screw feeder 3 is connected with preheating of mixed material system.

Mixing bunker 1 for being transported to preheating of mixed material system by hopper 2 and screw feeder 3 after defluorinate material and defluorinating agent fully mix.

Described gas absorption system comprises gas absorbing device 11 and gas-solid separator 11-1, and the inlet mouth of gas absorbing device 11 is connected with fluiddized-bed roasting system, and the air outlet of gas absorbing device 11 is connected with the inlet mouth of gas-solid separator 11-1.

Preferably, the air outlet of described gas-solid separator 11-1 is connected with water vapour pre-heating system, and the discharge port of gas-solid separator 11-1 is connected with gas absorbing device 11.The high-temperature gas that gas absorption system is discharged is used for preheating water steam, has reclaimed the waste heat in treating processes, has been conducive to save energy.

Preferably, described gas absorbing device 11 is fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed.

Preferably, fluorine fixing material is filled with in described gas absorbing device 11.

Adopt solid matter can avoid the waste of waste heat in purification fluoro-gas process as fluorine fixing material.

Preferably, described cooling system comprises cooling bed 8 and cooling bed separator 8-1, and the opening for feed of cooling bed 8 is connected with fluiddized-bed roasting system, and the air outlet of cooling bed 8 is connected with the inlet mouth of cooling bed separator 8-1.

Preferably, the air outlet of described cooling bed separator 8-1 is connected with water vapour pre-heating system, and the discharge port of cooling bed separator 8-1 is connected with cooling bed 8.The high-temperature gas that cooling bed 8 produces after cooling defluorinate ore deposit, for water vapour preheating, improves the utilising efficiency of waste heat, is conducive to save energy.

Preferably, described induced draught system comprises induced draft fan 12 or compressor 17.

Preferably, described induced draught system is connected with gas absorption system by water vapour pre-heating system.Because gas absorption system is connected with fluiddized-bed roasting system, induced draught system by gas absorption system and fluiddized-bed roasting system connectivity, can be convenient to fluiddized-bed roasting system and form subnormal ambient, be conducive to defluorination reaction.

Component Mixing System comprises mixing bunker 1, hopper 2 and screw feeder 3; Preheating of mixed material system comprises coal-fired fluidized bed 13, coal-fired fluidized bed separator 13-1, cyclone preheater and cyclonic separator 14; Fluiddized-bed roasting system comprises feed valve 5, fluidized-solids roaster 6, stoving oven separator 6-1 and bleeder valve 7; Water vapour pre-heating system comprises steam boiler 10 and combustion chamber 9; Gas absorption system comprises gas absorbing device 11 and gas-solid separator 11-1; Cooling system comprises cooling bed 8 and cooling bed separator 8-1; Induced draught system comprises induced draft fan 12 or compressor 17;

The discharge port of mixing bunker 1 is connected with the opening for feed of hopper 2, and the discharge port of hopper 2 is connected with the opening for feed of screw feeder 3, and the discharge port of screw feeder 3 is connected with the raw meal inlet of cyclone preheater; The air outlet of coal-fired fluidized bed 13 is connected with the inlet mouth of coal-fired fluidized bed separator 13-1, the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator 13-1, the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator 14, and the discharge port of cyclone preheater is connected with the opening for feed of fluidized-solids roaster 6 by feed valve 5;

The water outlet of steam boiler 10 is connected with the inlet mouth of combustion chamber 9, the water vapour air outlet of combustion chamber 9 is connected with the inlet mouth of fluidized-solids roaster 6, and the flue gas air outlet of combustion chamber 9 is connected with the inlet mouth of steam boiler 10, the air outlet of steam boiler 10 is connected with induced draft fan 12;

The discharge port of fluidized-solids roaster 6 is connected with the opening for feed of cooling bed 8 by bleeder valve 7, the air outlet of cooling bed 8 is connected with the inlet mouth of cooling bed separator 8-1, and the air outlet of cooling bed separator 8-1 is connected with the inlet mouth of combustion chamber 9 with the inlet mouth of steam boiler 10;

The air outlet of fluidized-solids roaster 6 is connected with the inlet mouth of gas absorbing device 11, and the air outlet of gas absorbing device 11 is connected with the inlet mouth of gas-solid separator 11-1, and the air outlet of gas-solid separator 11-1 is connected with the inlet mouth of steam boiler 10.

Present invention also offers a kind of roasting defluorination process, described technique comprises the steps:

(1) after defluorinate material mixes with defluorinating agent in mixing bunker 1, enter preheating of mixed material system and carry out preheating, obtain the mixture after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;

(2) mixture after preheating and the water vapour after preheating enter fluidized-solids roaster 6 and carry out defluorination reaction, obtain defluorinate thing, solid fluoride and fluoro-gas;

Treat that defluorinate material is for containing lithium minerals (as lepidolite ore), potassium-bearing mineral or the combination containing a kind of in cesium mineral or at least two kinds described in step (1).

The particle diameter treating defluorinate material described in step (1) is 50-500 μm, as 55 μm, 60 μm, 80 μm, 100 μm, 200 μm, 300 μm, 400 μm or 450 μm etc.

Preferably, step (1) described defluorinating agent is the mixture of a kind of in the oxide compound of Na, K, Ca or Mg, oxyhydroxide, vitriol or carbonate or at least two kinds, typical but non-limiting mixture is: the oxide compound of Na and the oxyhydroxide of K, the vitriol of Ca and the carbonate of Mg, the carbonate of the oxyhydroxide of Na, the vitriol of K and Ca, the oxide compound of Na, the oxyhydroxide of K, the vitriol of Ca and the carbonate etc. of Mg.

Preferably, the particle diameter of step (1) described defluorinating agent is 100-600 μm, as 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 500 μm or 550 μm etc.

Preferably, the stoichiometry of resultant after reacting according to defluorinating agent and F, the excessive 10-90% of usage quantity of step (1) described defluorinating agent, as excessive 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80% or 85% etc.

Preferably, the temperature of the mixture 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 > 10v% (" v% " all represents volume percent if no special instructions) of the water in vapor steam after step (2) described preheating, the content as water vapour is 15v%, 20v%, 30v%, 50v%, 70v%, 80v%, 90v% or 95v% etc.

Preferably, the temperature of step (2) described defluorination reaction is 830-860 DEG C, as 830 DEG C, 840 DEG C, 850 DEG C or 855 DEG C etc.

Preferably, the residence time of mixture in fluidized-solids roaster in step (2) after preheating is 30-120min, as 40min, 50min, 70min, 80min, 90min, 100min or 110min etc.

Preferably, the solid fluoride in step (2) obtains HF gas through dissolving, and reclaims, just obtains high-purity HF gas.

Preferably, the 10-90v% of the Purge gas that step (3) obtains for the water vapour preheating in step (1), if 20v%, 30v%, 40v%, 50v%, 60v%, 70v%, 80v% or 85v% etc. of Purge gas are for water vapour preheating.

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: Component Mixing System, preheating of mixed material system, fluosolids roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system.

Component Mixing System is used for being transported to preheating of mixed material system by after lithionite breeze and defluorinating agent mixing, comprises mixing bunker 1, hopper 2 and screw feeder 3;

Preheating of mixed material system is used for the compound of preheating lithionite breeze and defluorinating agent, its temperature is made to reach 800-850 DEG C, comprise coal-fired fluidized bed 13, coal-fired fluidized bed separator 13-1, Category Four cyclone preheater and cyclonic separator 14, Category Four cyclone preheater comprise be connected successively first step cyclone preheater 4-1, second stage cyclone preheater 4-2, third stage cyclone preheater 4-3 and fourth stage cyclone preheater 4-4;

Fluosolids roasting system is the place of lithionite breeze, water vapour and defluorinating agent reaction, comprise feed valve 5, fluidized-solids roaster 6, stoving oven separator 6-1 and bleeder valve 7, fluidized-solids roaster 6 is multistage fluidized bed reactor, be preferably 3-7 level, more preferably 3-5 level, the fluidisation section of fluidized-solids roaster 6 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 10 and combustion chamber 9;

The fluoro-gas that gas absorption system produces for purifying fluiddized-bed roasting system, absorbs HF and SiF comprised in fluoro-gas ₄reclaim F resource, 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 11 and gas-solid separator 11-1, gas absorbing device 11 can be fixed bed, fluidized-bed or moving-bed, be preferably fluidized-bed, in gas absorbing device 11, be placed with fluorine fixing material;

Cooling system is used for the defluorinate ore deposit that cooling bed roasting system produces, and the sensible heat in the process of cooling defluorinate ore deposit is used for the preheating of water vapour simultaneously, comprises cooling bed 8 and cooling bed separator 8-1;

Induced draught system is used for making fluidized-solids roaster form subnormal ambient, the lithionite in fluidized-solids roaster 6 is made to increase the dividing potential drop of water vapour in fluiddized-bed roasting system in boiling fluidized state, promote the Transport And Transformation of F in lepidolite ore, promote water vapour defluorination reaction, comprise induced draft fan 12;

The mode of connection of described Component Mixing System, preheating of mixed material 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 mixing bunker 1 is connected with the opening for feed of hopper 2, and the discharge port of hopper 2 is connected by the opening for feed of pipeline with screw feeder 3, and the discharge port of screw feeder 3 is connected by the opening for feed of pipeline with first step cyclone preheater 4-1;

The air outlet of coal-fired fluidized bed 13 is connected with the inlet mouth of coal-fired fluidized bed separator 13-1, the air outlet of coal-fired fluidized bed separator 13-1 is communicated with the inlet mouth of fourth stage cyclone preheater 4-4, the air outlet of first step cyclone preheater 4-1 is connected by the inlet mouth of pipeline with cyclonic separator 14, and the air outlet of cyclonic separator 14 is connected by the inlet mouth of pipeline with bagroom 15; The breeze that bagroom 15 is collected is back to hopper 2 through blanking machine 16; The discharge port of fourth stage cyclone preheater 4-4 is connected with feed valve 5 by pipeline;

The water outlet of steam boiler 10 is connected with the inlet mouth of combustion chamber 9, and the water vapour air outlet of combustion chamber 9 is connected with the inlet mouth of fluidized-solids roaster 6, and the flue gas air outlet of combustion chamber 9 is connected with the inlet mouth of steam boiler 10;

The opening for feed of fluidized-solids roaster 6 is communicated with the discharge port of fourth stage cyclone preheater 3-4, inlet mouth bottom fluidized-solids roaster 6 is connected by the air outlet of pipeline with combustion chamber 9, the air outlet at fluidized-solids roaster 6 top is connected with stoving oven separator 6-1 inlet mouth by pipeline, the discharge port of stoving oven separator 6-1 is connected with fluidized-solids roaster 6 by pipeline, and the air outlet of stoving oven separator 6-1 is connected by the inlet mouth of pipeline with gas absorbing device 11; The discharge port on fluidized-solids roaster 6 top is connected by the opening for feed of pipeline with bleeder valve 7, and the discharge port of bleeder valve 7 is connected by the opening for feed of pipeline with cooling bed 8 bottom;

The inlet mouth of gas absorbing device 11 is connected with the air outlet of stoving oven separator 6-1, the air outlet of gas absorbing device 11 is connected with the inlet mouth of gas-solid separator 11-1, the air outlet of gas-solid separator 11-1 is connected with the inlet mouth of steam boiler 10, and the discharge port of gas-solid separator 11-1 is connected with gas absorbing device 11;

Inlet mouth bottom cooling bed 8 is connected with air line by pipeline, the air outlet at cooling bed 8 top is communicated with by the inlet mouth of pipeline with cooling bed separator 8-1, the air outlet of cooling bed separator 8-1 is connected with the inlet mouth of combustion chamber 9 and the inlet mouth of steam boiler 10 by pipeline, cooling bed 8 bottom is provided with discharge port, discharges after the cooling of defluorinate ore deposit from discharge port;

Induced draft fan 12 is connected with the air outlet of steam boiler 10.

Employing roasting defluorinate device removes the fluorine in lepidolite ore, and its technique is as follows:

Lepidolite ore and defluorinating agent mix in mixing bunker 1, obtain mixture, and mixture enters first step cyclone preheater 4-1 through hopper 2 and screw feeder 3.

In coal-fired fluidized bed 13, coal dust and air fully contact and combustion reactions occurs produce high-temperature hot flue gas, and the high-temperature hot flue gas of generation sends into preheated mixture material in fourth stage cyclone preheater 4-4 after separator is separated, and makes its temperature reach 800-850 DEG C; The rear cinder of reaction is discharged from the bottom discharge mouth of coal-fired fluidized bed 13;

The cold water passed into from the water-in of steam boiler 10 and the high-temperature gas heat exchange from the gas-solid separator 11-1 of gas absorbing device, combustion chamber 9 and cooling bed separator 8-1, the water vapour of discharging from the water outlet of steam boiler 10 enters combustion chamber 9 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 6 with the compound of defluorinating agent by feed valve 5 and contacts with the water vapour from the 900-1000 bottom fluidized-solids roaster 6 DEG C and react, and produces defluorinate ore deposit, solid fluoride and fluoro-gas;

The defluorinate ore deposit that fluidized-solids roaster 6 produces enters cooling bed 8 by bleeder valve 7, discharges through cooled defluorinate ore deposit, and the high-temperature gas produced in process of cooling is used as the thermal source of steam boiler 10 and combustion chamber 9;

The solid fluoride produced by fluidized-solids roaster 6 dissolves, and obtains high-purity HF gas.

The fluoro-gas that fluidized-solids roaster 6 produces is separated through stoving oven separator 6-1, the solid particulate being separated generation returns fluidized-solids roaster 6 and proceeds calcination, be separated the gas produced and enter gas absorbing device 11, the high temperature purification gas produced after fluorine fixing material defluorinate enters steam boiler 10, as the thermal source of preheating water steam;

Induced draft fan 12 is connected with the air outlet of steam boiler 10, produces subnormal ambient for making fluidized-solids roaster 6.

Embodiment 2

Fig. 2 provides a kind of structural representation of lepidolite ore fluiddized-bed roasting defluorinate device, and described device comprises: Component Mixing System, preheating of mixed material system, fluosolids roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system.

Preheating of mixed material system is used for preheating lithionite breeze and defluorinating agent compound, its temperature is made to reach 800-850 DEG C, comprise coal-fired fluidized bed 13, coal-fired fluidized bed separator 13-1, Category Four cyclone preheater and cyclonic separator 14, Category Four cyclone preheater comprise be connected successively first step cyclone preheater 4-1, second stage cyclone preheater 4-2, third stage cyclone preheater 4-3 and fourth stage cyclone preheater 4-4;

Induced draught system is used for making fluidized-solids roaster 6 form subnormal ambient, the lithionite in fluidized-solids roaster 6 is made to increase the dividing potential drop of water vapour in fluiddized-bed roasting system in boiling fluidized state, promote the Transport And Transformation of F in lepidolite ore, promote water vapour defluorination reaction, comprise compressor 17;

The water outlet of steam boiler 10 is connected with the inlet mouth of combustion chamber 9, and the water vapour air outlet of combustion chamber 9 is connected with the inlet mouth of fluidized-solids roaster 6, and the flue gas air outlet of combustion chamber 9 is connected with the inlet mouth of fourth stage cyclone preheater 4-4;

The opening for feed of fluidized-solids roaster 6 is communicated with the discharge port of fourth stage cyclone preheater 3-4, inlet mouth bottom fluidized-solids roaster 6 is connected with the water vapour air outlet of combustion chamber 9 by pipeline, the air outlet at fluidized-solids roaster 6 top is connected with stoving oven separator 6-1 inlet mouth by pipeline, the discharge port of stoving oven separator 6-1 is connected with fluidized-solids roaster 6 by pipeline, and the air outlet of stoving oven separator 6-1 is connected by the inlet mouth of pipeline with gas absorbing device 11; The discharge port on fluidized-solids roaster 6 top is connected by the opening for feed of pipeline with bleeder valve 7, and the discharge port of bleeder valve 7 is connected by the opening for feed of pipeline with cooling bed 8 bottom;

The inlet mouth of gas absorbing device 11 is connected with the air outlet of stoving oven separator 6-1, the air outlet of gas absorbing device 11 is connected with the inlet mouth of gas-solid separator 11-1, the air outlet of gas-solid separator 11-1 is connected with the inlet mouth of steam boiler 10, and the discharge port of gas-solid separator 11-1 is connected with gas absorbing device 11; The air outlet of steam boiler 10 is connected with the inlet mouth of compressor 17, and the air outlet of compressor 17 is connected with the inlet mouth of combustion chamber 9;

Inlet mouth bottom cooling bed 8 is connected with air line by pipeline, the air outlet at cooling bed 8 top is communicated with by the inlet mouth of pipeline with cooling bed separator 8-1, the air outlet of cooling bed separator 8-1 is connected by the inlet mouth of pipeline with steam boiler 10, cooling bed 8 bottom is provided with discharge port, discharges after the cooling of defluorinate ore deposit from discharge port.

The cold water passed into from the water-in of steam boiler 10 and the high-temperature gas heat exchange from gas-solid separator 11-1 and cooling bed separator 8-1, the water vapour of discharging from the water outlet of steam boiler 10 enters combustion chamber 9 and improves temperature further, make the temperature of water vapour reach 900-1000 DEG C, after compressor 17 compresses, enter combustion chamber 9 by air inlet of combustion chamber from the air outlet expellant gas of steam boiler 10;

The lithionite breeze of 800-850 DEG C enters fluidized-solids roaster 6 with the mixture of defluorinating agent by feed valve 5 and contacts with the water vapour from the 900-1000 bottom fluidized-solids roaster 6 DEG C and react, and produces defluorinate ore deposit, solid fluoride and fluoro-gas;

The defluorinate ore deposit that fluidized-solids roaster 6 produces enters cooling bed 8 by bleeder valve 7, discharges through cooled defluorinate ore deposit, and the high-temperature gas produced in process of cooling is used as the thermal source of steam boiler 10;

The tail gas containing water vapour of discharging from steam boiler 10 mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, enters fluidized-solids roaster 6 again participate in water vapour defluorination reaction by combustion chamber 9.

Embodiment 3

The device utilizing embodiment 1 to provide carries out lithionite roasting defluorinate, comprises the steps:

(1) send in hopper 2 after lithionite breeze and defluorinating agent fully being mixed in mixing bunker 1, deliver to fourth stage cyclone preheater 4-4 through screw feeder 3, and carry out heat exchange by third stage cyclone preheater 4-3, second stage cyclone preheater 4-2 and first step cyclone preheater 4-1 and the high-temperature hot flue gas from coal-fired fluidized bed 13 successively; Meanwhile, steam boiler 10 and combustion chamber 9 produce high-temperature vapor;

(2) the lithionite breeze after preheating and the temperature of defluorinating agent rise to 800 DEG C, be admitted to fluidized-solids roaster 6, fully contact with the high-temperature vapor (900 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, lithionite breeze median size 150 μm, the median size of defluorinating agent is 300 μm, the addition of defluorinating agent measures than excessive 10% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 830 DEG C, and water vapour content is 50v%, fluidizing gas velocity is 0.1m/s, and residence time of material is 90min;

(3) that discharges from fluidized-solids roaster 6 contains micro-HF and SiH ₄gas be admitted in gas absorbing device 11 (fluidized-bed) and reclaim, be placed with fluorine fixing material in gas absorbing device, the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor;

(4) breeze after calcination is admitted in cooling bed 8 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 10 and combustion chamber 9.

In the present embodiment, fluorine fixing material and defluorinating agent are Na ₂o, the defluorinate rate of lepidolite ore is 90.9%, and the solid fluorine rate of fluorine fixing material is 97.1%.

Embodiment 4

The device utilizing embodiment 2 to provide carries out lithionite roasting defluorinate, comprises the steps:

(2) the lithionite breeze after preheating and the temperature of defluorinating agent rise to 800 DEG C, be admitted to fluidized-solids roaster 6, fully contact with the high-temperature vapor (1000 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 3 grades of fluidized-bed reactors, lithionite breeze median size 150 μm, the median size of defluorinating agent is 300 μm, the addition of defluorinating agent measures than excessive 10% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 830 DEG C, water vapour content 10v%, fluidizing gas velocity 0.1m/s, residence time of material 90min;

(3) that discharges from fluidized-solids roaster 6 contains HF and SiH ₄gas be admitted in gas absorbing device 11 (fluidized-bed) and reclaim, be placed with fluorine fixing material in gas absorbing device, the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (50v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, enter fluidized-solids roaster 6 by combustion chamber 9 and again participate in water vapour defluorination reaction, rest part is emptying;

(4) breeze after calcination is admitted in cooling bed 8 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 10 and combustion chamber 9; Defluorinate ore deposit is through sulfuric acid roasting and dissolving at low temperatures, and the valuable elements such as Li are converted into the vitriol of solubility, and solid fluoride dissolves simultaneously, and the HF gas discharging purity high is reclaimed.

In the present embodiment, fluorine fixing material and defluorinating agent are Na ₂o, the defluorinate rate of lepidolite ore is 90.9%, and the solid fluorine rate of fluorine fixing material is 98.9%.

Embodiment 5

The roasting defluorinate device utilizing embodiment 2 to provide carries out lepidolite ore defluorinate, comprises the steps:

(1) hopper 2 is sent into after lithionite breeze and defluorinating agent fully being mixed in blending bun 1, in hopper 2, the mixture of lithionite breeze and defluorinating agent delivers to fourth stage cyclone preheater 4-4 through screw feeder 3, and carries out heat exchange by third stage cyclone preheater 4-3, second stage cyclone preheater 4-2 and first step cyclone preheater 4-1 and the high-temperature hot flue gas from coal-fired fluidized bed 13 successively; Meanwhile, steam boiler 10 and combustion chamber 9 produce high-temperature vapor;

(2) the lithionite breeze after preheating and the temperature of defluorinating agent rise to 835 DEG C, be admitted in fluidized-solids roaster 6, fully contact with the high-temperature vapor (950 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, lithionite breeze median size 200 μm, the median size of defluorinating agent is 300 μm, the addition of defluorinating agent measures than excessive 90% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 850 DEG C, water vapour content 90v%, fluidizing gas velocity 0.1m/s, residence time of material 100min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (moving-bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (30v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, enter fluidized-solids roaster 6 by combustion chamber 9 and again participate in water vapour defluorination reaction, rest part is emptying;

(4) breeze after calcination is admitted in cooling bed 8 and cools, and obtains defluorinate ore deposit.Defluorinate ore deposit is through sulfuric acid roasting and dissolving at low temperatures, and the valuable elements such as Li are converted into the vitriol of solubility, and solid fluoride dissolves simultaneously, and the HF gas discharging purity high is reclaimed.

In the present embodiment, fluorine fixing material and defluorinating agent are K ₂cO ₃, the defluorinate rate of lepidolite ore is 93.3%, and the solid fluorine rate of fluorine fixing material is 96.9%.

Application examples 6

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 825 DEG C, be admitted in fluidized-solids roaster 6, fully contact with the high-temperature vapor (980 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, lithionite breeze median size 450 μm, the median size of defluorinating agent is 600 μm, the addition of defluorinating agent measures than excessive 16% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 840 DEG C, water vapour content 75v%, fluidizing gas velocity 0.1m/s, residence time of material 75min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fixed bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (34v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, enter fluidized-solids roaster 6 by combustion chamber 9 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are MgSO ₄, the defluorinate rate of lepidolite ore is 94.5%, and the solid fluorine rate of fluorine fixing material is 95.6%.

Embodiment 7

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 840 DEG C, be admitted in fluidized-solids roaster 6 fully to contact with the high-temperature vapor (1000 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 6 grades of fluidized-bed reactors, lithionite breeze median size 500 μm, the median size of defluorinating agent is 600 μm, the addition of defluorinating agent measures than excessive 45% according to the chemical reaction reacted with F, feeding rate is 300kg/h, temperature 840 DEG C, water vapour content 30v%, fluidizing gas velocity 0.1m/s, residence time of material 120min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fluidized-bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (65v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, and return fluidized-solids roaster 6 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are the Ca (OH) that mass ratio is 1:1 ₂and Na ₂cO ₃mixture, the defluorinate rate of lepidolite ore is 92.5%, and the solid fluorine rate of fluorine fixing material is 99.6%.

Embodiment 8

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 850 DEG C, be admitted in fluidized-solids roaster 6 fully to contact with the high-temperature vapor (1000 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 4 grades of fluidized-bed reactors, lithionite breeze median size 100 μm, the median size of defluorinating agent is 200 μm, the addition of defluorinating agent measures than excessive 33% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 860 DEG C, water vapour content 80v%, fluidizing gas velocity 0.1m/s, residence time of material 30min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fluidized-bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (62v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, and return fluidized-solids roaster 6 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are the K that mass ratio is 3:2 ₂sO ₄and MgCO ₃mixture, the defluorinate rate of lepidolite ore is 91.5%, and the solid fluorine rate of fluorine fixing material is 99.5%.

Embodiment 9

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 850 DEG C, be admitted in fluidized-solids roaster 6 fully to contact with the high-temperature vapor (920 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, lithionite breeze median size 300 μm, the median size of defluorinating agent is 100 μm, the addition of defluorinating agent measures than excessive 58% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 850 DEG C, water vapour content 15v%, fluidizing gas velocity 0.1m/s, residence time of material 90min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fluidized-bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (55v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, and return fluidized-solids roaster 6 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are the Na that mass ratio is 1:3 ₂o and Ca (OH) ₂mixture, the defluorinate rate of lepidolite ore is 95.6%, the solid fluorine rate 98.7% of fluorine fixing material.

Embodiment 10

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 820 DEG C, be admitted in fluidized-solids roaster 6 fully to contact with the high-temperature vapor (930 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, lithionite breeze median size 500 μm, the median size of defluorinating agent is 400 μm, the addition of defluorinating agent measures than excessive 50% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 845 DEG C, water vapour content 50v%, fluidizing gas velocity 0.1m/s, residence time of material 60min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fluidized-bed) Recovery Purifying, is placed with fluorine fixing material in gas absorbing device, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (82v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, and return fluidized-solids roaster 6 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are Na ₂o, the defluorinate rate of lepidolite ore is 93.2%, and the solid fluorine rate of fluorine fixing material is 99.0%.

Embodiment 11

(2) the lithionite breeze after preheating and the mixture temperature of defluorinating agent rise to 810 DEG C, be admitted in fluidized-solids roaster 6 fully to contact with the high-temperature vapor (910 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, lepidolite ore phase structure is changed.Its calcination condition is: fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, lithionite breeze median size 50 μm, the median size of defluorinating agent is 150 μm, the addition of defluorinating agent measures than excessive 10% according to the chemical reaction reacted with F, feeding rate is 300kg/h, maturing temperature 840 DEG C, water vapour content 10v%, fluidizing gas velocity 0.1m/s, residence time of material 120min;

(3) discharge tail gas containing micro-HF, SiH from fluidized-solids roaster 6 ₄gas is admitted to gas absorbing device 11 (fluidized-bed) Recovery Purifying, and the water that the high-temperature tail gas after purification is used in preheating steam boiler 10 produces high-temperature vapor; A tail gas part (68v%) of discharging from steam boiler mixes with the fresh water steam from steam boiler 10 after compressor 17 adherence pressure, and return fluidized-solids roaster 6 and again participate in water vapour defluorination reaction, rest part is emptying;

In the present embodiment, fluorine fixing material and defluorinating agent are the Na that mass ratio is 1:2 ₂the mixture of O and MgO, the defluorinate rate of lepidolite ore is 92.8%, and the solid fluorine rate of fluorine fixing material is 99.3%.

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

1. a roasting defluorinate device, it is characterized in that, described device comprises Component Mixing System, preheating of mixed material system, water vapour pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system comprises fluidized-solids roaster (6), Component Mixing System is connected with preheating of mixed material system, and preheating of mixed material system and water vapour pre-heating system are connected with fluiddized-bed roasting system;

2. device according to claim 1, it is characterized in that, described fluiddized-bed roasting system comprises feed valve (5), fluidized-solids roaster (6), stoving oven separator (6-1) and bleeder valve (7), the opening for feed of described fluidized-solids roaster (6) is connected with Component Mixing System by feed valve (5), the discharge port of fluidized-solids roaster (6) is connected with cooling system by bleeder valve (7), the inlet mouth of stoving oven separator (6-1) is connected with the air outlet of fluidized-solids roaster (6), the air outlet of stoving oven separator (6-1) is connected with gas absorption system,

Preferably, described fluidized-solids roaster (6) is 3-7 level fluidized-bed reactor, is preferably 3-5 level fluidized-bed reactor;

Preferably, the fluidisation section of described fluidized-solids roaster (6) is provided with vertical inner member;

3. device according to claim 1 and 2, it is characterized in that, described preheating of mixed material system comprises coal-fired fluidized bed (13), coal-fired fluidized bed separator (13-1), cyclone preheater and cyclonic separator (14), the air outlet of coal-fired fluidized bed (13) is connected with the inlet mouth of coal-fired fluidized bed separator (13-1), the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator (13-1), the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator (14), the raw meal inlet of cyclone preheater is connected with Component Mixing System,

Preferably, described cyclone preheater is 3-6 level cyclone preheater;

Preferably, the discharge port of described cyclonic separator (14) is connected with the raw meal inlet of cyclone preheater, and the air outlet of cyclonic separator (14) is connected with bagroom (15);

Preferably, described bagroom (15) is connected with Component Mixing System through blanking machine (16).

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 (10) and combustion chamber (9), the water outlet of steam boiler (10) is connected with the inlet mouth of combustion chamber (9), and the water vapour air outlet of combustion chamber (9) is connected with fluiddized-bed roasting system;

Preferably, the flue gas air outlet of described combustion chamber (9) is connected with the inlet mouth of preheating of mixed material system or steam boiler (10);

Preferably, the air outlet of described steam boiler (10) is connected with induced draught system.

5. according to the device one of claim 1-4 Suo Shu, it is characterized in that, described Component Mixing System comprises hopper (2), screw feeder (3) and mixing bunker (1), the discharge port of mixing bunker (1) is connected with the opening for feed of hopper (2), the discharge port of hopper (2) is connected with the opening for feed of screw feeder (3), and the discharge port of screw feeder (3) is connected with preheating of mixed material 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 (11) and gas-solid separator (11-1), the inlet mouth of gas absorbing device (11) is connected with fluiddized-bed roasting system, and the air outlet of gas absorbing device (11) is connected with the inlet mouth of gas-solid separator (11-1);

Preferably, the air outlet of described gas-solid separator (11-1) is connected with water vapour pre-heating system, and the discharge port of gas-solid separator (11-1) is connected with gas absorbing device (11);

Preferably, described gas absorbing device (11) is fixed bed, fluidized-bed or moving-bed, is preferably fluidized-bed;

Preferably, fluorine fixing material is filled with in described gas absorbing device (11);

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 (8) and cooling bed separator (8-1), the opening for feed of cooling bed (8) is connected with fluiddized-bed roasting system, and the air outlet of cooling bed (8) is connected with the inlet mouth of cooling bed separator (8-1);

Preferably, the air outlet of described cooling bed separator (8-1) is connected with water vapour pre-heating system, and the discharge port of cooling bed separator (8-1) is connected with cooling bed (8);

Preferably, described induced draught system comprises induced draft fan (12) or compressor (17);

7. according to the device one of claim 1-6 Suo Shu, it is characterized in that, described device comprises Component Mixing System, preheating of mixed material system, fluiddized-bed roasting system, water vapour pre-heating system, gas absorption system, cooling system and induced draught system;

Component Mixing System comprises mixing bunker (1), hopper (2) and screw feeder (3); Preheating of mixed material system comprises coal-fired fluidized bed (13), coal-fired fluidized bed separator (13-1), cyclone preheater and cyclonic separator (14); Fluiddized-bed roasting system comprises feed valve (5), fluidized-solids roaster (6), stoving oven separator (6-1) and bleeder valve (7); Water vapour pre-heating system comprises steam boiler (10) and combustion chamber (9); Gas absorption system comprises gas absorbing device (11) and gas-solid separator (11-1); Cooling system comprises cooling bed (8) and cooling bed separator (8-1); Induced draught system comprises induced draft fan (12) or compressor (17);

The discharge port of mixing bunker (1) is connected with the opening for feed of hopper (2), the discharge port of hopper (2) is connected with the opening for feed of screw feeder (3), and the discharge port of screw feeder (3) is connected with the raw meal inlet of cyclone preheater; The air outlet of coal-fired fluidized bed (13) is connected with the inlet mouth of coal-fired fluidized bed separator (13-1), the inlet mouth of cyclone preheater is connected with the air outlet of coal-fired fluidized bed separator (13-1), the air outlet of cyclone preheater is connected with the inlet mouth of cyclonic separator (14), and the discharge port of cyclone preheater is connected with the opening for feed of fluidized-solids roaster (6) by feed valve (5);

The water outlet of steam boiler (10) is connected with the inlet mouth of combustion chamber (9), the water vapour air outlet of combustion chamber (9) is connected with the inlet mouth of fluidized-solids roaster (6), the flue gas air outlet of combustion chamber (9) is connected with the inlet mouth of steam boiler (10), and the air outlet of steam boiler (10) is connected with induced draft fan (12);

The discharge port of fluidized-solids roaster (6) is connected with the opening for feed of cooling bed (8) by bleeder valve (7), the air outlet of cooling bed (8) is connected with the inlet mouth of cooling bed separator (8-1), and the air outlet of cooling bed separator (8-1) is connected with the inlet mouth of combustion chamber (9) with the inlet mouth of steam boiler (10);

The air outlet of fluidized-solids roaster (6) is connected with the inlet mouth of gas absorbing device (11), the air outlet of gas absorbing device (11) is connected with the inlet mouth of gas-solid separator (11-1), and the air outlet of gas-solid separator (11-1) is connected with the inlet mouth of steam boiler (10).

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) after defluorinate material mixes with defluorinating agent in mixing bunker (1), enter preheating of mixed material system and carry out preheating, obtain the mixture after preheating; Water vapour after the preheating of water vapour pre-heating system generation simultaneously;

(2) mixture after preheating and the water vapour after preheating enter fluidized-solids roaster (6) and carry out defluorination reaction, obtain defluorinate thing, solid fluoride and 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 described in step (1);

Preferably, treat described in step (1) that the particle diameter of defluorinate material is 50-500 μm;

Preferably, step (1) described defluorinating agent is the mixture of a kind of in the oxide compound of Na, K, Ca or Mg, oxyhydroxide, vitriol or carbonate or at least two kinds;

Preferably, the particle diameter of step (1) described defluorinating agent is 100-600 μm;

10. technique according to claim 8 or claim 9, it is characterized in that, the temperature of the mixture 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 > 10v% of the water in vapor steam after step (2) described preheating;

Preferably, the temperature of step (2) described defluorination reaction is 830-860 DEG C;

Preferably, the residence time of mixture in fluidized-solids roaster in step (2) after preheating is 30-120min;

Preferably, the solid fluoride in step (2) obtains HF gas through dissolving;

Preferably, the heat produced in the process of cooling of step (3) described defluorinate ore deposit is for the water vapour pre-heating system in step (1);

Preferably, the 10-90v% of Purge gas that obtains of step (3) 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;