CN105385844B

CN105385844B - One kind roasting defluorinate device and technique

Info

Publication number: CN105385844B
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: 2018-04-03
Anticipated expiration: 2035-10-27
Also published as: CN105385844A

Abstract

The invention provides one kind roasting defluorinate device and technique, the roasting defluorinate device includes Component Mixing System, preheating of mixed material system, vapor pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system includes fluidized-solids roaster, Component Mixing System is connected with preheating of mixed material system, and preheating of mixed material system and vapor pre-heating system are connected with fluiddized-bed roasting system；Optionally, described device also includes gas absorption system, cooling system and induced draught system, and gas absorption system and cooling system are connected with fluiddized-bed roasting system, and induced draught system is connected with gas absorption system.The device can realize defluorinate in situ, Gu fluorine rate, up to more than 95%, and defluorinate rate is up to more than 90%；It is high using heat production high-temperature vapor, heat utilization ratio caused by high-temperature flue gas caused by high temperature defluorinate tail gas, combustion chamber and cooling defluorinate material；Vapor consumption is low, roasting process good economy performance, is adapted to extensive continuous industry production.

Description

One kind roasting defluorinate device and technique

Technical field

The invention belongs to the processing method technical field of mineral raw material, is related to a kind of roasting defluorinate device and technique, especially It is related to a kind of lepidolite ore fluiddized-bed roasting defluorinate device and technique.

Background technology

Lithium and its compound are the important foundation raw materials of lithium electricity new energy materialses.The main of lithium resource deposits mode in nature For salt lake bittern and giant crystal rock and ore.Wherein, lepidolite typically only originates in giant crystal rock and ore, is two kinds of most important industrial lithium ore deposits One of thing.In order to effectively utilize lepidolite, domestic and international scientific worker has carried out substantial amounts of research work, achieve it is many from Produce the experience of lithium salts in lepidolite, but stopped production from U.S.'s potash and San Antonio lithium factory of chemical company in 1966 with Come, there has been no the factory of extensive processing lepidolite production lithium salts in the world.There are abundant reason mica resource, its Li in China₂O contains How efficiently, economic this part lithium resource of development and utilization amount is typically in 4-5%, significant to China's lithium industry.

At present, lepidolite extracted lithium method mainly include lime burning method, chlorinating roasting, sulfuric acid process, sulfate process and Autoclaving method.Industrially, lithium is extracted from lepidolite ore and generally uses lime burning method, i.e., lime stone and lepidolite are pressed 3：1 Part by weight in ball mill ball milling, mixing；Through 800~900 DEG C of high-temperature roastings, then through water quenching, fine grinding, leaching, filtering or Centrifuge and obtain leachate and residue, leachate obtains monohydrate lithium hydroxide through evaporating, crystallizing and centrifuge.Lime stone roasts Burning method has that technique is simple, the advantage such as low in raw material price, but has that lime stone proportioning is high, the rate of recovery of lithium is low, in leachate Lithium content is low and the shortcomings of evaporation energy consumption is high.Sulfating roasting method is usually used in handling silicate mineral, but is extracted for lepidolite During lithium, leached by dispensing, pelletizing, roasting, dilute sulfuric acid, leachate is purified, precipitation obtains lithium carbonate.Sulfuric acid process handles lithium cloud Female ore deposit needs advance vapor defluorinate roasting, then adds sulfuric acid baking dissolving.Chlorinating roasting is to be made using chlorinating agent in lepidolite Lithium and other valuable metals be converted into chloride.Compared with lime burning method, sulfuric acid process, autoclaving method and chlorinating roasting Energy consumption is low, the leaching rate of lithium is high, has the trend of substitution limestone-based process.

Due to lepidolite ore compact structure, lithium be by fluorine aluminosilicate it is complicated in the form of exist so that the leaching of ore grinding and lithium Go out very difficult.In order to improve the leaching rate of lithium, it is necessary to carry out high-temperature vapor defluorinate processing to lepidolite in advance, defluorinate processing Its short texture, grindability are good afterwards, are advantageous to improve the leaching rate of lithium.During lepidolite is calcined defluorinate, steam partial pressure It is principal element with sintering temperature.Document (research of Yichun lithia mica roasting process, mineral engineering, 1994,93,56-58) is tied Fruit is shown, defluorinate efficiency can be significantly improved in the presence of vapor.Think that high-temperature vapor when the lepidolite surface of red heat, is first inhaled Tell on mineral surfaces, be then dissociated into H⁺And OH^–, and escaped in the form of HF.In vapor-lepidolite reaction system, mainly Influenceed by two aspects of Thermodynamics (chemical potential) and lepidolite structure (physical factor), a large amount of steam partial pressures and high temperature Under be advantageous to the removing of fluorine in lepidolite.And diffusion or lithium-containing compound of the vapor to lepidolite internal structure to external migration It is the key for influenceing vapor defluorinate efficiency.Therefore, the abundant contact and reaction of vapor and lepidolite miberal powder are to influence to take off An important factor for fluorine efficiency.

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

(1) vapor and lepidolite material are insufficient contact, are unfavorable for vapor in the adsorbing of lepidolite surface, inwardly spread Or the migration of the material containing lithium, so as to cause its defluorinate rate low.Turned round such as in CN201210052443.6 patents using stainless steel Kiln reactor carries out roasting defluorinate, and vapor defluorination reaction 80min is carried out under 860 DEG C of high temperature, and F contents are still high in its defluorinate ore deposit Up to 2.0wt%, defluorinate rate only has 40%.

(2) under high temperature the problems such as the ring formation of furnace charge：Due to the presence of low melting point in lepidolite so that in rotary kiln plus When work handles lepidolite, when sintering temperature is too high, inevitably there is furnace charge and melt ring formation in furnace wall, so as to have a strong impact on The normal operating of rotary kiln technology；If sintering temperature is too low and the defluorinate efficiency of lepidolite can be influenceed.

(3) utilization rate of high temperature defluorinate tail gas is low, the shortcomings that high energy consumption, steam consumption quantity are big and less economical be present, and Restrict rotary kiln baking defluorinate industrial applications and the unfavorable factor promoted.

(4) fluorine resource recycling is unreasonable, and in lepidolite defluorinate roasting process, fluorine is mainly escaped in the form of HF, If not being acted upon being directly discharged in air, environment will be damaged.Therefore, the fluorine how recycled in lepidolite is Lepidolite defluorinate roasting technique problems faced.

CN 102530874A disclose the method that HF and fluoride are prepared from lepidolite defluorinate tail gas, using aqueous slkali (sodium hydroxide, milk of lime or ammoniacal liquor) absorbs HF, obtains corresponding villiaumite through drying and dehydrating, then can prepare through dense sulfuric acid treatment HF.The technique is simple, technology maturation, but this method can not utilize the energy of high-temperature tail gas due to using wet method alkali liquor absorption.

The content of the invention

The problem of existing for prior art, it is an object of the invention to provide one kind roasting defluorinate device and technique, institute Solid fluorine in situ can be realized by stating roasting defluorinate device, Gu fluorine rate reaches more than 95%, desorption rate reaches more than 90%, and water steams Gas consumption amount is low, roasting process good economy performance, is adapted to extensive continuous industry production.

To use following technical scheme up to this purpose, the present invention：

An object of the present invention is that providing one kind is calcined defluorinate device, and described device includes Component Mixing System, mixed Closing material pre-heating system, vapor pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system includes fluidized-solids roaster, thing Material hybrid system is connected with preheating of mixed material system, preheating of mixed material system and vapor pre-heating system and fluiddized-bed roasting system It is connected；

Optionally, described device also includes gas absorption system, cooling system and induced draught system, gas absorption system and cold But system is connected with fluiddized-bed roasting system, and induced draught system is connected with gas absorption system.

The fluiddized-bed roasting system includes inlet valve, fluidized-solids roaster, roaster separator and outlet valve, the stream The charging aperture for changing bed roaster is connected by inlet valve with Component Mixing System, and the discharging opening of fluidized-solids roaster passes through outlet valve It is connected with cooling system, the air inlet of roaster separator is connected with the gas outlet of fluidized-solids roaster, roaster separator Gas outlet is connected with gas absorption system.

Preferably, the fluidized-solids roaster is 3-7 level fluidized-bed reactors, preferably 3-5 levels fluidized-bed reactor.

Preferably, the fluidisation section of the fluidized-solids roaster is provided with vertical inner member.

Preferably, the gas distribution grid opening direction is tangential direction circumferentially.

The preheating of mixed material system includes coal-fired fluidized bed, coal-fired fluidized bed separator, cyclone preheater and whirlwind point From device, coal-fired fluidized bed gas outlet is connected with the air inlet of coal-fired fluidized bed separator, the air inlet of cyclone preheater and combustion The gas outlet of fluidized bed separator is connected, and the gas outlet of cyclone preheater is connected with the air inlet of cyclone separator, and whirlwind is pre- The raw meal inlet of hot device is connected with Component Mixing System.

Preferably, the cyclone preheater is 3-6 level cyclone preheaters.

Preferably, the discharging opening of the cyclone separator is connected with the raw meal inlet of cyclone preheater, cyclone separator Gas outlet is connected with bagroom.

Preferably, the bagroom is connected through blanking machine with Component Mixing System.

The vapor pre-heating system includes steam boiler and combustion chamber, the delivery port of steam boiler and the air inlet of combustion chamber Mouth is connected, and the vapor gas outlet of combustion chamber is connected with fluiddized-bed roasting system.

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

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

The Component Mixing System includes hopper, screw feeder and mixing bunker, the discharging opening of mixing bunker and entering for hopper Material mouth is connected, and the discharging opening of hopper is connected with the charging aperture of screw feeder, the discharging opening and preheating of mixed material of screw feeder System is connected.

The gas absorption system includes gas absorbing device and gas-solid separator, the air inlet and stream of gas absorbing device Change bed roasting system to be connected, the gas outlet of gas absorbing device is connected with the air inlet of gas-solid separator.

Preferably, the gas outlet of the gas-solid separator is connected with vapor pre-heating system, the discharging opening of gas-solid separator It is connected with gas absorbing device.

Preferably, the gas absorbing device is fixed bed, fluid bed or moving bed, preferably fluid bed.

Preferably, it is filled with fluorine fixing material in the gas absorbing device.

Preferably, the fluorine fixing material is alkali metal oxide, alkaline earth oxide, alkali metal hydroxide or alkaline earth gold Belong to hydroxide in any one or at least two combination.

Preferably, the cooling system includes cooling bed and cooling bed separator, the charging of cooling bed Mouth is connected with fluiddized-bed roasting system, and the gas outlet of cooling bed is connected with the air inlet of cooling bed separator.

Preferably, the gas outlet of the cooling bed separator is connected with vapor pre-heating system, cooling bed point Discharging opening from device is connected with cooling bed.

Preferably, the induced draught system includes air-introduced machine or compressor.

Preferably, the induced draught system is connected by vapor pre-heating system with gas absorption system.

As preferable technical scheme, the roasting defluorinate device includes Component Mixing System, preheating of mixed material system, stream Change bed roasting system, vapor pre-heating system, gas absorption system, cooling system and induced draught system；

Component Mixing System includes mixing bunker, hopper and screw feeder；Preheating of mixed material system include it is coal-fired fluidized bed, Coal-fired fluidized bed separator, cyclone preheater and cyclone separator；Fluiddized-bed roasting system includes inlet valve, fluiddized-bed roasting Stove, roaster separator and outlet valve；Vapor pre-heating system includes steam boiler and combustion chamber；Gas absorption system includes gas Body absorption plant and gas-solid separator；Cooling system includes cooling bed and cooling bed separator；Induced draught system includes Air-introduced machine or compressor；

The discharging opening of mixing bunker is connected with the charging aperture of hopper, the discharging opening of hopper and the charging aperture phase of screw feeder Even, the discharging opening of screw feeder is connected with the raw meal inlet of cyclone preheater；Coal-fired fluidized bed gas outlet fluidizes with coal-fired The air inlet of bed separator is connected, and the air inlet of cyclone preheater is connected with the gas outlet of coal-fired fluidized bed separator, and whirlwind is pre- The gas outlet of hot device is connected with the air inlet of cyclone separator, and the discharging opening of cyclone preheater passes through inlet valve and fluiddized-bed roasting The charging aperture of stove is connected；

The delivery port of steam boiler is connected with the air inlet of combustion chamber, the vapor gas outlet of combustion chamber and fluiddized-bed roasting The air inlet of stove is connected, and the flue gas gas outlet of combustion chamber is connected with the air inlet of steam boiler, the gas outlet of steam boiler It is connected with air-introduced machine；

The discharging opening of fluidized-solids roaster is connected by outlet valve with the charging aperture of cooling bed, and cooling bed goes out Gas port is connected with the air inlet of cooling bed separator, the gas outlet of cooling bed separator and the air inlet of steam boiler It is connected with the air inlet of combustion chamber；

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

The second object of the present invention is to provide a kind of technique for carrying out defluorinate using the roasting defluorinate device, the work Skill comprises the following steps：

(1) preheated, obtained into preheating of mixed material system after defluorinate material mixes with defluorinating agent in mixing bunker Mixed material after preheating；Vapor pre-heating system produces the vapor after preheating simultaneously；

(2) mixed material after preheating and the vapor after preheating enter fluidized-solids roaster and carry out defluorination reaction, obtain Defluorinate thing, solid fluoride and fluoro-gas；

Optionally, step (3) is carried out：Defluorinate ore deposit is cooled down and reclaimed, and fluoro-gas is purified.

Treat that defluorinate material is containing lithium minerals, potassium-bearing mineral or containing one kind in cesium mineral or at least two described in step (1) The combination of kind.

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

Preferably, step (1) described defluorinating agent is Na, K, Ca or Mg oxide, hydroxide, sulfate or carbonate In one kind or at least two mixture.

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

Preferably, according to the stoichiometry of product after defluorinating agent and F reactions, the usage amount of step (1) described defluorinating agent Excessive 10-90%.

The temperature of mixed material after step (2) described preheating is 800-850 DEG C.

Preferably, the temperature of the vapor 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, residence time of the mixed material in fluidized-solids roaster after being preheated in step (2) is 30- 120min。

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

Preferably, the vapor preheating that caused heat is used in step (1) in step (3) the defluorinate ore deposit cooling procedure System.

Preferably, the vapor preheating that the 10-90v% for the purification gas that step (3) obtains is used in step (1).

Preferably, step (3) is using alkali metal oxide, alkali metal hydroxide, alkaline earth oxide or alkaline earth gold Belong to one kind or at least two combination purification fluoro-gas in hydroxide.

Preferably, step (3) uses K₂O、Na₂O, one kind in CaO or MgO or at least two combination purification contain fluorine gas Body.

Compared with prior art, beneficial effects of the present invention are：

(1) roasting defluorinate device provided by the invention enables to due to carrying out defluorination reaction using fluidized-solids roaster Vapor and treat that defluorinate material fully contacts in fluidized-solids roaster, improve defluorinate efficiency (more than 90%), prevent that roasting is de- Sintering ring formation during fluorine, so as to promote the Transport And Transformation of F in lepidolite, defluorinate rate is up to more than 90%；

(2) roasting defluorinate device provided by the invention can realize defluorinate in situ, the solid fluorine rate of defluorinating agent be up to 95% with On, defluorinating agent can be converted into high-purity HF gases with the solid fluoride obtained after fluoro-gas reaction, it is therefore prevented that in course of reaction The effusion of HF gases, reduce the pollution of corrosion and environment of the HF gases to follow up device；

(3) the defluorinate efficiency high of roasting defluorinate device provided by the invention, defluorinate rate up to more than 90%, using fluorine fixing material and Defluorinating agent carries out double defluorinate, and defluorinate tail gas can return to fluidized-solids roaster and continue to participate in defluorination reaction, improves vapor profit With rate, vapor consumption, good economy performance are reduced；

(4) heat utilization ratio of roasting defluorinate device provided by the invention is high, utilizes high temperature defluorinate tail gas, combustion chamber heat cigarette Caused heat production high-temperature vapor, has reclaimed reaction end gas and the sensible heat of defluorinate ore deposit during gas and cooling defluorinate material, Reduce energy consumption.

Brief description of the drawings

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

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

Wherein：1, mixing bunker；2, hopper；3, screw feeder；4-1, first order cyclone preheater；4-2, first order whirlwind Preheater；4-3, third level cyclone preheater；4-4, fourth stage cyclone preheater；5, inlet valve；6, fluidized-solids roaster；6-1, Roaster separator；7, outlet 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, air-introduced machine；13, it is coal-fired fluidized bed；13-1, coal-fired fluidized bed separation Device；14, cyclone separator；15, bagroom；16, blanking machine；17, compressor.

Embodiment

Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.

The invention provides one kind be calcined defluorinate device, described device include Component Mixing System, preheating of mixed material system, Vapor pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system include fluidized-solids roaster 6, Component Mixing System with Preheating of mixed material system is connected, and preheating of mixed material system and vapor pre-heating system are connected with fluiddized-bed roasting system；

The Component Mixing System is used to that defluorinate material and defluorinating agent mixing will to be treated, and mixed material is transported into compound Pre-heating system；

The preheating of mixed material system is used to preheat the mixed material for treating defluorinate material and defluorinating agent, reaches its temperature 800-860 DEG C, and the mixed material after preheating is transported to fluiddized-bed roasting system；

The vapor pre-heating system is used to produce high-temperature vapor (900-1000 DEG C), and high-temperature vapor is transported to Fluiddized-bed roasting system；

The fluiddized-bed roasting system is used for the mixed material after preheating and high-temperature vapor carries out defluorination reaction, after reaction Defluorinate ore deposit, solid fluoride and fluoro-gas are produced, defluorinating agent can capture vapor rapidly and treat that defluorinate material reaction produces HF gases, generate solid fluoride, so as to realize defluorinate in situ, therefore, the concentration of the HF gases in fluoro-gas is very It is low；

The gas absorption system is used to absorb the fluorine in fluoro-gas, and purified gas is discharged；

The cooling system is used to cool down defluorinate ore deposit, is easy to the discharge of defluorinate ore deposit, collects.

The induced draught system is used to make fluidized-solids roaster 6 form subnormal ambient, strengthens the boiling fluidisation for treating defluorinate material State, prevent from treating sintering ring formation of the defluorinate material in roasting defluorinate process, promote vapor defluorination reaction.

The fluiddized-bed roasting system includes inlet valve 5, fluidized-solids roaster 6, roaster separator 6-1 and outlet valve 7, The charging aperture of the fluidized-solids roaster 6 is connected by inlet valve 5 with Component Mixing System, the discharging opening of fluidized-solids roaster 6 It is connected by outlet valve 7 with cooling system, roaster separator 6-1 air inlet is connected with the gas outlet of fluidized-solids roaster 6, Roaster separator 6-1 gas outlet is connected with gas absorption system.

Preferably, the fluidized-solids roaster 6 is 3-7 level fluidized-bed reactors, such as 3 grades, 4 grades, 5 grades, 6 grades or 7 grades streams Fluidized bed reactor, preferably 3-5 levels fluidized-bed reactor.

Preferably, the fluidisation section of the fluidized-solids roaster 6 is provided with vertical inner member.

Preferably, the gas distribution grid opening direction is tangential direction circumferentially, lepidolite ore is roasted in fluid bed Burn stove 6 to fluidize in a rotative pattern, residence time of the increase lepidolite ore in fluidized-solids roaster 6, steam lepidolite ore and water Gas fully contacts and defluorination reaction occurs.

The preheating of mixed material system includes coal-fired fluidized bed 13, coal-fired fluidized bed separation 13-1, cyclone preheater and rotation Wind separator 14, coal-fired fluidized bed 13 gas outlet are connected with coal-fired fluidized bed separator 13-1 air inlet, cyclone preheater Air inlet be connected with coal-fired fluidized bed separator 13-1 gas outlet, the gas outlet of cyclone preheater and cyclone separator 14 Air inlet is connected, and the raw meal inlet of cyclone preheater is connected with Component Mixing System.

Preferably, the cyclone preheater is 3-6 level cyclone preheaters, is such as 3 grades of cyclone preheaters, 4 grades of whirlwind preheatings Device, 5 grades of cyclone preheaters or 6 grades of cyclone preheaters etc..

Preferably, the discharging opening of the cyclone separator 14 is connected with the raw meal inlet of cyclone preheater, cyclone separator 14 gas outlet is connected with bagroom 15.

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

The vapor pre-heating system includes steam boiler 10 and combustion chamber 9, delivery port and the combustion chamber 9 of steam boiler 10 Air inlet be connected, the vapor gas outlet of combustion chamber 9 is connected with fluiddized-bed roasting system.

Preferably, the flue gas gas outlet of the combustion chamber 9 and preheating of mixed material system or the air inlet phase of steam boiler 10 Even.

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

The Component Mixing System includes hopper 2, screw feeder 3 and mixing bunker 1, discharging opening and the hopper 2 of mixing bunker 1 Charging aperture be connected, the discharging opening of hopper 2 is connected with the charging aperture of screw feeder 3, and the discharging opening of screw feeder 3 is with mixing Material pre-heating system is connected.

Mixing bunker 1 is used to be transported to by hopper 2 and screw feeder 3 after defluorinate material and defluorinating agent are sufficiently mixed Preheating of mixed material system.

The gas absorption system includes gas absorbing device 11 and gas-solid separator 11-1, and gas absorbing device 11 enters Gas port is connected with fluiddized-bed roasting system, and the gas outlet of gas absorbing device 11 is connected with gas-solid separator 11-1 air inlet.

Preferably, the gas outlet of the gas-solid separator 11-1 is connected with vapor pre-heating system, gas-solid separator 11-1 Discharging opening be connected with gas absorbing device 11.The high-temperature gas of gas absorption system discharge is used to preheat vapor, reclaims Waste heat in processing procedure, be advantageous to save the energy.

Preferably, the gas absorbing device 11 is fixed bed, fluid bed or moving bed, preferably fluid bed.

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

The waste of waste heat during purification fluoro-gas can be avoided as fluorine fixing material using solid matter.

Preferably, the cooling system includes cooling bed 8 and cooling bed separator 8-1, cooling bed 8 Charging aperture is connected with fluiddized-bed roasting system, the gas outlet of cooling bed 8 and cooling bed separator 8-1 air inlet phase Even.

Preferably, the gas outlet of the cooling bed separator 8-1 is connected with vapor pre-heating system, cooling bed Separator 8-1 discharging opening is connected with cooling bed 8.Caused high-temperature gas is used after cooling bed 8 cools down defluorinate ore deposit Preheated in vapor, improve the utilization ratio of waste heat, be advantageous to save the energy.

Preferably, the induced draught system includes air-introduced machine 12 or compressor 17.

Preferably, the induced draught system is connected by vapor pre-heating system with gas absorption system.Because gas absorbs System is connected with fluiddized-bed roasting system, and induced draught system can be by gas absorption system and fluiddized-bed roasting system connectivity, just Subnormal ambient is formed in fluiddized-bed roasting system, is advantageous to defluorination reaction.

Component Mixing System includes mixing bunker 1, hopper 2 and screw feeder 3；Preheating of mixed material system includes coal-fired fluidize Bed 13, coal-fired fluidized bed separator 13-1, cyclone preheater and cyclone separator 14；Fluiddized-bed roasting system include inlet valve 5, Fluidized-solids roaster 6, roaster separator 6-1 and outlet valve 7；Vapor pre-heating system includes steam boiler 10 and combustion chamber 9； Gas absorption system includes gas absorbing device 11 and gas-solid separator 11-1；Cooling system includes cooling bed 8 and cooling Fluid bed separator 8-1；Induced draught system includes air-introduced machine 12 or compressor 17；

The discharging opening of mixing bunker 1 is connected with the charging aperture of hopper 2, the discharging opening of hopper 2 and the charging aperture of screw feeder 3 It is connected, the discharging opening of screw feeder 3 is connected with the raw meal inlet of cyclone preheater；Coal-fired fluidized bed 13 gas outlet and fire coal Fluid bed separator 13-1 air inlet is connected, the gas outlet of the air inlet of cyclone preheater and coal-fired fluidized bed separator 13-1 It is connected, the gas outlet of cyclone preheater is connected with the air inlet of cyclone separator 14, and the discharging opening of cyclone preheater passes through charging Valve 5 is connected with the charging aperture of fluidized-solids roaster 6；

The delivery port of steam boiler 10 is connected with the air inlet of combustion chamber 9, the vapor gas outlet of combustion chamber 9 and fluid bed The air inlet of roaster 6 is connected, and the flue gas gas outlet of combustion chamber 9 is connected with the air inlet of steam boiler 10, steam boiler 10 gas outlet is connected with air-introduced machine 12；

The discharging opening of fluidized-solids roaster 6 is connected by outlet valve 7 with the charging aperture of cooling bed 8, cooling bed 8 Gas outlet be connected with cooling bed separator 8-1 air inlet, cooling bed separator 8-1 gas outlet and steam boiler The air inlet of stove 10 is connected with the air inlet of combustion chamber 9；

The gas outlet of fluidized-solids roaster 6 is connected with the air inlet of gas absorbing device 11, and gas absorbing device 11 goes out Gas port is connected with gas-solid separator 11-1 air inlet, gas-solid separator 11-1 gas outlet and the air inlet phase of steam boiler 10 Even.

Present invention also offers one kind to be calcined defluorination process, and the technique comprises the following steps：

(1) preheated, obtained into preheating of mixed material system after defluorinate material mixes with defluorinating agent in mixing bunker 1 Mixed material after preheating；Vapor pre-heating system produces the vapor after preheating simultaneously；

(2) mixed material after preheating and the vapor 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 containing lithium minerals (such as lepidolite ore), potassium-bearing mineral or containing in cesium mineral described in step (1) It is a kind of or at least two combination.

The particle diameter for treating defluorinate material described in step (1) is 50-500 μm, such 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 Na, K, Ca or Mg oxide, hydroxide, sulfate or carbonate In one kind or at least two mixture, typical but non-limiting mixture be：Na oxide and K hydroxide, Ca sulfate and Mg carbonate, the carbonate of Na hydroxide, K sulfate and Ca, Na oxide, K hydrogen-oxygen Carbonate of compound, Ca sulfate and Mg etc..

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

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

Preferably, the temperature of the mixed material after step (2) described preheating be 800-850 DEG C, such as 810 DEG C, 820 DEG C, 830 DEG C, 840 DEG C or 850 DEG C etc..

Preferably, the temperature of the vapor after step (2) described preheating be 900-1000 DEG C, such 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, (" v% " is such as without special theory by the content ＞ 10v% of the water in vapor steam after step (2) described preheating It is bright to represent percent by volume), if the content of vapor 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, such as 830 DEG C, 840 DEG C, 850 DEG C or 855 DEG C etc..

Preferably, residence time of the mixed material in fluidized-solids roaster after being preheated in step (2) is 30- 120min, such as 40min, 50min, 70min, 80min, 90min, 100min or 110min.

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

Preferably, the vapor preheating that the 10-90v% for the purification gas that step (3) obtains is used in step (1), it is such as net Change 20v%, 30v%, 40v%, 50v%, 60v%, 70v%, 80v% or 85v% of gas etc. and be used for vapor preheating.

Preferably, step (3) is using alkali metal oxide, alkali metal hydroxide, alkaline earth oxide or alkaline earth gold Belong to one kind or at least two combination purification fluoro-gas in hydroxide, it is typical but non-limiting to be combined as：Alkali metal Oxide and alkali metal hydroxide, alkaline earth oxide and alkaline earth metal hydroxide, alkali metal oxide and alkaline earth gold Belong to oxide, alkali metal oxide, alkali metal hydroxide and alkaline earth oxide, alkali metal oxide, alkali metal hydrogen-oxygen Compound, alkaline earth oxide and alkaline earth metal hydroxide etc..

Preferably, step (3) uses K₂O、Na₂O, one kind in CaO or MgO or at least two combination purification contain fluorine gas Body, it is typical but non-limiting to be combined as K₂O and Na₂O, CaO and MgO, K₂O and CaO, K₂O、Na₂O and CaO, K₂O、Na₂O、CaO With MgO etc..

Embodiment 1

Fig. 1 provides a kind of structural representation of lepidolite ore fluiddized-bed roasting defluorinate device, and described device includes：Material Hybrid system, preheating of mixed material system, fluosolids roasting system, vapor pre-heating system, gas absorption system, cooling system and draw Wind system.

Component Mixing System is used to after mixing lepidolite miberal powder and defluorinating agent be transported to preheating of mixed material system, including mixed Close storehouse 1, hopper 2 and screw feeder 3；

Preheating of mixed material system is used for the compound for preheating lepidolite miberal powder and defluorinating agent, its temperature is reached 800-850 DEG C, including coal-fired fluidized bed 13, coal-fired fluidized bed separator 13-1, Category Four cyclone preheater and cyclone separator 14, level Four rotation Wind preheater includes first order cyclone preheater 4-1, second level cyclone preheater 4-2, the third level whirlwind preheating being sequentially connected Device 4-3 and fourth stage cyclone preheater 4-4；

Fluosolids roasting system is the place of lepidolite miberal powder, vapor and defluorinating agent reaction, including inlet valve 5, fluid bed Roaster 6, roaster separator 6-1 and outlet valve 7, fluidized-solids roaster 6 are multistage fluidized bed reactor, preferably 3-7 levels, More preferably 3-5 levels, the fluidisation section of fluidized-solids roaster 6 are provided with vertical inner member, and gas distribution grid opening direction is edge The tangential direction of circumference；

Vapor pre-heating system is used to preheat vapor, the temperature of vapor is reached 900-1000 DEG C, after preheating Vapor is transported to fluiddized-bed roasting system, including steam boiler 10 and combustion chamber 9；

Gas absorption system is used to purify fluoro-gas caused by fluiddized-bed roasting system, absorbs what is included in fluoro-gas HF and SiF₄, F resources are reclaimed, while the high-temperature gas after purification is transported to vapor pre-heating system and is used to preheat vapor, Including gas absorbing device 11 and gas-solid separator 11-1, gas absorbing device 11 can be fixed bed, fluid bed or moving bed, excellent Elect fluid bed as, fluorine fixing material is placed with gas absorbing device 11；

Cooling system is used for defluorinate ore deposit caused by cooling bed roasting system, while will be aobvious during cooling defluorinate ore deposit Heat is used for the preheating of vapor, including cooling bed 8 and cooling bed separator 8-1；

Induced draught system is used to make fluidized-solids roaster form subnormal ambient, makes the lepidolite in fluidized-solids roaster 6 in boiling The partial pressure of vapor in fluidized state increase fluiddized-bed roasting system is risen, promotes the Transport And Transformation of F in lepidolite ore, promotes water to steam Gas defluorination reaction, including air-introduced machine 12；

The Component Mixing System, preheating of mixed material system, fluosolids roasting system, vapor pre-heating system, gas absorb The connected mode of system, cooling system and induced draught system is as follows：

The discharging opening of mixing bunker 1 is connected with the charging aperture of hopper 2, and the discharging opening of hopper 2 passes through pipeline and screw feeder 3 Charging aperture be connected, the discharging opening of screw feeder 3 is connected by pipeline with first order cyclone preheater 4-1 charging aperture；

Coal-fired fluidized bed 13 gas outlet is connected with coal-fired fluidized bed separator 13-1 air inlet, coal-fired fluidized bed separation Device 13-1 gas outlet connects with fourth stage cyclone preheater 4-4 air inlet, and first order cyclone preheater 4-1 gas outlet leads to Piping is connected with the air inlet of cyclone separator 14, and the gas outlet of cyclone separator 14 passes through pipeline and bagroom 15 Air inlet be connected；The miberal powder that bagroom 15 is collected is back to hopper 2 through blanking machine 16；Fourth stage cyclone preheater 4- 4 discharging opening is connected by pipeline with inlet valve 5；

The delivery port of steam boiler 10 is connected with the air inlet of combustion chamber 9, the vapor gas outlet of combustion chamber 9 and fluid bed The air inlet of roaster 6 is connected, and the flue gas gas outlet of combustion chamber 9 is connected with the air inlet of steam boiler 10；

The charging aperture of fluidized-solids roaster 6 connects with fourth stage cyclone preheater 3-4 discharging opening, fluidized-solids roaster 6 The air inlet of bottom is connected by pipeline with the gas outlet of combustion chamber 9, and the gas outlet at the top of fluidized-solids roaster 6 passes through pipeline It is connected with roaster separator 6-1 air inlets, roaster separator 6-1 discharging opening passes through pipeline and fluidized-solids roaster 6 It is connected, roaster separator 6-1 gas outlet is connected by pipeline with the air inlet of gas absorbing device 11；Fluid bed roasts The discharging opening for burning stove 6 top is connected by pipeline with the charging aperture of outlet valve 7, the discharging opening of outlet valve 7 by pipeline with it is cold But the charging aperture of the bottom of fluid bed 8 is connected；

The air inlet of gas absorbing device 11 is connected with roaster separator 6-1 gas outlet, gas absorbing device 11 Gas outlet is connected with gas-solid separator 11-1 air inlet, gas-solid separator 11-1 gas outlet and the air inlet of steam boiler 10 It is connected, gas-solid separator 11-1 discharging opening is connected with gas absorbing device 11；

The air inlet of the bottom of cooling bed 8 is connected by pipeline with air duct, the gas outlet at the top of cooling bed 8 Connected by pipeline with cooling bed separator 8-1 air inlet, cooling bed separator 8-1 gas outlet passes through pipeline It is connected with the air inlet of combustion chamber 9 and the air inlet of steam boiler 10, the bottom of cooling bed 8 is provided with discharging opening, defluorinate Discharged after ore deposit cooling from discharging opening；

Air-introduced machine 12 is connected with the gas outlet of steam boiler 10.

It is as follows using the fluorine in roasting defluorinate device removing lepidolite ore, its technique：

Lepidolite ore and defluorinating agent mix in mixing bunker 1, obtain mixed material, and mixed material adds through hopper 2 and spiral Glassware 3 enters first order cyclone preheater 4-1.

Coal dust fully contacts with air in coal-fired fluidized bed 13 occurs the high warm flue gas of combustion reaction generation, caused high temperature Heat smoke is sent into preheated mixture material in fourth stage cyclone preheater 4-4 after separator separates, and its temperature is reached 800-850 ℃；Cinder is discharged from coal-fired fluidized bed 13 bottom discharge mouth after reaction；

The cold water being passed through from the water inlet of steam boiler 10 and the gas-solid separator 11-1 from gas absorbing device, burning Room 9 and cooling bed separator 8-1 high-temperature gas exchange heat, and the vapor discharged from the delivery port of steam boiler 10 enters Temperature is further improved in combustion chamber 9, the temperature of vapor is reached 900-1000 DEG C；

800-850 DEG C of lepidolite miberal powder and the compound of defluorinating agent enter fluidized-solids roaster 6 with coming by inlet valve 5 900-1000 DEG C of vapor of the bottom of self-fluidized type bed roaster 6 is contacted and reacted, and produces defluorinate ore deposit, solid fluoride and fluorine-containing Gas；

Defluorinate ore deposit caused by fluidized-solids roaster 6 enters cooling bed 8, defluorinate ore deposit after cooling by outlet valve 7 Discharge, caused high-temperature gas is used as steam boiler 10 and the thermal source of combustion chamber 9 in cooling procedure；

Solid fluoride caused by fluidized-solids roaster 6 is dissolved, obtains high-purity HF gases.

The fired stove separator 6-1 separation of fluoro-gas caused by fluidized-solids roaster 6, solid particle caused by separation return Return fluidized-solids roaster 6 and continue calcination, gas caused by separation enters gas absorbing device 11, through fluorine fixing material defluorinate Caused high temperature purification gas enters steam boiler 10 afterwards, the thermal source as preheating vapor；

Air-introduced machine 12 is connected with the gas outlet of steam boiler 10, for making fluidized-solids roaster 6 produce subnormal ambient.

Embodiment 2

Fig. 2 provides a kind of structural representation of lepidolite ore fluiddized-bed roasting defluorinate device, and described device includes：Material Hybrid system, preheating of mixed material system, fluosolids roasting system, vapor pre-heating system, gas absorption system, cooling system and draw Wind system.

Preheating of mixed material system is used to preheat lepidolite miberal powder and defluorinating agent compound, its temperature is reached 800-850 DEG C, Including coal-fired fluidized bed 13, coal-fired fluidized bed separator 13-1, Category Four cyclone preheater and cyclone separator 14, Category Four cyclone is pre- Hot device includes first order cyclone preheater 4-1, second level cyclone preheater 4-2, the third level cyclone preheater 4-3 being sequentially connected With fourth stage cyclone preheater 4-4；

Induced draught system is used to make fluidized-solids roaster 6 form subnormal ambient, makes the lepidolite in fluidized-solids roaster 6 in boiling The partial pressure of vapor in fluidized state increase fluiddized-bed roasting system is risen, promotes the Transport And Transformation of F in lepidolite ore, promotes water to steam Gas defluorination reaction, including compressor 17；

The delivery port of steam boiler 10 is connected with the air inlet of combustion chamber 9, the vapor gas outlet of combustion chamber 9 and fluid bed The air inlet of roaster 6 is connected, and the flue gas gas outlet of combustion chamber 9 is connected with fourth stage cyclone preheater 4-4 air inlet；

The charging aperture of fluidized-solids roaster 6 connects with fourth stage cyclone preheater 3-4 discharging opening, fluidized-solids roaster 6 The air inlet of bottom is connected by pipeline with the vapor gas outlet of combustion chamber 9, and the gas outlet at the top of fluidized-solids roaster 6 leads to Piping is connected with roaster separator 6-1 air inlets, and roaster separator 6-1 discharging opening is roasted by pipeline and fluid bed Burn stove 6 to be connected, roaster separator 6-1 gas outlet is connected by pipeline with the air inlet of gas absorbing device 11；Stream The discharging opening for changing the top of bed roaster 6 is connected by pipeline with the charging aperture of outlet valve 7, and the discharging opening of outlet valve 7 passes through pipe Road is connected with the charging aperture of the bottom of cooling bed 8；

The air inlet of gas absorbing device 11 is connected with roaster separator 6-1 gas outlet, gas absorbing device 11 Gas outlet is connected with gas-solid separator 11-1 air inlet, gas-solid separator 11-1 gas outlet and the air inlet of steam boiler 10 It is connected, gas-solid separator 11-1 discharging opening is connected with gas absorbing device 11；The gas outlet of steam boiler 10 and compressor 17 Air inlet be connected, the gas outlet of compressor 17 is connected with the air inlet of combustion chamber 9；

The air inlet of the bottom of cooling bed 8 is connected by pipeline with air duct, the gas outlet at the top of cooling bed 8 Connected by pipeline with cooling bed separator 8-1 air inlet, cooling bed separator 8-1 gas outlet passes through pipeline It is connected with the air inlet of steam boiler 10, the bottom of cooling bed 8 is provided with discharging opening, is arranged after the cooling of defluorinate ore deposit from discharging opening Go out.

Separated from the cold water that the water inlet of steam boiler 10 is passed through with from gas-solid separator 11-1 and cooling bed Device 8-1 high-temperature gas heat exchange, the vapor discharged from the delivery port of steam boiler 10 enter combustion chamber 9 and further improve temperature Degree, makes the temperature of vapor reach 900-1000 DEG C, and the gas discharged from the gas outlet of steam boiler 10 compresses through compressor 17 Combustion chamber 9 is entered by air inlet of combustion chamber afterwards；

800-850 DEG C of lepidolite miberal powder and the mixed material of defluorinating agent by inlet valve 5 enter fluidized-solids roaster 6 with 900-1000 DEG C of the vapor from the bottom of fluidized-solids roaster 6 is contacted and reacted, and is produced defluorinate ore deposit, solid fluoride and is contained Fluorine gas；

Defluorinate ore deposit caused by fluidized-solids roaster 6 enters cooling bed 8, defluorinate ore deposit after cooling by outlet valve 7 Discharge, caused high-temperature gas is used as the thermal source of steam boiler 10 in cooling procedure；

The tail gas containing vapor discharged from steam boiler 10 is after the adherence pressure of compressor 17 with coming from steam boiler 10 fresh water steam mixing, vapor defluorination reaction is participated in by combustion chamber 9 again into fluidized-solids roaster 6.

Embodiment 3

The device provided using embodiment 1 carries out lepidolite roasting defluorinate, comprises the following steps：

(1) it is sent into after being sufficiently mixed lepidolite miberal powder and defluorinating agent in mixing bunker 1 in hopper 2, through screw feeder 3 Fourth stage cyclone preheater 4-4 is delivered to, and passes sequentially through third level cyclone preheater 4-3, second level cyclone preheater 4-2 and One cyclonic preheater 4-1 from coal-fired fluidized bed 13 high warm flue gas with being exchanged heat；At the same time, the He of steam boiler 10 Combustion chamber 9 produces high-temperature vapor；

(2) temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 800 DEG C, is admitted to fluidized-solids roaster 6, with coming The fully contact of the high-temperature vapor (900 DEG C) of spontaneous combustion room 9 carries out roasting defluorination reaction, makes lepidolite ore phase structure occur to turn Become.Its calcination condition is：Fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, 150 μm of lepidolite miberal powder average grain diameter, is taken off The average grain diameter of fluorine agent is 300 μm, and the addition of defluorinating agent, than excessively 10%, is fed according to the chemical reaction metering reacted with F Speed is 300kg/h, 830 DEG C, water vapour content 50v%, fluidizing gas velocity 0.1m/s of sintering temperature, and residence time of material is 90min；

(3) micro HF and SiH is contained from what fluidized-solids roaster 6 was discharged₄Gas be admitted to gas absorbing device 11 (stream Change bed) in reclaim, be placed with fluorine fixing material in gas absorbing device, the high-temperature tail gas after purification is used to preheat in steam boiler 10 Water produces high-temperature vapor；

(4) miberal powder after calcination is admitted in cooling bed 8 and cooled down, and obtains defluorinate ore deposit, is produced during defluorinate Heat be used to preheating water in steam boiler 10 and combustion chamber 9 and produce high-temperature vapor.

Fluorine fixing material and defluorinating agent are Na in the present embodiment₂O, the defluorinate rate of lepidolite ore is 90.9%, and fluorine fixing material is consolidated Fluorine rate is 97.1%.

Embodiment 4

The device provided using embodiment 2 carries out lepidolite roasting defluorinate, comprises the following steps：

(2) temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 800 DEG C, is admitted to fluidized-solids roaster 6, with coming The fully contact of the high-temperature vapor (1000 DEG C) of spontaneous combustion room 9 carries out roasting defluorination reaction, makes lepidolite ore phase structure occur to turn Become.Its calcination condition is：Fluidized-solids roaster 6 is 3 grades of fluidized-bed reactors, 150 μm of lepidolite miberal powder average grain diameter, is taken off The average grain diameter of fluorine agent is 300 μm, and the addition of defluorinating agent, than excessively 10%, is fed according to the chemical reaction metering reacted with F Speed is 300kg/h, 830 DEG C, water vapour content 10v%, fluidizing gas velocity 0.1m/s of sintering temperature, residence time of material 90min；

(3) HF and SiH is contained from what fluidized-solids roaster 6 was discharged₄Gas be admitted to gas absorbing device 11 (fluidisation Bed) in reclaim, be placed with fluorine fixing material in gas absorbing device, the high-temperature tail gas after purification is used to preheat the water in steam boiler 10 Produce high-temperature vapor；Steamed from the tail gas a part of (50v%) of steam boiler discharge after the adherence pressure of compressor 17 with coming from The fresh water steam mixing of gas boiler 10, vapor defluorination reaction is participated in by combustion chamber 9 again into fluidized-solids roaster 6, Remainder empties；

(4) miberal powder after calcination is admitted in cooling bed 8 and cooled down, and obtains defluorinate ore deposit, is produced during defluorinate Heat be used to preheating water in steam boiler 10 and combustion chamber 9 and produce high-temperature vapor；Defluorinate ore deposit roasts at low temperature through sulfuric acid Burn and the valuable element such as dissolving, Li is converted into soluble sulfate, while solid fluoride dissolves, and discharges the high HF of purity Gas is reclaimed.

Fluorine fixing material and defluorinating agent are Na in the present embodiment₂O, the defluorinate rate of lepidolite ore is 90.9%, and fluorine fixing material is consolidated Fluorine rate is 98.9%.

Embodiment 5

The roasting defluorinate device provided using embodiment 2 carries out lepidolite ore defluorinate, comprises the following steps：

(1) it is sent into hopper 2 after being sufficiently mixed lepidolite miberal powder and defluorinating agent in blending bunker 1, lepidolite in hopper 2 The mixture of miberal powder and defluorinating agent delivers to fourth stage cyclone preheater 4-4 through screw feeder 3, and passes sequentially through third level whirlwind Preheater 4-3, second level cyclone preheater 4-2 and first order cyclone preheater 4-1 from coal-fired fluidized bed 13 height with warming Flue gas is exchanged heat；At the same time, steam boiler 10 and combustion chamber 9 produce high-temperature vapor；

(2) temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 835 DEG C, is admitted in fluidized-solids roaster 6, with The fully contact of high-temperature vapor (950 DEG C) from combustion chamber 9 carries out roasting defluorination reaction, makes lepidolite ore phase structure occur to turn Become.Its calcination condition is：Fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, 200 μm of lepidolite miberal powder average grain diameter, is taken off The average grain diameter of fluorine agent is 300 μm, and the addition of defluorinating agent, than excessively 90%, is fed according to the chemical reaction metering reacted with F Speed is 300kg/h, 850 DEG C, water vapour content 90v%, fluidizing gas velocity 0.1m/s of sintering temperature, residence time of material 100min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (moving bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (30v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, participating in vapor again into fluidized-solids roaster 6 by combustion chamber 9 takes off Fluorine reacts, remainder emptying；

(4) miberal powder after calcination is admitted in cooling bed 8 and cooled down, and obtains defluorinate ore deposit.Defluorinate ore deposit exists through sulfuric acid It is calcined and dissolves under low temperature, the valuable element such as Li is converted into the sulfate of solubility, while solid fluoride dissolves, and discharges pure High HF gases are spent to be reclaimed.

Fluorine fixing material and defluorinating agent are K in the present embodiment₂CO₃, the defluorinate rate of lepidolite ore is 93.3%, and fluorine fixing material is consolidated Fluorine rate is 96.9%.

Application examples 6

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 825 DEG C, is admitted to fluidized-solids roaster In 6, fully contacted with the high-temperature vapor (980 DEG C) from combustion chamber 9 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 450 μm, the average grain diameter of defluorinating agent is 600 μm, and the addition of defluorinating agent is excessive according to the chemical reaction metering ratio reacted with F 16%, feed rate 300kg/h, 840 DEG C, water vapour content 75v%, fluidizing gas velocity 0.1m/s of sintering temperature, material stop Time 75min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fixed bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (34v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, participating in vapor again into fluidized-solids roaster 6 by combustion chamber 9 takes off Fluorine reacts, remainder emptying；

Fluorine fixing material and defluorinating agent are MgSO in the present embodiment₄, the defluorinate rate of lepidolite ore is 94.5%, and fluorine fixing material is consolidated Fluorine rate is 95.6%.

Embodiment 7

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 840 DEG C, is admitted to fluidized-solids roaster Fully contacted with the high-temperature vapor (1000 DEG C) from combustion chamber 9 in 6 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 6 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 500 μm, the average grain diameter of defluorinating agent is 600 μm, and the addition of defluorinating agent is excessive according to the chemical reaction metering ratio reacted with F 45%, feed rate 300kg/h, 840 DEG C, water vapour content 30v%, fluidizing gas velocity 0.1m/s of temperature, residence time of material 120min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fluid bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (65v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, return to fluidized-solids roaster 6 and participate in vapor defluorination reaction again, remaining Partially draining；

Fluorine fixing material is that mass ratio is 1 with defluorinating agent in the present embodiment:1 Ca (OH)₂And Na₂CO₃Mixture, lithium cloud The defluorinate rate of female ore deposit is 92.5%, and the solid fluorine rate of fluorine fixing material is 99.6%.

Embodiment 8

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 850 DEG C, is admitted to fluidized-solids roaster Fully contacted with the high-temperature vapor (1000 DEG C) from combustion chamber 9 in 6 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 4 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 100 μm, the average grain diameter of defluorinating agent is 200 μm, and the addition of defluorinating agent is excessive according to the chemical reaction metering ratio reacted with F 33%, feed rate 300kg/h, 860 DEG C, water vapour content 80v%, fluidizing gas velocity 0.1m/s of sintering temperature, material stop Time 30min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fluid bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (62v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, return to fluidized-solids roaster 6 and participate in vapor defluorination reaction again, remaining Partially draining；

Fluorine fixing material is that mass ratio is 3 with defluorinating agent in the present embodiment:2 K₂SO₄And MgCO₃Mixture, lepidolite ore Defluorinate rate be 91.5%, the solid fluorine rate of fluorine fixing material is 99.5%.

Embodiment 9

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 850 DEG C, is admitted to fluidized-solids roaster Fully contacted with the high-temperature vapor (920 DEG C) from combustion chamber 9 in 6 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 300 μm, the average grain diameter of defluorinating agent is 100 μm, and the addition of defluorinating agent is excessive according to the chemical reaction metering ratio reacted with F 58%, feed rate 300kg/h, 850 DEG C, water vapour content 15v%, fluidizing gas velocity 0.1m/s of sintering temperature, material stop Time 90min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fluid bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (55v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, return to fluidized-solids roaster 6 and participate in vapor defluorination reaction again, remaining Partially draining；

Fluorine fixing material is that mass ratio is 1 with defluorinating agent in the present embodiment:3 Na₂O and Ca (OH)₂Mixture, lepidolite The defluorinate rate of ore deposit is 95.6%, the solid fluorine rate 98.7% of fluorine fixing material.

Embodiment 10

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 820 DEG C, is admitted to fluidized-solids roaster Fully contacted with the high-temperature vapor (930 DEG C) from combustion chamber 9 in 6 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 7 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 500 μm, the average grain diameter of defluorinating agent is 400 μm, and the addition of defluorinating agent is excessive according to the chemical reaction metering ratio reacted with F 50%, feed rate 300kg/h, 845 DEG C, water vapour content 50v%, fluidizing gas velocity 0.1m/s of sintering temperature, material stop Time 60min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fluid bed) Recovery Purifying, fluorine fixing material is placed with gas absorbing device, the high-temperature tail gas after purification is used to preheat steam boiler Water in 10 produces high-temperature vapor；The tail gas a part of (82v%) discharged from steam boiler is after the adherence pressure of compressor 17 Mixed with the fresh water steam from steam boiler 10, return to fluidized-solids roaster 6 and participate in vapor defluorination reaction again, remaining Partially draining；

Fluorine fixing material and defluorinating agent are Na in the present embodiment₂O, the defluorinate rate of lepidolite ore is 93.2%, and fluorine fixing material is consolidated Fluorine rate is 99.0%.

Embodiment 11

(2) mixture temperature of lepidolite miberal powder and defluorinating agent after preheating rises to 810 DEG C, is admitted to fluidized-solids roaster Fully contacted with the high-temperature vapor (910 DEG C) from combustion chamber 9 in 6 and carry out roasting defluorination reaction, make lepidolite ore phase structure Change.Its calcination condition is：Fluidized-solids roaster 6 is 5 grades of fluidized-bed reactors, lepidolite miberal powder average grain diameter 50 μm, the average grain diameter of defluorinating agent is 150 μm, and the addition of defluorinating agent is measured than excessive by 10% according to the chemical reaction reacted with F, Feed rate is 300kg/h, 840 DEG C, water vapour content 10v%, fluidizing gas velocity 0.1m/s of sintering temperature, residence time of material 120min；

(3) discharged from fluidized-solids roaster 6 in tail gas and contain micro HF, SiH₄Gas is admitted to gas absorbing device 11 (fluid bed) Recovery Purifying, the water that the high-temperature tail gas after purification is used to preheat in steam boiler 10 produce high-temperature vapor；From steaming The tail gas a part of (68v%) of boiler furnace discharge after the adherence pressure of compressor 17 with the fresh water steam from steam boiler 10 Mixing, return to fluidized-solids roaster 6 and participate in vapor defluorination reaction, remainder emptying again；

Fluorine fixing material is that mass ratio is 1 with defluorinating agent in the present embodiment:2 Na₂O and MgO mixture, lepidolite ore Defluorinate rate is 92.8%, and the solid fluorine rate of fluorine fixing material is 99.3%.

Applicant states, the foregoing is only the embodiment of the present invention, but protection scope of the present invention not office It is limited to this, person of ordinary skill in the field is it will be clearly understood that any belong to those skilled in the art and taken off in the present invention In the technical scope of dew, the change or replacement that can readily occur in, all fall within protection scope of the present invention and it is open within the scope of.

Claims

1. one kind roasting defluorinate device, it is characterised in that described device includes Component Mixing System, preheating of mixed material system, water Steam pre-heating system and fluiddized-bed roasting system, fluiddized-bed roasting system include fluidized-solids roaster (6), Component Mixing System with Preheating of mixed material system is connected, and preheating of mixed material system and vapor pre-heating system are connected with fluiddized-bed roasting system；

Optionally, described device also includes gas absorption system, cooling system and induced draught system, gas absorption system and cooling system System is connected with fluiddized-bed roasting system, and induced draught system is connected with gas absorption system；

The fluiddized-bed roasting system includes inlet valve (5), fluidized-solids roaster (6), roaster separator (6-1) and outlet valve (7), the charging aperture of the fluidized-solids roaster (6) is connected by inlet valve (5) with Component Mixing System, fluidized-solids roaster (6) discharging opening is connected by outlet valve (7) with cooling system, the air inlet of roaster separator (6-1) and fluiddized-bed roasting The gas outlet of stove (6) is connected, and the gas outlet of roaster separator (6-1) is connected with gas absorption system；

The cooling system includes cooling bed (8) and cooling bed separator (8-1), the charging of cooling bed (8) Mouth is connected with fluiddized-bed roasting system, the gas outlet of cooling bed (8) and the air inlet phase of cooling bed separator (8-1) Even；

The gas outlet of the cooling bed separator (8-1) is connected with vapor pre-heating system, cooling bed separator (8- 1) discharging opening is connected with cooling bed (8).

2. device according to claim 1, it is characterised in that the fluidized-solids roaster (6) is 3-7 level fluidized-bed reactions Device.

3. device according to claim 1, it is characterised in that the fluidized-solids roaster (6) is 3-5 level fluidized-bed reactions Device.

4. device according to claim 1, it is characterised in that the fluidisation section of the fluidized-solids roaster (6) is provided with vertical Straight inner member.

5. device according to claim 1, it is characterised in that gas distribution grid is set in the fluidized-solids roaster (6), The gas distribution grid opening direction is tangential direction circumferentially.

6. device according to claim 1 or 2, it is characterised in that the preheating of mixed material system includes coal-fired fluidized bed (13), coal-fired fluidized bed separator (13-1), cyclone preheater and cyclone separator (14), the gas outlet of coal-fired fluidized bed (13) It is connected with the air inlet of coal-fired fluidized bed separator (13-1), the air inlet of cyclone preheater and coal-fired fluidized bed separator (13- 1) gas outlet is connected, and the gas outlet of cyclone preheater is connected with the air inlet of cyclone separator (14), the life of cyclone preheater Material import is connected with Component Mixing System.

7. device according to claim 6, it is characterised in that the cyclone preheater is 3-6 level cyclone preheaters.

8. device according to claim 6, it is characterised in that the discharging opening of the cyclone separator (14) preheats with whirlwind The raw meal inlet of device is connected, and the gas outlet of cyclone separator (14) is connected with bagroom (15).

9. device according to claim 8, it is characterised in that the bagroom (15) is through blanking machine (16) and material Hybrid system is connected.

10. according to the device described in one of claim 1-3, it is characterised in that the vapor pre-heating system includes steam boiler Stove (10) and combustion chamber (9), the delivery port of steam boiler (10) are connected with the air inlet of combustion chamber (9), and the water of combustion chamber (9) steams Gas gas outlet is connected with fluiddized-bed roasting system.

11. device according to claim 10, it is characterised in that the flue gas gas outlet of the combustion chamber (9) and compound The air inlet of pre-heating system or steam boiler (10) is connected.

12. device according to claim 10, it is characterised in that the gas outlet of the steam boiler (10) and induced draught system It is connected.

13. according to the device described in one of claim 1-4, it is characterised in that the Component Mixing System include hopper (2), Screw feeder (3) and mixing bunker (1), the discharging opening of mixing bunker (1) are connected with the charging aperture of hopper (2), the discharging of hopper (2) Mouth is connected with the charging aperture of screw feeder (3), and the discharging opening of screw feeder (3) is connected with preheating of mixed material system.

14. according to the device described in one of claim 1-5, it is characterised in that the gas absorption system absorbs including gas Device (11) and gas-solid separator (11-1), the air inlet of gas absorbing device (11) are connected with fluiddized-bed roasting system, gas The gas outlet of absorption plant (11) is connected with the air inlet of gas-solid separator (11-1).

15. device according to claim 14, it is characterised in that steamed with water the gas outlet of the gas-solid separator (11-1) Gas pre-heating system is connected, and the discharging opening of gas-solid separator (11-1) is connected with gas absorbing device (11).

16. device according to claim 14, it is characterised in that the gas absorbing device (11) is fixed bed, fluidisation Bed or moving bed.

17. device according to claim 14, it is characterised in that the gas absorbing device (11) is fluid bed.

18. device according to claim 14, it is characterised in that be filled with solid fluorine in the gas absorbing device (11) Agent.

19. device according to claim 18, it is characterised in that the fluorine fixing material is alkali metal oxide, alkaline-earth metal In oxide, alkali metal hydroxide or alkaline earth metal hydroxide any one or at least two combination.

20. device according to claim 1, it is characterised in that the induced draught system includes air-introduced machine (12) or compressor (17)。

21. device according to claim 1, it is characterised in that the induced draught system passes through vapor pre-heating system and gas Body absorption system is connected.

22. device according to claim 1, it is characterised in that described device includes Component Mixing System, preheating of mixed material System, fluiddized-bed roasting system, vapor pre-heating system, gas absorption system, cooling system and induced draught system；

Component Mixing System includes mixing bunker (1), hopper (2) and screw feeder (3)；Preheating of mixed material system includes coal-fired flow Change bed (13), coal-fired fluidized bed separator (13-1), cyclone preheater and cyclone separator (14)；Fluiddized-bed roasting system includes Inlet valve (5), fluidized-solids roaster (6), roaster separator (6-1) and outlet valve (7)；Vapor pre-heating system includes steam Boiler (10) and combustion chamber (9)；Gas absorption system includes gas absorbing device (11) and gas-solid separator (11-1)；Cooling system System includes cooling bed (8) and cooling bed separator (8-1)；Induced draught system includes air-introduced machine (12) or compressor (17)；

The discharging opening of mixing bunker (1) is connected with the charging aperture of hopper (2), the discharging opening of hopper (2) and entering for screw feeder (3) Material mouth is connected, and the discharging opening of screw feeder (3) is connected with the raw meal inlet of cyclone preheater；The outlet of coal-fired fluidized bed (13) Mouth is connected with the air inlet of coal-fired fluidized bed separator (13-1), the air inlet of cyclone preheater and coal-fired fluidized bed separator The gas outlet of (13-1) is connected, and the gas outlet of cyclone preheater is connected with the air inlet of cyclone separator (14), cyclone preheater Discharging opening be connected by inlet valve (5) with the charging aperture of fluidized-solids roaster (6)；

The delivery port of steam boiler (10) is connected with the air inlet of combustion chamber (9), vapor gas outlet and the fluidisation of combustion chamber (9) The air inlet of bed roaster (6) is connected, and the flue gas gas outlet of combustion chamber (9) is connected with the air inlet of steam boiler (10), steam The gas outlet of boiler (10) is connected with air-introduced machine (12)；

The discharging opening of fluidized-solids roaster (6) is connected by outlet valve (7) with the charging aperture of cooling bed (8), cooling fluidisation The gas outlet of bed (8) is connected with the air inlet of cooling bed separator (8-1), the outlet of cooling bed separator (8-1) Mouth is connected with the air inlet of steam boiler (10) and the air inlet of combustion chamber (9)；

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

A kind of 23. technique that device using described in one of claim 1-22 carries out defluorinate, it is characterised in that the technique bag Include following steps：

(1) preheated, obtained pre- into preheating of mixed material system after defluorinate material mixes with defluorinating agent in mixing bunker (1) Mixed material after heat；Vapor pre-heating system produces the vapor after preheating simultaneously；

(2) mixed material after preheating and the vapor after preheating enter fluidized-solids roaster (6) and carry out defluorination reaction, are taken off Fluorine thing, solid fluoride and fluoro-gas；

24. technique according to claim 23, it is characterised in that described in step (1) treat defluorinate material be containing lithium minerals, Potassium-bearing mineral or containing one kind in cesium mineral or at least two combination.

25. technique according to claim 23, it is characterised in that step (1) particle diameter for treating defluorinate material is 50- 500μm。

26. technique according to claim 23, it is characterised in that step (1) described defluorinating agent is Na, K, Ca or Mg oxygen One kind or at least two mixture in compound, hydroxide, sulfate or carbonate.

27. technique according to claim 23, it is characterised in that the particle diameter of step (1) described defluorinating agent is 100-600 μ m。

28. technique according to claim 23, it is characterised in that the chemistry according to product after defluorinating agent and F reactions is counted Amount, the usage amount excess 10-90% of step (1) described defluorinating agent.

29. technique according to claim 23, it is characterised in that the temperature of the mixed material after step (2) described preheating For 800-850 DEG C.

30. technique according to claim 23, it is characterised in that the temperature of the vapor after step (2) described preheating is 900-1000℃。

31. technique according to claim 23, it is characterised in that the water in vapor steam after step (2) described preheating Content ＞ 10v%.

32. technique according to claim 23, it is characterised in that the temperature of step (2) described defluorination reaction is 830-860 ℃。

33. technique according to claim 23, it is characterised in that the mixed material after being preheated in step (2) is in fluid bed Residence time in roaster is 30-120min.

34. technique according to claim 23, it is characterised in that the solid fluoride in step (2) obtains HF through dissolving Gas.

35. technique according to claim 23, it is characterised in that caused by step (3) the defluorinate ore deposit cooling procedure The vapor pre-heating system that heat is used in step (1).

36. technique according to claim 23, it is characterised in that the 10-90v% for the purification gas that step (3) obtains is used Vapor pre-heating system in step (1).

37. technique according to claim 23, it is characterised in that step (3) is using alkali metal oxide, alkali metal hydrogen-oxygen One kind or at least two combination purification fluoro-gas in compound, alkaline earth oxide or alkaline earth metal hydroxide.

38. technique according to claim 23, it is characterised in that step (3) uses K₂O、Na₂O, one in CaO or MgO Kind or at least two combination purification fluoro-gas.