CN208995150U - A kind of device preparing aluminum fouoride - Google Patents

Abstract

The utility model relates to a kind of devices for preparing aluminum fouoride, including inlet duct, wet hydrogen aluminium oxide dosing feeder, single-bed fluidized reactor (301), aluminum fluoride gas-solid separator (302), alumina reactor (303), aluminium oxide gas-solid separator (304), aluminium hydroxide drier (305), aluminium hydroxide gas-solid separator (306), aluminum fluoride static state cooler (501) and exhaust gas processing device；The inlet duct includes air heater (101), hydrogen fluoride vaporizer (103) and hydrogen fluoride mixer (102), and the air heater (101) and the hydrogen fluoride vaporizer (103) are connected with the hydrogen fluoride mixer (102) respectively；The hydrogen fluoride mixer (102) is connected with the single-bed fluidized reactor (301).Product quality made from the utility model is more preferable: content is high, impurity is low, than great, good fluidity, and low energy consumption.

Description

A kind of device preparing aluminum fouoride

Technical field

The utility model relates to a kind of device for preparing aluminum fouoride, belong to chemical technology field, more specifically one Kind produces the device of aluminum fouoride using anhydrous hydrogen fluoride and wet hydrogen aluminium oxide as raw material.

Background technique

Aluminum fluoride (AlF3), white crystal or powder；Relative density 2.882 (25 DEG C), is slightly soluble in water, acid and alkali solution, Insoluble in most of organic solvent, there is biggish solubility in a solution of hydrofluoric acid.Aluminum fouoride property is highly stable；With liquid Ammonia is even heated to smoke still Fails To Respond with the concentrated sulfuric acid, unchanged with potassium hydroxide congruent melting, and not by hydrogen reducing, heating is not yet It decomposes, but distils, 1291 DEG C of sublimation temperature.At 300~400 DEG C, hydrogen fluoride and aluminium oxide can be hydrolyzed to by water vapor portion. It is toxic.

Aluminum fluoride (AlF3) purposes: it is mainly used for aluminum electrolysis industry (accounting for 95% of total amount or more), the tune as electrolyte Whole dose, to reduce fusing point and improve the conductivity of electrolyte；It is also used for making the inhibitor to ferment when production alcohol；As ceramics Outer layer muffle painting and the fluxing agent of vitreous enamel, nonferrous metal flux；Soldering fluid is used in metal welding；For manufacturing optics Lens；Also serve as the catalyst of organic synthesis and the raw material of cryolith etc..

The production technology of aluminum fluoride is divided into wet processing and dry process；Dry process is divided into " crude acid-dry hydrogen aluminium oxide again Technique " and " smart acid-wet hydrogen alumina technology ".

Wet processing is the technology continuing to use last century the fifties and introducing from the former Soviet Union；It is generated with fluorite and sulfuric acid reaction There are water hydrofluoric acid or fluorine silicic acid aqueous solution and aluminium hydroxide to carry out liquid-solid reaction, generate containing there are three after the aluminum fluoride of the crystallization water, It is made again through high temperature dehydration；Due to being reacted in hydrofluoric acid solution, so being known as " wet processing ".The technique is produced Product not only purity it is low, it is aqueous it is high, specific gravity is small, poor fluidity, but also process flow is long, equipment is more, seriously corroded, consumption of raw materials High, energy consumption height, easily leading to downstream industry aluminium electroloysis, environmental pollution is serious, has been eliminated.2004, wet process aluminum fluoride technique by " national industry structural adjustment guidance list " is included in superseded process sequence；2007, in national development and reform committee member Regulation in No. 64 " the aluminium industry access condition " that can be announced: wet processing is forbidden to produce aluminium fluoride salt.

Crude acid-dry hydrogen alumina technology, the technique for being derived from BUSS company, Switzerland.

1970s, Switzerland's Buss (BUSS) company develop the production technology of dry production aluminum fluoride, it may be assumed that fluorite The AHF gas of powder and the sulfuric acid output after converter reaction, fluidized-bed reactor is imported after dedusting and sulfuric acid scrubbing, has been dried Dry (sloughing surface water) aluminium hydroxide enters fluidized bed, is changed into aluminium oxide at high temperature；AHF gas and aluminium oxide are sufficiently anti- It answers, generates aluminum fluoride, be finished product after supercooling.The technique is compared with wet processing, and the energy consumption of ton product and material consumption are Decline, production environment are greatly improved；Most importantly product quality improves a lot, and especially water content is significantly Decline, external form have become sand shape, and mobility is preferable.Indices can be controlled in the model of AF-1 in Chinese Industrial Standards (CIS) GB/T4292-2007 In enclosing.But if Fluorspar Powder quality is not fine (such as dioxide-containing silica SiO2 >=1.2% in Fluorspar Powder), these dioxies SiClx generates silicon tetrafluoride gas with hydrogen fluoride reaction in converter, and aluminum fluoride fluidized bed is entered together with hydrogen fluoride gas It in reactor, wherein about 25%~50% ocratation is re-converted to silica, is mixed in aluminum fluoride, causes to be fluorinated Dioxide-containing silica is exceeded in aluminium product；Phosphorus index is also because same reason may be exceeded.According to the more works using above-mentioned technique Factory reflection, production aluminium fluoride product in dioxide-containing silica be not achieved AF-0 in GB/T4292-2007 requirement (SiO2≤ 0.1%) index for, even connecting AF-1 sometimes can not reach.

In addition to silica, other impurity components are not also effectively removed in Fluorspar Powder, so that aluminium fluoride product In some impurity, the content such as phosphorus pentoxide (P2O5) is also very high, especially with some regional (such as north of China) The higher Fluorspar Powder of phosphorus content, P2O5 even meeting >=0.08% in aluminum fluoride is very unfavorable to Aluminum Electrolysis Production, makes electrolytic aluminium Factory cannot use.

Crude acid-dry hydrogen alumina technology other the disadvantage is that: 1, quantity of wastewater effluent is bigger；And due in sewage both Hydrofluoric acid containing also fluorine-containing silicic acid, cannot comprehensively utilize, can only be discharged into Sewage Disposal, so that cost of sewage disposal is higher.2, hydrogen The volume of aluminium oxide drying oven, pre-reactor, two-stage fluidized, tail gas absorbing system etc. is larger, causes plant investment bigger. 3, technique controlling difficulty is higher.4, larger, the especially barometric condenser and Water-ring vacuum of tail gas absorbing system is corroded to equipment Pump, easily corrosion and damage.5, energy utilization rate is low, and energy consumption is larger.

Smart acid-wet hydrogen alumina technology: this is the technology of German CHENCO company, which starts from last century 90 Age is made a big improvement in terms of process flow and relative special-purpose equipment for " crude acid-dry hydrogen alumina technology ".

Smart acid-wet hydrogen alumina technology process is: Fluorspar Powder and sulfuric acid are in pre- anti-device and turn to generate after reaction in furnace thick HF gas into a collection dedusting, is washed, is cooled in integrated prewashing column, HF gas scrubbing is carried out, subsequently into condensation HF gas-condensate liquid is turned to HF liquid by system.The HF liquid condensed out enters distillation system, remove SO2, H2SO4, The impurity such as SiF4, H2O obtain liquefied pure anhydrous hydrogen fluoride (AHF), HF >=99.9% after purification.

AHF enters aluminum fluoride fluidized-bed reactor after evaporator gasifies；It is anti-that wet hydrogen aluminium oxide also enters fluidized bed simultaneously Device system is answered, by dehydration, and hydrogen fluoride gas pyroreaction becomes aluminum fluoride, and aluminum fluoride is from fluidized-bed reactor discharge port Aluminium fluoride product is obtained after being discharged into rotary cooling furnace water spray cooling.

Due to raw material fluorinated hydrogen HF >=99.9%, every quality index of the aluminium fluoride product of technique production is much higher than The AF-0 of national standard GB/T4292-2007；Wherein: SiO2≤0.03%；Fe2O3≤0.03%；SO42-≤0.10%；P2O5 ≤ 0.008%；Bulk density is greater than 1.5g/cm3, and mobility is more preferable.But due to improving product quality, its production cost ratio is " thick The high about 200 yuan/MT of acid-dry hydrogen alumina technology ".Simultaneously there is also some disadvantages: although 1, be utilized reaction heat abstraction wet hydrogen The surface water of aluminium oxide, but hot air furnace will work always, not so the reaction high temperature in fluidized bed (560~620 DEG C) is no It can maintain.2, it is contacted when wet hydrogen aluminium oxide enters system with high temperature gas flow (560~620 DEG C), it may occur that " explosion " phenomenon makes hydrogen Alumina particle fragmentation reduces product particle degree and mobility.3, exhaust temperature is excessively high (320~380 DEG C), heat-energy losses compared with Seriously, moreover, tail gas absorbing system equipment is caused to be easily damaged, it is larger to absorb water requirement.4, entrained by high-temperature fluorination aluminium The energy is not utilized effectively；There should be rotary motive power when cooling, also there are a large amount of circulation water sprays, energy consumption is higher.5, it absorbs Waste water drains into Sewage Disposal, and effective component is not utilized rationally, and resource is wasted, and improves at production cost and sewage Manage cost.

Aluminum fluoride by dry process production technology has had leaping for matter compared with wet process aluminum fluoride production technology；Just because of this, Dry method has eliminated wet process.But aluminum fluoride by dry process there are the problem of, biggish restriction still is generated to aluminum fluoride production, especially can High problem is consumed, is not consistent with energy-saving mainstream of society.

Solvent one of of the aluminum fluoride as electrolytic process, is the important component of electrolyte, is adjustment electrolyte molecule Than, the thermally equilibrated important means of control electrolytic process.The physicochemical property difference of the aluminium fluoride product differently produced is very big, The physicochemical property for directly affecting electrolyte influences technological operation, the technic index control, environmental pollution journey of Aluminum Electrolysis Production process The product quality of degree and electrolytic aluminium.Requirement with the raising of Aluminum Electrolysis Production process automation degree, to aluminum fluoride quality Also higher and higher.The existing aluminum fluoride by dry process production technology of improve and perfect and technology, independent research high-performance aluminium fluoride product New Technologies, the aluminum fluoride by dry process for producing high quality is that domestic and international fluoride salt industry and aluminum electrolysis industry will be lasting, steady from now on The most important thing that is fixed, developing in a healthy way.

Utility model content

The utility model provides a kind of device for preparing aluminum fouoride, solve existing aluminum fluoride by dry process energy consumption it is high, The problems such as unstable quality.

In order to solve the above technical problems, the technical solution adopted by the utility model is:

A kind of device preparing aluminum fouoride, including inlet duct, wet hydrogen aluminium oxide dosing feeder, single layer fluidisation Bed reactor, aluminum fluoride gas-solid separator, alumina reactor, aluminium oxide gas-solid separator, aluminium hydroxide drier, hydroxide Aluminium gas-solid separator, aluminum fluoride static state cooler and exhaust gas processing device；

The single-bed fluidized reactor is equipped with airflow inlet, high temperature gas flow outlet, the outlet of high-temperature fluorination aluminium, aluminum fluoride go back to Head piece and aluminium oxide import；Airflow inlet is connected with the inlet duct, high temperature gas flow outlet and the aluminum fluoride gas solid separation The high-temperature gas import of device is connected, and the outlet of high-temperature fluorination aluminium is connected with the material inlet of the aluminum fluoride static state cooler, is fluorinated Aluminium refluxing opening is connected with the feed opening of the aluminum fluoride gas-solid separator, aluminium oxide import and the aluminium oxide gas-solid separator Feed opening is connected.

The high temperature gas flow import phase of the high-temperature gas outlet and the alumina reactor of the aluminum fluoride gas-solid separator Even, the feed opening of the aluminum fluoride gas-solid separator is connected with the aluminum fluoride refluxing opening of the single-bed fluidized reactor；

The dry hydrogen aluminium oxide import of the alumina reactor is connected with the feed opening of the aluminium hydroxide gas-solid separator, The medium temperature gas-solid outlet of the alumina reactor is connected with the material inlet of the aluminium oxide gas-solid separator；

The medium temperature airflow inlet of the medium temperature air stream outlet of the aluminium oxide gas-solid separator and the aluminium hydroxide drier It is connected；

The wet hydrogen aluminium oxide import of the aluminium hydroxide drier is connected with the wet hydrogen aluminium oxide dosing feeder, institute The low temperature gas-solid outlet for stating aluminium hydroxide drier is connected with the aluminium hydroxide gas-solid separator；

The low-temperature airflow outlet of the aluminium hydroxide gas-solid separator is connected with the exhaust gas processing device.

The inlet duct includes air heater, hydrogen fluoride vaporizer and hydrogen fluoride as a preferred technical solution, Mixer, the air heater and the hydrogen fluoride vaporizer are connected with the hydrogen fluoride mixer respectively；The hydrogen fluoride Mixer is connected with the single-bed fluidized reactor；The heat source import of the hydrogen fluoride vaporizer is connected with external heating system Or it is connected with the steam (vapor) outlet of aluminum fluoride static state cooler.

The wet hydrogen aluminium oxide dosing feeder includes sequentially connected wet hydrogen oxidation as a preferred technical solution, Aluminium metering feed bin is connected with wet hydrogen feeds of alumina spiral, wet aluminum hydroxide outlet and the hydrogen of the wet hydrogen feeds of alumina spiral Aluminium oxide drier is connected.

The exhaust gas processing device includes tail gas absorber as a preferred technical solution, the tail gas absorber and suction It receives liquid circulating slot to be connected, then is connected with absorbing liquid subsider；Absorbing liquid circulating pump is connected with absorbing liquid circulating slot, then with absorbing liquid Cooler is connected, and absorbing liquid cooler outlet is connected with the tail gas absorber；The outlet of absorbing liquid circulating slot and tail gas water scrubber It is connected, is then connected with gas-liquid separator, is finally connected with exhaust fan.

The single-bed fluidized reactor is cylinder type rising structure as a preferred technical solution, cylinder heights and The ratio between drum diameter is 3.5~6.0；The aluminum fluoride static state cooler is dividing wall type heat exchanger structure or pipe heat exchanger knot Structure.

The alumina reactor is pipeline reactor structure, duct length and pipe as a preferred technical solution, Road diameter ratio is 10~120, and the reaction temperature in the pipeline is 520 DEG C~660 DEG C；The aluminium hydroxide drier is pipe Road formula gas flow dryer structure, the ratio between duct length and pipe diameter are 10~150, and the operating temperature in the pipeline is 150 DEG C~520 DEG C.

The hydrogen fluoride vaporizer is reboiler structure as a preferred technical solution, with high-temperature steam or with super pressure-high temperature Water as heating hydrogen fluoride vaporization heat source, heat source temperature be 120 DEG C~260 DEG C, hydrogen fluoride vaporization after temperature be 80 DEG C~ 220℃。

The tail gas absorber is water injection venturi tube structure as a preferred technical solution,.

The utility model be also disclosed it is a kind of prepare aluminum fouoride method, using the device of the utility model, comprising with Lower step:

(1) anhydrous liquid hydrogen fluoride is converted into gaseous state in the hydrogen fluoride vaporizer；Air is heated by the air Device mixes in the hydrogen fluoride mixer with gaseous hydrogen fluoride, into the bottom of the single-bed fluidized reactor, first When restarting after secondary starting or parking, air is heated to 300~450 DEG C in the air heater, during normal production, The air heater is as just air duct；

(2) room temperature wet hydrogen aluminium oxide passes through the wet hydrogen aluminium oxide after wet hydrogen aluminium oxide metering feed bin metering Feed auger enters the aluminium hydroxide drier, is 320~450 DEG C with the temperature from the aluminium oxide gas-solid separator Middle warm air is sufficiently mixed, and removes the surface water of wet hydrogen aluminium oxide, and becoming dry hydrogen aluminium oxide and temperature is 150~260 DEG C low Warm air, the gas solid separation in the aluminium hydroxide gas-solid separator, low-temperature airflow enter the tail gas absorber；

(3) high temperature gas flow one that dry hydrogen aluminium oxide and the temperature from the aluminum fluoride gas-solid separator are 550~650 DEG C It rises and enters the alumina reactor, under the action of high temperature gas flow, aluminium hydroxide is changed into aluminium oxide and water vapour；High Temperature Gas At middle warm air after banishing heat and being mixed with vapor；Aluminium oxide and middle warm air divide in the aluminium oxide gas-solid separator From aluminium oxide enters the single-bed fluidized reactor, and middle warm air enters the aluminium hydroxide drier；

(4) in the single-bed fluidized reactor, the alumina particle entered from middle part and the gaseous state entered from bottom Hydrogen fluoride carries out fluidisation state reaction, generates fluorination alumina particles and high temperature gas flow, and high temperature gas flow is from the single-bed fluidized reactor Top output, after the aluminum fluoride gas-solid separator, the aluminum fluoride of entrainment is backed within the single-layer fluidized bed In reactor, high temperature gas flow enters the alumina reactor, and the high-temperature fluorination alumina particles generated after reaction are from the single layer stream Fluidized bed reactor output enters the aluminum fluoride static state cooler, and aluminum fluoride after cooling becomes product；

(5) low-temperature airflow in the aluminium hydroxide gas-solid separator after gas solid separation is followed in the tail gas absorber Ring water absorbs, into absorbing liquid circulating slot；Unabsorbed HF enters tail gas water scrubber by clear water spray-absorption, spray liquid also into Enter absorbing liquid circulating slot；Unabsorbable air is arranged after removing liquid mist in gas-liquid separator by exhaust fan in tail gas It puts；Absorbing liquid circulating pump sprays into tail gas absorber after the absorbing liquid pump in absorbing liquid circulating slot to absorbing liquid cooler is cooled down Interior, absorbing liquid circulating slot is connected directly with absorbing liquid subsider, settles the particulate matter in absorbing liquid, and reaching, regulation is dense It is sent after degree to ice crystal production line as ice crystal raw materials for production.

The aluminum fluoride temperature for entering the aluminum fluoride static state cooler as a preferred technical solution, is 520 DEG C~720 DEG C, temperature when aluminum fluoride leaves aluminum fluoride static state cooler is 50 DEG C~90 DEG C, and cooling water is deionized water or pure water, is entered Temperature when aluminum fluoride static state cooler is 25 DEG C~65 DEG C, by the heat exchange with aluminum fluoride, becomes high-temperature steam or height with pressure Warm water leaves aluminum fluoride static state cooler, and temperature is 120 DEG C~350 DEG C, can be used for the heat source of the hydrogen fluoride vaporizer, It can be to external heat outputting energy.

The utility model has the beneficial effects that

Compared with prior art, the utility model has the advantage that

1, wet hydrogen aluminium oxide is directly entered the utility model process units, does not need separately to build drying equipment；By utilizing fluorine Change the reaction heat of aluminium to remove the surface water and the crystallization water of aluminium hydroxide, plays energy-saving effect.

2, when wet hydrogen aluminium oxide is directly entered the utility model process units, be not with high temperature gas flow (temperature be 550~ 650 DEG C) contact, but contacted with middle warm air (temperature is 320~450 DEG C), avoid the Decrepitation Phenomena of aluminium hydroxide；So that Aluminium fluoride product quality increases, and the granularity and mobility of product are more preferable.

3, high temperature gas flow (temperature is 550~650 DEG C) removing crystalline aluminum hydroxide water, makes aluminium oxide, middle wet Stream (temperature be 320~450 DEG C) removes the surface water of removing aluminium hydroxide again so that the gas flow temperature for leaving reaction system be down to it is low Warm air (temperature is 150~260 DEG C), is equivalent to more energy " staying " in aluminum fluoride preparation system；Meanwhile also The HF gas carried secretly in tail gas more " adsorbs " on hydrogen aluminium, comes back in fluidized-bed reactor；Play energy conservation, consumption reduction Double action.

4, single-bed fluidized reactor control is simple, and operation is easy；It is and with low investment: the identical production capacity the case where Under, single-layer fluidized bed volume only has the 55%~75% of two-stage fluidized volume；It can investment reduction cost.

5, the aluminum fouoride product quality prepared using the utility model device is more preferable: content is high, impurity is low, specific gravity Greatly, good fluidity.

6, since exhaust temperature reduces, the active principle in tail gas is easier to be absorbed；Absorption plant can become more Simply, qualified discharge is easier.Meanwhile tail gas absorption liquid can produce fluorine-containing other products (such as ice crystal).Reach section About resource, recycle chemical industry cleaning procedure production requirement.

7, since exhaust temperature reduces, the operating temperature of device for absorbing tail gas can be reduced, so that lectotype selection range It is wider；And absorbing liquid heat exchange amount is smaller, can reach investment reduction cost, energy-saving effect.

8, the cooling of high-temperature fluorination aluminium uses static cooler and does not have compared with the revolution cooler (furnace) of the prior art There is rotary motive power consumption, without the circulation of shower water, many energy consumptions can be saved.Moreover, cooling procedure obtains height Warm steam or high-temperature water with pressure, can be used as heat source for the utility model hydrogen fluoride evaporate, thermal energy can also be exported to It uses, has also achieved the purpose that energy-saving outside this system.

Detailed description of the invention

In order to illustrate more clearly of the technical solution of the utility model, letter will be made to attached drawing needed in the embodiment Singly introduce.

Fig. 1 is the structural schematic diagram of one embodiment of the utility model.

Specific embodiment

Below in conjunction with the utility model attached drawing, the technical solution of the utility model is clearly and completely described, is shown So, described content is only the utility model one embodiment, instead of all the embodiments.Based in the utility model Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, It fall within the protection scope of the utility model.

Embodiment 1

As shown in Figure 1, a kind of device for preparing aluminum fouoride, comprising: air heater 101, hydrogen fluoride vaporizer 103, hydrogen fluoride mixer 102, wet hydrogen aluminium oxide metering feed bin 201, wet hydrogen feeds of alumina spiral 202, single-layer fluidized bed are anti- Answer device 301, aluminum fluoride gas-solid separator 302, alumina reactor 303, aluminium oxide gas-solid separator 304, aluminium hydroxide dry Device 305, tail gas absorber 401, absorbing liquid circulating slot 402, absorbing liquid subsider 403, is inhaled aluminium hydroxide gas-solid separator 306 Receive liquid circulating pump 404, absorbing liquid cooler 405, tail gas water scrubber 406, gas-liquid separator 407, exhaust fan 408, aluminum fluoride Static cooler 501 and the pipeline and valve that these equipment are linked together.

Air heater 101 is equipped with 1 air intlet and 1 air outlet slit；Air intlet is connected with atmosphere, or by empty It is connected after gas purifier with atmosphere；Air outlet slit is connected with hydrogen fluoride mixer 102；In the present embodiment with air intlet and atmosphere It is connected；

Hydrogen fluoride vaporizer 103 is equipped with 1 AHF liquid-inlet, 1 AHF gas vent, 1 heat source import and 1 condensation Water out；AHF liquid-inlet is connected with external AHF acid supplying system, and AHF gas vent is connected with hydrogen fluoride mixer 102；Heat Source import is connected with external heating system or is connected with the steam (vapor) outlet of aluminum fluoride static state cooler 501, and condensation-water drain is row Put mouth.

Hydrogen fluoride mixer 102 is equipped with 1 AHF gas feed, 1 air intlet, 1 high temperature air import and one Switching valve；AHF gas feed is connected with hydrogen fluoride vaporizer 103, and air intlet is connected with air heater 101, high temperature air Import is connected with external heating wind system, and switching valve is for the switching between air intlet and high temperature air import.

Wet hydrogen aluminium oxide measures feed bin 201 and is equipped with 1 wet aluminum hydroxide import and wet aluminum hydroxide outlet；Wet aluminum hydroxide import and outside are wet Aluminium hydroxide feed bin is connected；Wet aluminum hydroxide outlet is connected with wet hydrogen feeds of alumina spiral 202.

Wet hydrogen feeds of alumina spiral 202 is equipped with 1 wet aluminum hydroxide import and wet aluminum hydroxide exports；Wet aluminum hydroxide import and wet hydrogen oxygen Change aluminium metering feed bin 201 to be connected；Wet aluminum hydroxide outlet is connected with aluminium hydroxide drier 305.

Single-bed fluidized reactor 301 is equipped with 1 airflow inlet, 1 high temperature gas flow exports, 1 high-temperature fluorination aluminium exports, 1 aluminum fluoride refluxing opening and 1 aluminium oxide import；Airflow inlet is connected with the gas vent of hydrogen fluoride mixer 102, High Temperature Gas Outflux is connected with aluminum fluoride gas-solid separator 302, the material inlet of high-temperature fluorination aluminium outlet and aluminum fluoride static state cooler 501 It is connected, aluminum fluoride refluxing opening is connected with the feed opening of hydrogen fluoride mixer 102, aluminium oxide import and aluminium oxide gas-solid separator 304 feed opening is connected.

Aluminum fluoride static state cooler 501 is equipped with 1 material inlet, 1 material outlet, 1 clear water import and 1 high temperature and steams Vapour (or high-temperature water with pressure) outlet；Material inlet is connected with single-bed fluidized reactor 301, material outlet and external aluminum fluoride Product warehouse is connected, and clear water import is connected with the delivery outlet of external pure water system, high-temperature steam (or high-temperature water with pressure) export and External user is connected, or, high-temperature steam (or high-temperature water with pressure) outlet is connected with the heat source interface of hydrogen fluoride vaporizer 103.

Aluminum fluoride gas-solid separator 302 is equipped with 1 high temperature gas flow import, 1 high temperature gas flow outlet and 1 feed opening.It is high Warm gas feed is connected with single-bed fluidized reactor 301, and high-temperature gas outlet is connected with alumina reactor 303, feed opening It is connected with single-bed fluidized reactor 301.

Alumina reactor 303 is equipped with 1 high temperature gas flow import, 1 dry hydrogen aluminium oxide import and 1 medium temperature gas-solid and goes out Mouthful；High temperature gas flow import is connected with the outlet of the high temperature gas flow of aluminum fluoride gas-solid separator 302, the import of dry hydrogen aluminium oxide and hydroxide The feed opening of aluminium gas-solid separator 306 is connected, and medium temperature gas-solid outlet is connected with the material inlet of aluminium oxide gas-solid separator 304.

Aluminium oxide gas-solid separator 304 is equipped with 1 material inlet, alumina blanking mouth and medium temperature air stream outlet；Material into Mouthful be connected with alumina reactor 303, alumina blanking mouth is connected with single-bed fluidized reactor 301, medium temperature air stream outlet and Aluminium hydroxide drier 305 is connected.

Aluminium hydroxide drier 305 is equipped with 1 medium temperature airflow inlet, 1 wet hydrogen aluminium oxide import and 1 low temperature gas-solid and goes out Mouthful；Medium temperature airflow inlet is connected with aluminium oxide gas-solid separator 304, the import of wet hydrogen aluminium oxide and wet hydrogen feeds of alumina spiral 202 are connected, and low temperature gas-solid outlet is connected with aluminium hydroxide gas-solid separator 306.

Aluminium hydroxide gas-solid separator 306 is equipped with 1 material inlet, dry hydrogen alumina blanking mouth and low-temperature airflow outlet； Material inlet is connected with aluminium hydroxide drier 305, and dry hydrogen alumina blanking mouth is connected with alumina reactor 303, low temperature gas Outflux is connected with tail gas absorber 401.

Tail gas absorber 401 is connected with absorbing liquid circulating slot 402, then is connected with absorbing liquid subsider 403；Absorbing liquid circulation Pump 404 is connected with absorbing liquid circulating slot 402, then is connected with absorbing liquid cooler 405, the outlet of absorbing liquid cooler 405 and tail gas Absorber (401) is connected；Absorbing liquid circulating slot 402 outlet is connected with tail gas water scrubber 406, then with 407 phase of gas-liquid separator Even, finally it is connected with exhaust fan 408, forms complete tail gas absorbing system.

Single-bed fluidized reactor is cylinder type rising structure, belongs to gas solid reactor；The ratio between cylinder heights and drum diameter It is 3.5~6.0；In general, drum diameter is 1.5 meters~7 meters, cylinder heights are 4 meters~42 meters.The present embodiment uses cylinder heights It is 5 in general, drum diameter is 3 with the ratio between drum diameter, cylinder heights are 15 meters.

Single-bed fluidized reactor bottom is equipped with air inlet；Gas outlet is equipped at the top of single-bed fluidized reactor；Single layer stream The middle and upper part of the cylinder of fluidized bed reactor is equipped with solid material import；The middle and lower part of the cylinder of single-bed fluidized reactor is equipped with solid Body material outlet.

Aluminum fluoride static state cooler is dividing wall type heat exchanger structure, using water as cooling medium, high-temperature fluorination aluminium and cooling Jie Across heat exchanger plates reverse flow between matter.Temperature when aluminum fluoride enters cooler is 520 DEG C~660 DEG C, and aluminum fluoride leaves cold But temperature when device is 50 DEG C~90 DEG C, and temperature when cooling water enters cooler is 25 DEG C~65 DEG C, by with aluminum fluoride Heat exchange, becomes high-temperature steam or high temperature water with pressure leaves cooler, and temperature is 120 DEG C~260 DEG C.

Alternatively, aluminum fluoride static state cooler is pipe heat exchanger structure, and using water as cooling medium, high-temperature fluorination aluminium and cooling Across heat exchanger tube reverse flow between medium.Temperature when aluminum fluoride enters cooler is 520 DEG C~660 DEG C, and aluminum fluoride leaves Temperature when cooler is 50 DEG C~90 DEG C；Temperature when cooling water enters cooler is 25 DEG C~65 DEG C, by with aluminum fluoride Heat exchange, become high-temperature steam or high-temperature water with pressure leave cooler, temperature is 120 DEG C~260 DEG C.

Alumina reactor is pipeline reactor structure, and the ratio between duct length and pipe diameter are 10~120；Pipeline Interior reaction temperature is 520 DEG C~660 DEG C.The present embodiment uses the ratio between duct length and pipe diameter for 30, and duct length is 12 meters, pipe diameter is 0.4 meter.

Aluminium hydroxide drier is ducted air dryer configuration, the ratio between duct length and pipe diameter be 10~ 150；Operating temperature in pipeline is 150 DEG C~520 DEG C.The present embodiment uses the ratio between duct length and pipe diameter for 40, pipe Road length is 16 meters, and pipe diameter is 0.4 meter.

Hydrogen fluoride vaporizer is reboiler structure；Using high-temperature steam or high-temperature water with pressure as the heat of heating hydrogen fluoride vaporization Source；Heat source temperature is 120 DEG C~260 DEG C, and the temperature after hydrogen fluoride vaporization is 80 DEG C~220 DEG C.

Tail gas absorber is water injection venturi tube structure；Recirculated water is sprayed into tail gas absorber by absorbing liquid circulating pump 404 401, the tail gas that aluminium hydroxide gas-solid separator 306 exports is aspirated into tail gas absorber under the effect of exhaust fan 408 401, water vapour, a small amount of hydrogen fluoride gas and the dust carried secretly on a small quantity in tail gas are only absorbed by the water, into absorbing liquid circulating slot 402 and solids is settled in absorbing liquid subsider 403；The hydrogen fluoride gas and powder not absorbed by tail gas absorber 401 Dirt is further absorbed by clear water in tail gas water scrubber 406；Unabsorbable air is removed by gas-liquid separator 407 in tail gas It is emptied after going liquid mist.Absorbing liquid cooler 405 can keep circulating water temperature within the scope of 25~70 DEG C.Absorbing liquid subsider 403 Obtained in solid sediment ice crystal process units is drained into together with liquid with partially absorbing, for producing ice crystal product.

HF content in absorbing liquid controls within 2.0%, it is ensured that exhaust emissions meets national standard.

High-temperature steam or high-temperature water with pressure for hydrogen fluoride vaporizer as heating hydrogen fluoride vaporize heat source.Alternatively, High-temperature steam or high-temperature water with pressure exported to external system as heat source for hydrogen fluoride vaporizer.

Equipment, pipeline and valve etc. in the device of the utility model using temperature greater than 50 DEG C are thermally shielded heat preservation.

Embodiment 2

A method of aluminum fouoride being prepared, using the device of embodiment 1, comprising the following steps:

(1) air is heated to 450 DEG C of hot-air in air heater 101, is sent into this system, makes whole system Temperature rises to 400 DEG C or more.It is gaseous state AHF that liquid-fluorination hydrogen 700kg, which is put into thermal conversion in hydrogen fluoride vaporizer 103,； Hot-air enters the bottom of single-bed fluidized reactor 301 after mixing in hydrogen fluoride mixer 102 with gaseous state AHF.

(2) wet hydrogen aluminium oxide (moisture content 7%) the about 1070kg of room temperature is measured by wet hydrogen aluminium oxide metering feed bin 201 Afterwards, aluminium hydroxide drier 305 is entered by wet hydrogen feeds of alumina spiral 202, and carrys out self-alumina gas-solid separator 304 Middle warm air (420 DEG C of temperature) is sufficiently mixed, and removes the surface water of wet hydrogen aluminium oxide, becomes dry hydrogen aluminium oxide and low-temperature airflow (260 DEG C of temperature), the gas solid separation in aluminium hydroxide gas-solid separator 306, low-temperature airflow enters tail gas absorber 401.

(3) (temperature when fluorination reactive aluminum does not occur for dry hydrogen aluminium oxide and the high temperature gas flow from aluminum fluoride gas-solid separator 302 Degree is 450 DEG C；Temperature is 660 DEG C after fluorination reactive aluminum occurs) enter alumina reactor 303 together, in the work of high temperature gas flow Under, aluminium hydroxide is changed into aluminium oxide and water vapour；Aluminium oxide and middle warm air divide in aluminium oxide gas-solid separator 304 From aluminium oxide enters the middle and upper part of single-bed fluidized reactor (301), and middle warm air enters aluminium hydroxide drier 305.

(4) in single-bed fluidized reactor 301, the alumina particle entered from middle part and the gaseous fluorine entered from bottom Change hydrogen and carry out fluidisation state reaction, generates fluorination alumina particles and high temperature gas flow (660 DEG C of temperature).High temperature gas flow is anti-from single-layer fluidized bed It answers the top of device 301 to export, after aluminum fluoride gas-solid separator 302, the aluminum fluoride of entrainment is backed within single layer fluidisation In bed reactor 301, high temperature gas flow enters alumina reactor 303.The high-temperature fluorination alumina particles generated after reaction are from single layer stream The middle and lower part output of fluidized bed reactor 301 enters aluminum fluoride static state cooler 501, obtains 1000kg aluminum fluoride finished product after cooling.

(5) cooling water is deionized water, and temperature when into aluminum fluoride static state cooler is 25 DEG C~65 DEG C, by with fluorine The heat exchange for changing aluminium becomes high-temperature steam and leaves aluminum fluoride static state cooler, and temperature is 260 DEG C, for hydrogen fluoride vaporizer 103 Heat source.Aluminum fluoride temperature into aluminum fluoride static state cooler 501 is 660 DEG C, when aluminum fluoride leaves aluminum fluoride static state cooler Temperature be 70 DEG C.By aluminum fluoride static state cooler 501, aluminum fluoride is cooled down, and obtains high-temperature steam, and thermal energy obtains again To utilization.

(6) low-temperature airflow in aluminium hydroxide gas-solid separator 306 after gas solid separation is (including water vapour, hot-air, a small amount of Aluminum-containing grits and a small amount of HF gas etc., 260 DEG C of temperature) it is absorbed in tail gas absorber 401 by recirculated water, it is recycled into absorbing liquid Slot 402；Unabsorbed HF enters tail gas water scrubber 406 by clear water spray-absorption, and spray liquid also enters absorbing liquid circulating slot 402；Unabsorbable air is discharged after removing liquid mist in gas-liquid separator 407 by exhaust fan 408 in tail gas；It absorbs Liquid circulating pump 404 sprays into tail gas absorber after the absorbing liquid pump in absorbing liquid circulating slot 402 to absorbing liquid cooler 405 is cooled down In 401.Absorbing liquid circulating slot 402 is connected directly with absorbing liquid subsider 403, settles the particulate matter in absorbing liquid, It send to ice crystal production line after reaching normal concentration as ice crystal raw materials for production.

Embodiment 3

A method of aluminum fouoride being prepared, using the device of embodiment 1, comprising the following steps:

(1) first air is heated to 450 DEG C of hot-air in air heater 101, is sent into this system, make entirely be System temperature rises to 400 DEG C or more.It is gaseous state that liquid-fluorination hydrogen 1400kg, which is put into thermal conversion in hydrogen fluoride vaporizer 103, AHF；Hot-air enters the bottom of single-bed fluidized reactor 301 after mixing in hydrogen fluoride mixer 102 with gaseous state AHF.

(2) wet hydrogen aluminium oxide (moisture content 7%) the about 2140kg of room temperature is measured by wet hydrogen aluminium oxide metering feed bin 201 Afterwards, aluminium hydroxide drier 305 is entered by wet hydrogen feeds of alumina spiral 202, and carrys out self-alumina gas-solid separator 304 Middle warm air (420 DEG C of temperature) is sufficiently mixed, and removes the surface water of wet hydrogen aluminium oxide, becomes dry hydrogen aluminium oxide and low-temperature airflow (150 DEG C of temperature), the gas solid separation in aluminium hydroxide gas-solid separator 306, low-temperature airflow enters tail gas absorber 401.

(3) (temperature when fluorination reactive aluminum does not occur for dry hydrogen aluminium oxide and the high temperature gas flow from aluminum fluoride gas-solid separator 302 Degree is 450 DEG C；Temperature is 520 DEG C after fluorination reactive aluminum occurs) enter alumina reactor 303 together, in the work of high temperature gas flow Under, aluminium hydroxide is changed into aluminium oxide and water vapour；Aluminium oxide and middle warm air divide in aluminium oxide gas-solid separator 304 From aluminium oxide enters the middle and upper part of single-bed fluidized reactor 301, and middle warm air enters aluminium hydroxide drier 305.

(4) in single-bed fluidized reactor 301, the alumina particle entered from middle part and the gaseous fluorine entered from bottom Change hydrogen and carry out fluidisation state reaction, generates fluorination alumina particles and high temperature gas flow (520 DEG C of temperature).High temperature gas flow is anti-from single-layer fluidized bed It answers the top of device 301 to export, after aluminum fluoride gas-solid separator 302, the aluminum fluoride of entrainment is backed within single layer fluidisation In bed reactor 301, high temperature gas flow enters alumina reactor 303.The high-temperature fluorination alumina particles generated after reaction are from single layer stream The middle and lower part output of fluidized bed reactor 301 enters aluminum fluoride static state cooler 501, obtains 1998kg aluminum fluoride finished product after cooling.

(5) cooling water is deionized water, and temperature when into aluminum fluoride static state cooler is 25 DEG C~65 DEG C, by with fluorine The heat exchange for changing aluminium becomes high-temperature water with pressure and leaves aluminum fluoride static state cooler, and temperature is 150 DEG C, is used for hydrogen fluoride vaporizer 103 Heat source.Aluminum fluoride temperature into aluminum fluoride static state cooler 501 is 520 DEG C, and aluminum fluoride leaves aluminum fluoride static state cooler When temperature be 65 DEG C.By aluminum fluoride static state cooler 501, aluminum fluoride is cooled down, and obtains high-temperature water with pressure, thermal energy weight Newly it is utilized.

(6) low-temperature airflow in aluminium hydroxide gas-solid separator 306 after gas solid separation is (including water vapour, hot-air, a small amount of Aluminum-containing grits and a small amount of HF gas etc., 150 DEG C of temperature) it is absorbed in tail gas absorber 401 by recirculated water, it is recycled into absorbing liquid Slot 402；Unabsorbed HF enters tail gas water scrubber 406 by clear water spray-absorption, and spray liquid also enters absorbing liquid circulating slot 402；Unabsorbable air is discharged after removing liquid mist in gas-liquid separator 407 by exhaust fan 408 in tail gas；It absorbs Liquid circulating pump 404 sprays into tail gas absorber after the absorbing liquid pump in absorbing liquid circulating slot 402 to absorbing liquid cooler 405 is cooled down In 401.Absorbing liquid circulating slot 402 is connected directly with absorbing liquid subsider 403, settles the particulate matter in absorbing liquid, It send to ice crystal production line after reaching normal concentration as ice crystal raw materials for production.

The quality analysis results of aluminum fouoride finished product made from embodiment 2 and embodiment 3 are shown in Table 1.

The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this Within the spirit and principle of utility model, any modification, equivalent replacement, improvement and so on should be included in the utility model Protection scope within.

Claims (8)

1. a kind of device for preparing aluminum fouoride, it is characterised in that: filled including inlet duct, wet hydrogen aluminium oxide metering feeding It sets, single-bed fluidized reactor (301), aluminum fluoride gas-solid separator (302), alumina reactor (303), aluminium oxide gas-solid point From device (304), aluminium hydroxide drier (305), aluminium hydroxide gas-solid separator (306), aluminum fluoride static state cooler (501) and Exhaust gas processing device；

The single-bed fluidized reactor (301) is equipped with airflow inlet, high temperature gas flow outlet, the outlet of high-temperature fluorination aluminium, aluminum fluoride Refluxing opening and aluminium oxide import；Airflow inlet is connected with the inlet duct, high temperature gas flow outlet and the aluminum fluoride gas-solid point High-temperature gas import from device (302) is connected, the material of the outlet of high-temperature fluorination aluminium and the aluminum fluoride static state cooler (501) into Mouth is connected, and aluminum fluoride refluxing opening is connected with the feed opening of the aluminum fluoride gas-solid separator (302), aluminium oxide import and the oxygen The feed opening for changing aluminium gas-solid separator (304) is connected；

The high temperature gas flow of the high-temperature gas outlet and the alumina reactor (303) of the aluminum fluoride gas-solid separator (302) Import is connected, the feed opening of the aluminum fluoride gas-solid separator (302) and the aluminum fluoride of the single-bed fluidized reactor (301) Refluxing opening is connected；

The blanking of the dry hydrogen aluminium oxide import of the alumina reactor (303) and the aluminium hydroxide gas-solid separator (306) Mouthful be connected, the material of the medium temperature gas-solid of the alumina reactor (303) outlet and the aluminium oxide gas-solid separator (304) into Mouth is connected；

The middle wet of the medium temperature air stream outlet of the aluminium oxide gas-solid separator (304) and the aluminium hydroxide drier (305) Mouth is flowed into be connected；

The wet hydrogen aluminium oxide import of the aluminium hydroxide drier (305) is connected with the wet hydrogen aluminium oxide dosing feeder, The low temperature gas-solid outlet of the aluminium hydroxide drier (305) is connected with the aluminium hydroxide gas-solid separator (306)；

The low-temperature airflow outlet of the aluminium hydroxide gas-solid separator (306) is connected with the exhaust gas processing device.

2. a kind of device for preparing aluminum fouoride according to claim 1, it is characterised in that: the inlet duct packet Include air heater (101), hydrogen fluoride vaporizer (103) and hydrogen fluoride mixer (102), the air heater (101) and The hydrogen fluoride vaporizer (103) is connected with the hydrogen fluoride mixer (102) respectively；The hydrogen fluoride mixer (102) It is connected with the single-bed fluidized reactor (301)；The heat source import and external heating system of the hydrogen fluoride vaporizer (103) It is connected or is connected with the steam (vapor) outlet of aluminum fluoride static state cooler (501).

3. a kind of device for preparing aluminum fouoride according to claim 1, it is characterised in that: the wet hydrogen aluminium oxide Dosing feeder includes sequentially connected wet hydrogen aluminium oxide metering feed bin (201) and wet hydrogen feeds of alumina spiral (202), institute The wet aluminum hydroxide outlet for stating wet hydrogen feeds of alumina spiral (202) is connected with the aluminium hydroxide drier (305).

4. a kind of device for preparing aluminum fouoride according to claim 1, it is characterised in that: the exhaust gas processing device Including tail gas absorber (401), the tail gas absorber (401) is connected with absorbing liquid circulating slot (402), then settles with absorbing liquid Slot (403) is connected；Absorbing liquid circulating pump (404) is connected with absorbing liquid circulating slot (402), then with absorbing liquid cooler (405) phase Even, absorbing liquid cooler (405) outlet is connected with the tail gas absorber (401)；Absorbing liquid circulating slot (402) outlet and tail gas Water scrubber (406) is connected, and is then connected with gas-liquid separator (407), is finally connected with exhaust fan (408).

5. a kind of device for preparing aluminum fouoride according to claim 1, it is characterised in that: the single-layer fluidized bed Reactor is cylinder type rising structure, and the ratio between cylinder heights and drum diameter are 3.5~6.0；The aluminum fluoride static state cooler It is dividing wall type heat exchanger structure or pipe heat exchanger structure.

6. a kind of device for preparing aluminum fouoride according to claim 1, it is characterised in that: the alumina reactor It is pipeline reactor structure, the ratio between duct length and pipe diameter are 10~120, and the reaction temperature in the pipeline is 520 DEG C~660 DEG C；The aluminium hydroxide drier is ducted air dryer configuration, duct length and pipe diameter it Than being 10~150；Operating temperature in the pipeline is 150 DEG C~520 DEG C.

7. a kind of device for preparing aluminum fouoride according to claim 2, it is characterised in that: the hydrogen fluoride vaporizer It is reboiler structure, using high-temperature steam or high-temperature water with pressure as the heat source of heating hydrogen fluoride vaporization, heat source temperature is 120 DEG C~ 260 DEG C, the temperature after hydrogen fluoride vaporization is 80 DEG C~220 DEG C.

8. a kind of device for preparing aluminum fouoride according to claim 4, it is characterised in that: the tail gas absorber is Water injection venturi tube structure.