CN105502451B - A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio - Google Patents
A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio Download PDFInfo
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- CN105502451B CN105502451B CN201511017661.6A CN201511017661A CN105502451B CN 105502451 B CN105502451 B CN 105502451B CN 201511017661 A CN201511017661 A CN 201511017661A CN 105502451 B CN105502451 B CN 105502451B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
Abstract
A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio, comprises the following steps, the preparation of (1) aluminum fluoride：It is that 13~14% fluosilicic acid are heated to 65 DEG C~75 DEG C by heat exchanger by concentration, with aluminium hydroxide at 70~80 DEG C, 12~16min of stirring reaction；Then desiliconization is filtered, is crystallized, dries, calcine, cooling, producing aluminum fluoride；(2) preparation of cryolite with high molecular ratio：By the mother liquor of aluminum fluoride after filtering and sodium fluoride in 80~90 DEG C of 50~60min of stirring reaction, reaction, which finishes, filters reactant, and filtrate is sent into cesspool and handled, and filter cake produces cryolite with high molecular ratio in 120 DEG C~150 DEG C expansion dryings.Aluminum fluoride concentration prepared by the present invention is low, stably, high income；Coproduction cryolite with high molecular ratio quality is high, yield is also high.At the same time, the sewage of the present invention in process of production only has mother liquor of aluminum fluoride to bring into, and compared with other production technologies, its sewage quantity is few, and disposable.
Description
Technical field
The present invention relates to a kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio, is utilized more particularly to one kind low dense
Spend the method for fluosilicic acid production aluminum fluoride coproduction cryolite with high molecular ratio.
Background technology
Aluminum fluoride be the fluosilicic acid as byproduct direct synthesis technique ice making spar in fluorite and phophatic fertilizer production process it is important in
Between product, be mainly used in aluminium metallurgy production.Ice crystal, also referred to as cryolite, its molecular formula are Na3AlF6, by its sodium fluoride and fluorination
The ratio between molecule of aluminium, cryolite with high molecular ratio and lower molecular ratio ice crystal can be divided into.Wherein, cryolite with high molecular ratio
(nNaF.AlF3, n：2.8~3.0) it is mixture based on positive ice crystal, can has as the cosolvent of aluminum smelting industry
The advantages of volatilization loss is few, and heat endurance is good, and environmental pollution is small, low molecule is superior in environmental protection and economic benefit etc.
Ice crystal.However, current domestic each electrolytic aluminium factory largely uses the lower molecular ratio ice crystal that molecular proportion is 1.8~2.2
Make the electrolyte of aluminium electroloysis.Therefore, study and make the electrolyte of aluminium electroloysis using cryolite with high molecular ratio, be when business
It is anxious, and the at the same time preparation of aluminum fluoride is to synthesize the critical process of cryolite with high molecular ratio.
At present, when traditional direct synthesis technique production aluminum fluoride and cryolite with high molecular ratio, fluosilicic acid is mainly derived from fluorite
With the accessory substance in phophatic fertilizer production process, concentration produces more intermediate product hydrogen fluoride gas or hydrogen between 18~20%
Oxygen acid, selection and environmental protection to production equipment material all propose higher requirement；Meanwhile original fluosilicic acid concentration is higher,
The aluminum fluoride concentration of generation is corresponding also high, more early to separate out crystallization, and aluminum fluoride yield reduces.And original fluosilicic acid concentration is lower, instead
Answer speed slow, the silica crystals particle of precipitation is thin, and slurry is in colloidal, and viscosity is big, hinders the reaction with aluminium hydroxide, together
When the rate of filtration it is slow, filter cake washing is difficult, and liquid content is high in filter cake, and aluminum fluoride yield reduces.Therefore, research prepares a kind of low dense
Degree, the aluminun fluoride solution of high stability have important industrial value to coproduction cryolite with high molecular ratio.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of utilization low concentration H in high yield2SiF6Produce aluminum fluoride
The method of coproduction cryolite with high molecular ratio.
The present invention solves the technical scheme that its technical problem uses, one kind production aluminum fluoride coproduction cryolite with high molecular ratio
Method, comprise the following steps：
(1) react：By concentration be 13~14% (preferred concentration 13%) fluosilicic acid by heat exchanger be heated to 65 DEG C~
75 DEG C, reactor is then added after metering, is subsequently added into the aluminium hydroxide of metering, wherein, the meter of fluosilicic acid and aluminium hydroxide
Amount is than being 1:1.01~1：1.05 (preferably metering than be 1: 1.02), at 70~80 DEG C (preferably 80 DEG C), stirring reaction 12~
16min (preferred reaction time 16min), after completion of the reaction, resultant product in reactive tank is rinsed with water, is closed with reaction product
And；
(2) desiliconization, crystallization, cooling：The reaction product of merging is filtered, filter cake is washed with water, merging filtrate and washing lotion, dimension
Temperature is held at 90~100 DEG C (preferably 95 DEG C), 3~4h of crystallization (preferably crystallization time is 4h), when slurry is discharged, stays one
Partially crystallizable slurry is used as strain, and remaining slurry, which is drained into crystallization tank, to be cooled down；
(3) filter, dry, calcining, cooling：The aluminum fluoride slurry of cooling is filtered, and with 50~90 DEG C (preferably 60
~70 DEG C) hot water washs to aluminum fluoride crystal, and filtrate flows into mother liquor tank with washing lotion, and filter cake aluminum fluoride trihydrate carries out air-flow and done
It is dry, and calcined at 500~600 DEG C, cooling, produce aluminum fluoride；
(4) ice crystal synthesizes：By the mother liquor of aluminum fluoride after filtering and sodium fluoride by metering ratio 1:2.8~1：3.2 (preferably count
Amount is than being 1: 3), under 80~90 DEG C (preferably 90 DEG C), stirs lower 50~60min of reaction (preferred reaction time 60min), instead
It should finish and filter reactant, filtrate is sent into cesspool and handled, filter cake control expansion drying at 120 DEG C~150 DEG C, i.e.,
The son that secures satisfactory grades compares ice crystal.
Further, three sections of the pneumatic conveying drying point, one section of temperature control are deviate from aluminum fluoride trihydrate at 180 DEG C~250 DEG C
All free waters, two sections abjection aluminum fluoride trihydrates in 2.5 crystallizations water；3rd section of last half of the crystallization water of abjection, it is whole dry
Dry calcination process is three sections of completions more than.
The present invention is with the phosphoric acid,diluted concentration process neutralization reaction of warm therapy phosphoric acid production and production calcium superphosphate neutralization reaction
In obtained low dose fluoride silicic acid, aluminum fluoride, coproduction cryolite with high molecular ratio, the aluminum fluoride not only prepared are produced using direct method
Concentration is low, stably, high income；And coproduction cryolite with high molecular ratio quality is high, yield is also high.At the same time, the present invention is in life
Sewage during production only has mother liquor of aluminum fluoride to bring into, and compared with other production technologies, its sewage quantity is few, and disposable.
Embodiment
The invention will be further described with reference to embodiments.
First use H2SiF6With AL (OH)3It is prepared into ALF3Solution, solid fluorinated sodium is then added, prepares high molecule ratio
Ice crystal, reaction equation are as follows：
2AL(OH)3+H2SiF6=2ALF3+SiO2+4H2O (1)
ALF3++ 3NaF=Na3ALF6 (2)
Embodiment 1：The method for producing aluminum fluoride coproduction cryolite with high molecular ratio
1st, the preparation of aluminum fluoride
(1) react：It is that 13% fluosilicic acid is heated to 65 DEG C~75 DEG C by graphite heat exchanger by concentration, then after metering
Reactor is added, is subsequently added into the aluminium hydroxide of metering, wherein, the metering of fluosilicic acid and aluminium hydroxide is compared for 1: 2, reaction temperature
At 80 DEG C, stirring reaction 16min, reacting gas is pumped into washing tail gas emptying for control, after completion of the reaction, is rinsed with water in reactive tank
Resultant product, the Sio of next procedure is discharged into reactant in the lump2Filtered on filter.
(2) desiliconization：By reaction product and product is rinsed through vacuum movement disk filter filtering, and then filter cake is washed with water
Wash, send subsequent processing to be crystallized with filtrate.
(3) crystallize：The filtrate obtained during by desiliconization and washing lotion flow into crystallization tank, and being passed through steam with coil pipe during crystallization heats,
Maintaining crystallization temperature, charging and discharging time are about 2h in addition, are stirred in crystallization process at 95 DEG C, crystallization time 4h,
It is uniform with keeping temperature；When slurry is discharged, a part of slurry is stayed to be used as strain, slurry is drained into crystallization tank
Cooling enters next procedure.
(4) filter：The aluminum fluoride slurry cooled down in geosyncline is filtered with band filter, and with 65 DEG C of hot water to aluminum fluoride
Crystal is washed, and filtrate flows into ALF with washing lotion3Mother liquor tank, filter cake aluminum fluoride trihydrate enter subsequent processing through chute.
(5) dry, calcine：Aluminum fluoride trihydrate is dried from chute inflow stream, three sections of pneumatic conveying drying point：One section is abjection
All free waters in aluminum fluoride trihydrate；Two sections are 2.5 crystallizations water in abjection aluminum fluoride trihydrate；3rd section is deviate from last half
The crystallization water, whole drying and calcining process are three sections of completions more than, and one section of temperature control is at 180 DEG C~250 DEG C, the temperature of calcining
600 DEG C of control.
(6) cool down：The complete aluminum fluoride of drying and calcination is passed through in chilling roll and cooled down, is sent into aluminum fluoride warehouse, bag
Dress.
(7) vent gas washing system：It is made up of a Venturi scrubber and a scrubber sealing groove, reaction end gas warp
Emptied after Venturi scrubbing, calcined gas empty then first through Venturi scrubbing, then after liquid seal trough enters scrubbing tower after drying.
The Al yields of aluminum fluoride are made up to more than 95%, F yields up to more than 90%, and can place for a long time in atmosphere
Without absorbing water.
2nd, the preparation of cryolite with high molecular ratio
(1) ice crystal synthesizes：Mother liquor of aluminum fluoride after filtering is squeezed into ice crystal measuring tank from mother liquor of aluminum fluoride groove, counted
Ice crystal synth sink is sent into after amount, synth sink is also added after sodium fluoride metering, wherein, the metering ratio of mother liquor of aluminum fluoride and sodium fluoride
For 1: 3, reacted under agitation, for reaction temperature at 90 DEG C, reaction time 60min, reacting gas is sent into washing tail gas, washing
After empty, reaction finishes and filters reactant, and filtrate is sent into cesspool and handled, and filter cake is sent into drying system.
(2) ice crystal is dried：Ice crystal filter cake is sent into flash distillation dryer with auger and dried, material is from bottom to top through wind
Cyclone charging hole and cloth bag case feed opening are delivered to, then ice crystal warehouse is sent into through cooling down auger, then metering packing ice crystal produces
Product, 120 DEG C~150 DEG C of temperature control, drying empty after cloth bag division.
Obtained ice crystal w (F) >=52%, w (Al) >=13%, w (Na)≤32% meets GB/T4291-2007 ice crystals
Technical requirements, and ice crystal molecular proportion has reached height up to (fluorine 54.5%, aluminium 13%, sodium 31.6%) between 2.8 to 3.0
The requirement of molecular proportion ice crystal.
Claims (3)
- A kind of 1. method for producing aluminum fluoride coproduction cryolite with high molecular ratio, it is characterised in that comprise the following steps,(1) react：It is that 13~14% fluosilicic acid are heated to 65 DEG C~75 DEG C by heat exchanger by concentration, then adds after metering Reactor, the aluminium hydroxide through metering is subsequently added into, wherein, the metering of fluosilicic acid and aluminium hydroxide is compared for 1:1.01~1： 1.05, at 70~80 DEG C, 12~16min of stirring reaction, after completion of the reaction, resultant product in reactive tank is rinsed with water, with reaction Product merges；(2) desiliconization, crystallization, cooling：The reaction product of merging is filtered, filter cake is washed with water, merging filtrate and washing lotion, maintains temperature Degree crystallizes 3~4h, when slurry is discharged, stays a part of slurry to be used as strain at 90~100 DEG C, remaining crystallization material Slurry, which is drained into crystallization tank, to be cooled down；(3) filter, dry, calcining, cooling：The aluminum fluoride slurry of cooling is filtered, and with 50~90 DEG C of hot water to fluorination Aluminium crystal is washed, and filtrate flows into mother liquor tank with washing lotion, and filter cake aluminum fluoride trihydrate carries out pneumatic conveying drying, and at 500~600 DEG C Calcining, cooling, produces aluminum fluoride；(4) ice crystal synthesizes：By the mother liquor of aluminum fluoride after filtering and sodium fluoride by metering ratio 1:2.8~1：3.2, at 80~90 DEG C Under, 50~60min of lower reaction is stirred, reaction, which finishes, filters reactant, and filtrate is sent into cesspool and handled, and filter cake control exists Expansion drying at 120 DEG C~150 DEG C, produces cryolite with high molecular ratio.
- 2. it is according to claim 1 production aluminum fluoride coproduction cryolite with high molecular ratio method, it is characterised in that including with Lower step,(1) react：It is that 13% fluosilicic acid is heated to 65 DEG C~75 DEG C by graphite heat exchanger by concentration, then adds after metering Reactor, the hydrofluorination aluminium of metering is subsequently added into, wherein, the metering of fluosilicic acid and aluminium hydroxide is compared for 1: 1.02, at 80 DEG C, stirs Reaction 16min is mixed, after completion of the reaction, resultant product in reactive tank is rinsed with water, merges with reaction product；(2) desiliconization, crystallization, cooling：The reaction product of merging is washed with water through vacuum movement disk filter filtering, filter cake, Merging filtrate and washing lotion, temperature is maintained to crystallize 4h at 95 DEG C, when slurry is discharged, stay a part of slurry to make strain With remaining slurry, which is drained into crystallization tank, to be cooled down；(3) filter, dry, calcining, cooling：The aluminum fluoride slurry of cooling is filtered with band filter, and with 60~70 DEG C hot water washs to aluminum fluoride crystal, and filtrate flows into mother liquor tank with washing lotion, and filter cake aluminum fluoride trihydrate carries out pneumatic conveying drying, and In 500~600 DEG C of calcinings, cooling, aluminum fluoride is produced；(4) ice crystal synthesizes：It is anti-under stirring at 90 DEG C by the mother liquor of aluminum fluoride after filtering and sodium fluoride by metering than being 1: 3 60min is answered, reaction, which finishes, filters reactant, and filtrate is sent into cesspool and handled, and filter cake is controlled at 120 DEG C~150 DEG C Expansion drying, produce cryolite with high molecular ratio.
- 3. the method for production aluminum fluoride coproduction cryolite with high molecular ratio according to claim 1 or 2, it is characterised in that institute Three sections of pneumatic conveying drying point is stated, one section of temperature control is at 180 DEG C~250 DEG C, all free waters in abjection aluminum fluoride trihydrate, two sections Deviate from 2.5 crystallizations water in aluminum fluoride trihydrate；3rd section of last half of the crystallization water of abjection, whole drying and calcining process is in the above Three sections of completions.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477610B (en) * | 2016-09-21 | 2018-05-01 | 广西大学 | A kind of preparation method of technical grade cryolite with high molecular ratio |
| CN108017077A (en) * | 2017-12-11 | 2018-05-11 | 达州励志环保科技有限公司 | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio |
| CN109231247A (en) * | 2018-11-28 | 2019-01-18 | 达州励志环保科技有限公司 | A kind of method that the by-product of fluosilicic acid legal system aluminum fluoride prepares ice crystal |
| CN113697835A (en) * | 2021-01-05 | 2021-11-26 | 蔡从美 | Method for extracting aluminum fluoride from silicon dioxide slag |
| CN115010157A (en) * | 2022-06-22 | 2022-09-06 | 中石化南京工程有限公司 | System and method for producing anhydrous aluminum fluoride by using fluosilicic acid |
| CN115196660A (en) * | 2022-06-22 | 2022-10-18 | 中石化南京工程有限公司 | Method and system for producing cryolite from fluosilicic acid |
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| US4623528A (en) * | 1985-06-17 | 1986-11-18 | James C. Barber And Associates, Inc. | Recovery of fluorine from waste gases |
| CN1868888A (en) * | 2005-05-23 | 2006-11-29 | 多氟多化工股份有限公司 | Method of producing cryolite |
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