CN100595156C - Method for producing ultra-fine cryolite - Google Patents
Method for producing ultra-fine cryolite Download PDFInfo
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- CN100595156C CN100595156C CN200810049609A CN200810049609A CN100595156C CN 100595156 C CN100595156 C CN 100595156C CN 200810049609 A CN200810049609 A CN 200810049609A CN 200810049609 A CN200810049609 A CN 200810049609A CN 100595156 C CN100595156 C CN 100595156C
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- cryolite
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- fine
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- hydrofluoric acid
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Abstract
The invention discloses a production method for a super fine cryolite, which is characterized in that Bayer process concentrate solution, caustic soda, and hydrofluoric acid are used as raw materials;wherein, caustic soda is added into the Bayer process concentrate solution to obtain complex liquid, which is then added into a synthesis tank together with hydrofluoric acid for reaction, the reaction temperature is 40 to 60 DEG C, and the Ph value is larger than or equal to 10; after adding the materials, ageing is conducted for 20 to 30 minutes; subsequently, after filtering, the filter cake is dried under the temperature of 150 to 300 DEG C until the water content drops below, thus acquiring the finished cryolite. The production method has the advantages that: as the production method iscarried out under normal temperature, the process is simple and easy to operate and control; and the heat source comes from heat of reaction, the need for adding a heating apparatus is obviated; by adjusting the parameter like reaction temperature, pH value and the ageing time, the product grain size D 50 is controlled within the range of 1 to 5 Mu m, and shows a desirable normal distribution; themolecular ration of NaF to AlF3 in the product is adjustable between 1.7 and 2.9; the production cost is pretty low yet with little pollution, and the treatment of three wastes, namely, wastewater, waste gas and waste residue, thus facilitating the environmental protection.
Description
One, technical field:
The present invention relates to a kind of electrolysis of aluminum fusing assistant, particularly relate to a kind of production method of ultra-fine cryolite.
Two, background technology:
Cryolith is mainly used in the fusing assistant of electrolysis of aluminum, also be used for the aspects such as wear-resistant filler, enamel opacifier, glass opalizer, wlding fusing assistant, casting reductor, alkene composite catalyst, agricultural chemical insecticide and cosmetics additive of rubber, emery wheel, wherein be used for the electrolysis of aluminum fusing assistant more than 90%.
Traditional cryolith is a wet production, as aluminium hydroxide-hydrofluoric acid-soda ash method, Sodium Silicofluoride-aluminium hydroxide-soda ash method, Neutral ammonium fluoride-sodium aluminate method, sodium aluminate-hydrofluoric acid-methods such as soda processes, generally about 15 μ m, filter cake moisture content is generally 30～35% for synthetic sodium aluminum fluoride particle diameter D50.These method gained sodium aluminum fluoride granularities are bigger, and filter cake moisture content is higher, and it is bigger to consume heat energy during oven dry, thereby production cost is higher.In the cryolith production process, consider and fly upward and operational issue such as flowability that the granularity of general requirement sodium aluminum fluoride is bigger, considering more is the problem that how to obtain than volume particle size, even employs the granulation means, to avoid flying upward loss.The sodium aluminum fluoride apparent particle size of selling on the market is generally at 1～10mm.At present, how produce and consider aspect the less sodium aluminum fluoride product of particle diameter lessly, limited sodium aluminum fluoride application in other respects.Then need the sodium aluminum fluoride of particulate in the fields such as additive of alkene recombiner, agricultural chemical insecticide, makeup, existing product can not meet the demands.
Three, summary of the invention:
The technical problem to be solved in the present invention: overcome the defective in the background technology, provide a kind of technology simple, be easy to control, the production method of particle diameter is little, production cost is low ultra-fine cryolite.
Technical scheme of the present invention is:
Method of the present invention is to be raw material synthesizing superfine sodium aluminum fluoride with Bayer process seminal fluid, hydrofluoric acid, caustic soda, and the equation of its reaction is:
Na
2O.Al
2O
3+4NaOH+12HF→2Na
3AlF
6↓+8H
2O
Its production method may further comprise the steps,
(1) be raw material with Bayer process seminal fluid, caustic soda and hydrofluoric acid, the feed molar proportioning is Al: Na: F=1: 1.8～3: 5～6;
Earlier add caustic soda in the Bayer process seminal fluid when (2) synthesizing, stir, mixing gets complex liquid;
(3) 10～80% complex liquid is added synthetic groove, stir while feed in raw material then, progressively hydrofluoric acid and remaining complex liquid are added synthetic groove, control feed rate in the process of feeding in raw material, make that temperature of reaction remains between 40～60 ℃, reaction solution pH 〉=10; Add material back termination reaction, ageing is 20～30 minutes again;
(4) cryolite slurry after the ageing is filtered filter cake and filtrate, then filter cake is dried to water ratio below 0.2% under 150～300 ℃, promptly get the sodium aluminum fluoride finished product.
The causticity of described Bayer process seminal fluid compares α
k=1.5～2.0, wherein contain Al
2O
3140～150g/L, SiO
2＜0.6g/L, Fe
2O
3＜0.03g/L;
Described caustic soda mass percent 〉=96%; Described hydrofluoric acid mass percent is 25～32%, wherein H
2SiF
6Mass percent＜0.3%;
The rotating speed of described stirring is 100～150 rev/mins, and described filtration adopts plate-and-frame filter press or band filter to filter, described dry air-flow expansion drying or the spraying drying of adopting, and drying temperature is 150～300 ℃;
Described filtrate need be returned the hydrogen fluoride absorption system, recycles.
Beneficial effect of the present invention:
(1) method of the present invention is a wet production, and reaction is carried out at normal temperatures and pressures, and technology is simple, is easy to operate and control, and thermal source need not to increase heating installation from reaction heat, need not to increase investment; By adjusting parameters such as temperature of reaction, pH value and digestion time, make product cut size D50 be controlled at 1～5 μ m, be good normal distribution; NaF and AlF in the product
3Molecular ratio adjustable, can be adjusted to 1.7～2.9, more can satisfy the needs of aluminum electrolysis industry development.
(2) method cryolite slurry of the present invention is easily filtered, and filter cake moisture content is 15～20%, and water ratio is lower, can save a large amount of oven dry expenses, saves production cost; Filtrate filtered is returned the recycle of hydrogen fluoride absorption system; The sodium aluminum fluoride finished product rate of recovery is more than 95%; Pollute during production and lack, do not need the three wastes to handle, help environmental protection.Product meets national standard, referring to table one, table two.
(3) product of the inventive method production can be used for fields such as alkene recombiner, agricultural chemical insecticide and cosmetics additive, can meet the need of market, and has better economic and social benefit.
Table one: sodium aluminum fluoride product of the present invention, the result of laboratory test data following (the quality percentage composition, %):
| Sequence number | Composition | F | Al | Na | SiO 2 | Fe 2O 3 | SO 4 2- | CaO | P 2O 5 | H 2O | Igloss | D50 |
| 1 | Content | 53.5 | 14.2 | 26.5 | 0.23 | 0.04 | 0.54 | 0.19 | 0.02 | 0.20 | 1.60 | 2.30 |
| 2 | Content | 54.0 | 14.3 | 26.3 | 0.22 | 0.04 | 0.53 | 0.188 | 0.02 | 0.19 | 1.70 | 3.20 |
| 3 | Content | 52.8 | 13.8 | 27.3 | 0.23 | 0.03 | 0.55 | 0.193 | 0.02 | 0.18 | 1.50 | 2.50 |
Table two: sodium aluminum fluoride product national standard (GB/T4291-2007):
Annotate: the condition of igloss is 550 ℃, 30min in table one, the table two, and the unit of D50 is μ m in the table one.
Contrast as seen, sodium aluminum fluoride quality product of the present invention reaches the GB/T4291-2007 standard.
Four, description of drawings:
Fig. 1: the technological process of production figure of ultra-fine cryolite
Five, embodiment:
Embodiment one: the production method of ultra-fine cryolite, referring to accompanying drawing 1, may further comprise the steps,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 3: 6, i.e. and Al
3+: Na
+: F
-=1: 3: 6;
Require: the causticity of Bayer process seminal fluid compares α
k=1.5～2.0, wherein contain Al
2O
3140～150g/L, SiO
2＜0.6g/L, Fe
2O
3＜0.03g/L; The mass percent of NaOH 〉=96% in the caustic soda; Hydrofluoric acid is absorbed through water by HF and forms, and wherein the HF mass percent is 25～32%, wherein H
2SiF
6Mass percent＜0.3%.
Add caustic soda when (2) synthetic in the Bayer process seminal fluid, the limit edged stirs, and makes the caustic soda dissolving, mixed after evenly complex liquid;
(3) earlier groove is synthesized in 40% complex liquid adding, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, rotating speed is 100 rev/mins during stirring, by the control feed rate, makes that temperature of reaction remains between 40～60 ℃, reaction solution pH 〉=10 in the reinforced process; The reinforced back termination reaction that finishes is again with slip ageing 20 minutes;
(4) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 150 ℃, adopt the air-flow expansion drying to water ratio below 0.2% (mass ratio), promptly get the sodium aluminum fluoride product; The sodium aluminum fluoride product yield is 97.5%.
(5) filtrate is returned the hydrogen fluoride absorption cell,, recycled as hydrofluoric absorption liquid.
Embodiment two: the production method of ultra-fine cryolite, no longer repeat with embodiment one something in common, and difference is,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 3: 5;
(2) earlier groove is synthesized in 20% complex liquid adding, stir, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, rotating speed is 150 rev/mins during stirring, by the control feed rate, make that temperature of reaction remains between 50～60 ℃, reaction solution pH 〉=10 in the reinforced process; The reinforced back termination reaction that finishes, terminal point control pH is 12, again with slip ageing 20 minutes;
(3) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 300 ℃, to adopt the air-flow expansion drying be below 0.2% (mass ratio), promptly to get the sodium aluminum fluoride product to water ratio, yield is 95.2%.
Embodiment three: the production method of ultra-fine cryolite, no longer repeat with embodiment one something in common, and difference is,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 2: 6;
(2) earlier groove is synthesized in 70% complex liquid adding, stir, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, pass through the control feed rate in the reinforced process, rotating speed is 120 rev/mins during stirring, makes that temperature of reaction remains between 40～50 ℃, reaction solution pH 〉=10; The reinforced back termination reaction that finishes is again with slip ageing 30 minutes;
(3) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 200 ℃, adopt the air-flow expansion drying to water ratio below 0.2% (mass ratio), promptly get the sodium aluminum fluoride product, yield is 97.4%.
Embodiment four: the production method of ultra-fine cryolite, no longer repeat with embodiment one something in common, and difference is,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 2.5: 5.5;
(2) earlier groove is synthesized in 60% complex liquid adding, stir, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, pass through the control feed rate in the reinforced process, rotating speed is 140 rev/mins during stirring, makes that temperature of reaction remains between 45～55 ℃, reaction solution pH 〉=10; The reinforced back termination reaction that finishes, pH is between 10～12, again with slip ageing 25 minutes in terminal point control;
(3) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 280 ℃, adopt the air-flow expansion drying to water ratio below 0.2% (mass ratio), promptly get the sodium aluminum fluoride product, yield is 98.5%.
Embodiment five: the production method of ultra-fine cryolite, no longer repeat with embodiment one something in common, and difference is,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 1.8: 5.7;
(2) earlier groove is synthesized in 30% complex liquid adding, stir, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, pass through the control feed rate in the reinforced process, rotating speed is 130 rev/mins during stirring, makes that temperature of reaction remains between 40～60 ℃, reaction solution pH 〉=10; The reinforced back termination reaction that finishes, pH is between 8～10, again with slip ageing 22 minutes in terminal point control;
(3) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 180 ℃, adopt the air-flow expansion drying to water ratio below 0.2% (mass ratio), promptly get the sodium aluminum fluoride product, yield is 96.4%.
Embodiment six: the production method of ultra-fine cryolite, no longer repeat with embodiment one something in common, and difference is,
(1) raw material and consumption: with Bayer process seminal fluid, caustic soda and hydrofluoric acid is raw material, and the feed molar proportioning is Al: Na: F=1: 2.2: 6;
(2) earlier groove is synthesized in 50% complex liquid adding, stir, under agitation progressively hydrofluoric acid and remaining complex liquid are added synthetic groove then, pass through the control feed rate in the reinforced process, rotating speed is 150 rev/mins during stirring, makes that temperature of reaction remains between 55～60 ℃, reaction solution pH 〉=10; The reinforced back termination reaction that finishes, pH is between 9～10, again with slip ageing 24 minutes in terminal point control;
(3) with the slip after the ageing with band filter filter filter cake and filtrate, with filter cake 220 ℃, adopt the air-flow expansion drying to water ratio below 0.2% (mass ratio), promptly get the sodium aluminum fluoride product, yield is 96.8%.
Claims (6)
1, a kind of production method of ultra-fine cryolite is characterized in that: may further comprise the steps,
(1) be raw material with Bayer process seminal fluid, caustic soda and hydrofluoric acid, the feed molar proportioning is Al: Na: F=1: 1.8～3: 5～6;
Earlier add caustic soda in the Bayer process seminal fluid when (2) producing, stir, mixing gets complex liquid;
(3) 10～80% complex liquid is added produce groove, stir while feed in raw material then, progressively hydrofluoric acid and remaining complex liquid are added and produce groove, control feed rate in the process of feeding in raw material, make that temperature of reaction remains between 40～60 ℃, reaction solution pH 〉=10; Add material back termination reaction, ageing is 20～30 minutes again;
(4) cryolite slurry after the ageing is filtered filter cake and filtrate, then filter cake is dried to water ratio below 0.2% under 150～300 ℃, promptly get the sodium aluminum fluoride finished product; Gained sodium aluminum fluoride product D
50Particle diameter be 1～5 μ m.
2, the production method of ultra-fine cryolite according to claim 1 is characterized in that: the causticity of described Bayer process seminal fluid compares α
k=1.5～2.0, wherein contain Al
2O
3140～150g/L, SiO
2＜0.6g/L, Fe
2O
3＜0.03g/L.
3, the production method of ultra-fine cryolite according to claim 1 is characterized in that: described caustic soda mass percent 〉=96%.
4, the production method of ultra-fine cryolite according to claim 1 is characterized in that: described hydrofluoric acid mass percent is 25～32%, wherein H
2SiF
6Mass percent＜0.3%.
5, according to the production method of each described ultra-fine cryolite of claim 1～4, it is characterized in that: the rotating speed of described stirring is 100～150 rev/mins, described filtration adopts plate-and-frame filter press or band filter to filter, described dry air-flow expansion drying or the spraying drying of adopting, drying temperature is 150～300 ℃.
6, according to the production method of each described ultra-fine cryolite of claim 1～4, it is characterized in that: described filtrate is returned the hydrogen fluoride absorption system, recycle.
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|---|---|---|---|
| CN200810049609A CN100595156C (en) | 2008-04-23 | 2008-04-23 | Method for producing ultra-fine cryolite |
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|---|---|---|---|
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| CN100595156C true CN100595156C (en) | 2010-03-24 |
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| CN102703932B (en) * | 2012-05-30 | 2013-03-13 | 深圳市新星轻合金材料股份有限公司 | Electrolyte replenishment system in aluminum electrolysis process and preparation method thereof |
| CN102732914A (en) * | 2012-07-25 | 2012-10-17 | 深圳市新星轻合金材料股份有限公司 | Method for preparing electrolyte and supplementing system thereof in aluminum electrolysis process |
| CN109534571A (en) * | 2018-12-07 | 2019-03-29 | 湖南涌鑫源环保有限公司 | The processing system of fluoride waste in a kind of recovery processing of cathode carbon pieces |
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Non-Patent Citations (2)
| Title |
|---|
| 冰晶石生产方法综述. 冯双青.甘肃联合大学学报（自然科学版），第20卷第4期. 2006 |
| 冰晶石生产方法综述. 冯双青.甘肃联合大学学报(自然科学版)，第20卷第4期. 2006 * |
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