CN1117944A - Method for production of high-molecular-ratio ice spar - Google Patents
Method for production of high-molecular-ratio ice spar Download PDFInfo
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- CN1117944A CN1117944A CN 94111147 CN94111147A CN1117944A CN 1117944 A CN1117944 A CN 1117944A CN 94111147 CN94111147 CN 94111147 CN 94111147 A CN94111147 A CN 94111147A CN 1117944 A CN1117944 A CN 1117944A
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- cryolite
- acid
- high molecular
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- hydrofluoric acid
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Abstract
This invention relates to a method for preparing cryolite with high molecular ratio. It uses hydrofluoric acid, aluminium hydroxide and sodium carbonate to be synthesized continuously in several series-connected synthetic tanks with agitators. The hydrofluoric acid and aluminium hydroxide mud are simultaneously, continuously and uniformly added to the fluoaluminic acid synthesizing tank with agitator at the temp. of 70 deg.C-boiling point according to the demand which their mol ratio is 6F/Al=1.0-1.2, and reacted to obtain fluoaluminic acid, then the fluoaluminic acid and sodium carbonate solution are continuously and uniformly added to its cryolite synthesizing tank according to the mol ratio of that Na/Al is greater than 3 so as to obtain the high molecular ratio cryolite whose mol ratio of WaF and AlF3 is greater than 2.7, tilter property is good and impurity content is low.
Description
The invention belongs to the compound technical of aluminium, relate to a kind of manufacture method of cryolite with high molecular ratio from.
Sodium aluminum fluoride is to be that raw material is produced with hydrofluoric acid, yellow soda ash, aluminium hydroxide, and the sodium aluminum fluoride that the above-mentioned raw material production of domestic present usefulness is come out is that the lower molecular ratio sodium aluminum fluoride is that the Na/Al molecular ratio generally (is consulted G84291-84) about 2.Mainly as the flux of aluminium cell, because aluminium cell is high temperature (800-1000 ℃), the sodium aluminum fluoride of use will run into very big ignition loss to sodium aluminum fluoride, and the lower molecular ratio sodium aluminum fluoride contains Na
3AlF
6Low, and contain chiolite (Na
5Al
3F
14) and the bonding water of sodium aluminum fluoride more, these impurity will cause that the loss of fluorine in the sodium aluminum fluoride increases, and cause atmospheric pollution, increase the consumption of sodium aluminum fluoride in the electrolytic aluminum.USSR (Union of Soviet Socialist Republics) patent SU1116010 introduces with NaF and AlF
3Two solution mix, and it is that 2-3 sodium aluminum fluoride suspension are handled that precipitation separation gets molecular ratio, mixes the sub-ratio ice spar that secures satisfactory grades with NaF solution then.It is long that these methods all have technological process, all must be dilute solution with aluminum fluoride, Fluorinse, and therefore, the streams flux is big, and the production unit volume that needs is big, and facility investment is big, the production cost height.
Purpose of the present invention aims to provide a kind of equipment of producing the lower molecular ratio sodium aluminum fluoride that utilizes, the manufacture method of using hydrofluoric acid, aluminium hydroxide, yellow soda ash to produce cryolite with high molecular ratio from.
The objective of the invention is to realize with the following methods.This manufacture method is to use hydrofluoric acid, aluminium hydroxide and yellow soda ash carry out continuously synthetic in by several placed in-line synthetic grooves that have a stirring, it is characterized in that with hydrofluoric acid and aluminium hydroxide mud continuous simultaneously according to the requirement between the mol ratio 6F/Al=1.0-1.2, adding temperature equably is 70 ℃-boiling point, react in the synthetic groove that band stirs hydrofluoaluminic acid, with hydrofluoaluminic acid and the sodium carbonate solution requirement of Na/Al 〉=3 in molar ratio, simultaneously, continuously, adding temperature equably is 70 ℃-boiling point, in the synthetic groove that band stirs, sodium carbonate solution adds as far as possible dispersedly, at synthetic groove internal reaction, make NaF and AlF
3Mol ratio 〉=2.7, strainability is good, the cryolite with high molecular ratio from that foreign matter content is lower.
In the present invention, be according to synthetic cryolite (Na
3AlF
6) required NA, Al, the theoretical amount of F, mol ratio 6F/Al=1.00 in the hydrofluoaluminic acid, the sodium in the sodium carbonate solution and the mol ratio Na/Al=3 of the aluminium in the hydrofluoaluminic acid.In order to prepare cryolite with high molecular ratio from and to reach the thick easy filtering purpose of sodium aluminum fluoride crystal grain, pH value is the key factor that influences the strainability quality, when the preparation hydrofluoaluminic acid, takes to add slightly the method for hydrofluoric acid for this reason.Make feed liquid PH≤4 in the reactive tank of synthetic cryolite, therefore when the preparation hydrofluoaluminic acid, determine the add-on of aluminium hydroxide mud and hydrofluoric acid according to the amount of mol ratio 6F/Al=1.0-1.2, in order to make cryolite with high molecular ratio from, just must fill up the amount of sodium carbonate solution, so mol ratio Na/Al 〉=3 of sodium in the sodium carbonate solution and the aluminium in the hydrofluoaluminic acid.
When continuous synthetic cryolite, if adopt 1 groove system hydrofluoaluminic acid, aluminium hydroxide reacts incomplete with hydrofluoric acid, just has a lot of unreacted Al (oH)
3Enter the sodium aluminum fluoride synthesis phase, the quality of sodium aluminum fluoride is played detrimentally affect.Adopt two hydrofluoaluminic acid preparation vessels, just the reaction times can be prolonged, make and react completely, obtain the second best in quality hydrofluoaluminic acid, again hydrofluoaluminic acid and sodium carbonate solution are added the synthetic groove internal reaction of sodium aluminum fluoride simultaneously continuously equably according to the amount of mol ratio Na/Al 〉=3, so just can prevent the generation of chiolite.But the adding of sodium carbonate solution should prevent local pH value and increase, the quality and the strainability that guarantee sodium aluminum fluoride are good, help producing and carry out, for this reason in the synthetic groove of sodium aluminum fluoride under the violent stirring of feed liquid, sodium carbonate solution is joined the following depths in feed liquid surface or feed liquid surface dispersedly, and the mode of Jia Ruing can add in the reaction solution continuously by the filling tube homodisperse ground that is drilled with a plurality of apertures under the liquid in the synthetic groove of dark insertion dispersedly.During hydrofluoaluminic acid preparation and sodium aluminum fluoride are synthetic, in order to guarantee to react completely, the temperature that all should guarantee whole reaction system is 70 a ℃-boiling point, in the process of making sodium aluminum fluoride, equivalence ratio and the mol ratio measured in the feed liquid are difficult, for this reason, mol ratio Na/Al when mol ratio 6F/Al when controlling hydrofluoaluminic acid and prepare and synthetic cryolite by means of the method for measuring the feed liquid total acidity, general control hydrofluoaluminic acid total acidity 90-130g/l, 100-110g/l preferably, cryolite slurry total acidity≤12g/l, be generally 4-8g/l, be: hydrofluoric acid and aluminium hydroxide are added to reaction generates hydrofluoaluminic acid in first synthetic groove according to the production process of the above the inventive method; Enter second synthetic groove then and continue reaction, make and react completely, obtain the second best in quality hydrofluoaluminic acid, hydrofluoaluminic acid flows into the 3rd synthetic groove, generate cryolite slurry with the sodium carbonate solution reaction, cryolite slurry flows in the 4th the synthetic groove and to continue reaction, with resultant send filter filter wet sodium aluminum fluoride, the drying sub-ratio ice spar finished product that secures satisfactory grades.Below in conjunction with drawings and Examples the present invention is made describing in further detail,
Fig. 1 is a process flow sheet in the experimental study
Fig. 2 is used for the industrial production process flow sheet
Among the figure: 1-hydraulic pipe, 2-aluminium hydroxide input tube, 3-aluminium hydroxide pulping tank
4,7,13,17-upflow tube 5,8,23,25-hydrofluoaluminic acid preparation vessel
6,21-hydrofluoric acid transfer lime 10,12,28, the synthetic groove of 30-sodium aluminum fluoride
11-yellow soda ash transfer lime 14,15,16,32,33,34-under meter
22-aluminium hydroxide slurry pipeline 24,26,29 ,-connecting pipe 27-carbon
Acid sodium solution transfer lime 31-cryolite slurry transfer lime
Flow process according to Fig. 1, water and aluminium hydroxide are made aluminium hydroxide mud from the 1 and 2 aluminium hydroxide pulping tanks (3) that required amount adding is stirred according to desired aluminium hydroxide mud balance, by overflow pipe (4) through flowmeter (14) be 70 ℃-boiling point from hydrofluoric acid carrier pipe (6) and through the hydrofluoric acid of flowmeter (15) according to simultaneously continuous uniform ground adding of the ratio temperature of mol ratio 6F/Al=1.0-1.2, on the charge level of the fluoaluminic acid preparation vessel (5) that band stirs, get fluoaluminic acid at the groove internal reaction, feed liquid in the fluoaluminic acid preparation vessel (5) flows in the reactive tank (8) that temperature is the stirring of 70 ℃-boiling point band through overflow pipe (7) and continues reaction, make the second best in quality fluoaluminic acid, fluoaluminic acid is that the ice crystal that 70 ℃-boiling point stirs synthesizes reaction in the groove (10) through overflow pipe (9) with adding temperature through the sodium carbonate liquor while continuous uniform ground of flowmeter (16) from sodium carbonate liquor carrier pipe (11) again, and sodium carbonate liquor is added on the charge level dispersedly according to the amount of mol ratio Na/Al 〉=3. Ice crystal suspension flow in the groove same with (10) (12) through overflow pipe (17) and continues reaction, is sent to the filter ice crystal that must wet through overflow pipe (13) again, and drying gets the ice crystal finished product. According to above-mentioned flow process, realize producing continuously.
The technical process of Fig. 2 and the difference of Fig. 1, to add in the groove charge level upper outside except aluminium hydroxide mud, it all is that joining in the synthetic groove (28) of ice crystal at each below the groove charge level or depths insertion sodium carbonate liquor is to insert depths under the liquid that synthesizes groove (28) by sodium carbonate liquor conveyance conduit (27) that all the other each materials enter groove, the afterbody of conveyance conduit (27) is to be drilled with to be permitted lacunary charge pipe, be conducive to sodium carbonate liquor Uniform Dispersion ground and add in the reactant liquor continuously, process control condition is identical with the described condition of Fig. 1 technical process.
Among the present invention, used hydrofluoric acid can be the hydrofluoric acid of gained after the dissolving of anhydrous hydrogen fluoride water and the smart acid behind the sodium carbonate refining crude hydrofluoric acid silica removal, and hydrofluoric acid concentration is 20-30%. Used sodium carbonate liquor Na2CO
3Concentration is 220-400g/l. Used aluminium hydroxide mud balance is 1.33-1.53
Example I
Carry out continuous production according to the described technical process of Fig. 1.The aluminium hydroxide mud balance is 1.33, and sodium carbonate solution concentration is Na
2CO
3220 grams per liters (g/l), hydrofluoric acid HF concentration is 24.52%, 70 ℃-boiling point of hydrofluoaluminic acid temperature, 70 ℃-boiling point of hydrofluoaluminic acid total acidity 100-125g/l cryolite slurry temperature, cryolite slurry PH≤3.
The chemical ingredients of gained sodium aluminum fluoride finished product is: F54.32%, Al13.04%, Na31.35% (weight percent).
The molecular ratio Na/Al=2.78 of gained sodium aluminum fluoride finished product
Example II
Carry out continuous production according to the described technical process of Fig. 1.Aluminium hydroxide mud balance 1.33, sodium carbonate solution concentration are 230g/l, hydrofluoric acid concentration 25.5%, 70 ℃-boiling point of hydrofluoaluminic acid temperature cryolite slurry total acidity, 1.5-9g/l, cryolite slurry PH≤3.
The chemical ingredients of gained sodium aluminum fluoride is F53.32% Al13.04% Na31.35%.
The molecular ratio of gained sodium aluminum fluoride: Na/Al=2.82
EXAMPLE III
Carry out continuous production according to the described technical process of Fig. 1.Aluminium hydroxide mud balance 1.34, carbon
Acid sodium solution concentration 365-397g/l, hydrofluoric acid concentration 25.29%, hydrofluoaluminic acid total acidity 110-120g/l, 70 ℃-boiling point of hydrofluoaluminic acid temperature, 70 ℃-boiling point of cryolite slurry temperature, cryolite slurry total acidity 0.5-12g/l, PH≤4.
The molecular ratio of gained sodium aluminum fluoride: Na/Al=2.82
EXAMPLE IV
Carry out continuous production according to technology shown in Figure 2, the throughput of sodium aluminum fluoride is 2.5 tons/hour, and used aluminium hydroxide mud balance is 1.5-1.53 in the production, sodium carbonate solution Na
2CO
3Concentration is 373-393g/l, and hydrofluoric acid HF concentration is 22-25%, 70 ℃-boiling point of hydrofluoaluminic acid temperature, hydrofluoaluminic acid total acidity 90-120g/l, 70 ℃-boiling point of cryolite slurry temperature, cryolite slurry PH≤4, total acidity≤10g/l, quality product such as following table
| Sodium aluminum fluoride quantity (ton) | Sodium aluminum fluoride chemical ingredients (%) | Sodium aluminum fluoride molecular ratio Na/Al | ||||
| ????F | ????Al | ?Na | ?Sio 2 | ?Fe 2o 3 | ||
| ????100 | ?54.32 | ?13.20 | ?31.29 | ?0.21 | ?0.048 | ????2.78 |
| ????100 | ?53.89 | ?13.23 | ?31.56 | ?0.19 | ?0.032 | ????2.80 |
| ????100 | ?54.75 | ?13.42 | ?31.12 | ?0.20 | ?0.034 | ????2.72 |
Polymeric matte spathous manufacture method of the present invention, its technical process is simple, and the processing condition in the production are easy to control, and facility investment is few, and the products production cost is low, constant product quality.
Claims (7)
1, a kind of manufacture method of cryolite with high molecular ratio from, be to use hydrofluoric acid, aluminium hydroxide and yellow soda ash carry out continuously synthetic in by several placed in-line synthetic grooves that have a stirring, it is characterized in that using hydrofluoric acid and aluminium hydroxide mud simultaneously according to the requirement between the mol ratio 6F/Al=1.0-1.2, continuously, adding temperature equably is 70 ℃-boiling point, the synthetic groove internal reaction that band stirs gets hydrofluoaluminic acid, with hydrofluoaluminic acid and the sodium carbonate solution requirement of Na/Al 〉=3 in molar ratio, simultaneously, adding temperature continuously equably is 70 ℃-boiling point, in the synthetic groove that band stirs, sodium carbonate solution disperses to add as far as possible, makes NaF and AlF at synthetic groove internal reaction
3Mol ratio 〉=2.7, strainability is good, the cryolite with high molecular ratio from that foreign matter content is lower.
2, the manufacture method of cryolite with high molecular ratio from according to claim 1 is characterized in that the mode that sodium carbonate solution adds dispersedly is to add in the reaction solution by the filling tube homodisperse ground that is drilled with a plurality of apertures under the liquid in the synthetic groove of dark insertion.
3, the manufacture method of cryolite with high molecular ratio from according to claim 1, it is characterized in that controlling mol ratio 6F/Al=1.0-1.2 and mol ratio Na/Al 〉=3rd, realize by the mensuration of feed liquid total acidity, control hydrofluoaluminic acid total acidity is at 90-130g/l, 100-110g/l cryolite slurry total acidity≤12g/l preferably, pH value≤4.
4, the manufacture method of cryolite with high molecular ratio from according to claim 1, it is characterized in that hydrofluoric acid and aluminium hydroxide are added to reaction generation hydrofluoaluminic acid in first synthetic groove, enter second synthetic groove then and continue reaction, make and react completely, obtain the second best in quality hydrofluoaluminic acid, hydrofluoaluminic acid flows into the 3rd synthetic groove, generate cryolite slurry with the sodium carbonate solution reaction, cryolite slurry flows into and continues reaction in the 4th the synthetic groove, with resultant send filter filter wet sodium aluminum fluoride, the drying sub-ratio ice spar finished product that secures satisfactory grades.
5, the manufacture method of cryolite with high molecular ratio from according to claim 1, it is characterized in that used hydrofluoric acid be anhydrous hydrogen fluoride with water dissolution after smart acid behind the hydrofluoric acid of gained and the refining thick hydrofluoric acid silica removal of yellow soda ash, hydrofluoric acid HF concentration is 20-30%.
6, the manufacture method of cryolite with high molecular ratio from according to claim 1 is characterized in that used sodium carbonate solution Na
2CO
3Concentration is 220-400g/l.
7, the manufacture method of cryolite with high molecular ratio from according to claim 1 is characterized in that the aluminium hydroxide mud balance is 1.33-1.53.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111147A CN1043033C (en) | 1994-08-30 | 1994-08-30 | Method for production of high-molecular-ratio ice spar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94111147A CN1043033C (en) | 1994-08-30 | 1994-08-30 | Method for production of high-molecular-ratio ice spar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117944A true CN1117944A (en) | 1996-03-06 |
| CN1043033C CN1043033C (en) | 1999-04-21 |
Family
ID=5035045
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94111147A Expired - Fee Related CN1043033C (en) | 1994-08-30 | 1994-08-30 | Method for production of high-molecular-ratio ice spar |
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| Country | Link |
|---|---|
| CN (1) | CN1043033C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329302C (en) * | 2003-02-21 | 2007-08-01 | 姜战 | Method for manufacturing sodium aluminium fluoride by pickling aluminium slag |
| CN104310450A (en) * | 2014-09-29 | 2015-01-28 | 湖南康盟环保科技有限公司 | Treatment method for ammonia-containing wastes produced in ammonia process production of cryolite |
| CN109019649A (en) * | 2018-09-18 | 2018-12-18 | 福建省漳平市九鼎氟化工有限公司 | A kind of preparation method of high molecule ratio potassium fluoroaluminate |
| CN115583709A (en) * | 2022-10-13 | 2023-01-10 | 广州楷诚干燥设备有限公司 | Efficient fluoride ion removing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2996355A (en) * | 1958-09-12 | 1961-08-15 | Reynolds Metals Co | Process for the manufacture of sodium aluminum fluorides |
| RO93136B1 (en) * | 1985-10-15 | 1987-12-31 | Institutul De Inginerie Tehnologica Si Proiectare Pentru Industria Chimica | Process for preparing cryolite |
-
1994
- 1994-08-30 CN CN94111147A patent/CN1043033C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329302C (en) * | 2003-02-21 | 2007-08-01 | 姜战 | Method for manufacturing sodium aluminium fluoride by pickling aluminium slag |
| CN104310450A (en) * | 2014-09-29 | 2015-01-28 | 湖南康盟环保科技有限公司 | Treatment method for ammonia-containing wastes produced in ammonia process production of cryolite |
| CN104310450B (en) * | 2014-09-29 | 2016-08-17 | 湖南康盟环保科技有限公司 | Ammonia process produce produce during cryolite containing ammonia waste treatment method |
| CN109019649A (en) * | 2018-09-18 | 2018-12-18 | 福建省漳平市九鼎氟化工有限公司 | A kind of preparation method of high molecule ratio potassium fluoroaluminate |
| CN115583709A (en) * | 2022-10-13 | 2023-01-10 | 广州楷诚干燥设备有限公司 | Efficient fluoride ion removing method |
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| Publication number | Publication date |
|---|---|
| CN1043033C (en) | 1999-04-21 |
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Granted publication date: 19990421 Termination date: 20090930 |