CN1048959C - Method for producing aluminium fluoride and cryolite with kaoline - Google Patents
Method for producing aluminium fluoride and cryolite with kaoline Download PDFInfo
- Publication number
- CN1048959C CN1048959C CN94112436A CN94112436A CN1048959C CN 1048959 C CN1048959 C CN 1048959C CN 94112436 A CN94112436 A CN 94112436A CN 94112436 A CN94112436 A CN 94112436A CN 1048959 C CN1048959 C CN 1048959C
- Authority
- CN
- China
- Prior art keywords
- kaolin
- cryolite
- aluminum fluoride
- hydrofluoric acid
- aluminium fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for producing aluminium fluoride and cryolite by kaolin (clay) and mirabilite instead of the existing aluminium hydroxide and sodium carbonate. The method is novel technology which has the advantages of obvious economic benefit and environmental pollution reduction. The method uses kaolin as raw materials, and the kaolin contains aluminum oxide more than 30% and ferric oxide not more than 2%. Aluminum sulfate is prepared by high-temperature roasting and low-temperature leaching firstly, and then, the aluminum sulfate respectively reacts with hydrofluoric acid and sodium sulfate to prepare aluminium fluoride and cryolite. Compared with the existing production method, the cost of per ton of aluminium fluoride can be reduced by about 500 yuan, and the cost of per ton of cryolite can be reduced by about 900 yuan. Mother liquor can be used circularly, and the method does not discharge harmful waste water and waste gas. The product quality of aluminium fluoride and cryolite can reach prime products of Chinese Standard.
Description
The invention belongs to the preparation method of inorganic fluoride.
At present, producing the method for aluminum fluoride both at home and abroad, all is to adopt aluminium hydroxide and hydrofluoric acid (or hydrogen fluoride gas) to make for raw material; And sodium aluminum fluoride all is to adopt aluminium hydroxide, hydrofluoric acid and soda ash (or salt) to make.These production methods, used main raw material aluminium hydroxide, soda ash, price is higher, and domestic aluminum oxide shortage, all needs import every year.In addition, when producing, the mother liquor of generation can not recycle, in the large quantity of exhaust gas of generation, contains hydrogen fluoride, and environment is caused severe contamination.When the preparation sodium aluminum fluoride, if without soda ash, and be to use salt, the mother liquor that is produced contains hydrofluoric acid and hydrochloric acid, can't recycle, and also results in hand cramps.
The objective of the invention is to adopt domesticly be easy to get, cheap kaolin (it contains aluminum oxide) makes raw material, prepares aluminum fluoride and sodium aluminum fluoride with hydrofluoric acid and saltcake respectively, can reduce production costs on the one hand, can reduce environomental pollution source on the other hand.
It is raw material that the present invention adopts kaolin (clay), hydrofluoric acid and saltcake, by the first Tai-Ace S 150 of preparation, and then produces aluminum fluoride and sodium aluminum fluoride respectively with it.
The composition of kaolin (clay) is the aluminum oxide (AL that contains more than 30%
2O
3) and be not more than 2% ferric oxide (Fe
2O
3).
The principle of preparation is:
1. the kaolin that will contain 30% above aluminum oxide is pulverized, and roasting at high temperature with sulphuric acid soln leaching, filtration, obtains the alum liquor that concentration is not less than 80 grams per liters then.
Its chemical equation is:
2, with the Tai-Ace S 150 and the hydrofluoric acid reaction of gained, make aluminum fluoride (ALF
3).
Chemical equation is:
3, Tai-Ace S 150 and hydrofluoric acid and sodium sulfate (saltcake) effect generates sodium aluminum fluoride (Na
3ALF
6).
Chemical equation is:
Specific embodiments of the present invention is as follows:
1, the preparation of alum liquor:
To contain 30% above aluminum oxide,＜kaolin (clay) that 2% ferric oxide is formed pulverizes, roasting under 650-700 ℃ of high temperature, be not less than the solution of 200 grams per liters then with sulfur acid, in the good kaolin (clay) of about 100 ℃ of normal pressures leaching roasting aluminum oxide 1-2 hour, the pH value of leaching liquid is 2.5-3.0, filter, obtain the alum liquor that concentration is the 80-120 grams per liter.
Filter is also washed three times, and with the previous washing lotion washing second time, washing lotion is washed with clear water for the third time with last washing lotion washing for the third time for the second time for the first time.
2, the preparation of aluminum fluoride:
Alum liquor is added to synthetic groove, is heated to 95 ℃, add purified hydrofluoric acid while stirring, and add 5% aluminium fluoride seed crystal, insulation crystallization 3 hours is filtered, and isolation of crystalline and mother liquor are filtered and washed with water to PH=2.5-3.0, drying is pulverized, and gets the aluminium fluoride product of moisture content＜7%.
The mother liquor that filters out is used for preparing alum liquor again, and washing lotion is used for the hydrogen manufacturing fluoric acid, and concentration is about 27%.
3, the preparation of metabisulfite solution:
The saltcake that will contain more than 70% is pulverized, and adds above-mentioned Tai-Ace S 150 washing lotion (or water), be heated to 90-100 ℃ of dissolving after, filter immediately, make 40% metabisulfite solution.
4, the preparation of sodium aluminum fluoride:
Press NaF and ALF
3Mol ratio is 2: 1-3: 1 ratiometric conversion becomes the dosage of Tai-Ace S 150, hydrofluoric acid and sodium sulfate.
Earlier alum liquor is added synthetic groove, be heated to 95 ℃, add a part of hydrofluoric acid earlier, keep 90-95 ℃, more remaining hydrofluoric acid and metabisulfite solution are added synthetic groove, react after 30 minutes, filter isolation of crystalline and mother liquor.When synthetic for the first time, need to add earlier 5% sodium aluminum fluoride of sodium aluminum fluoride growing amount as crystal seed.
The filter that filters out and wash with water to PH be 2.5-3.0, will filter then and dry, moisture is not more than 0.8%, makes the sodium aluminum fluoride product.
All can reach country-level product standard with the aluminum fluoride of this method production and the quality of sodium aluminum fluoride product.The result of laboratory test of finished product composition is as follows:
Aluminum fluoride sodium aluminum fluoride F 63.5-65.2 53.7-55.9AL 30-32 16.2-19.0Na 2-3 21.2-22.5SiO
20.01-0.1 0.05-0.23Fe
2O
30.20-0.2 5 0.025-0.068SO
4 2-1.02-1.2 0 0.40-0.57H
2O 6.0-6.8 0.10-0.57P
2O
5--vestige
The mother liquor for preparing aluminum fluoride, sodium aluminum fluoride with the present invention can recycle, and unnecessary mother liquor can be produced the Tai-Ace S 150 product for paper grade (stock).The remaining waste residue of system Tai-Ace S 150 can be used for producing cement.Equipment is airtight in process of production, can significantly reduce the pollution of waste gas to environment.
The raw material consumption of aluminum fluoride and expense comparison sheet one
| Existing production method | The inventive method | ||||||
| Material name | Unit price unit/ton | Unit consumption ton/ton | Actual cost (unit) | Material name | Unit price unit/ton | Unit consumption ton/ton | Actual cost (unit) |
| Aluminium hydroxide | 120000 | 0.97 | 1164.00 | Kaolin | 200.00 | 3.00 | 600.00 |
| Water | 1.00 | 20.00 | 20.00 | ||||
| Electricity | 0.40 | 50 degree | 20.00 | ||||
The raw material consumption of sodium aluminum fluoride and expense comparison sheet two
Annotate: the existing method of (1) hydrofluoric acid unit consumption is suitable with inventive method, so unlisted at this.
| Existing production method | The inventive method | ||||||
| Material name | Unit price unit/ton | Unit consumption ton/ton | Actual cost (unit) | Material name | Unit price unit/ton | Unit consumption ton/ton | Actual cost (unit) |
| The hydrogen aluminum hydride | 120000 | 0.565 | 678.00 | Kaolin | 200.00 | 1.70 | 340.00 |
| Soda ash | 140000 | 0.630 | 882.00 | Saltcake | 200.00 | 1.25 | 250.00 |
| Water | 1.00 | 20.00 | 20.00 | ||||
| Electricity | 0.40 | 50 degree | 20.00 | ||||
(2) unit price of kaolin (clay) is made into to convert behind the alum liquor.
The inventive method can reduce by 524 yuan than the cost of existing production method aluminum fluoride per ton; The cost of sodium aluminum fluoride per ton can reduce by 930 yuan, the economic benefit highly significant.
Embodiment
1, the preparation of alum liquor:
To contain AL
2O
3More than 30%, Fa
2O
3＜2% kaolin powder is broken into 60 orders, by 90%, and roasting in cyclone furnace, temperature of charge reaches 650-700 ℃, adopts the cyclone dust suction, uses mother liquor (to contain H then
2SO
4Be not less than 200 grams per liters) under normal pressure, 100-102 ℃ of AL that leaches in the good kaolin of roasting
2O
3, 1-2 hour, the solution pH value that leaching is finished was 2.5-3.0, filtered with vacuum filter, the concentration that obtains alum liquor is more than the 80-120 grams per liter.
2, the preparation of metabisulfite solution:
To contain the Na more than 70%
2SO
4(saltcake) pulverized, and is heated to 90-100 ℃ of dissolving saltcake with the washing lotion for preparing Tai-Ace S 150, and vacuum filtration obtains 40%Na
2SO
4Solution.
3, the preparation of aluminum fluoride:
Alum liquor is added in the synthetic groove that has agitator sealing and condensing works, is heated to 95 ℃, keep under this temperature, add refined hydrofluoric acid while stirring gradually with 15 minutes, add 5% aluminium fluoride seed crystal, insulated and stirred crystallization 3 hours with open steam.
The material of advantages of good crystallization is through vacuum or centrifuging, and till the crystal that filters out washed with water and is 2.5-3.0 to pH, washed filter cake was dry in rotary kiln or pneumatic conveying dryer, pulverize, and makes＜aluminum fluoride of 7% moisture.
4. the preparation of sodium aluminum fluoride:
Alum liquor is added in the synthetic groove that has stirring, sealing and condensing works, feed open steam and be heated to 95 ℃, added a part of hydrofluoric acid at 10 minutes, be incubated 90-95 ℃, add remaining hydrofluoric acid again, add metabisulfite solution simultaneously, added in 10-15 minute, sustained reaction 30 minutes, vacuum or centrifuging then separates crystal and mother liquor.Filter cake wash with water to the pH value for till the 2.5-3.0, that the gained filter cake is put is dry in people's rotary kiln or the air stream drying stove, pulverize, moisture content be not more than 0.8% sodium aluminum fluoride product.
Claims (3)
1, a kind of is raw material with kaolin, method with sulfuric acid reaction generation Tai-Ace S 150 refabrication sodium aluminum fluoride, it is characterized in that kaolin raw material that present method adopts be contain more than 30% aluminum oxide and less than 2% ferric oxide, earlier with kaolin pulverizing, roasting, use sulfuric acid to leach, after making Tai-Ace S 150, react with hydrofluoric acid and saltcake one again and make the sodium aluminum fluoride product.
2,, it is characterized in that kaolin in 650～700 ℃ of high temperature after the roasting, with the sulphuric acid soln of 200 grams per liters according to the described preparation method of claim 1, under the normal pressure, 100～102 ℃ leached 2 hours, made PH=2.5～3.0, and concentration is the alum liquor of 80～120 grams per liters.
3, according to claim 1 or 2 described preparation methods, it is characterized in that alum liquor is heated to 95 ℃, add 5% ice crystal masonry crystal seed, add a part of hydrofluoric acid earlier, at 90～95 ℃, remaining hydrofluoric acid and saltcake were added simultaneously in 10～15 minutes then, reacted 30 minutes, the crystal that filters out is a sodium aluminum fluoride, and the moisture content of dry back product is not more than 0.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112436A CN1048959C (en) | 1994-08-06 | 1994-08-06 | Method for producing aluminium fluoride and cryolite with kaoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112436A CN1048959C (en) | 1994-08-06 | 1994-08-06 | Method for producing aluminium fluoride and cryolite with kaoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116609A CN1116609A (en) | 1996-02-14 |
| CN1048959C true CN1048959C (en) | 2000-02-02 |
Family
ID=5036119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112436A Expired - Fee Related CN1048959C (en) | 1994-08-06 | 1994-08-06 | Method for producing aluminium fluoride and cryolite with kaoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048959C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258804A (en) * | 2014-09-10 | 2015-01-07 | 陕西科技大学 | Comprehensive utilization method of coal gangue |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301908C (en) * | 2003-12-12 | 2007-02-28 | 焦作市多氟多化工有限公司 | Method of preparing aluminum fluoride |
| CN1315723C (en) * | 2005-02-21 | 2007-05-16 | 浙江大学 | Method for preparing high-purity ultrnfine silicone powder and aluminium sulphate using kadin as raw material |
| CN100360413C (en) * | 2005-03-07 | 2008-01-09 | 多氟多化工股份有限公司 | Production method of aluminium fluoride |
| CN100348495C (en) * | 2005-03-07 | 2007-11-14 | 多氟多化工股份有限公司 | Method of producing aluminium fluoride |
| CN101134591B (en) * | 2006-09-01 | 2010-09-15 | 多氟多化工股份有限公司 | Method for preparing aluminun fluoride and waterless magnesium sulfate |
| CN101264919B (en) * | 2008-04-23 | 2010-06-02 | 河南未来铝业（集团）有限公司 | Cosmetics-stage cryolite and producing technique thereof |
| CN104692436B (en) * | 2015-02-11 | 2017-03-29 | 南阳东方应用化工研究所 | It is a kind of by coal ash for manufacturing for cryolite method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056091A (en) * | 1990-04-28 | 1991-11-13 | 唐仲友 | Producing sand like synthetic cryolite by clay bittern method |
-
1994
- 1994-08-06 CN CN94112436A patent/CN1048959C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056091A (en) * | 1990-04-28 | 1991-11-13 | 唐仲友 | Producing sand like synthetic cryolite by clay bittern method |
Non-Patent Citations (1)
| Title |
|---|
| 化工词典第三版 1992.7.1 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104258804A (en) * | 2014-09-10 | 2015-01-07 | 陕西科技大学 | Comprehensive utilization method of coal gangue |
| CN104258804B (en) * | 2014-09-10 | 2016-05-25 | 陕西科技大学 | A kind of method of comprehensive utilization of gangue |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1116609A (en) | 1996-02-14 |
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