CN110316749A - A kind of method of fluosilicic acid direct method production aluminum fluoride - Google Patents
A kind of method of fluosilicic acid direct method production aluminum fluoride Download PDFInfo
- Publication number
- CN110316749A CN110316749A CN201910618120.0A CN201910618120A CN110316749A CN 110316749 A CN110316749 A CN 110316749A CN 201910618120 A CN201910618120 A CN 201910618120A CN 110316749 A CN110316749 A CN 110316749A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- aluminum fluoride
- fluoride
- fluosilicic acid
- hydroxide
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Cosmetics (AREA)
Abstract
The present invention relates to a kind of methods of fluosilicic acid direct method production aluminum fluoride, it is using phosphoric acid industry by-product fluosilicic acid, aluminium hydroxide and aluminum fluoride crystalline mother solution as raw material, aluminium-hydroxide powder is adjusted to pulpous state in advance with aluminum fluoride crystalline mother solution, slurry obtains aluminium fluoride product through desiliconization, crystallization, drying, calcining pumped to reacting in the silicate fluoride solution after preheating.The present invention is not under the premise of changing aluminium hydroxide and fluosilicic acid reaction rate, crystalline mother solution is recycled to size mixing in advance with aluminium hydroxide, react aluminium hydroxide sufficiently with fluosilicic acid, avoid aluminium-hydroxide powder directly with the package phenomenon and foam that are generated in fluosilicic acid reaction process it is excessive caused by unrestrained slot phenomenon, produce aluminum fluoride for fluosilicic acid direct method and provide that a kind of aluminium utilization rate is high, technique smoothness, the production technology of stable operation.
Description
Technical field
The invention belongs to chemical industry inorganic fluoride production technical fields, and in particular to a kind of fluosilicic acid direct method production aluminum fluoride
Method.
Background technique
Aluminum fluoride is the fluxing agent of aluminum smelting industry, and the fusing point of aluminium oxide can be greatly reduced in it.Used in domestic aluminum smelting industry
Aluminum fluoride be mostly fluorite method production, with the propulsion of national Ecological Civilization Construction, increase the protection to fluorite resource,
In recent years, more and more producers start the aluminum fluoride using wet process phosphoric acid by-product production aluminum smelting industry.Fluosilicic acid production
The representative process of aluminum fluoride mainly has an ammonia process and two kinds of direct method, direct method due to, operation simple with process be easy,
The advantages such as raw material variety is few, production cost is low, are widely used.
Currently, the technique that fluosilicic acid direct method production aluminum fluoride mainly uses aluminium-hydroxide powder to react with fluosilicic acid, behaviour
Often there is reaction acutely during making, foaming is serious in reactor the phenomenon that unrestrained slot even occurs, is forced to stop aluminium hydroxide
The addition of powder extends reaction time increase β-AlF indirectly3·3H2A possibility that O crystallization is precipitated, even results in environmental pollution thing
Therefore；Simultaneously because the silica gel that the aluminium-hydroxide powder that is acutely added of reaction can also be generated by reaction wraps up, cause reaction not exclusively,
Al utilization rate is low, increases production cost.Although the AP technique of French Aluminum Pechiney company exploitation is using aluminium hydroxide
The mode of slurrying, but slurry is filtered into wet cake by rotary drum filter by filter progress again after slurrying and adds preheating
The drawbacks such as in silicate fluoride solution, that there are aluminium hydroxide filtering rates is low, process is long, aluminium hydroxide metering is not accurate enough.
Summary of the invention
It is an object of the invention to solve aluminium-hydroxide powder in traditional fluosilicic acid direct method production aluminum fluoride process flow
With the unrestrained slot that occurs in fluosilicic acid reaction process and package phenomenon, provide that a kind of aluminium utilization rate is high, technique is smooth, stable operation
The technique of fluosilicic acid direct method production aluminum fluoride.
Experiment shows: under the conditions of same reaction temperature, when fluosilicic acid concentration changes between 10%~20%, and hydroxide
The variation of the reaction speed of aluminium and fluosilicic acid is little, but as the increase of fluosilicic acid concentration reaction can become violent.The silica gel of generation
Meeting wrapping portion aluminium-hydroxide powder, the interior foaming of reactor is serious even to will appear unrestrained slot phenomenon, the aluminium hydrate powder being newly added
It is incomplete that end can float on reaction above foam；More detrimental effect is after occurring foaming serious phenomenon in reactor, it is necessary to quilt
Compel to stop being added aluminium-hydroxide powder and add material after lather collapse, extending the reaction time indirectly is unfavorable for subsequent work
The operation of sequence.After being sized mixing in advance by the crystalline mother solution and aluminium-hydroxide powder that are added 1.0~1.5 times of aluminium-hydroxide powder, then with
Silicate fluoride solution reacts, and silicate fluoride solution concentration is positively retained between 13.3%~16.2% in reaction process, not will cause anti-
The large change of speed is answered, and foaming, unrestrained slot phenomenon no longer occurs, technique is more smooth, reaction carries out more abundant.
A kind of method of fluosilicic acid direct method production aluminum fluoride, the present invention is with aluminum fluoride crystalline mother solution by aluminium-hydroxide powder
It is adjusted to pulpous state in advance, slurry through desiliconization, crystallization, filtering, drying, is calcined pumped to reacting in the silicate fluoride solution after preheating
To aluminium fluoride product, the present invention is achieved by following steps:
1) fluorination crystalline aluminophosphate filtered fluid is sized mixing in advance with aluminium hydroxide, obtains aluminum hydroxide slime；
2) aluminum hydroxide slime of metering is delivered in the silicate fluoride solution for be pre-heated to 85 DEG C or so with pump and is carried out instead
It answers；
3) slurry after reacting obtains wet white carbon black filter cake and filtrate, wash water after being filtered, washed；
4) it is crystallized under the conditions of 95 DEG C after filtrate merges with wash water；
5) crystallize after slurry through cooling down, be filtered, washed after obtain wet aluminum fluoride and crystalline mother solution；
6) aluminium fluoride product is obtained after wet aluminum fluoride drying, calcining.
Wherein the crystalline mother solution is sized mixing in advance with aluminium hydroxide, and the mass ratio of the crystalline mother solution and aluminium hydroxide is 1.0:
1~1.5:1, preferably 1.2:1~1.5:1.
Fluosilicic acid of the present invention refers to phosphoric acid by wet process and Phosphate Fertilizer Industry by-product, fluosilicic acid (H2SiF6) mass percent
18%~23%, P2O5Mass percent is not higher than F/Si molar ratio 5:1~6:1 in 0.01%, solution.
The beneficial effects of the present invention are:
1) it is sized mixing using crystalline mother solution water to aluminium hydroxide, aluminium hydroxide and fluosilicic acid is made to react more abundant；
2) it is sized mixing using crystalline mother solution water to aluminium hydroxide, makes to react more stable, technique more process, avoid foaming
To the package of aluminium hydroxide, the Al rate of recovery is higher for serious and unrestrained slot phenomenon and silica gel；
3) fluorine contained in crystalline mother solution, Al resource have sufficiently been recycled, production cost further decreases；
4) aluminium hydroxide sized mixing in advance using pump conveying, metering is more convenient, operation is more smooth；
5) loose, uniformly low without seed shape object, aluminium content after the white carbon black drying of by-product, it is conducive to subsequent comprehensive utilization.
Detailed description of the invention
Fig. 1 is process flow diagram in the embodiment of the present invention.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below with reference to embodiment to of the invention
Essential characteristics and advantage are described further.
Embodiment
1) fluorination crystalline aluminophosphate filtered fluid is sized mixing in advance with aluminium hydroxide 1.5:1 in mass ratio, obtains aluminum hydroxide slime, slurry
48 DEG C of temperature；
2) aluminum hydroxide slime of metering is delivered in the silicate fluoride solution for the metering for being pre-heated to 85 DEG C with pump and is carried out
It reacts, fluosilicic acid excessive 3%, feed time 4min, fluosilicic acid (H in silicate fluoride solution2SiF6) mass percent 20.73%, F/
Si molar ratio 5.3, P2O5Mass percent 0.007%, 93 DEG C of reaction temperature, reaction time (after having fed) 17min；
3) slurry after reacting obtains wet white carbon black filter cake and filtrate, wash water after being filtered, washed；
4) it is crystallized under the conditions of 95 DEG C after filtrate merges with wash water, crystallization time 4.5h；
5) crystallize after slurry cooling down to 60 DEG C, be filtered, washed to obtain wet aluminum fluoride and crystalline mother solution；
6) wet aluminum fluoride obtains after 180 DEG C of calcining 1.5h, 550 DEG C of calcining 1h abjection crystallizations water in 120 DEG C of drying attached waters
To aluminium fluoride product, aluminium fluoride product meets AF-2 trade mark index as defined in GB/T4292-2017.
Above-mentioned technological operation is smooth, and instantaneous dispersing reacts uniformly in silicate fluoride solution after aluminum hydroxide slime is added, and adds
Do not occur foaming, unrestrained slot phenomenon during material, the white carbon black filter cake obtained by above-mentioned technique is uniformly without seed shape object, after drying
It is even, loose.White carbon black obtained by embodiment, aluminum fluoride physical and chemical indexes are as shown in table 1.
1 embodiment white carbon black of table, aluminum fluoride physical and chemical indexes
Reference examples
1) aluminium-hydroxide powder of metering is delivered to weighing belt in the silicate fluoride solution for the metering for being pre-heated to 85 DEG C
It is reacted, fluosilicic acid excessive 3%, feed time 6min, fluosilicic acid (H in silicate fluoride solution2SiF6) mass percent
20.73%, F/Si molar ratio 5.3, P2O5Mass percent 0.007%, 93 DEG C of reaction temperature, the reaction time (after having fed)
17min；
2) slurry after reacting obtains wet white carbon black filter cake and filtrate, wash water after being filtered, washed；
3) it is crystallized under the conditions of 95 DEG C after filtrate merges with wash water, crystallization time 4.5h；
4) crystallize after slurry cooling down to 60 DEG C, be filtered, washed to obtain wet aluminum fluoride and crystalline mother solution；
5) wet aluminum fluoride obtains after 180 DEG C of calcining 1.5h, 550 DEG C of calcining 1h abjection crystallizations water in 120 DEG C of drying attached waters
To aluminium fluoride product, aluminium fluoride product meets AF-2 trade mark index as defined in GB/T4292-2017.
Aluminium-hydroxide powder disperses not enough uniformly after being added, and aluminium-hydroxide powder feeds to the half or so of metered mass
Afterwards, foaming is serious in reactor, and unmixing aluminium-hydroxide powder can be obviously observed on foam, is forced to stop feeding and add
Foam, which fades away, after fast mixing speed 2min continuously adds aluminium-hydroxide powder, the white carbon black filter cake obtained by above-mentioned technique
It can obviously observe seed shape object, white carbon black has a small amount of harder seed shape object after drying.White carbon black, aluminum fluoride materialization obtained by reference examples
Index is as shown in table 2.
2 embodiment white carbon black of table, aluminum fluoride physical and chemical indexes
Claims (3)
1. a kind of method of fluosilicic acid direct method production aluminum fluoride, which is characterized in that use aluminum fluoride crystalline mother solution by aluminium hydroxide
Powder is adjusted to pulpous state in advance, and slurry through desiliconization, crystallization, filtering, is dried, forged pumped to reacting in the silicate fluoride solution after preheating
Burning obtains aluminium fluoride product；Include the following steps:
1) fluorination crystalline aluminophosphate filtered fluid is sized mixing in advance with aluminium hydroxide, obtains aluminum hydroxide slime；
2) aluminum hydroxide slime of metering is delivered in the silicate fluoride solution for be pre-heated to 85 DEG C with pump and is reacted；
3) slurry after reacting obtains wet white carbon black filter cake and filtrate, wash water after being filtered, washed；
4) it is crystallized under the conditions of 95 DEG C after filtrate merges with wash water；
5) crystallize after slurry through cooling down, be filtered, washed after obtain wet aluminum fluoride and crystalline mother solution；
6) aluminium fluoride product is obtained after wet aluminum fluoride drying, calcining.
2. a kind of method of fluosilicic acid direct method production aluminum fluoride according to claim 1, which is characterized in that use aluminum fluoride
Crystalline mother solution is sized mixing in advance with aluminium hydroxide, and the mass ratio of aluminum fluoride crystalline mother solution and aluminium hydroxide is 1.0:1~1.5:1.
3. a kind of method of fluosilicic acid direct method production aluminum fluoride according to claim 1, which is characterized in that the fluorine silicon
Acid is phosphoric acid by wet process and Phosphate Fertilizer Industry by-product, fluosilicic acid (H2SiF6) mass percent 18%~23%, P2O5Mass percent
Not higher than F/Si molar ratio 5:1~6:1 in 0.01%, solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910618120.0A CN110316749A (en) | 2019-07-10 | 2019-07-10 | A kind of method of fluosilicic acid direct method production aluminum fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910618120.0A CN110316749A (en) | 2019-07-10 | 2019-07-10 | A kind of method of fluosilicic acid direct method production aluminum fluoride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110316749A true CN110316749A (en) | 2019-10-11 |
Family
ID=68123203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910618120.0A Pending CN110316749A (en) | 2019-07-10 | 2019-07-10 | A kind of method of fluosilicic acid direct method production aluminum fluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110316749A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111186852A (en) * | 2020-02-24 | 2020-05-22 | 黄冈师范学院 | Process for purifying quartz material and preparing aluminum fluoride and high-purity white carbon black by using by-product fluosilicic acid |
| CN111943243A (en) * | 2020-07-17 | 2020-11-17 | 湖北宜化松滋肥业有限公司 | Method for producing aluminum fluoride by using fluosilicic acid |
| CN114011110A (en) * | 2021-12-10 | 2022-02-08 | 云南云天化氟化学有限公司 | Crystallization method for aluminum fluoride production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB782423A (en) * | 1954-09-13 | 1957-09-04 | Fisons Ltd | Production of aluminium fluoride |
-
2019
- 2019-07-10 CN CN201910618120.0A patent/CN110316749A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB782423A (en) * | 1954-09-13 | 1957-09-04 | Fisons Ltd | Production of aluminium fluoride |
Non-Patent Citations (2)
| Title |
|---|
| 丁运玲等: ""粘土一氢氟酸法生产氟化铝新工艺"", 《河北化工》 * |
| 化学工业部建设协调司，化工部硫酸和磷肥设计技术中心组织编写: "《磷酸 磷铵 重钙技术与设计手册》", 31 January 1997, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111186852A (en) * | 2020-02-24 | 2020-05-22 | 黄冈师范学院 | Process for purifying quartz material and preparing aluminum fluoride and high-purity white carbon black by using by-product fluosilicic acid |
| CN111186852B (en) * | 2020-02-24 | 2022-06-14 | 黄冈师范学院 | Process for purifying quartz material and preparing aluminum fluoride and high-purity white carbon black by using byproduct fluosilicic acid |
| CN111943243A (en) * | 2020-07-17 | 2020-11-17 | 湖北宜化松滋肥业有限公司 | Method for producing aluminum fluoride by using fluosilicic acid |
| CN114011110A (en) * | 2021-12-10 | 2022-02-08 | 云南云天化氟化学有限公司 | Crystallization method for aluminum fluoride production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110316749A (en) | A kind of method of fluosilicic acid direct method production aluminum fluoride | |
| CN103466637B (en) | Method for producing precipitate silicon dioxide by using sodium bicarbonate to control supersaturation degree | |
| CN101066767B (en) | Improved wet process for producing ammonium bifluoride | |
| CN101555033B (en) | Method for preparing cryolite and coproducing soluble glass by using hydrof luorosilicic acid | |
| CN105502441B (en) | Method for continuously producing cell-grade lithium carbonate | |
| CN105502451B (en) | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio | |
| CN105645447B (en) | A kind of method that cryolite with high molecular ratio is produced using low dose fluoride silicic acid | |
| CN101613229A (en) | A kind of improved method for preparing sulfur base fertilizer | |
| CN102828037A (en) | Method of preparing low-silicon low-phosphorus potassium metavanadate solution from vanadium slag | |
| CN108017077A (en) | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio | |
| CN102849744A (en) | Technology for producing sodium fluosilicate | |
| CN103880058B (en) | A kind of precipitated chalk production technique of falling magnesium increasing calcium | |
| CN109665549A (en) | A kind of technique preparing calcium aluminum hydrotalcite using carbon dioxide | |
| CN101863482B (en) | Method for continuously preparing white carbon black and ammonium fluoride by carrying out fluosilicic acid ammoniation | |
| CN1899963A (en) | Method for preparing boric acid from borax | |
| CN103663499B (en) | The method of Potassium monofluoride co-production of ultrafine white carbon black is prepared with phosphate fertilizer by-product ammonium silicofluoride | |
| CN105350066B (en) | A kind of method that ardealite prepares hemihydrate calcium sulfate crystal whisker | |
| CN104525064A (en) | Alkaline silica sol and preparation method thereof | |
| CN104909489B (en) | A kind of process for producing of trichloro-isocyanuric acid sewage water treatment method | |
| CN103435069B (en) | Method for realizing continuous production of ammonium hydrogen fluoride | |
| CN101531367A (en) | Process for producing silicane | |
| CN101659416B (en) | Method for preparing white carbon black co-product calcium chloride | |
| CN101462732A (en) | Method for preparing sodium silicate from fluorine-containing silica gel | |
| CN105858676A (en) | Production method for coproducing sodium silicate and sodium fluoride | |
| CN102491342B (en) | Method for preparing white carbon black by using fluosilicic acid gas ammonification process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191011 |