CN106865588B - A method of preparing ice crystal with fluorite - Google Patents
A method of preparing ice crystal with fluorite Download PDFInfo
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- CN106865588B CN106865588B CN201710112252.7A CN201710112252A CN106865588B CN 106865588 B CN106865588 B CN 106865588B CN 201710112252 A CN201710112252 A CN 201710112252A CN 106865588 B CN106865588 B CN 106865588B
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- filtrate
- ice crystal
- fluorspar powder
- fluorite
- sodium hydroxide
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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
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- 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
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a kind of methods preparing ice crystal with fluorite, belong to the technical field of ice crystal preparation method, include the preparation process of fluorine extraction process and ice crystal, specifically include following steps：1）Fluorite mineral are broken, milling, sieving, obtain Fluorspar Powder；2）Fluorspar Powder is mixed with aluminium chloride in proportion, obtains mixture；3）It is added with stirring hydrochloric acid into mixture to size mixing and temperature reaction, filtrate is obtained after filtering；4）Sodium hydroxide solution is slowly added into filtrate, to reduce the acidity of filtrate；5）By step 4）In solution ageing, then filter again, filter residue is ice crystal.The preparation method process safety environmental protection of the present invention, process are brief.
Description
Technical field
The present invention relates to a kind of preparation method field of ice crystal, more particularly to one kind preparing ice crystal by raw material of fluorite
Method.
Background technology
Fluorite is also known as fluorite, is the important chemical industry mineral in China, and the entirely basis of fluorine chemical industry, is subsequently fluorinated work
Product is all deep processing on its basis.Fluorite is widely used in metallurgy, aluminium metallurgy, ceramics, cement, glass, fluorination work etc.
Industry, product are chiefly used in space flight, aviation, medicine, refrigeration, anti-corrosion, pesticide, fire-fighting, electronics, electric power, machinery and atomic energy etc.
Field affects national security, national economy and the development of society.China's fluorite resource is abundant, forms development fluorination work
Inherent advantage.But China's fluorine Chemical Manufacture and the stage of ripeness is not entered, the method master that China's fluorite resource develops and uses at present
It is：By Fluorspar Powder and hydrofluoric acid hybrid reaction, fluorine gas, fluoride salt, fluoro-containing intermediate etc. are produced.Magnify allusion quotation in document《Low product
Position fluorite ore prepares the new method of ice crystal》Disclosed in method, process is cumbersome and generates a large amount of toxic gas.Cause
This, it is very necessary to find new Process of Producing Cryolite.
Invention content
The technical problem to be solved in the invention is to provide a kind of method preparing ice crystal with fluorite, reaction process safety
Environmental protection, process are brief.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A method of ice crystal being prepared with fluorite, specifically includes following steps,
1）Fluorite mineral are broken, milling, sieving, obtain Fluorspar Powder；
2）Fluorspar Powder is mixed with aluminium chloride in proportion, obtains mixture；
3）It is added with stirring hydrochloric acid into mixture to size mixing and temperature reaction, filtrate is obtained after filtering；
4）Sodium hydroxide solution is slowly added into filtrate, to reduce the acidity of filtrate；
5）By step 4）In solution ageing, then filter again, filter residue is ice crystal.
Technical solution of the present invention further improvement lies in that：Step 1）The granularity of middle Fluorspar Powder is 250~325 mesh.
Technical solution of the present invention further improvement lies in that：Step 2）The calcirm-fluoride of middle Fluorspar Powder and the molar ratio of aluminium chloride
It is 5:2~3:1.
Technical solution of the present invention further improvement lies in that：Step 3）In size mixing the mass ratio of used hydrochloric acid and Fluorspar Powder
It is 2:1~5:1, a concentration of 2~5 mol/L of hydrochloric acid.
Technical solution of the present invention further improvement lies in that：Step 3）Reaction temperature be 80 DEG C~100 DEG C, the reaction time
It is 2~8 hours.
Technical solution of the present invention further improvement lies in that：Step 4）It is middle control sodium hydroxide rate of addition be 0.05~
0.07ml/s, a concentration of 7~10mol/L of sodium hydroxide, be added sodium hydroxide solution the pH value of filtrate is adjusted to as 2.0~
3.0。
Technical solution of the present invention further improvement lies in that：Step 4）Reaction temperature be 80 DEG C~100 DEG C.Skill of the present invention
Art scheme further improvement lies in that：Step 5）Digestion time is 1~2 hour.
By adopting the above-described technical solution, the technological progress that the present invention obtains is：
The present invention prepares raw material using fluorite ore in preparation process, thus the cost of raw material is low；In addition,
In preparation process, the corrosivity such as hydrogen fluoride and poisonous gas will not be generated, safety and the feature of environmental protection are good.
Fluorite mineral are crushed by the present invention in the preparation stage of raw material, are milled and are sieved, so as to get fluorite Powder Particle Size it is big
It is small within the scope of 250~325 mesh, increase the contact area of reactant so that reaction can be sufficiently carried out.
Present invention mixed material in such a way that aluminium salt first mixes acid adding again with Fluorspar Powder, a large amount of aluminium ion will be with fluorine shape
At stable complex compound, fluorine is made to be difficult to become hydrogen fluoride volatilization.Fluorspar Powder is avoided individually to contact to occur with a large amount of concentrated acids
Reaction, generates a large amount of hydrofluoric acid.Therefore, the technique is more safe and environment-friendly, significantly reduces the fluorite fluorine extraction process stage pair and sets
Standby requirement.
The precipitation just generated is placed a period of time progress ripening, such operation processing by the present invention together with mother liquor
The impurity contained in precipitation can be removed, the purity of precipitation is improved；Meanwhile, it is capable to which precipitating crystalline is allowed to grow the grain for increasing crystal
Diameter keeps its particle diameter distribution relatively uniform.
Specific implementation mode
The present invention is described in further details below：
A method of ice crystal being prepared with fluorite, includes the preparation process of fluorine extraction process and ice crystal, specifically includes
Following steps,
I, fluorine extraction process
1）Fluorite mineral are broken, milling, the sieve for crossing 250~325 mesh, obtain Fluorspar Powder；
2）The molar ratio of the content for first detecting calcirm-fluoride in Fluorspar Powder, the calcirm-fluoride and aluminium chloride of then pressing Fluorspar Powder is 5：
2~3：1 ratio mixes Fluorspar Powder with aluminium chloride, obtains mixture；
3）Into mixture stir under according to the mass ratio of hydrochloric acid and Fluorspar Powder be 2：1~5：Hydrochloric acid tune is added in 1 ratio
Slurry, a concentration of 2~5 mol/L of hydrochloric acid are warming up to 80 DEG C~100 DEG C and react 2~8 hours, filtrate is obtained after filtering；
II, the preparation process of ice crystal
1）The sodium hydroxide solution of 7~10mol/L is slowly added into filtrate, the rate of addition for controlling sodium hydroxide is
0.05~0.07ml/s, reaction temperature are 80 DEG C~100 DEG C, reduce the acidity of filtrate, until the pH value of solution be adjusted to as 2.0~
3.0；
2）By step 4）In solution digestion time be 1~2 hour, then filter again, filter residue is ice crystal.
The present invention is described in further details with reference to embodiment：
Embodiment 1,
I, fluorine extraction process
1Kg fluorite mineral crushing and grindings are obtained into Fluorspar Powder after crossing 325 mesh sieve；Calcirm-fluoride in Fluorspar Powder is first detected to contain
The molar ratio of amount, the calcirm-fluoride and aluminium chloride of then pressing Fluorspar Powder is 5：2 ratio mixes Fluorspar Powder with aluminium chloride, is mixed
Close object；Into mixture stir under according to the mass ratio of hydrochloric acid and Fluorspar Powder be 2：1 ratio is added hydrochloric acid and sizes mixing, hydrochloric acid it is dense
Degree is 2mol/L, is warming up to 80 DEG C and reacts 2 hours, filtrate is obtained after filtering, and filtrate is the acid solution of fluorine aluminium complex, is used
In subsequent ice crystal preparation section.
II, the preparation process of ice crystal
After the completion of waiting for above-mentioned reaction, 7mol/L sodium hydroxide solutions are slowly added into filtrate to adjust the pH value of filtrate
And sodium source is introduced, until the pH value of solution is adjusted to 2.0, the rate of addition of sodium hydroxide solution is 0.05 ml/s, reaction
Temperature is 80 DEG C, drips and is filtered again after being aged 1 hour after sodium hydroxide solution to complete to be separated by solid-liquid separation, filter residue is ice crystal
Stone.
Embodiment 2,
I, fluorine extraction process
1Kg fluorite mineral crushing and grindings are obtained into Fluorspar Powder after crossing 300 mesh sieve；Calcirm-fluoride in Fluorspar Powder is first detected to contain
The molar ratio of amount, the calcirm-fluoride and aluminium chloride of then pressing Fluorspar Powder is 3：1 ratio mixes Fluorspar Powder with aluminium chloride, is mixed
Close object；Into mixture stir under according to the mass ratio of hydrochloric acid and Fluorspar Powder be 5：1 ratio is added hydrochloric acid and sizes mixing, hydrochloric acid it is dense
Degree is 5mol/L, is warming up to 100 DEG C and reacts 8 hours, filtrate is obtained after filtering, and filtrate is the acid solution of fluorine aluminium complex,
For subsequent ice crystal preparation section.
II, the preparation process of ice crystal
After the completion of waiting for above-mentioned reaction, 10mol/L sodium hydroxide solutions are slowly added into filtrate to adjust the pH of filtrate
It is worth and introduces sodium source, until the pH value of solution is adjusted to 3.0, the rate of addition of sodium hydroxide solution is 0.07ml/s, instead
It is 100 DEG C to answer temperature, drips and is filtered again after being aged 2 hours after sodium hydroxide solution to complete to be separated by solid-liquid separation, filter residue is
Ice crystal.
Embodiment 3,
I, fluorine extraction process
1Kg fluorite mineral crushing and grindings are obtained into Fluorspar Powder after crossing 275 mesh sieve；Calcirm-fluoride in Fluorspar Powder is first detected to contain
The molar ratio of amount, the calcirm-fluoride and aluminium chloride of then pressing Fluorspar Powder is 2.7：1 ratio mixes Fluorspar Powder with aluminium chloride, obtains
Mixture；Into mixture stir under according to the mass ratio of hydrochloric acid and Fluorspar Powder be 4：1 ratio is added hydrochloric acid and sizes mixing, hydrochloric acid
A concentration of 3mol/L is warming up to 95 DEG C and reacts 6 hours, filtrate is obtained after filtering, and filtrate is the acid solution of fluorine aluminium complex,
For subsequent ice crystal preparation section.
II, the preparation process of ice crystal
After the completion of waiting for above-mentioned reaction, 8mol/L sodium hydroxide solutions are slowly added into filtrate to adjust the pH value of filtrate
And sodium source is introduced, until the pH value of solution is adjusted to 3.0, the rate of addition of sodium hydroxide solution is 0.06ml/s, reaction
Temperature is 95 DEG C, drips and is filtered again after being aged 1 hour after sodium hydroxide solution to complete to be separated by solid-liquid separation, filter residue is ice crystal
Stone.
Embodiment 4,
I, fluorine extraction process
1Kg fluorite mineral crushing and grindings are obtained into Fluorspar Powder after crossing 250 mesh sieve；Calcirm-fluoride in Fluorspar Powder is first detected to contain
The molar ratio of amount, the calcirm-fluoride and aluminium chloride of then pressing Fluorspar Powder is 14：5 ratio mixes Fluorspar Powder with aluminium chloride, obtains
Mixture；Into mixture stir under according to the mass ratio of hydrochloric acid and Fluorspar Powder be 4：1 ratio is added hydrochloric acid and sizes mixing, hydrochloric acid
A concentration of 3mol/L is warming up to 85 DEG C and reacts 7 hours, filtrate is obtained after filtering, and filtrate is the acid solution of fluorine aluminium complex,
For subsequent ice crystal preparation section.
II, the preparation process of ice crystal
After the completion of waiting for above-mentioned reaction, 8mol/L sodium hydroxide solutions are slowly added into filtrate to adjust the pH value of filtrate
And sodium source is introduced, until the pH value of solution is adjusted to 2.0, the rate of addition of sodium hydroxide solution is 0.05ml/s, reaction
Temperature is 89 DEG C, drips and is filtered again after being aged 1.5 hours after sodium hydroxide solution to complete to be separated by solid-liquid separation, filter residue is ice
Spar.
Claims (2)
1. a kind of method preparing ice crystal with fluorite, it is characterised in that：Specifically include following steps,
1）Fluorite mineral are broken, milling, sieving, obtain Fluorspar Powder；The granularity of Fluorspar Powder is 250~325 mesh；
2）Fluorspar Powder is mixed with aluminium chloride in proportion, obtains mixture；The calcirm-fluoride of Fluorspar Powder and the molar ratio of aluminium chloride are
5:2~3:1；
3）It is added with stirring hydrochloric acid into mixture to size mixing and temperature reaction, filtrate is obtained after filtering；Size mixing hydrochloric acid used with
The mass ratio of Fluorspar Powder is 2:1~5:1, a concentration of 2~5 mol/L of hydrochloric acid, reaction temperature are 80 DEG C~85 DEG C, the reaction time
It is 2~8 hours；
4）Sodium hydroxide solution is slowly added into filtrate, to reduce the acidity of filtrate；Control sodium hydroxide rate of addition be
0.05~0.07mL/s, a concentration of 7~10mol/L of sodium hydroxide, be added sodium hydroxide solution by the pH value of filtrate be adjusted to for
2.0~3.0, reaction temperature is 80 DEG C~89 DEG C；
5）By step 4）In solution ageing, then filter again, filter residue is ice crystal.
2. a kind of method preparing ice crystal with fluorite according to claim 1, it is characterised in that：Step 5）Digestion time
It is 1~2 hour.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101607731A (en) * | 2008-06-18 | 2009-12-23 | 北京有色金属研究总院 | A kind of rare earth doped cryolite and preparation method thereof |
| CN102312093A (en) * | 2010-06-30 | 2012-01-11 | 鹿鸣 | Preparation process for cryolite |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269816A (en) * | 2008-05-16 | 2008-09-24 | 夏克立 | Method for producing fluorine series compounds and white carbon black |
| CN101607731A (en) * | 2008-06-18 | 2009-12-23 | 北京有色金属研究总院 | A kind of rare earth doped cryolite and preparation method thereof |
| CN102312093A (en) * | 2010-06-30 | 2012-01-11 | 鹿鸣 | Preparation process for cryolite |
Non-Patent Citations (1)
| Title |
|---|
| 利用氟铝络合物溶液合成冰晶石的研究;王春梅等;《稀有金属》;20091031;第33卷(第5期);第737-741页 * |
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