CN108203104A - The preparation method of ammonium fluoride - Google Patents
The preparation method of ammonium fluoride Download PDFInfo
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- CN108203104A CN108203104A CN201611187371.0A CN201611187371A CN108203104A CN 108203104 A CN108203104 A CN 108203104A CN 201611187371 A CN201611187371 A CN 201611187371A CN 108203104 A CN108203104 A CN 108203104A
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- ammonolysis
- ammonium fluoride
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- absorption tower
- fluoride
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/162—Ammonium fluoride
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of preparation method of ammonium fluoride, and the gas containing silicon fluoride that albite decomposition reaction generates is passed through in absorption tower by this method, and then hydrolysis generation silicate fluoride solution occurs；Then the silicate fluoride solution is placed in ammonolysis kettle, ammonolysis reaction occurs, generates the solution containing ammonium fluoride and white carbon；The solution containing ammonium fluoride and white carbon is finally filtered, filtrate concentrated crystallization, filtering, drying in crystallization kettle of generation obtains fluorination ammonium product.The above method is easy to operate, economically feasible, and avoids environmental pollution.
Description
Technical field
Preparation method more particularly to a kind of side that ammonium fluoride is prepared using albite the present invention relates to a kind of ammonium fluoride
Method.
Background technology
Ammonium fluoride, molecular formula be NH4F relative molecular masses 37.04, relative density be 1.015 (25 DEG C), it is colourless lobate or
Acicular crystal is hexagonal column crystal after distillation；Easy deliquescence easily lumps, and dissolves in cold water, is slightly soluble in alcohol, insoluble in acetone and liquid
Ammonia.Heated or heat water i.e. decomposition loses ammonia and is converted to more stable ammonium fluoride.Ammonium fluoride is widely used, is such as used as glass etching
Agent, the chemical polishing agent of metal surface, timber and wine brewing preservative, disinfectant, the mordant of fiber and extraction rare element
Solvent etc. is alternatively arranged as mordant of the screening agent of chemical analysis intermediate ion detection, the disinfectant of wine brewing, preservative, fiber etc..
Traditional ammonium fluoride production method is liquid phase method：In lead system or plastic containers, quantitative hydrofluoric acid and ammonia are put into,
Until reacting liquid pH value until 4 or so.Ammonium fluoride product is made through crystallisation by cooling, centrifugation, pneumatic conveying drying in reaction solution.
The production method would generally so that environmental pollution is serious, and mother liquid disposal energy containing more hydrofluoric acid and ammonia in air
Consumption is big.
Invention content
By in consideration of it, of the invention it is necessory to provide a kind of preparation method of environmental-friendly ammonium fluoride.
A kind of preparation method of ammonium fluoride, includes the following steps：
Albite decomposes：By albite, fluorite, 98% sulfuric acid according to 1：(1.55~2.57)：(3.28~4.62)
Mass ratio mixes, and gaseous products of the reaction generation containing silicon fluoride under 100 DEG C~200 DEG C and self-generated pressure；Gas is inhaled
Receive hydrolysis：The gaseous products containing silicon fluoride are filtered using dust removal filter；Gas after dust removal and filtration is generated
Object leads in I and II absorption tower and is hydrolyzed successively；Ammonolysis：The hydrolysate is placed in ammonolysis kettle, passes through ammonium hydroxide tune
It is 7~8 to save pH；The ammonolysis temperature in the kettle is controlled to be aged 2 hours~3 hours after neutralization at 27 DEG C~50 DEG C, ageing temperature
Spend is 30 DEG C~40 DEG C；Prepare ammonium fluoride product：The ammonia products filtered in the ammonolysis kettle obtain the filtrate containing ammonium fluoride；
Condensing crystallizing, filtering, drying process are carried out to the filtrate containing ammonium fluoride, obtain ammonium fluoride crystal.
Based on the preparation method of above-mentioned ammonium fluoride, it is first right at 100 DEG C~200 DEG C that the step of albite decomposes, includes
The albite and fluorite preheat 15 minutes~30 minutes, remove the moisture in raw material, obtain dry albite and fluorite
Raw material；Again 98% sulfuric acid is added to react 2 hours~5 hours in the albite of the drying and fluorite raw material and obtains solid
Residue and the gaseous products containing silicon fluoride.In this step, the reaction temperature can be 100 DEG C, 150 DEG C, 180 DEG C,
200 DEG C, preferably 120 DEG C~200 DEG C；The reaction time is preferably 2.5 hours~4 hours.
Based on the preparation method of above-mentioned ammonium fluoride, the gas absorbs the step of hydrolyzing and includes：The gas reactant warp
Absorbing liquid absorbs, produces the hydrolysate after hydrolysis in the first grade absorption tower, which enters the collection of level-one concentrated phase
In slot, the concentrated phase object of level-one concentrated phase collecting tank collection, which is transported in ammonolysis kettle, carries out ammonolysis, wherein, in the first grade absorption tower
Absorbing liquid be 10%~30% ethanol water；The liquid flooding that the level-one concentrated phase collecting tank is collected is followed to first order absorption
Annular groove is returned through pump and continues to absorb in first grade absorption tower；It is inhaled by the tail gas that the first grade absorption tower comes out into the two level
It receives tower to absorb through absorbing liquid in the two-level absorption tower, continue to hydrolyze, the liquid after the two-level absorption tower hydrolysis enters two level
Concentrated phase absorbs slot, and the concentrated phase object that the two level concentrated phase absorption slot is collected, which is transported in ammonolysis kettle, carries out ammonolysis, wherein, the two level
The ethanol water that absorbing liquid in absorption tower is 10%~30%；The liquid flooding that the two level concentrated phase collecting tank is collected is to two
Grade absorption cycle slot, returns in the two-level absorption tower through pump and continues to absorb；Detect the first order absorption circulating slot, described two
When the fluorinion concentration in silicate fluoride solution in grade absorption cycle slot reaches 10mol/L, absorbing liquid reaches saturation, by the suction
Receipts liquid, which is also transported in the ammonolysis kettle, carries out ammonolysis.
Based on the preparation method of above-mentioned ammonium fluoride, described the step of preparing ammonium fluoride product, includes：By the ammonia products
It is transported to and the filtrate containing ammonium fluoride and white carbon is obtained by filtration in filter press.
Based on the preparation method of above-mentioned ammonium fluoride, described the step of preparing ammonium fluoride product, includes：Described it will contain ammonium fluoride
Filtrate by pump be transported in ammonium fluoride condensing crystallizing kettle, be allowed to the ammonium fluoride condensing crystallizing kettle concentrate, condensing crystallizing
Temperature in the kettle is controlled at 60 DEG C~80 DEG C, and vacuum degree control is in 0.05Mpa~0.07Mpa；When the ammonium fluoride condensing crystallizing kettle
In fluorination ammonium concentration when reaching 12mol/L, stop heating, open cooling water recirculation system and carry out crystallisation by cooling, cooling temperature
Control is at 20 DEG C~30 DEG C；Magma after crystallization is detached through centrifuge, it is dry, obtain ammonium fluoride crystal.
Compared with prior art, the preparation method of ammonium fluoride provided by the invention has the following advantages：Main profit of the invention
The silicon fluoride gas decomposed by the use of albite prepares ammonium fluoride as raw material, makes full use of waste gas containing fluoride, reduces fluoride waste
Discharge rate, while avoid the waste of fluorine resource, also reduce the pollution to environment, saved production cost；The present invention carries
In the preparation method of the ammonium fluoride of confession, for the decomposition temperature of albite at 100 DEG C~200 DEG C, reaction condition is mild, and equipment is wanted
It asks than relatively low；And ammonium fluoride crystal is made using the method for low temperature concentration, low temperature crystallization, and it is simple for process, it is easy to implement, it reduces
Cost, comprehensive utilization degree is high, technique is advanced, economically feasible.
Specific embodiment
It is further illustrated the present invention below by specific embodiment.These embodiments are not the limitations to invention content,
Any equivalent replacement or known change belong to the scope of the present invention.
Embodiment 1
A kind of preparation method of ammonium fluoride, includes the following steps：
Albite decomposes：First albite and fluorite at 100 DEG C are preheated 30 minutes or so, add 98% sulfuric acid
Three is made to be reacted 5 hours or so under 100 DEG C and self-generated pressure, obtains solid residue and the gaseous products containing silicon fluoride,
Wherein, albite, fluorite, 98% sulfuric acid mass ratio be 1：1.55：3.28, reaction principle is：
CaF2+H2SO4=2HF+CaSO4
2NaAlSi3O8+24HF+4H2SO4=Na2SO4+Al2 (SO4) 3+6SiF4 ↑+16H2O
Gas absorbs hydrolysis：The above-mentioned gaseous products containing silicon fluoride are introduced into dedusting in dust removal filter；Through dedusting
Gas after filtering, which is passed through in first grade absorption tower, to be hydrolyzed to form hydrolysate, and hydrolysate enters level-one concentrated phase collecting tank
In, the concentrated phase object that the level-one concentrated phase collecting tank is collected is transported to ammonolysis in ammonolysis kettle, wherein, hydrolysis principle is：
3SiF4+2H2O=2H2SiF6+SiO2 ↓；
The liquid flooding that the level-one concentrated phase collecting tank is collected returns first grade absorption tower to first order absorption circulating slot through pump
In continue to absorb；The tail gas come out by first grade absorption tower, which enters two-level absorption tower, to be continued to hydrolyze, what the two-level absorption tower came out
Liquid is returned in the two-level absorption tower through pump to two level absorption cycle slot and continues to absorb；Detect the first order absorption cycle
When the fluorinion concentration in silicate fluoride solution in slot, the two level absorption cycle slot reaches 10mol/L, absorbing liquid reaches full
With, the absorbing liquid is also transported in ammonolysis kettle and carries out ammonolysis, wherein, the absorbing liquid in the I and II absorption tower is dense
Spend the ethanol water for 10% or so；
Ammonolysis：At 50 DEG C or so, to entering concentrated phase object and fluosilicic acid liquid in the ammonolysis kettle, pH is adjusted by ammonium hydroxide
=7.1；It is aged 3 hours at 40 DEG C or so after neutralization；
Prepare ammonium fluoride product：Ammonia products in the ammonolysis kettle are transported in filter press the hard charcoal for filtering, obtaining
The black washed rear white carbon black product dried, finally obtain high-purity；The filtrate containing ammonium fluoride filtered through filter press, passes through
Pump is transported in ammonium fluoride reactive crystallization kettle；Ammonium fluoride condensing crystallizing temperature in the kettle is controlled at 60 DEG C or so, and adjusts vacuum degree,
When fluorination ammonium concentration reaches 12mol/L in solution, stop heating, open cooling water recirculation system and carry out crystallisation by cooling, cool down
Temperature is controlled at 20 DEG C, and filtrate is made to concentrate, crystallize in ammonium fluoride condensing crystallizing kettle；Magma after crystallization through centrifuge carry out from
The heart detaches, and returning potassium feldspar reacting furnace after the ammonium fluoride drying being centrifuged out recycles；Filtrate is transported to level-one by pump and inhales
It receives and continues to absorb in circulating slot, two level absorption cycle slot.Ammonium fluoride condensing crystallizing kettle vacuum degree control is in 0.052Mpa.
Embodiment 2
A kind of preparation method of ammonium fluoride, includes the following steps：
Albite decomposes：The tool that the specific embodiment of the step of the present embodiment is decomposed with the albite in embodiment 1
Body embodiment is essentially identical, the difference lies in：Pre-warmed temperature is 150 DEG C, and the pre-warmed time is 20 minutes；Reaction
Temperature for 150 DEG C, the time of reaction is 3.5 hours；Wherein, albite, fluorite, 98% sulfuric acid mass ratio be 1：2：4；
Gas absorbs hydrolysis：The specific embodiment of the present embodiment step absorbs hydrolysis with the gas in embodiment 1
The embodiment of step is essentially identical, and the difference lies in the ethanol waters that the absorbing liquid is a concentration of 20% or so；
Ammonolysis：At 40 DEG C or so, to entering concentrated phase object and fluosilicic acid liquid in the ammonolysis kettle, pH is adjusted by ammonium hydroxide
=7.5；It is aged 2.5 hours at 35 DEG C or so after neutralization；
Prepare ammonium fluoride product：The specific embodiment of the step of the present embodiment in embodiment 1 with preparing ammonium fluoride
The embodiment of the step of product is essentially identical, the difference lies in：About 70 DEG C of temperature in the ammonium fluoride condensing crystallizing kettle,
Vacuum degree about 0.06Mpa, the cooling temperature control about 25 DEG C.
Embodiment 3
A kind of preparation method of ammonium fluoride, includes the following steps：
Albite decomposes：The tool that the specific embodiment of the step of the present embodiment is decomposed with the albite in embodiment 1
Body embodiment is essentially identical, the difference lies in：Pre-warmed temperature is 200 DEG C, and the pre-warmed time is 15 minutes；Reaction
Temperature for 200 DEG C, the time of reaction is 2 hours；Wherein, albite, fluorite, 98% sulfuric acid mass ratio be 1：2.5：
4.6；
Gas absorbs hydrolysis：The specific embodiment of the present embodiment step absorbs hydrolysis with the gas in embodiment 1
The embodiment of step is essentially identical, and the difference lies in the ethanol waters that the absorbing liquid is a concentration of 30% or so；
Ammonolysis：At 30 DEG C or so, to entering concentrated phase object and fluosilicic acid liquid in the ammonolysis kettle, pH is adjusted by ammonium hydroxide
=7.9；It is aged 2 hours at 30 DEG C or so after neutralization；
Prepare ammonium fluoride product：The specific embodiment of the step of the present embodiment in embodiment 1 with preparing ammonium fluoride
The embodiment of the step of product is essentially identical, the difference lies in：About 80 DEG C of temperature in the ammonium fluoride condensing crystallizing kettle,
Vacuum degree about 0.07Mpa, the cooling temperature control about 30 DEG C.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent
The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still
It can modify to the specific embodiment of the present invention or equivalent replacement is carried out to some technical characteristics；Without departing from this hair
The spirit of bright technical solution should all cover in the claimed technical solution range of the present invention.
Claims (3)
1. a kind of preparation method of ammonium fluoride, includes the following steps：
Albite decomposes：By albite, fluorite, 98% sulfuric acid according to 1：(1.55~2.57)：The quality of (3.28~4.62)
Than mixing, and gaseous products of the reaction generation containing silicon fluoride under 100 DEG C~200 DEG C and self-generated pressure；
Gas absorbs hydrolysis：The gaseous products containing silicon fluoride are filtered using dust removal filter；It will be after dust removal and filtration
Gaseous products lead to successively in I and II absorption tower generation hydrolysate be hydrolyzed；
Ammonolysis：The hydrolysate is placed in ammonolysis kettle, it is 7~8 to adjust pH by ammonium hydroxide；Control the ammonolysis temperature in the kettle
It at 27 DEG C~50 DEG C, is aged 2 hours~3 hours after neutralization, Aging Temperature is 30 DEG C~40 DEG C；
Prepare ammonium fluoride product：The ammonia products filtered in the ammonolysis kettle obtain the filtrate containing ammonium fluoride；Contain to described
The filtrate of ammonium fluoride carries out condensing crystallizing, filtering, drying process, obtains ammonium fluoride crystal.
2. the preparation method of ammonium fluoride according to claim 1, it is characterised in that：The step of albite decomposes includes
First the albite and fluorite are preheated 15 minutes~30 minutes at 100 DEG C~200 DEG C, the moisture in raw material is removed, obtains
To dry albite and fluorite raw material；98% sulfuric acid is added in the albite of the drying and fluorite raw material again and is reacted
Obtain solid residue and the gaseous products containing silicon fluoride within 2 hours~5 hours.
3. the preparation method of ammonium fluoride according to claim 1, it is characterised in that：The gas absorbs the step of hydrolyzing and wraps
It includes：The gas reactant forms the hydrolysate after absorbing liquid in the first grade absorption tower is absorbed, hydrolyzed, hydrolysis production
Object enters in level-one concentrated phase collecting tank, and the concentrated phase object which collects, which is transported in ammonolysis kettle, carries out ammonolysis,
In, absorbing liquid in the first grade absorption tower is 10%~30% ethanol water；What the level-one concentrated phase collecting tank was collected
Liquid flooding is returned through pump to first order absorption circulating slot and continues to absorb in first grade absorption tower；It is come out by the first grade absorption tower
Tail gas enter the two-level absorption tower through in the two-level absorption tower absorbing liquid absorb, continue to hydrolyze, the two-level absorption tower
Liquid after hydrolysis enters two level concentrated phase and absorbs slot, the two level concentrated phase absorb the concentrated phase object that slot is collected be transported in ammonolysis kettle into
Row ammonolysis, wherein, the ethanol water that the absorbing liquid in the two-level absorption tower is 10%~30%；The two level concentrated phase is collected
The liquid flooding that slot is collected is returned in the two-level absorption tower through pump to two level absorption cycle slot and continues to absorb；Described in detection
When the fluorinion concentration in silicate fluoride solution in first order absorption circulating slot, the two level absorption cycle slot reaches 10mol/L, inhale
It receives liquid and reaches saturation, the absorbing liquid is also transported in the ammonolysis kettle and carries out ammonolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187371.0A CN108203104A (en) | 2016-12-20 | 2016-12-20 | The preparation method of ammonium fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611187371.0A CN108203104A (en) | 2016-12-20 | 2016-12-20 | The preparation method of ammonium fluoride |
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| Publication Number | Publication Date |
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| CN108203104A true CN108203104A (en) | 2018-06-26 |
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| CN201611187371.0A Pending CN108203104A (en) | 2016-12-20 | 2016-12-20 | The preparation method of ammonium fluoride |
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- 2016-12-20 CN CN201611187371.0A patent/CN108203104A/en active Pending
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180626 |
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