CN106966418A - A kind of low-density aluminum fluoride and its production technology - Google Patents
A kind of low-density aluminum fluoride and its production technology Download PDFInfo
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- CN106966418A CN106966418A CN201710345885.2A CN201710345885A CN106966418A CN 106966418 A CN106966418 A CN 106966418A CN 201710345885 A CN201710345885 A CN 201710345885A CN 106966418 A CN106966418 A CN 106966418A
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- aluminum fluoride
- low
- density aluminum
- acid
- warming
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 title claims abstract description 59
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 28
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000010792 warming Methods 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 18
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 230000011218 segmentation Effects 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 2
- 239000001099 ammonium carbonate Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001398 aluminium Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910001749 rosenbergite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009866 aluminium metallurgy Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/16—Pore diameter
Abstract
The invention discloses a kind of low-density aluminum fluoride and its production technology, comprise the following steps：S1, in the retort equipped with fluosilicic acid, template is added to be well mixed, 45~50 DEG C are heated to, sodium acid carbonate is added portionwise, when sodium acid carbonate addition is total amount 1/3rd, add sulfuric acid, 80~90 DEG C are warming up to, and adds sodium acid carbonate, 1~1.5h is reacted, filtering, washing takes filtrate to obtain reaction solution 1；S2, reaction solution 1 is heated to 60~65 DEG C, Aluminium chloride hexahydrate is added under agitation, 0.5~1h is reacted, template is added, is warming up to 90~95 DEG C, is concentrated to give crystallization and obtains wet stock；S3, wet stock is dried at 70~80 DEG C after carry out sectional temperature-controlled calcining and obtain low-density aluminum fluoride, calcining heat is 300~600 DEG C.Using fluosilicic acid, ammonium hydrogen carbonate and Aluminium chloride hexahydrate as raw material, it with the addition of template and coordinate sectional temperature-controlled calcining, improve the specific surface area of aluminum fluoride, reduce the density of product, improve reactivity.
Description
Technical field
The present invention relates to aluminum fluoride preparing technical field, more particularly to a kind of low-density aluminum fluoride and its production technology.
Background technology
Aluminum fluoride is mainly used in aluminium metallurgy industry and field of fine chemical as one of important inorganic fluoride product.Fluorine
The production method for changing aluminium is broadly divided into two classes, and a class is that metallurgical industry is used till today with sulfuric acid decomposition fluorite generation hydrofluoric acid, then
Aluminum fluoride is made with aluminium hydroxide reaction；Another kind of is Phosphate Fertilizer Industry acid technological process production phosphate fertilizer such as phosphoric acid money, weight peroxophosphoric acid
The fluosilicic acid of the by-products such as calcium, calcium superphosphate, aluminum fluoride wet feed is obtained with aluminium hydroxide reaction, then is burnt through drying, satin, cooled down and make
Obtain aluminium fluoride product.
Fluosilicic acid direct method production aluminum fluoride achieves larger success abroad, but the aluminum fluoride produced at present is close
Degree is larger, and specific surface area is smaller.AlF3It is to be used for F/Cl exchange reactions while having strong L acid due to stable in HF environment
Preferred material, AlF3Catalytic reaction activity it is closely related, and high-specific surface area be increase catalytic activity premise.Therefore,
High-specific surface area, low-density aluminum fluoride is prepared to cause concern and pay attention to.
The content of the invention
The present invention proposes a kind of low-density aluminum fluoride and its production technology, with fluosilicic acid, ammonium hydrogen carbonate and six hydration chlorine
Change aluminium is raw material, prepares high-specific surface area, low-density aluminum fluoride.
A kind of production technology of low-density aluminum fluoride proposed by the present invention, comprises the following steps：
S1, in the retort equipped with fluosilicic acid, add template be well mixed, be heated to 45~50 DEG C, be added portionwise
Sodium acid carbonate, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 80~90 DEG C, and add carbonic acid
Hydrogen sodium, reacts 1~1.5h, filters to take filtrate and obtain reaction solution 1；
S2, reaction solution 1 is heated to 60~65 DEG C, Aluminium chloride hexahydrate added under agitation, 0.5~1h is reacted,
Template is added, 90~95 DEG C is warming up to, is concentrated to give crystallization and obtains wet stock；
S3, wet stock is dried at 70~80 DEG C after carry out sectional temperature-controlled calcining and obtain low-density aluminum fluoride, calcining temperature
Spend for 300~600 DEG C.
Preferably, in S1, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6~6.5.
Preferably, in S2, the weight ratio of template and fluosilicic acid is 2~3：100.
Preferably, in S1, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.5~0.6：100.
Preferably, in S2, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2~2.2：1.
Preferably, in S2, the weight ratio of template and Aluminium chloride hexahydrate is 4~6：100.
Preferably, in S3, sectional temperature-controlled calcining is concretely comprised the following steps：Room temperature is in warming-up section between 350 DEG C, heating rate
For 3 DEG C/min, temperature reaches constant temperature 3h after 350 DEG C, in 350 DEG C to 500 DEG C warming-up sections, and heating rate is 2 DEG C/min, temperature
Constant temperature 3h after 500 DEG C is reached, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 1 DEG C/min, and temperature reaches permanent after 600 DEG C
Warm 1h.
Preferably, template is one or both of triethanolamine, polyethylene glycol, polyvinyl alcohol thing mixed above.
The present invention proposes a kind of low-density aluminum fluoride, is made by the production technology of low-density aluminum fluoride.
Preferably, the specific surface area of low-density aluminum fluoride is 95~150m2/ g, aperture is 18~25nm.
The present invention obtains ammonium fluoride solution using fluosilicic acid and sodium acid carbonate as raw material reaction, and sodium acid carbonate is added in batches and is kept away
Precipitation of silica is exempted from and the substantial amounts of generation of carbon dioxide causes supersaturation to cause the splashing of liquid, carbon is added after adding sulfuric acid
Sour hydrogen sodium ensures that silicon is fully converted to silica precipitation, reduces silicone content in aluminium fluoride product and ensures product purity；Add mould
Plate agent is acted on of both primarily serving, on the one hand in S1, the silica that template absorption is separated out, and is conducive to silica
Following process utilize, while reducing the loss of ammonium fluoride during washing, improve the yield of fluorine element；On the other hand, it is dense
When sheepshank is brilliant, template contains nitrogen-atoms and oxygen atom, it is easy to which coordination occurs for aluminium atom, while template is with stronger
Structure-directing effect, and molecular proportion is larger, can occupy larger space, aluminum fluoride molecule is crystallized around template,
Removed in calcination stage template and obtain porous fluorinated aluminium, the specific surface area and density of aluminum fluoride greatly improved；Using segmentation
Temperature control calcine technology, using three sections of temperature programmings, early stage slowly heats up, and the crystallization water of aluminum fluoride is removed, while avoiding excessively waving
Hair, programming rate is improved in the crystal transformation stage in later stage, accelerates α~AlF3·3H2O is to β~AlF3·3H2O changes to form coarse-grain
Grain, then reduces programming rate, and the porous fluorinated aluminium stablized is incubated again.
Embodiment
Below, technical scheme is described in detail by specific embodiment.
Embodiment 1
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, add template be well mixed, be heated to 45 DEG C, carbonic acid be added portionwise
Hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 90 DEG C, and adds sodium acid carbonate, reacts
1h, filtering, washing takes filtrate to obtain reaction solution 1；
S2, reaction solution 1 is heated to 60 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, template is added
Agent, is warming up to 95 DEG C, is concentrated to give crystallization and obtains wet stock；
S3, by wet stock at 80 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C.
Embodiment 2
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, add template be well mixed, be heated to 50 DEG C, carbonic acid be added portionwise
Hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 80 DEG C, and adds sodium acid carbonate, reacts
1.5h, filtering, washing takes filtrate to obtain reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6, template and fluorine
The weight ratio of silicic acid is 2：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.5：100；
S2, reaction solution 1 is heated to 65 DEG C, Aluminium chloride hexahydrate is added under agitation, 0.5h is reacted, template is added
Agent, is warming up to 90 DEG C, is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2：1,
The weight ratio of template and Aluminium chloride hexahydrate is 4：100；
S3, by wet stock at 70 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C.
Embodiment 3
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, add polyethylene glycol be well mixed, be heated to 48 DEG C, carbon be added portionwise
Sour hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 85 DEG C, and adds sodium acid carbonate, instead
1.5h is answered, is filtered, washing takes filtrate to obtain reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6.5, poly- second two
The weight ratio of alcohol and fluosilicic acid is 3：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.6：100；
S2, reaction solution 1 is heated to 63 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, poly- second two is added
Alcohol, is warming up to 92 DEG C, is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2.2：
1, the weight ratio of polyethylene glycol and Aluminium chloride hexahydrate is 6：100；
S3, by wet stock at 75 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C, sectional temperature-controlled calcining is concretely comprised the following steps：Room temperature in warming-up section between 350 DEG C, heating rate is 2 DEG C/
Min, temperature reaches constant temperature 2h after 350 DEG C, in 350 DEG C to 500 DEG C warming-up sections, and heating rate is 3 DEG C/min, and temperature reaches
Constant temperature 3h after 500 DEG C, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 2 DEG C/min, and temperature reaches constant temperature 1h after 600 DEG C.
Embodiment 4
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, add triethanolamine be well mixed, be heated to 48 DEG C, carbon be added portionwise
Sour hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 85 DEG C, and adds sodium acid carbonate, instead
1.5h is answered, is filtered, washing takes filtrate to obtain reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6.3, three ethanol
The weight ratio of amine and fluosilicic acid is 2.5：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.55：
100；
S2, reaction solution 1 is heated to 63 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, three ethanol are added
Amine, is warming up to 92 DEG C, is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2.1：
1, the weight ratio of triethanolamine and Aluminium chloride hexahydrate is 5：100；
S3, by wet stock at 75 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C, sectional temperature-controlled calcining is concretely comprised the following steps：Room temperature in warming-up section between 350 DEG C, heating rate is 2 DEG C/
Min, temperature reaches constant temperature 4h after 350 DEG C, in 350 DEG C to 500 DEG C warming-up sections, and heating rate is 3 DEG C/min, and temperature reaches
Constant temperature 2h after 500 DEG C, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 2 DEG C/min, and temperature reaches constant temperature after 600 DEG C
1.5h。
Embodiment 5
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, it is uniform to add polyvinyl alcohol, is heated to 48 DEG C, carbon is added portionwise
Sour hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 85 DEG C, and adds sodium acid carbonate, instead
1.5h is answered, is filtered, washing takes filtrate to obtain reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6.3, polyethylene
The weight ratio of alcohol and fluosilicic acid is 2.5：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.55：
100；
S2, reaction solution 1 is heated to 63 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, polyethylene is added
Alcohol, is warming up to 92 DEG C, is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2.1：
1, the weight ratio of polyvinyl alcohol and Aluminium chloride hexahydrate is 5：100；
S3, by wet stock at 75 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C, sectional temperature-controlled calcining is concretely comprised the following steps：Room temperature in warming-up section between 350 DEG C, heating rate is 2 DEG C/
Min, temperature reaches constant temperature 3h after 350 DEG C, in 350 DEG C to 500 DEG C warming-up sections, and heating rate is 3 DEG C/min, and temperature reaches
Constant temperature 2.5h after 500 DEG C, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 2 DEG C/min, and temperature reaches constant temperature after 600 DEG C
1h。
Embodiment 6
A kind of low-density aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, add polyethylene glycol be well mixed, be heated to 48 DEG C, carbon be added portionwise
Sour hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 85 DEG C, and adds sodium acid carbonate, instead
1.5h is answered, is filtered, washing takes filtrate to obtain reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6.3, poly- second two
The weight ratio of alcohol and fluosilicic acid is 2.5：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.55：
100；
S2, reaction solution 1 is heated to 63 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, poly- second two is added
Alcohol, is warming up to 92 DEG C, is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2.1：
1, the weight ratio of polyethylene glycol and Aluminium chloride hexahydrate is 5：100；
S3, by wet stock at 75 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C, sectional temperature-controlled calcining is concretely comprised the following steps：Room temperature in warming-up section between 350 DEG C, heating rate is 2 DEG C/
Min, temperature reaches constant temperature 3h after 350 DEG C, in 350 DEG C to 500 DEG C warming-up sections, and heating rate is 3 DEG C/min, and temperature reaches
Constant temperature 2.5h after 500 DEG C, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 2 DEG C/min, and temperature reaches constant temperature after 600 DEG C
1h。
Reference examples
A kind of aluminum fluoride, is made by following steps：
S1, in the retort equipped with fluosilicic acid, be heated to 48 DEG C, sodium acid carbonate be added portionwise, sodium acid carbonate add
When measuring as total amount 1/3rd, sulfuric acid is added, 85 DEG C are warming up to, and adds sodium acid carbonate, 1.5h is reacted, filtering, washing takes filter
Liquid obtains reaction solution 1, wherein, the mol ratio of fluosilicic acid and sodium acid carbonate is 1：6.3, the weight ratio of polyethylene glycol and fluosilicic acid is
2.5：100, the concentration of sulfuric acid is 98wt%, and the mol ratio of sulfuric acid and sodium acid carbonate is 0.55：100；
S2, reaction solution 1 is heated to 63 DEG C, Aluminium chloride hexahydrate is added under agitation, 1h is reacted, is warming up to 92
DEG C, it is concentrated to give crystallization and obtains wet stock, wherein, the mol ratio of Aluminium chloride hexahydrate and fluosilicic acid is 2.1：1, polyethylene glycol with
The weight ratio of Aluminium chloride hexahydrate is 5：100；
S3, by wet stock at 75 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C.
The obtained low-density aluminum fluorides of 4-6 will be implemented and carry out performance test with the obtained aluminum fluoride of reference examples, test result is as follows
It is shown：
| Performance | Embodiment 4 | Embodiment 5 | Embodiment 6 | Reference examples |
| Specific surface area/(m2/g) | 132 | 148 | 150 | 50 |
| Aperture/nm | 24 | 23 | 20 | - |
From performance data it can be seen that the present invention, the present invention adds template and coordinates sectional temperature-controlled calcining, it greatly improved
The specific surface area of aluminum fluoride, reduces the density of product, improves reactivity.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (10)
1. a kind of production technology of low-density aluminum fluoride, it is characterised in that comprise the following steps：
S1, in the retort equipped with fluosilicic acid, add template be well mixed, be heated to 45~50 DEG C, carbonic acid be added portionwise
Hydrogen sodium, when sodium acid carbonate addition is total amount 1/3rd, adds sulfuric acid, is warming up to 80~90 DEG C, and adds sodium acid carbonate,
1~1.5h is reacted, filtering, washing takes filtrate to obtain reaction solution 1；
S2, reaction solution 1 is heated to 60~65 DEG C, Aluminium chloride hexahydrate is added under agitation, 0.5~1h is reacted, added
Template, is warming up to 90~95 DEG C, is concentrated to give crystallization and obtains wet stock；
S3, by wet stock at 70~80 DEG C dry after carry out it is sectional temperature-controlled calcining obtain low-density aluminum fluoride, calcining heat is
300~600 DEG C.
2. the production technology of low-density aluminum fluoride according to claim 1, it is characterised in that in S1, fluosilicic acid and carbonic acid
The mol ratio of hydrogen sodium is 1：6~6.5.
3. the production technology of low-density aluminum fluoride according to claim 1 or 2, it is characterised in that in S1, template and fluorine
The weight ratio of silicic acid is 2~3：100.
4. the production technology of the low-density aluminum fluoride according to claim any one of 1-3, it is characterised in that in S1, sulfuric acid
Concentration be 98wt%, the mol ratio of sulfuric acid and sodium acid carbonate is 0.5~0.6：100.
5. the production technology of the low-density aluminum fluoride according to claim any one of 1-4, it is characterised in that in S2, six water
The mol ratio for closing aluminium chloride and fluosilicic acid is 2~2.2：1.
6. the production technology of the low-density aluminum fluoride according to claim any one of 1-5, it is characterised in that in S2, template
The weight ratio of agent and Aluminium chloride hexahydrate is 4~6：100.
7. the production technology of the low-density aluminum fluoride according to claim any one of 1-6, it is characterised in that in S3, segmentation
What temperature control was calcined concretely comprises the following steps：Room temperature is in warming-up section between 350 DEG C, and heating rate is 2 DEG C/min, and temperature reaches 350 DEG C
2~4h of constant temperature afterwards, in 350 DEG C to 500 DEG C warming-up sections, heating rate is 3 DEG C/min, temperature reach constant temperature 2 after 500 DEG C~
3h, in 500 DEG C to 600 DEG C warming-up sections, heating rate is 2 DEG C/min, and temperature reaches 1~1.5h of constant temperature after 600 DEG C.
8. the production technology of the low-density aluminum fluoride according to claim any one of 1-7, it is characterised in that template is three
One or both of monoethanolamine, polyethylene glycol, polyvinyl alcohol thing mixed above.
9. a kind of low-density aluminum fluoride, it is characterised in that as the life of the low-density aluminum fluoride described in any one of claim 1~8
Production. art is made.
10. low-density aluminum fluoride according to claim 9, it is characterised in that the specific surface area of low-density aluminum fluoride is 95
~150m2/ g, aperture is 18~25nm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892161A (en) * | 2018-08-22 | 2018-11-27 | 淮阴师范学院 | The octahedral method of nanometer aluminum fluoride is prepared by raw material of nano aluminum |
| CN109485081A (en) * | 2018-12-29 | 2019-03-19 | 云南云天化氟化学有限公司 | A kind of fluosilicic acid production low-density aluminum fluoride device |
| CN111762805A (en) * | 2020-06-19 | 2020-10-13 | 锦洋高新材料股份有限公司 | Process method for removing low-density aluminum fluoride crystal water |
| CN111807399A (en) * | 2020-07-07 | 2020-10-23 | 锦洋高新材料股份有限公司 | Production process method of low-density aluminum fluoride |
| CN114314624A (en) * | 2021-12-29 | 2022-04-12 | 锦洋高新材料股份有限公司 | Method for removing impurity phosphorus in aluminum fluoride by fluorosilicic acid method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134590A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Method for producing aluminun fluoride with combined production of white carbon black and ammonia sulfate |
| CN101134588A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Method for producing aluminun fluoride |
| CN101654273A (en) * | 2008-08-20 | 2010-02-24 | 湖北富驰化工医药股份有限公司 | Production process for preparing aluminium fluoride by using ammonium bicarbonate |
| CN105597795A (en) * | 2015-11-06 | 2016-05-25 | 西安近代化学研究所 | Preparation method of nanometer aluminum fluoride-based catalyst |
| CN106256429A (en) * | 2015-06-18 | 2016-12-28 | 中化近代环保化工(西安)有限公司 | The aluminum fluoride catalyst of a kind of high-specific surface area and application thereof |
-
2017
- 2017-05-17 CN CN201710345885.2A patent/CN106966418B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134590A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Method for producing aluminun fluoride with combined production of white carbon black and ammonia sulfate |
| CN101134588A (en) * | 2006-09-01 | 2008-03-05 | 多氟多化工股份有限公司 | Method for producing aluminun fluoride |
| CN101654273A (en) * | 2008-08-20 | 2010-02-24 | 湖北富驰化工医药股份有限公司 | Production process for preparing aluminium fluoride by using ammonium bicarbonate |
| CN106256429A (en) * | 2015-06-18 | 2016-12-28 | 中化近代环保化工(西安)有限公司 | The aluminum fluoride catalyst of a kind of high-specific surface area and application thereof |
| CN105597795A (en) * | 2015-11-06 | 2016-05-25 | 西安近代化学研究所 | Preparation method of nanometer aluminum fluoride-based catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892161A (en) * | 2018-08-22 | 2018-11-27 | 淮阴师范学院 | The octahedral method of nanometer aluminum fluoride is prepared by raw material of nano aluminum |
| CN108892161B (en) * | 2018-08-22 | 2020-05-05 | 淮阴师范学院 | Method for preparing nano aluminum fluoride octahedron by using nano aluminum as raw material |
| CN109485081A (en) * | 2018-12-29 | 2019-03-19 | 云南云天化氟化学有限公司 | A kind of fluosilicic acid production low-density aluminum fluoride device |
| CN111762805A (en) * | 2020-06-19 | 2020-10-13 | 锦洋高新材料股份有限公司 | Process method for removing low-density aluminum fluoride crystal water |
| CN111807399A (en) * | 2020-07-07 | 2020-10-23 | 锦洋高新材料股份有限公司 | Production process method of low-density aluminum fluoride |
| CN114314624A (en) * | 2021-12-29 | 2022-04-12 | 锦洋高新材料股份有限公司 | Method for removing impurity phosphorus in aluminum fluoride by fluorosilicic acid method |
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Denomination of invention: A low-density aluminum fluoride and its production process Effective date of registration: 20231204 Granted publication date: 20190201 Pledgee: Ningguo SME financing Company limited by guarantee Pledgor: Jinyang hi tech material Limited by Share Ltd. Registration number: Y2023980069192 |