CN111943243A - Method for producing aluminum fluoride by using fluosilicic acid - Google Patents
Method for producing aluminum fluoride by using fluosilicic acid Download PDFInfo
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- CN111943243A CN111943243A CN202010692815.6A CN202010692815A CN111943243A CN 111943243 A CN111943243 A CN 111943243A CN 202010692815 A CN202010692815 A CN 202010692815A CN 111943243 A CN111943243 A CN 111943243A
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 title claims abstract description 77
- 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 75
- 239000002253 acid Substances 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000013078 crystal Substances 0.000 claims abstract description 47
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 32
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 23
- TXBSWQWDLFJQMU-UHFFFAOYSA-N 4-(chloromethyl)-1,2-diethoxybenzene Chemical compound CCOC1=CC=C(CCl)C=C1OCC TXBSWQWDLFJQMU-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 43
- 239000007789 gas Substances 0.000 description 33
- 239000000377 silicon dioxide Substances 0.000 description 32
- 235000012239 silicon dioxide Nutrition 0.000 description 30
- 239000007788 liquid Substances 0.000 description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 229910004074 SiF6 Inorganic materials 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002426 superphosphate Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
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
- C01P2006/10—Solid density
Abstract
The invention provides a method for producing aluminum fluoride by using fluosilicic acid, which comprises the following steps: preheating fluorosilicic acid solution to 75-80 ℃; adding aluminum hydroxide particles into the heated fluosilicic acid solution for heating reaction, wherein the reaction temperature is controlled to be 95-105 ℃ in the heating reaction process, and mixed slurry is obtained after the reaction is finished; filtering and washing the obtained mixed slurry to obtain filtrate, and crystallizing the filtrate to obtain aluminum fluoride slurry; centrifuging the obtained aluminum fluoride slurry to obtain aluminum fluoride trihydrate crystals; drying, calcining and cooling the obtained aluminum fluoride trihydrate crystals to obtain the finished product of the anhydrous aluminum fluoride. The production process of the invention has simple process, fully utilizes the raw materials by strictly controlling the temperature and time of each step, and improves the reaction rate to the maximum extent.
Description
Technical Field
The invention relates to the technical field of aluminum fluoride production, in particular to a method for producing aluminum fluoride by utilizing fluosilicic acid.
Background
Aluminum fluoride is one of important inorganic fluoride products, and is mainly used in the aluminum smelting industry and the fine chemical industry field. The production method of the aluminum fluoride mainly comprises two methods, one method is that fluorite is decomposed by sulfuric acid to generate hydrofluoric acid, and then the hydrofluoric acid reacts with aluminum hydroxide to prepare the aluminum fluoride; the other is that fluosilicic acid which is a byproduct in producing phosphate fertilizers such as phosphoric acid, triple superphosphate, superphosphate and the like by an acid method in phosphate fertilizer industry reacts with aluminum hydroxide to obtain wet aluminum fluoride, and the wet aluminum fluoride is dried, satin-burned and cooled to obtain aluminum fluoride products.
Disclosure of Invention
In view of the above, the invention provides a method for producing aluminum fluoride by using fluosilicic acid, which has a simple process.
The invention provides a method for producing aluminum fluoride by using fluosilicic acid, which comprises the following steps:
s1, preheating the fluorosilicic acid solution to 75-80 ℃ by using steam; the reaction of the fluosilicic acid and the aluminum hydroxide is exothermic, and the reaction is not favorably carried out at too low or too high temperature;
s2, adding aluminum hydroxide particles into the heated fluosilicic acid solution for heating reaction, wherein the reaction temperature is controlled to be 95-105 ℃ in the heating reaction process, and mixed slurry is obtained after the reaction is finished; when the reaction temperature is 95-105 ℃, the reaction rate can be improved to the maximum extent;
s3, filtering and washing the obtained mixed slurry to obtain silicon dioxide solids and filtrate, stacking the silicon dioxide solids in a concentrated manner, and crystallizing the filtrate to obtain aluminum fluoride slurry;
s4, centrifuging the obtained aluminum fluoride slurry to obtain aluminum fluoride trihydrate crystals;
and S5, drying, calcining and cooling the obtained aluminum fluoride trihydrate crystals to obtain the finished anhydrous aluminum fluoride.
Further, the mass concentration of the fluorosilicic acid solution is 15% -20%, and the mass ratio of the usage amount of the fluorosilicic acid solution to the aluminum hydroxide particles is 4: 1-6: 1. The greater the concentration of the fluorosilicic acid solution, the shorter the complete reaction time of the aluminum hydroxide particles, but if the fluorosilicic acid solution is presentIf the concentration of the liquid is too high, the reaction is too strong, the concentration of the aluminum fluoride in the obtained mixed slurry is high, more crystals can be separated out before filtration, and the crystals and the silicon dioxide filter cake are brought out together, so that the loss of the aluminum fluoride is caused, and the yield of the product is reduced; on the contrary, the concentration of the fluorosilicic acid solution is too low, and SiO is generated2The crystals are fine and difficult to filter. Therefore, the method controls the mass concentration of the fluorosilicic acid solution to be 15-20%.
Further, the particle size of the aluminum hydroxide particles is less than 100 mesh. During the heating reaction process, the reaction rate of the aluminum hydroxide particles is inversely proportional to the radius of the particles; the larger the radius of the particles, the longer the complete reaction time of the particles, which indicates poor reactivity of the large particles, and thus the method controls the particle size of the aluminum hydroxide particles to be 100 mesh or less.
Further, in step S2, the pH value of the heating reaction is 1.2 to 1.8. The pH is too low, the consumption of fluosilicic acid is increased, and the silicon dioxide particles become thin; the pH value is too high, the consumption of aluminum hydroxide is increased, the reaction environment is optimal when the pH value is 1.2-1.8, and the consumption of fluosilicic acid and aluminum hydroxide is at the optimal level.
Further, in the step S2, the heating reaction time is 13-17 minutes, if the reaction time is too short, the reaction is insufficient, and the silicon content in the mother liquor is high; if the reaction time is too long, the amount of aluminum fluoride precipitated in the reaction step increases, and the yield of aluminum fluoride is finally affected.
Further, in step S3, the temperature of crystallization is controlled to be 95-105 ℃ by introducing steam, the crystallization time is 4.5-5 h, and pure, large enough and uniform aluminum fluoride trihydrate crystals can be obtained through crystallization. In the crystallization process, if the temperature is too high, the steam consumption is large; if the temperature is too low, another crystal form of high-solubility aluminum fluoride trihydrate (alpha form) is easily generated, and the crystallization and the final yield of the product are influenced. If the crystallization time is too short, the crystallization is insufficient, and the yield of aluminum fluoride and the size of crystal particles are influenced; too long a crystallization time wastes time and resources.
Further, in step S4, the mass content of water in the aluminum fluoride trihydrate crystal is controlled to be less than or equal to 12%, the water content is too high, and the water and the fluoride in the calcining process can be mixedAluminum generates side reaction, the content and the impurity amount of aluminum fluoride are influenced, the finished aluminum fluoride product is not up to standard, and the specific control mode is as follows: at a distance of 0.5m during centrifugation3The water is added for washing or the centrifugal time is prolonged according to the water content of the aluminum fluoride slurry.
Further, in step S5, the drying temperature is 140 ℃ to 220 ℃, the calcining temperature is 400 ℃ to 650 ℃, and the temperature of the obtained aluminum fluoride finished product is less than 50 ℃. Because aluminum fluoride and water generate side reaction at 300-400 ℃ to generate aluminum oxide and HF, the side reaction reduces the yield of aluminum fluoride and increases the impurity content of the product, and the dissipated HF acid mist can corrode equipment and pollute the environment. Therefore, the drying temperature is controlled between 140 ℃ and 220 ℃, the calcining temperature is controlled between 400 ℃ and 650 ℃, and the temperature in the drying process and the moisture in the calcining process can not reach the standards of side reactions.
Further, in step S5, the ignition loss of the anhydrous aluminum fluoride finished product is less than or equal to 2.5%, and if the ignition loss is too high, the calcination of the aluminum fluoride is insufficient, the content of crystal water is high, and the product quality is unqualified.
The reaction process of the fluosilicic acid and the aluminum hydroxide is as follows: firstly, generating aluminum fluosilicate, wherein the reaction is accompanied with heat release, then the aluminum fluosilicate is decomposed to form aluminum fluoride, silicon dioxide and hydrofluoric acid, the hydrofluoric acid continuously reacts with the aluminum hydroxide to obtain the aluminum fluoride, and the stepwise reaction equation is as follows:
3H2SiF6+2Al(OH)3＝Al2(SiF6)3+6H2O
Al2(SiF6)3+6H2O＝3SiO2↓+2AlF3+12HF
6HF+2Al(OH)3＝2AlF3+6H2O
the overall reaction equation: h2SiF6+2Al(OH)3＝SiO2↓+2AlF3+4H2O
The technical scheme provided by the invention has the beneficial effects that: the method provided by the invention takes fluosilicic acid and aluminum hydroxide as raw materials, silicon dioxide precipitates are separated out through direct heating reaction, after the silicon dioxide is removed through filtration, aluminum fluoride mother liquor is obtained through separation, steam is heated for crystallization, aluminum fluoride trihydrate crystals are obtained after solid-liquid separation, and final products are obtained through drying and calcining.
Drawings
FIG. 1 is a schematic flow diagram of a process for producing aluminum fluoride using fluorosilicic acid in accordance with the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings and examples.
In the following examples, the fluosilicic acid used meets the index of qualified products in the national standard HG/T2832-2008 of industrial fluosilicic acid, and the mass concentration of the fluosilicic acid solution is 15-20%; the aluminium hydroxide used meets the requirements of national standard GBT4294-2010, Al (OH)3The content is more than or equal to 99.6 percent.
Example 1:
preheating a fluorosilicic acid solution with the mass concentration of 15.5% to 75 ℃ by using steam, adding 4530.77 tons of the heated fluorosilicic acid solution into a reaction tank, then weighing 808.93 tons of aluminum hydroxide particles with the particle size of less than 100 meshes, adding the aluminum hydroxide particles into the reaction tank for heating reaction, reacting the fluorosilicic acid with aluminum hydroxide in the reaction tank, maintaining the reaction temperature in the reaction tank at 95-105 ℃, maintaining the pH value in the reaction tank at 1.2-1.8, reacting for 15 minutes, and obtaining mixed slurry after the reaction is finished; discharging the mixed slurry to a silicon dioxide belt filter for filtering and washing, directly discharging separated silicon dioxide solids to a silicon dioxide storage yard, respectively adding filtrate into eight recycled crystallization tanks through an aluminum fluoride solution distributor, sending reaction tail gas to a reaction tail gas washing tower for treatment, simultaneously washing residual silicon dioxide on filter cloth by using clear water, carrying out filter pressing on obtained washing water through a plate and frame filter press, enabling filter cakes to enter the silicon dioxide storage yard, enabling clear liquid to enter the clear liquid tank, recycling a part of the clear liquid as filter cloth washing water of the belt filter, and sending the other part of the clear liquid to the tail gas washing tower for water supplement; introducing steam into the crystallization tank to control the crystallization temperature to be 95-105 ℃, and crystallizing for 4.5h to obtain aluminum fluoride slurry; adding the aluminum fluoride slurry into a centrifuge for centrifugation to obtain 1346.03 tons of aluminum fluoride trihydrate crystals (the water content is less than or equal to 12%) meeting the water content requirement, and concentrating the waste liquid; feeding the aluminum fluoride trihydrate crystals into a dryer, preheating and drying the crystals in the dryer by tail gas of a calcining kiln to remove free water and part of crystal water, wherein the drying temperature is about 180 ℃, then feeding the crystals into the calcining kiln heated by high-temperature gas obtained by calcining natural gas, calcining the crystals in the calcining kiln to remove the crystal water, the calcining temperature is about 450 ℃, after calcining, feeding the crystals into a cooler to cool until the final temperature is reduced to below 50 ℃ to obtain a finished product of anhydrous aluminum fluoride, dedusting the dried tail gas by a cyclone dust collector and a bag-type dust collector, feeding the tail gas to a dry tail gas washing tower to wash and discharge after reaching the standard.
The preparation scheme of example 1 is schematically shown in FIG. 1.
Example 1 totally 819.32 tons of anhydrous aluminum fluoride finished product was obtained, the yield of anhydrous aluminum fluoride was 94.05%, 292.61 tons of silica was obtained, and about 3.93 tons of wastewater was generated.
Example 2:
preheating a fluorosilicic acid solution with the mass concentration of 16% to 75 ℃ by using steam, adding 4549.7718 tons of the heated fluorosilicic acid solution into a reaction tank, then weighing 838.41 tons of aluminum hydroxide particles with the particle size of less than 100 meshes, adding the aluminum hydroxide particles into the reaction tank for heating reaction, reacting the fluorosilicic acid with the aluminum hydroxide in the reaction tank, maintaining the reaction temperature in the reaction tank at 95-105 ℃, maintaining the pH value in the reaction tank at 1.2-1.8, reacting for 16 minutes, and obtaining mixed slurry after the reaction is finished; discharging the mixed slurry to a silicon dioxide belt filter for filtering and washing, directly discharging separated silicon dioxide solids to a silicon dioxide storage yard, respectively adding filtrate into eight recycled crystallization tanks through an aluminum fluoride solution distributor, sending reaction tail gas to a reaction tail gas washing tower for treatment, simultaneously washing residual silicon dioxide on filter cloth by using clear water, carrying out filter pressing on obtained washing water through a plate and frame filter press, enabling filter cakes to enter the silicon dioxide storage yard, enabling clear liquid to enter the clear liquid tank, recycling a part of the clear liquid as filter cloth washing water of the belt filter, and sending the other part of the clear liquid to the tail gas washing tower for water supplement; introducing steam into the crystallization tank to control the crystallization temperature to be 95-105 ℃, and crystallizing for 5 hours to obtain aluminum fluoride slurry; adding the aluminum fluoride slurry into a centrifuge for centrifugation to obtain 1395.09 tons of aluminum fluoride trihydrate crystals (the water content is less than or equal to 12%) meeting the water content requirement, and concentrating the waste liquid; feeding the aluminum fluoride trihydrate crystals into a dryer, preheating and drying the crystals in the dryer by tail gas of a calcining kiln to remove free water and part of crystal water, wherein the drying temperature is about 160 ℃, then feeding the crystals into the calcining kiln heated by high-temperature gas obtained by calcining natural gas, calcining the crystals in the calcining kiln to remove the crystal water, the calcining temperature is about 500 ℃, after calcining, feeding the crystals into a cooler to cool until the final temperature is reduced to below 50 ℃ to obtain a finished product of anhydrous aluminum fluoride, dedusting the dried tail gas by a cyclone dust collector and a bag-type dust collector, feeding the tail gas to a dry tail gas washing tower to wash and discharge after reaching the standard.
Example 2 totally 849.18 tons of anhydrous aluminum fluoride finished product was obtained, the yield of anhydrous aluminum fluoride was 94.05%, 303.28 tons of silicon dioxide was obtained, and about 3.91 tons of wastewater was generated.
Example 3:
preheating 18% of fluosilicic acid solution by using steam to 80 ℃, adding 4623.6 tons of heated fluosilicic acid solution into a reaction tank, then weighing 958.64 tons of aluminum hydroxide particles with the granularity smaller than 100 meshes, adding the aluminum hydroxide particles into the reaction tank for heating reaction, reacting the fluosilicic acid with the aluminum hydroxide in the reaction tank, maintaining the reaction temperature in the reaction tank at 95-105 ℃, maintaining the pH value in the reaction tank at 1.2-1.8, reacting for 14 minutes, and obtaining mixed slurry after the reaction is finished; discharging the mixed slurry to a silicon dioxide belt filter for filtering and washing, directly discharging separated silicon dioxide solids to a silicon dioxide storage yard, respectively adding filtrate into eight recycled crystallization tanks through an aluminum fluoride solution distributor, sending reaction tail gas to a reaction tail gas washing tower for treatment, simultaneously washing residual silicon dioxide on filter cloth by using clear water, carrying out filter pressing on obtained washing water through a plate and frame filter press, enabling filter cakes to enter the silicon dioxide storage yard, enabling clear liquid to enter the clear liquid tank, recycling a part of the clear liquid as filter cloth washing water of the belt filter, and sending the other part of the clear liquid to the tail gas washing tower for water supplement; introducing steam into the crystallization tank to control the crystallization temperature to be 95-105 ℃, and crystallizing for 4.5h to obtain aluminum fluoride slurry; adding the aluminum fluoride slurry into a centrifuge for centrifugation to obtain 1595.14 tons of aluminum fluoride trihydrate crystals (the water content is less than or equal to 12%) meeting the water content requirement, and concentrating the waste liquid; feeding the aluminum fluoride trihydrate crystals into a dryer, preheating and drying the crystals in the dryer by tail gas of a calcining kiln to remove free water and part of crystal water, wherein the drying temperature is about 200 ℃, then feeding the crystals into the calcining kiln heated by high-temperature gas obtained by calcining natural gas, calcining the crystals in the calcining kiln to remove the crystal water, the calcining temperature is about 550 ℃, after calcining, feeding the crystals into a cooler to cool until the final temperature is reduced to below 50 ℃, thus obtaining the anhydrous aluminum fluoride finished product, dedusting the dried tail gas by a cyclone dust collector and a bag-type dust collector, feeding the tail gas to a dry tail gas washing tower to wash and discharge the tail gas after reaching the standard.
Example 3 totally 970.96 tons of anhydrous aluminum fluoride finished product was obtained, the yield of anhydrous aluminum fluoride was 94.05%, 346.77 tons of silicon dioxide was obtained, and about 3.82 tons of wastewater was generated.
Example 4:
preheating a 19.5 mass percent fluosilicic acid solution to 80 ℃ by using steam, adding 4680.4 tons of the heated fluosilicic acid solution into a reaction tank, then weighing 1051.29 tons of aluminum hydroxide particles with the particle size smaller than 100 meshes, adding the aluminum hydroxide particles into the reaction tank for heating reaction, reacting the fluosilicic acid with the aluminum hydroxide in the reaction tank, maintaining the reaction temperature in the reaction tank at 95-105 ℃, maintaining the pH value in the reaction tank at 1.2-1.8, reacting for 15 minutes, and obtaining mixed slurry after the reaction is finished; discharging the mixed slurry to a silicon dioxide belt filter for filtering and washing, directly discharging separated silicon dioxide solids to a silicon dioxide storage yard, respectively adding filtrate into eight recycled crystallization tanks through an aluminum fluoride solution distributor, sending reaction tail gas to a reaction tail gas washing tower for treatment, simultaneously washing residual silicon dioxide on filter cloth by using clear water, carrying out filter pressing on obtained washing water through a plate and frame filter press, enabling filter cakes to enter the silicon dioxide storage yard, enabling clear liquid to enter the clear liquid tank, recycling a part of the clear liquid as filter cloth washing water of the belt filter, and sending the other part of the clear liquid to the tail gas washing tower for water supplement; introducing steam into the crystallization tank to control the crystallization temperature to be 95-105 ℃, and crystallizing for 4.5h to obtain aluminum fluoride slurry; adding the aluminum fluoride slurry into a centrifuge for centrifugation to obtain 1749.30 tons of aluminum fluoride trihydrate crystals (the water content is less than or equal to 12%) meeting the water content requirement, and concentrating the waste liquid; feeding the aluminum fluoride trihydrate crystals into a dryer, preheating and drying the crystals in the dryer by tail gas of a calcining kiln to remove free water and part of crystal water, wherein the drying temperature is about 145 ℃, then feeding the crystals into the calcining kiln heated by high-temperature gas obtained by calcining natural gas, calcining the crystals in the calcining kiln to remove the crystal water, the calcining temperature is about 600 ℃, after calcining, feeding the crystals into a cooler to cool until the final temperature is reduced to below 50 ℃ to obtain a finished product of anhydrous aluminum fluoride, dedusting the dried tail gas by a cyclone dust collector and a bag-type dust collector, feeding the tail gas to a dry tail gas washing tower to wash and discharge after reaching the standard.
Example 4 totally 1064.79 tons of anhydrous aluminum fluoride finished product was obtained, the yield of anhydrous aluminum fluoride was 94.05%, 380.28 tons of silicon dioxide was obtained, and about 3.75 tons of wastewater was generated.
The chemical component analysis and the physical property detection of the anhydrous aluminum fluoride finished products obtained in the embodiments 1 to 4 show that the anhydrous aluminum fluoride finished products obtained in the embodiments 1 to 4 meet the requirements AF-2 of the national standard GB/T4292-2017 on wet aluminum fluoride, and the requirements of the national standard GB/T4292-2017 on aluminum fluoride are shown in Table 1:
table 1: requirements for aluminium fluoride in national standard GB/T4292-2017
The features of the embodiments and embodiments described herein above may be combined with each other without conflict.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A method for producing aluminum fluoride by utilizing fluosilicic acid is characterized by comprising the following steps:
s1, preheating the fluorosilicic acid solution to 75-80 ℃;
s2, adding aluminum hydroxide particles into the heated fluosilicic acid solution for heating reaction, wherein the reaction temperature is controlled to be 95-105 ℃ in the heating reaction process, and mixed slurry is obtained after the reaction is finished;
s3, filtering and washing the obtained mixed slurry to obtain filtrate, and crystallizing the filtrate to obtain aluminum fluoride slurry;
s4, centrifuging the obtained aluminum fluoride slurry to obtain aluminum fluoride trihydrate crystals;
and S5, drying, calcining and cooling the obtained aluminum fluoride trihydrate crystals to obtain the finished anhydrous aluminum fluoride.
2. The method for producing aluminum fluoride by using fluosilicic acid according to claim 1, wherein the mass concentration of the fluosilicic acid solution is 15-20%, and the mass ratio of the usage amount of the fluosilicic acid solution to the aluminum hydroxide particles is 4: 1-6: 1.
3. The method for producing aluminum fluoride by using fluosilicic acid as claimed in claim 1, wherein the particle size of the aluminum hydroxide particles is less than 100 mesh.
4. The method for producing aluminum fluoride by using fluosilicic acid according to claim 1, wherein in the step S2, the pH value of the heating reaction is 1.2 to 1.8.
5. The method for producing aluminum fluoride by using fluosilicic acid according to claim 1, wherein in the step S2, the heating reaction time is 13 to 17 minutes.
6. The method for producing aluminum fluoride by using fluosilicic acid according to claim 1, wherein in the step S3, the crystallization temperature is 95-105 ℃ and the crystallization time is 4.5-5 h.
7. The method for producing aluminum fluoride by using fluosilicic acid according to claim 1, wherein in the step S5, the drying temperature is 140 ℃ to 220 ℃, the calcining temperature is 400 ℃ to 650 ℃, and the temperature of the aluminum fluoride finished product obtained after cooling is less than 50 ℃.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114149018A (en) * | 2021-12-10 | 2022-03-08 | 云南云天化氟化学有限公司 | Low-density aluminum fluoride drying process |
| CN114180609A (en) * | 2021-12-10 | 2022-03-15 | 云南云天化氟化学有限公司 | Aluminum fluoride standby production line and process flow |
| CN115010157A (en) * | 2022-06-22 | 2022-09-06 | 中石化南京工程有限公司 | System and method for producing anhydrous aluminum fluoride by using fluosilicic acid |
| CN115196660A (en) * | 2022-06-22 | 2022-10-18 | 中石化南京工程有限公司 | Method and system for producing cryolite from fluosilicic acid |
| CN115650272A (en) * | 2022-11-04 | 2023-01-31 | 湖北宜氟特环保科技有限公司 | Production method for producing aluminum fluoride by using fluosilicic acid as raw material |
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| CN108017077A (en) * | 2017-12-11 | 2018-05-11 | 达州励志环保科技有限公司 | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio |
| CN110316749A (en) * | 2019-07-10 | 2019-10-11 | 昆明川金诺化工股份有限公司 | A kind of method of fluosilicic acid direct method production aluminum fluoride |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108017077A (en) * | 2017-12-11 | 2018-05-11 | 达州励志环保科技有限公司 | A kind of method for producing aluminum fluoride coproduction cryolite with high molecular ratio |
| CN110316749A (en) * | 2019-07-10 | 2019-10-11 | 昆明川金诺化工股份有限公司 | A kind of method of fluosilicic acid direct method production aluminum fluoride |
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114149018A (en) * | 2021-12-10 | 2022-03-08 | 云南云天化氟化学有限公司 | Low-density aluminum fluoride drying process |
| CN114180609A (en) * | 2021-12-10 | 2022-03-15 | 云南云天化氟化学有限公司 | Aluminum fluoride standby production line and process flow |
| CN115010157A (en) * | 2022-06-22 | 2022-09-06 | 中石化南京工程有限公司 | System and method for producing anhydrous aluminum fluoride by using fluosilicic acid |
| CN115196660A (en) * | 2022-06-22 | 2022-10-18 | 中石化南京工程有限公司 | Method and system for producing cryolite from fluosilicic acid |
| CN115650272A (en) * | 2022-11-04 | 2023-01-31 | 湖北宜氟特环保科技有限公司 | Production method for producing aluminum fluoride by using fluosilicic acid as raw material |
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