CN111874932A - Method for controlling phosphorus content in aluminum fluoride production - Google Patents
Method for controlling phosphorus content in aluminum fluoride production Download PDFInfo
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- CN111874932A CN111874932A CN202010808783.1A CN202010808783A CN111874932A CN 111874932 A CN111874932 A CN 111874932A CN 202010808783 A CN202010808783 A CN 202010808783A CN 111874932 A CN111874932 A CN 111874932A
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- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 title claims abstract description 52
- 239000011574 phosphorus Substances 0.000 title claims abstract description 51
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 51
- 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 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000007789 gas Substances 0.000 claims abstract description 81
- 239000002253 acid Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 41
- 238000005406 washing Methods 0.000 claims abstract description 37
- 239000010436 fluorite Substances 0.000 claims abstract description 36
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000003595 mist Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 2
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/192—Preparation from fluorspar
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
- C01B7/195—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the technical field of aluminum fluoride preparation, and particularly relates to a method for controlling phosphorus content in aluminum fluoride production. Reacting mixed sulfuric acid and high-phosphorus fluorite powder in an external heating type rotary reaction furnace to produce crude hydrogen fluoride gas; firstly, removing impurities from crude hydrogen fluoride gas by using pre-purified acid, cooling to 40-60 ℃, purifying by using a washing and distilling device, and removing acid mist by using a demister to obtain hydrogen fluoride gas; introducing hydrogen fluoride gas into a fluidized bed reactor, and directly reacting with aluminum hydroxide to prepare the aluminum fluoride. The method for controlling the phosphorus content in the production of the aluminum fluoride comprises the step of adding P in fluorite2O5The mass content is improved to 0.3-0.5%, the qualified aluminum fluoride can be produced, the produced dry-process aluminum fluoride product completely reaches the national standard AF-1 grade in GB/T4292-2007, and the normal use of electrolytic aluminum production can be met.
Description
Technical Field
The invention belongs to the technical field of aluminum fluoride preparation, and particularly relates to a method for controlling phosphorus content in aluminum fluoride production.
Background
The dry aluminum fluoride production mainly comprises two parts of hydrogen fluoride preparation and aluminum fluoride preparation, firstly, mixed sulfuric acid and high-phosphorus fluorite powder are reacted in an external heating type rotary reaction furnace to generate hydrogen fluoride gas H2SO4+CaF2＝2HF+CaSO4(ii) a Then heated externallyFully purifying, drying and cooling crude hydrogen fluoride generated in the converter in a pre-purification system; and finally, introducing the purified hydrogen fluoride gas into the bottom of the fluidized bed reactor as fluidizing gas, directly reacting with dried aluminum hydroxide added from the upper part of the reactor in the fluidized bed to obtain dry-process aluminum fluoride, and then introducing the dry-process aluminum fluoride into the bottom layer of the fluidized bed for reaction.
In the production of dry-method aluminium fluoride, P in the product2O5Most of the phosphorus comes from the fluorite and a small amount of phosphorus comes from the acid in use. The level of fluorite phosphorus determines the level of phosphorus in the product, and the side reaction of phosphorus in the process of preparing aluminum fluoride is shown in the following aspects:
(1) the phosphorus in fluorite exists in the form of calcium phosphate and calcium phosphite in the fluorite, and phosphoric acid and phosphorous acid can be generated by reaction with sulfuric acid, and the reaction equation is as follows:
Ca3(PO4)2+3H2SO4＝3CaSO4+2H3PO4；
Ca3(PO3)2+3H2SO4＝2H3PO3+3CaSO4。
(2) reacting hydrogen fluoride with phosphoric acid to generate hexafluorophosphoric acid, and decomposing to generate phosphorus pentafluoride: reacting phosphorous acid with hydrogen fluoride to generate phosphorus trifluoride, and decomposing phosphorous acid to generate phosphoric acid and phosphane; the reaction equation is as follows:
H3PO4+5HF＝PF5↑+4H2O；
H3PO3+3HF＝PF3↑+3H2O；
H3PO3＝3H3PO4+PH3↑。
(3) in the process of generating aluminum fluoride, phosphoric acid reacts with aluminum oxide to generate aluminum phosphate, and the reaction equation is as follows:
2H3PO4+Al2O3＝2AlPO4+3H2O。
in order to reduce the phosphorus content in the aluminum fluoride product, in the prior art, the phosphorus content is controlled in two aspects of raw material collocation and pre-purified acid water control:
(1) the raw material collocation aspect is as follows: the phosphorus content of the low-phosphorus fluorite is controlled to be less than or equal to about 0.01 percent, the high-phosphorus common fluorite with the phosphorus content of less than or equal to about 0.03 percent is reasonably matched, and the batching result is controlled to be less than or equal to about 0.015 percent.
(2) The crude HF gas generated by the reaction of the low-phosphorus fluorite and the acid after reasonable collocation enters a pre-purification system for purification, drying and cooling, and the purified gas enters a fluidized bed to react with the aluminum hydroxide in the fluidized bed.
In the prepurification system, the prepurification scrubbing acid has a temperature of about 80 ℃ and a substantial component of H2SO4(68％)、HF(17％)、H2O (15%), controlling the content of the pre-purified acid to be about 25-40%, increasing the temperature of a pre-purification system when the content of the pre-purified acid is increased, enabling the temperature of gas entering a cone of a fluidized bed to reach about 110 ℃, heating and dehydrating phosphoric acid from a reaction furnace to obtain pyrophosphoric acid, and further dehydrating to obtain metaphosphoric acid. The metaphosphoric acid forms polymetaphosphoric acid, forms a complex with Ca and Mg ions, is dissolved in the pre-purified acid, reduces the content of phosphoric acid entering the fluidized bed, thereby reducing P in the finished product of aluminum fluoride2O5And (4) content.
However, the above method has the following disadvantages:
(1) raw material matching: firstly, the quality of the raw fluorite must be statistically analyzed, the fluorites of different manufacturers are stacked according to the phosphorus level, and the fluorite phosphorus is matched in a reasonable application range according to theoretical calculation and production practice, so that the production cost is increased.
(2) Controlling the moisture of the pre-purified acid: the silicon and phosphorus reduction are completely opposite processes. Only in the case of low fluorite silica, the phosphorous in the product can be reduced by increasing the content of the pre-purified acid.
(3) In the process of improving the acid content of the pre-purified acid, the temperature of the pre-purification system is higher, the amount of the generated pre-purified acid is larger, and if the redundant pre-purified acid is returned to the production system again to participate in the reaction, P in the aluminum fluoride product can be caused2O5The content is rapidly increased, which is easy to cause unqualified P in the aluminum fluoride product, if the excessive pre-purification is carried outThe chemical acid is completely discharged, and the unit consumption of fluorite and acid production is increased.
Therefore, there is a need to find a new method for controlling the phosphorus content in the production of aluminum fluoride.
Disclosure of Invention
The purpose of the invention is: the method for controlling the phosphorus content in the production of the aluminum fluoride has the advantages of high yield of the aluminum fluoride, low production cost and good quality, and can meet the normal use requirement of the production of electrolytic aluminum.
The invention relates to a method for controlling the phosphorus content in the production of aluminum fluoride, which comprises the following steps:
(1) reacting mixed sulfuric acid and high-phosphorus fluorite powder in an external heating type rotary reaction furnace to produce crude hydrogen fluoride gas, wherein the outlet temperature of the external heating type rotary reaction furnace is 570-590 ℃, and the rotating speed is 1.6-1.8 rpm;
(2) firstly, removing impurities from crude hydrogen fluoride gas by using pre-purified acid, cooling to 40-60 ℃, purifying by using a washing and distilling device, and removing acid mist by using a demister to obtain hydrogen fluoride gas;
(3) introducing hydrogen fluoride gas into a fluidized bed reactor, and directly reacting with aluminum hydroxide to prepare the aluminum fluoride.
Wherein:
the mixed sulfuric acid in the step (1) is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, and the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 2.5-5: 1.
The high-phosphorus fluorite powder in the step (1) is P2O5Fluorite powder with the mass content of 0.3-0.5%.
The mass ratio of the mixed sulfuric acid to the high-phosphorus fluorite powder in the step (1) is 1.15: 1-1.2: 1.
The specific outlet temperature of the external heating type rotary reaction furnace in the step (1) is set according to the feeding amount.
The chemical equation of the reaction generated in the step (1) is H2SO4+CaF2＝2HF+CaSO4。
And (3) the crude hydrogen fluoride gas in the step (2) enters from the lower part of the pre-purification tower and fully contacts with pre-purification acid flowing reversely to wash away dust, sulfuric acid mist, moisture and partial impurities in the gas, wherein the pre-purification acid is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 2.5-5: 1, and the moisture in the pre-purification acid is 25 wt% or more.
The washing distillation device in the step (2) consists of a water washing tower and an acid washing tower; the washing tower is filled with Na2CO3Solution, Na2CO3The mass concentration of the solution is 25-35%; the acid washing tower is internally provided with 98 percent of sulfuric acid by mass concentration, and the flow rate is 25m3/h。
The hydrogen fluoride gas after temperature reduction in the step (2) enters Na flowing in the reverse direction from the bottom of the water washing tower2CO3Contacting the solution with hydrogen in HF gas3PO4、H3PO3And other impurities are sprayed and washed until the cone of the washing tower is formed into colloidal crystals, the colloidal crystals are externally placed after precipitation, the liquid level of the washing tower is maintained at 40 percent, and the liquid level is not too high so as to ensure that HF gas is fully contacted with water and then is discharged out of the tower; the HF gas purified from the water scrubber enters from the bottom of the acid scrubber and contacts 98 acid from the head tank to generate a violent exothermic reaction, and water contained in the purified HF gas is evaporated to dry the HF gas, and the liquid level of the acid scrubber is maintained at 50-80%, preferably 50%.
The working principle of the water washing tower is as follows: the prepared sodium carbonate solution enters from the top of the tower to contact with the hydrogen fluoride gas purified from the pre-purification tower, and H in the gas3PO4And H3PO3With Na2CO3React to generate Na3PO4White crystals.
The chemical equation is as follows:
3Na2CO3+3H3PO4＝2Na3PO4+3H2O+3CO2。
and the colloidal precipitate is formed with phosphoric acid, phosphorous acid and hexafluorophosphoric acid in HF entering the pre-purification tower and is discharged to a storage tank from a sewage port at the bottom of the washing tower.
The working principle of the pickling tower is as follows: the HF gas purified from the water washing tower enters from the bottom of the acid washing tower to contact with 98 acid from the head tank to produce violent exothermic reaction, and water contained in the purified HF gas is evaporated to dry.
In the step (3), the top bed reaction temperature in the fluidized bed reactor is 380-500 ℃, the bottom bed reaction temperature is 580-640 ℃, the top bed reaction pressure is-15-22 Kpa, and the bottom bed reaction pressure is-15-0 Kpa.
Wherein, the chemical equation for synthesizing the aluminum fluoride is as follows:
Al(OH)3＝Al2O3+H2O，
6HF+Al2O3＝2AlF3+3H2O。
preferably, the method for controlling the phosphorus content in the aluminum fluoride production comprises the following steps:
(1) adding mixed sulfuric acid and high-silicon fluorite powder into an external heating type rotary reaction furnace according to the mass ratio of 1.15: 1-1.2: 1 to react to prepare crude hydrogen fluoride gas, controlling the outlet temperature of a mixing chamber of the external heating type rotary reaction furnace to be 580 ℃, and controlling the rotating speed of the external heating type rotary reaction furnace to be 1.6rpm-1.8 rpm. Wherein the mixed sulfuric acid is a mixed acid of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid with the mass ratio of 2.5-5: 1, and the high-phosphorus fluorite powder is P2O5Fluorite powder with the mass content of 0.5 percent.
(2) Crude hydrogen fluoride gas generated in an external heating type rotary furnace enters the tower from the lower part of a pre-purification tower and is fully contacted with pre-purification acid flowing reversely to wash off dust, sulfuric acid mist, moisture and partial impurities in the gas, the pre-purification acid is a mixed solution of 98 wt% sulfuric acid and 105 wt%, the moisture in the pre-purification acid is controlled to be 25 wt%, the purified HF gas enters a novel cooling device to reduce the temperature of the HF gas to about 50 ℃, and then enters Na flowing reversely from the bottom of a water washing tower2CO3Solution phase contact of H in HF gas3PO4And H3PO3And other impurities are sprayed and washed until the cone of the washing tower forms colloidal crystals, and the colloidal crystals are deposited and then are discharged. (the liquid level of the water washing tower is maintained at 40 percent, and the liquid level is not suitable to be too high so as to ensure that the HF gas is discharged from the tower after being fully contacted with water) the gas discharged from the tower enters the acid washing tower from the bottomCounter-current to 98 acid (flow rate maintained at 25 m)3H) drying, evaporating and heating the excessive water by contact, and separating the acid mist carried by the purified hydrogen fluoride gas by a demister to obtain the relatively pure hydrogen fluoride gas. The acid flowing out from the pre-purification tower and the acid washing tower flows into the mixed sulfuric acid after being dehydrated by the head tank, and is recycled as the raw material of the mixed sulfuric acid.
(3) Introducing pure hydrogen fluoride gas into the bottom of the fluidized bed reactor as fluidizing gas, and adding dried aluminum hydroxide into the fluidized bed reactor to directly react with the upper part of the fluidized bed reactor to obtain dry-process aluminum fluoride.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for controlling the phosphorus content in the aluminum fluoride production does not cause the waste of HF gas, and is beneficial to improving the yield.
(2) The method for controlling the phosphorus content in the aluminum fluoride production does not cause burden to the pre-purification tower and the acid cooling discharge.
(3) The method for controlling the phosphorus content in the production of the aluminum fluoride comprises the step of adding P in fluorite2O5The mass content is improved to 0.3-0.5%, qualified aluminum fluoride can still be produced, and by applying the method to production, compared with the prior art, the cost of the high-phosphorus fluorite used in the method can be reduced by about 200 yuan per ton of aluminum fluoride, the cost can be saved by 600 yuan per year by 3 million tons per year of capacity, and the produced dry-process aluminum fluoride product completely reaches the national standard AF-1 grade in GB/T4292-2007, and can meet the normal use of electrolytic aluminum production.
Detailed Description
The present invention is further described below with reference to examples.
The method for controlling the phosphorus content in the aluminum fluoride production described in the embodiment 1 comprises the following steps:
(1) adding mixed sulfuric acid and high-silicon fluorite powder into an external heating type rotary reaction furnace according to the mass ratio of 1.2:1 to react to obtain crude hydrogen fluoride gas, controlling the outlet temperature of a mixing chamber of the external heating type rotary reaction furnace to be 580 ℃, and controlling the rotating speed of the external heating type rotary reaction furnace to be 1.8 rpm. WhereinThe mixed sulfuric acid is the mixed acid of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid with the mass ratio of 3.8:1, and the high-phosphorus fluorite powder is P2O5Fluorite powder with the mass content of 0.5 percent.
(2) Crude hydrogen fluoride gas generated in an external heating type rotary furnace enters the tower from the lower part of a pre-purification tower and is fully contacted with pre-purification acid flowing reversely to wash off dust, sulfuric acid mist, moisture and partial impurities in the gas, the pre-purification acid is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 3.8:1, the moisture in the pre-purification acid is controlled to be 25 wt%, the purified HF gas enters a novel cooling device to reduce the temperature of the HF gas to about 50 ℃, and the HF gas enters Na flowing reversely from the bottom of a water washing tower2CO3Solution phase contact of H in HF gas3PO4And H3PO3Spraying and washing other impurities until the cone of the washing tower forms colloidal crystals, and putting the colloidal crystals outside after precipitation; na (Na)2CO3The mass concentration of the solution is 25 percent. (the liquid level of the water scrubber is maintained at 40% and should not be too high to ensure that the HF gas is discharged from the tower after fully contacting with water), the gas discharged from the tower enters the sulfuric acid scrubber from the bottom and flows in the reverse direction with 98 acid (the flow rate is maintained at 25 m)3H) drying and evaporating excessive water by contact, heating, and separating acid mist carried by the purified hydrogen fluoride gas by a demister to obtain pure hydrogen fluoride gas. The pre-purified acid flowing out of the pre-purification tower and the sulfuric acid washing tower flows into the mixed sulfuric acid after being dehydrated by the head tank, and is recycled as the raw material of the mixed sulfuric acid.
(3) Introducing pure hydrogen fluoride gas into the bottom of the fluidized bed reactor as fluidizing gas, and adding dried aluminum hydroxide into the fluidized bed reactor to directly react with the upper part of the fluidized bed reactor to obtain dry-process aluminum fluoride.
Wherein the top bed reaction temperature in the fluidized bed reactor is 500 ℃, the bottom bed reaction temperature is 640 ℃, the top bed reaction pressure is 22Kpa, and the bottom bed reaction pressure is 0 Kpa.
Example 2
The method for controlling the phosphorus content in the aluminum fluoride production described in the embodiment 2 comprises the following steps:
(1) adding mixed sulfuric acid and high-silicon fluorite powder into an external heating type rotary reaction furnace according to the mass ratio of 1.15:1 to react to obtain crude hydrogen fluoride gas, controlling the outlet temperature of a mixing chamber of the external heating type rotary reaction furnace to be 570 ℃, and controlling the rotating speed of the external heating type rotary reaction furnace to be 1.7 rpm. Wherein the mixed sulfuric acid is a mixed acid of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid with the mass ratio of 2.5:1, and the high-phosphorus fluorite powder is P2O5Fluorite powder with the mass content of 0.4 percent.
(2) Crude hydrogen fluoride gas generated in an external heating type rotary furnace enters the tower from the lower part of a pre-purification tower and is fully contacted with pre-purification acid flowing reversely to wash off dust, sulfuric acid mist, moisture and partial impurities in the gas, the pre-purification acid is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 2.5:1, the moisture in the pre-purification acid is controlled to be 25 wt%, the purified HF gas enters a novel cooling device to reduce the temperature of the HF gas to about 50 ℃, and the HF gas enters Na flowing reversely from the bottom of a water washing tower2CO3Solution phase contact of H in HF gas3PO4And H3PO3Spraying and washing other impurities until the cone of the washing tower forms colloidal crystals, and putting the colloidal crystals outside after precipitation; na (Na)2CO3The mass concentration of the solution is 30 percent. (the liquid level of the water scrubber is maintained at 40% and should not be too high to ensure that the HF gas is discharged from the tower after fully contacting with water), the gas discharged from the tower enters the sulfuric acid scrubber from the bottom and flows in the reverse direction with 98 acid (the flow rate is maintained at 25 m)3H) drying and evaporating excessive water by contact, heating, and separating acid mist carried by the purified hydrogen fluoride gas by a demister to obtain pure hydrogen fluoride gas. The pre-purified acid flowing out of the pre-purification tower and the sulfuric acid washing tower flows into the mixed sulfuric acid after being dehydrated by the head tank, and is recycled as the raw material of the mixed sulfuric acid.
(3) Introducing pure hydrogen fluoride gas into the bottom of the fluidized bed reactor as fluidizing gas, and adding dried aluminum hydroxide into the fluidized bed reactor to directly react with the upper part of the fluidized bed reactor to obtain dry-process aluminum fluoride.
Wherein the top bed reaction temperature in the fluidized bed reactor is 420 ℃, the bottom bed reaction temperature is 600 ℃, the top bed reaction pressure is 10Kpa, and the bottom bed reaction pressure is-7 Kpa.
Example 3
The method for controlling the phosphorus content in the aluminum fluoride production described in the embodiment 3 comprises the following steps:
(1) adding mixed sulfuric acid and high-silicon fluorite powder into an external heating type rotary reaction furnace according to the mass ratio of 1.18:1 to react to obtain crude hydrogen fluoride gas, controlling the outlet temperature of a mixing chamber of the external heating type rotary reaction furnace to be 590 ℃, and controlling the rotating speed of the external heating type rotary reaction furnace to be 1.6 rpm. Wherein the mixed sulfuric acid is a mixed acid of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid with the mass ratio of 5:1, and the high-phosphorus fluorite powder is P2O5Fluorite powder with the mass content of 0.3 percent.
(2) Crude hydrogen fluoride gas generated in an external heating type rotary furnace enters the tower from the lower part of a pre-purification tower and is fully contacted with pre-purification acid flowing reversely to wash off dust, sulfuric acid mist, moisture and partial impurities in the gas, the pre-purification acid is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 5:1, the moisture in the pre-purification acid is controlled to be 25 wt%, the purified HF gas enters a novel cooling device to reduce the temperature of the HF gas to about 50 ℃, and then enters Na flowing reversely from the bottom of a washing tower2CO3Solution phase contact of H in HF gas3PO4And H3PO3Spraying and washing other impurities until the cone of the washing tower forms colloidal crystals, and putting the colloidal crystals outside after precipitation; na (Na)2CO3The mass concentration of the solution is 35%. (the liquid level of the water scrubber is maintained at 40% and should not be too high to ensure that the HF gas is discharged from the tower after fully contacting with water), the gas discharged from the tower enters the sulfuric acid scrubber from the bottom and flows in the reverse direction with 98 acid (the flow rate is maintained at 25 m)3H) drying and evaporating excessive water by contact, heating, and separating acid mist carried by the purified hydrogen fluoride gas by a demister to obtain pure hydrogen fluoride gas. The pre-purified acid flowing out of the pre-purification tower and the sulfuric acid washing tower flows into the mixed sulfuric acid after being dehydrated by the head tank, and is recycled as the raw material of the mixed sulfuric acid.
(3) Introducing pure hydrogen fluoride gas into the bottom of the fluidized bed reactor as fluidizing gas, and adding dried aluminum hydroxide into the fluidized bed reactor to directly react with the upper part of the fluidized bed reactor to obtain dry-process aluminum fluoride.
Wherein the top bed reaction temperature in the fluidized bed reactor is 380 ℃, the bottom bed reaction temperature is 580 ℃, the top bed reaction pressure is-15 Kpa, and the bottom bed reaction pressure is-3 Kpa.
The aluminum fluoride prepared in the examples 1 to 3 is subjected to index test according to the national standard GB/T4292-2007, and the test results are shown in Table 1.
Technical indices of aluminum fluoride obtained in examples 1 to 3
| Item | National standard AF-1 | Example 1 | Example 2 | Example 3 |
| Element F (wt%) | ≥60 | 61.09 | 61.50 | 62.00 |
| Al(wt％) | ≥31 | 32.00 | 32.60 | 33.00 |
| P2O5Element (wt%) | ≤0.04 | 0.025 | 0.023 | 0.020 |
| SiO2(wt％) | ≤0.30 | 0.20 | 0.18 | 0.18 |
| Fe2O3(wt％) | ≤0.1 | 0.026 | 0.023 | 0.020 |
| SO4 2-(wt％) | ≤0.6 | 0.40 | 0.35 | 0.30 |
| Weight loss by burning (wt%) | ≤1.0 | 0.72 | 0.65 | 0.60 |
| Bulk Density (g/cm)3) | ≥1.30 | 1.35 | 1.37 | 1.42 |
Claims (7)
1. A method for controlling the phosphorus content in the production of aluminum fluoride is characterized in that: the method comprises the following steps:
(1) reacting mixed sulfuric acid and high-phosphorus fluorite powder in an external heating type rotary reaction furnace to produce crude hydrogen fluoride gas, wherein the outlet temperature of the external heating type rotary reaction furnace is 570-590 ℃, and the rotating speed is 1.6-1.8 rpm;
(2) firstly, removing impurities from crude hydrogen fluoride gas by using pre-purified acid, cooling to 40-60 ℃, purifying by using a washing and distilling device, and removing acid mist by using a demister to obtain hydrogen fluoride gas;
(3) introducing hydrogen fluoride gas into a fluidized bed reactor, and directly reacting with aluminum hydroxide to prepare the aluminum fluoride.
2. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: the mixed sulfuric acid in the step (1) is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, and the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 2.5-5: 1.
3. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: the high-phosphorus fluorite powder in the step (1) is P2O5Fluorite powder with the mass content of 0.3-0.5%.
4. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: the mass ratio of the mixed sulfuric acid to the high-phosphorus fluorite powder in the step (1) is 1.15: 1-1.2: 1.
5. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: the pre-purification acid in the step (2) is a mixed solution of 98 wt% sulfuric acid and 105 wt% fuming sulfuric acid, the mass ratio of the 98 wt% sulfuric acid to the 105 wt% fuming sulfuric acid is 2.5-5: 1, and the water content in the pre-purification acid is 25 wt% or more.
6. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: the washing distillation device in the step (2) consists of a water washing tower and an acid washing tower; the washing tower is filled with Na2CO3Solution, Na2CO3The mass concentration of the solution is 25-35%; the acid washing tower is internally provided with 98 percent of sulfuric acid by mass concentration, and the flow rate is 25m3/h。
7. The method for controlling the phosphorus content in the production of aluminum fluoride according to claim 1, wherein: in the step (3), the top bed reaction temperature in the fluidized bed reactor is 380-500 ℃, the bottom bed reaction temperature is 580-640 ℃, the top bed reaction pressure is-15-22 Kpa, and the bottom bed reaction pressure is-15-0 Kpa.
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