CN109790045A - Smelter grade alumina production method (embodiment) - Google Patents
Smelter grade alumina production method (embodiment) Download PDFInfo
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- CN109790045A CN109790045A CN201780060150.3A CN201780060150A CN109790045A CN 109790045 A CN109790045 A CN 109790045A CN 201780060150 A CN201780060150 A CN 201780060150A CN 109790045 A CN109790045 A CN 109790045A
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- Prior art keywords
- chloride
- waste liquid
- aluminium oxide
- aluminium
- method described
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 253
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 99
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 85
- 239000007788 liquid Substances 0.000 claims abstract description 71
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 50
- 230000008569 process Effects 0.000 claims abstract description 35
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 24
- 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 23
- 239000000047 product Substances 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000013067 intermediate product Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 150000004645 aluminates Chemical class 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 34
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 23
- 230000004087 circulation Effects 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 238000004131 Bayer process Methods 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000013505 freshwater Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 235000019504 cigarettes Nutrition 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000000498 cooling water Substances 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 10
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000005352 clarification Methods 0.000 abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 14
- 239000011575 calcium Substances 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- 239000003518 caustics Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000004411 aluminium Substances 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 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 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 5
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 5
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000013178 mathematical model Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 208000014674 injury Diseases 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000011165 process development Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241001417490 Sillaginidae Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
- C01F7/22—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with halides or halogen acids
-
- 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
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
- C01F7/306—Thermal decomposition of hydrated chlorides, e.g. of aluminium trichloride hexahydrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to metallurgy.Propose some embodiments of smelter grade alumina production method, following operation is provided: using hydrochloric acid extraction aluminum-containing raw material, by the chloride pulp separation of formation at useless precipitation of silica object and clarification chloride solution, Aluminium chloride hexahydrate is crystallized from clarification chloride solution, Aluminium chloride hexahydrate thermoprecipitation is at aluminium oxide, then the thick aluminium oxide of production is calcined as intermediate product, thick aluminium oxide is leached with alkaline waste liquor and makes gained aluminate solution precipitating, then isolated aluminium hydroxide washing is calcined, the waste liquid for leaving settling zone and the boiling for being used for washing aluminum hydroxide is dense to generate the alkaline waste liquor for returning to intermediate alumina product leaching stage.In this case, about 15% acid waste liquid carries out pyrohydrolysis, chlorine ion concentration is maintained at 0.2~5.0% in thick aluminium oxide, chlorine ion concentration in alkaline waste liquor is maintained at 40~90g/L, the waste liquid boiling down of settling zone (10~40 weight % of total flow) will be left, until isolating the chlorine-containing compound crystal to remove from the process.Waste liquid is mainly used for leaching aluminum-containing raw material, and only a part is sent through pyrohydrolysis removal impurity.Technical result is that aluminium oxide quality is more preferable when producing smelter grade alumina by low grade raw material, and energy consumption is lower.
Description
The present invention relates to field of metallurgy, more particularly to the acid process of production aluminium oxide, and it is high to can be used for handling low grade
Silicon aluminum-containing raw material, the wastes such as flyash generated including coal combustion.Smelter grade alumina and its semi-finished product (aluminium hydroxide)
With extensive industrial application, mainly for the production of aluminum metal.
Alumina refinery all over the world mainly uses Bayer technology by low silicon (Bayer) bauxite (wherein Al2O3/
SiO2Concentration ratio (the ratio between aluminium oxide and silica) be not less than 3) production high-quality smelter grade alumina.When aluminium oxide and two
The ratio of silica is in 3~7 range, it is necessary to use Bayer-sintering group technology, this is the technique more to consume energy.For height
Sintering process, energy of the energy cost than Bayer process is industrially used only in silica aluminum-containing raw material, such as nepheline and kaolin
About 5 times at high cost of source.
Meanwhile it developing by the acid process of high silicon aluminum-containing raw material production aluminium oxide.Wherein, hydrochloric acid method is presently considered to
It is the most reasonable approach.
It is well known that aluminium oxide can be produced by hydrochloric acid method by high silicon dioxide bauxite comprising up to 700
DEG C temperature lower calcination aluminum-containing raw material, it is handled with hydrochloric acid, by making clear chloride solution with gaseous hydrogen chloride
It is saturated and makes Aluminium chloride hexahydrate (AlCl3·6H2O it) saltouts, calcines aluminium chloride to produce aluminium oxide (alumina), keep waste liquid hot
The hydrochloric acid that hydrolysis and rectifying are absorbed is included in sour processing stage return hydrogen chloride, and respectively with the gentle bodily form of aqueous solution
Formula is saltoutd (Elsner D., Jenkins D.H. and Sinha H.N.Alumina via hydrochloric acid
leaching of high silica bauxites-process development.Light metals,1984,411-
Page 426).
According to known methods, the hydrochloric acid of rectifying is only sent to feedstock processing area, this eliminate acid circulation in impurity (such as
Iron, sodium, potassium, calcium etc.) circulation and accumulation, and reduce its content in Aluminium chloride hexahydrate as far as possible.In crystalline A lCl3·
6H2After O, by carrying out complete pyrohydrolysis to waste liquid, using impurity as oxide removal.Nevertheless, the phosphorus in final product
Content is 1.5 times higher than the allowable value of smelter grade alumina.
The disadvantages of this method also including extremely complex equipment and process flow and should provide the complete regenerated of hydrochloric acid
The equipment of many valuableness, this needs high Capital expenditure just to build the alumina refinery using the technology.In crystalline A lCl3·
6H2The region of the complete pyrohydrolysis of implementation waste liquid is the region consumed energy very much after O and fuel cost is significantly increased and is produced into
This.
In addition, the aluminium oxide and traditional smelter grade alumina by calcining Aluminium chloride hexahydrate production are substantially different,
Granule strength is low, Yi Fenhua, bulk density are 1.5 to 3 times low, and rheological behavior is entirely different (mobility is excessively poor), therefore
It leads to the problem of during its transportation and during electrolytic production of aluminum.When calcining this aluminium oxide, as a consequence it is hardly possible to same
When obtain low content chlorine residue and α phase, this is one of the major requirement to smelter grade alumina.Such as the creator institute of known method
Show, if raw material contains any phosphorus compound, almost its whole volume will all enter final product.
A kind of method (patent disclosed on November 27th, 2008 for extracting aluminium and iron from aluminum ore known
CA2684696)；This method includes preparing aluminum-containing raw material (kaolinite race argillite), by it with 6 mole hydrochlorides at 100~110 DEG C
Resulting suspension is separated into solid phase and liquid phase by lower leaching, and the washing water of liquid phase and solid phase is distilled to 90% degree, packet
It includes and hydrogen chloride is regenerated by rectifying and returns it into leaching stage.Remaining 10% liquid phase is neutralized to pH > 10 with caustic alkali,
To produce liquor alumini chloridi and isolate iron oxide precipitating.Liquor alumini chloridi is neutralized with hydrochloric acid to pH=3 ÷ 4, and passes through liquid
Aluminium is isolated in body extraction, is then converted to aluminium hydroxide and oxide (aluminium oxide).
This method needs larger numbers of thermal energy also to provide the entire liquid of boiling down after the degree of consumption of raw materials to 90%
Stream and washing water, and hydrochloric acid and caustic alkali are largely consumed, to selectively recycle iron and aluminium from liquid.
Immediate with method claimed is the soda acid combined method that aluminium oxide is produced by HCl treatment raw material,
Including separate precipitation of silica object, Aluminium chloride hexahydrate is crystallized out from clear chloride solution, then calcined with
Just intermediate alumina product is produced, due to the iron and other impurities (in addition to silicon) of significant content, creator is referred to as " former
Begin " or " thick " aluminium oxide.Then intermediate alumina product is leached with alkaline waste liquor, precipitates resulting mother liquor, washing is then forged
The aluminium hydroxide isolated is burnt, the waste liquid for leaving settling zone and the boiling for being used for washing aluminum hydroxide is dense, and form return
To the region for leaching intermediate alumina product alkaline waste liquor (nonferrous production with reference to aluminium oxide refine the Moscow:
Metallurgiya, 1970,236-237 page).
Substantially, the processing of intermediate alumina product is the alkalinity recrystallization carried out according to simplified Bayer process process,
It is used to remove iron/phosphorus and other impurities, and produces smelter grade alumina in terms of chemical composition and physical property.
One critical defect of the process is, during acid circulation, the iron, sodium, potassium, calcium, the magnesium that are conveyed with raw material
It is accumulated with other impurities, and under this methodology, chloride solution and maximum possible is evaporated by depth in this case
Ground carries out chloride crystallization to solve the problems, such as this.After thick aluminium oxide calcining, a large amount of alkali metal chloride is sent to Bayer alkali and is followed
In ring；This chloride will be accumulated inevitably in recycle stream, and not provide their removal.
The shortcomings that method of known production aluminium oxide further includes amounting to higher energy cost and additional alkali consumption
Up to 36-37kg/ tons of aluminium oxide.For these reasons, this method does not obtain industrial application.
The present invention is based on following problems: a kind of method by low grade (high silicon) raw material production smelter grade alumina is developed,
It allows to handle barren high silicon ore and waste material.
Technical result is (in other words, to handle barren high silicon mine when producing smelter grade alumina by low grade raw material
When stone and waste material) it improves the quality of aluminium oxide and reduces energy consumption.
By the method for the production smelter grade alumina proposed, the problem can solve, and above-mentioned skill may be implemented
Art is as a result, the method includes with the next stage:
With hydrochloric acid extraction aluminum-containing raw material,
By resulting chloride pulp separation at useless precipitation of silica object and clear chloride solution,
Aluminium chloride hexahydrate is crystallized out from clear chloride solution,
Aluminium chloride hexahydrate is thermally decomposed into aluminium oxide, is then calcined to produce thick aluminium oxide as intermediate product,
Thick alumina leaching is carried out with alkaline waste liquor and precipitates resulting aluminate solution,
Isolated aluminium hydroxide is washed and is then calcined, and
The waste liquid for leaving settling zone and the boiling for being used for washing aluminum hydroxide is dense to be formed back to intermediate alumina production
The alkaline waste liquor of object leaching stage.
In addition, in order to optimize this method, the chlorine ion concentration in intermediate alumina product should be maintained at 0.2 weight %~
The level of 5.0 weight %, the chlorine ion concentration in alkaline waste liquor should be maintained at the level of 40~90g/L, and should will leave it is heavy
Waste liquid (the 10-40 weight % of the total flow) boiling down in shallow lake area, until it is brilliant to isolate the chlorine-containing compound to remove during this
Body.
According to one embodiment, smelter grade alumina production method includes with the next stage:
Aluminum-containing raw material is ground, then extracts it with hydrochloric acid (acid waste liquid),
By resulting chloride pulp separation at useless precipitation of silica object and clear chloride solution,
Aluminium chloride hexahydrate is crystallized out from clear chloride solution,
Aluminium chloride hexahydrate is thermally decomposed into aluminium oxide, is then calcined to produce thick aluminium oxide as intermediate product,
Thick alumina leaching is carried out with alkaline waste liquor and precipitates resulting aluminate solution, and then calcines separation
Aluminium hydroxide, when will about 15% acid waste liquid carry out pyrohydrolysis when, the chlorine ion concentration in thick aluminium oxide is maintained at 0.2%~
5.0%, the chlorine ion concentration in alkaline waste liquor is maintained at the level of 40~90g/L, by 10 weights of weight %~40 of total flow
Alkaline waste liquor boiling down after measuring the precipitating of the amount of %, until isolating the chlorine-containing compound crystal to remove during this.
According to second embodiment, smelter grade alumina production method includes with the next stage:
Aluminum-containing raw material is ground, then leaches it with hydrochloride waste (acid waste liquid),
By resulting chloride pulp separation at the useless precipitation of silica object toppled over after being washed with water and clear chlorination
Aluminum solutions, and the water for being used to wash purpose is supplied to from the smog generated by calcining Aluminium chloride hexahydrate and by pyrohydrolysis process
The region of adiabatic absorption hydrogen chloride in the smog of generation, and the amount of washing water is determined by the water for adiabatic absorption,
Aluminium chloride hexahydrate is crystallized out from clear liquor alumini chloridi；After separating crystal, resulting waste liquid is supplied
To rectification zone, the hydrogen cloride concentration in waste liquid is reduced to form hydrogen chloride gas herein, by the dry then confession of hydrogen chloride gas
Area of saltouing should be arrived；The waste liquid being discharged from rectification zone is divided into two unequal parts: it is useless that biggish part is supplied directly into preparation
Liquid, another part, which is supplied to, removes impurity by pyrohydrolysis,
Aluminium chloride hexahydrate is decomposed thermally to form aluminium oxide, is then calcined to produce thick aluminium oxide as intermediate product,
Smog is calcined simultaneously to be absorbed by the water for washing useless precipitation of silica object,
Thick alumina leaching is carried out with alkaline waste liquor according to Bayer process and precipitates resulting aluminate solution,
Isolated aluminium hydroxide is washed and is then calcined,
The waste liquid for leaving settling zone and the boiling for being used for washing aluminum hydroxide is dense to form intermediate alumina production to be returned
The alkaline waste liquor of object leaching stage, and
Waste liquid is mainly used for carrying out aluminum-containing raw material leaching, and its only some by pyrohydrolysis removes impurity.
Two embodiments of this method ensure the realization of total technical result, i.e., are producing smelting by low grade raw material
Aluminium oxide quality is improved when grade aluminum oxide and reduces energy cost.
As addition thereto, following measures are preferably implemented:
Boiling down, alkali carbonate exist in two stages for the waste liquid being discharged from settling zone and the water for washing aluminum hydroxide
First stage crystallization, alkali metal chloride are crystallized in second stage.
Alkali metal chloride (mainly sodium chloride and potassium chloride) is purified, and carries out film or diaphragm in form of an aqueous solutions
Electrolysis.
The chlorine and hydrogen formed during the film of aqueous alkali metal chloride or diaphragm electrolysis is sent for synthesizing
It removes to extract the hydrochloric acid of initial aluminum-containing raw material, and will be formed during the film of aqueous alkali metal chloride or diaphragm electrolysis
Partial alkaline-metal hydroxide aqueous solution is mixed with the alkaline waste liquor back to intermediate alumina product leaching stage.
It will be sent to by the partial alkaline-metal hydroxide solution of the film of aqueous alkali metal chloride or diaphragm electrolysis generation
Neutralize precipitation of silica object.
Detailed description of the invention
Fig. 1 --- schematic alumina production process flow.
Illustrate the present invention by schematic alumina production process flow shown in FIG. 1, in terms of process and mode two
Clearly illustrate the reasonable optimum combination of the bronsted lowry acids and bases bronsted lowry circulation of the technology, this provides the realization of technical result on the whole.
Such as under autoclave conditions, the aluminum-containing raw material of crushing (such as kaolin or kaolin argillite) is used into hydrochloride waste
It carries out acidic extraction (leaching).After leaching, by pulp separation at the sediment (Si material) and chlorine for containing about 90% silica
Change aluminum solutions.The Si material being washed with water is toppled over.
The water for being used to wash Si material is supplied to from by calcining Aluminium chloride hexahydrate (ACH, AlCl3·6H2O it) generates
Smog and by pyrohydrolysis process generate smog in adiabatic absorption hydrogen chloride (HCl) region.And the HCl in liquor alumini chloridi
Concentration reaches 17%~19%.In absorption process, due to the amount of heat discharged in HCl absorption process, liquor alumini chloridi
Spontaneous evaporation and all water for being used to wash Si material that removal is supplied from circulation.It is worth noting that, Si material washing water
Amount by being determined in adiabatic absorption stage transpirable water.
The liquor alumini chloridi separated with Si material is sent to crystallization (to saltout) area, the hydrogen chloride gas generated by rectifying herein
It is bubbled through solution, and the HCl concentration in solution reaches 32%, most of (~95%) aluminum precipitation is that Aluminium chloride hexahydrate is brilliant
Body.After separating crystal (crystalline particle), resulting waste liquid is sent into rectification zone, is herein down to the HCl concentration in waste liquid about
22%-27%HCl) and gaseous state HCl is formed, is dried to~5%H2The content of O is simultaneously supplied to area of saltouing.It is arranged from rectification zone
Waste liquid (containing 22%~27%HCl) out is divided into two unequal parts: it is acid that biggish part is supplied directly into preparation
Waste liquid；Another part, which is supplied to, removes impurity by pyrohydrolysis.
The ratio for sending to the waste liquid of pyrohydrolysis is determined by the permission content of the impurity in the waste liquid for leaching.For hot water
The ratio of the waste liquid of solution is about 15%.It is worth noting that, the impurity content ratio in liquor alumini chloridi leaches ore with pure hydrochloric acid
When about 6 times of impurity content increase.In pyrohydrolysis process, all free acids contained in waste liquid and by metal (including Al,
Fe, Ca, Mg) HCl that hydrolyzes to form of chloride enters gas phase.Pyrohydrolysis product will be including smog and by iron oxide (Fe2O3) and portion
Divide the pyrohydrolysis cake of Al, Ca, Mg oxide and other trace impurities composition.It include regenerated HCl by the smog that pyrohydrolysis generates,
And it is conveyed to absorb the region of HCl with Si material washing water.
The ACH of production is supplied to calcining zone to generate thick aluminium oxide and containing the smog of HCl.It will be generated by calcination process
Smoke delivery to the absorption stage, wherein being absorbed using Si material washing water.In order to which recovery will be lost, rank is leached to sending to
Fresh acid is added in the waste liquid of section；Furthermore, it is possible to be added by washing the ACH product for being applied to rectifying.
It adds fresh water and washing Si material (is subsequently used for by the smog calcined and pyrohydrolysis process generates with health purification
Material).
The advantages of process flow is, most of waste liquid for leaching ore, and its only some is sent through
Pyrohydrolysis removes impurity.Complicated boiling down and salt rectification area there is no big, pyrohydrolysis area minimize and with thick aluminium oxide
Production it is unrelated, instead for impurity part remove, this significantly reduces energy costs.
It should be noted that containing minimal amount of impurity (including chloride) according to the thick aluminium oxide of art methods.In order to
This point is realized in art methods, it is necessary to keep liquor alumini chloridi to contain the impurity of minimum tolerable injury level, such as iron and
Potassium, sodium, calcium, magnesium for being put into together with raw material etc.；For this purpose, acid waste liquid should be purified from these impurity.For example, prior art side
Method shows to be difficult to carry out this purifying from iron.The common technology done so is pyrohydrolysis, especially such as similar approach (Elsner
D., Jenkins D.H. and Sinha H.N.Alumina via hydrochloric acid leaching of high
Silica bauxites-process development.Light metals, page 1984,423) shown in, at up to 850 DEG C
At a temperature of evaporating completely acid waste liquid, therefore energy cost is very high in this case.
According to method claimed, thick alumina transferring is then used for the alkalinity based on known Bayer process and is tied again
It is brilliant.The product of Bayer process is aluminium oxide, is translated into smelter grade alumina by calcining.
In order to prepare waste liquid, fresh caustic alkali is also put into, consumption depends on the machinery of useless mud and alumina product
Metal chloride (the AlCl contained in loss, and thick aluminium oxide3、FeCl3、MgCl2、CaCl2) take off in causticization process at it
Alkali loss.In this case, the NaCl and KCl contained in thick aluminium oxide is directly entered any damage of the solution without causing alkali
It loses.
By Bayer process (opposite with natural bauxite processing method) to a special spy of the basic treatment of thick aluminium oxide
Sign is, since the mud amount of formation is few, it is therefore desirable to which seldom water washs mud.Therefore, it is raw that aluminium oxide can be compensated
Water balance during production and do not have to entire waste liquor stream boiling down because addition come wash the water of hydrate correspond roughly to
The water that alumina product removes together.Further, since a small amount of mud does not need so a large amount of condensate to wash mud,
Therefore slurry-slurry heat exchanger can be used and recycle heat by autoclave leaching without making discharge slurry spontaneous evaporation.
In order to go to dechlorinate in recycling from Bayer, need to carry out a part of waste liquid the combination operation of depth boiling down and crystallization.
Only in Na2The highly concentrated region O, solubility of the NaCl in caustic solution can just significantly reduce；Therefore, we talk about
Be by a part of waste liquid depth boiling down to causticity alkali content be 25%~33% (Na2O)。
Waste liquid amount supplied to boiling down area is determined by the tolerable injury level of chloride accumulation in Bayer process.Chlorine in Solution compound
Acceptable level it is higher, the waste liquid ratio for sending to boiling down area is smaller, therefore, evaporate water (and thermal energy consumption) amount will for (with
The content of chloride is identical in thick aluminium oxide).
According to the experience of creator, in industrial conditions, the tolerable injury level of chloride is in waste liquid used in Bayer process
90g/L is (for chloride ion Cl-)。
The crystallization sodium chloride and partial oxidation potassium separated after boiling down process sends to known diaphragm or film electrolysis to discharge
Caustic alkali and hydrogen and chlorine, by its synthesizing chlorinated hydrogen.Caustic alkali and hydrogen chloride return to the bronsted lowry acids and bases bronsted lowry of the technique respectively
Part is inevitably lost with compensating these reagents.
Therefore, method claimed is closed loop process process, can handle low grade (high silicon) aluminum-containing raw material
To produce smelter grade alumina.
Since thick aluminium oxide is intermediate product, rather than vendible product, thus wherein put into together with raw material iron,
The content of the impurity such as potassium, sodium, calcium, magnesium is not necessarily minimum permission content.It is thus possible to increase acid circulation in these impurity it is dense
Degree, this will reduce chloride solution and evaporate cost.For this purpose, in crystallization stage, it may be desirable to using simple equipment and be easy to real
The process applied most sufficiently and rapidly extracts Aluminium chloride hexahydrate in solid phase, and does not have to worry to be conveyed to calcining zone life
Produce the purity of the crystalline A CH of thick aluminium oxide.In addition, being produced in calcination process without depth calcining to decompose chloride completely
Object.On the one hand, it reduce heat costs relevant to calcining；On the other hand, this will not be to form indissoluble in thick aluminium oxide
α phase create conditions.Mainly using potassium chloride, sodium chloride, calcium chloride and magnesium chloride as the chlorine residue of representative together with thick aluminium oxide by
It extracts in the sour phase of process flow, it will inevitably be accumulated herein.However, creator studies have shown that, alkalinity
The performance that the level of chloride ions accumulated to 40~90g/L not will lead to Bayer process in waste liquid is remarkably decreased.In order to avoid in the work
Chlorine is further accumulated in the alkali circulation of skill, by the amount after precipitating for 10%~40% part waste liquid boiling down of overall flow rate until dividing
Separate out the chlorine-containing compound crystal to remove during this.Laboratory experiment and cyclic process calculation shows that, this method is enough
Chlorine ion concentration in alkaline waste liquor is maintained at required level, and ensures the water balance of Bayer process.
Selection method can not be determined as the running parameter of this multilink circulating technology of method claimed
Optimal combination.Creator solves this problem by using the thermally equilibrated mathematical model of process matter specially developed.Meanwhile
Creator is it was unexpectedly observed that if it is intended that impurity (is recycled to alkali circulation from acid in the bronsted lowry acids and bases bronsted lowry circulation of technique and thick aluminium oxide
Intermediate product) in accumulation, then can reduce the energy consumption of fuel, heat and electrical energy form.
The numerical experiment discovery carried out according to the Optimized Iterative calculated result based on above-mentioned mathematical model is as follows: if about
15% is conveyed to pyrohydrolysis area, then the content of impurity (iron, sodium, potassium, magnesium, calcium etc.) is set in equilibrium level, this will not reduce from
Former material expects the aluminium recovery of thick aluminium oxide, but will lead to the impurity in Aluminium chloride hexahydrate and further in thick aluminium oxide
In concentration increase.However, iron, calcium and magnesium compound are direct when carrying out thick alumina leaching in the alkali circulation of the technique
Into in insoluble precipitate and being removed.In this case, it should be taken into account the ratio for sending to the acid waste liquid in pyrohydrolysis area
Smaller, energy cost relevant to the fuel combustion in the area is lower.
As provided by prior art approaches, if carrying out depth to thick aluminium oxide before leaching in Bayer circulation
High-temperature calcination is simultaneously washed with water to remove soluble chloride, then can reduce cost relevant to pyrohydrolysis.In such case
Under, the chloride ion content in thick aluminium oxide is reduced to ten thousand/several and some thousandths of, but the content of the alpha-aluminium oxide of indissoluble increases.
Its alkali process is to leach to realize by high temperature and high pressure kettle, therefore lead to the increase of thermal energy consumption.
On the other hand, it will therefore be apparent that if the technological temperature or heat and mass exchange intensity of reduction calcining zone, energy consumption
It will significantly reduce, but the chlorinity in thick aluminium oxide will increase, and the chlorine of this chloride ion form will be followed in the alkali of the technique
Continue to accumulate in ring.The loss that will inevitably lead to hydrochloric acid and caustic alkali to the chloride shift that alkali recycles is recycled from acid.Institute
In claimed method, these losses are by (generating NaOH and chlorine and hydrogen, by it from alkali circulation and its electrolysis processing
Synthesis HCl) in some potassium chloride of removal and sodium chloride compensate.But it is this regeneration from alkaline solution evaporate potassium chloride and
Thermal energy is needed when sodium chloride, and it also requires the electric energy for being electrolysed these aqueous chloride solutions.
However, although numerical experiment shows to optimize the heat of the process and mass balance is very complicated, creator's exploitation
Mathematical model allows to find some unconspicuous alternative combinations connected each other of technological parameter in bronsted lowry acids and bases bronsted lowry circulation, thus
While quality needed for keeping smelter grade alumina product, make energy consumption minimized.When the chlorine ion concentration in thick aluminium oxide is kept
Chlorine ion concentration in the level of 0.2 weight of weight %~5.0 %, alkaline waste liquor is maintained at the level of 40~90g/L, and
By the waste liquid for leaving settling zone (the 10 weight % of weight %~40 of total flow) boiling down until isolate and to be removed during this
Chlorine-containing compound crystal when, this may be implemented.In the presence of the optimal combination of above-mentioned technological parameter, to claimed
Method has carried out experiment and has implemented.
Embodiment
It is that (aluminum-containing raw material is with weight % by 100 μm of < that 540g aluminum-containing raw material (kaolin argillite), which is crushed to partial size,
Meter includes: Al2O327.1；SiO256.8；Fe2O32.0；Na2O 0.31；K2O < 0.15；TiO20.48；CaO 0.45；MgO
0.27；P2O5；0.05；11.8) it, and 20% mixed in hydrochloric acid with 1,650ml, is placed in autoclave and is protected under 160 DEG C of stirrings
It holds 3 hours.Resulting chloride slurry is isolated by filtration, solid sediment (useless Si material) is washed with water.It is used at 70 DEG C
Dry hydrogen chloride gas is bubbled clear liquor alumini chloridi, until isolating ACH crystal and stopping.Using filter from useless
The ACH of crystallization is isolated in liquid, and is calcined at 600 DEG C to produce thick aluminium oxide.Waste liquid is diluted to Si material washing water
20%HCl dissociate to generate, acid waste liquid is sent to and extracts kaolin argillite repeatedly with acid, and repeats above-mentioned all
(circulation) operation.
After carrying out above-mentioned totally 6 circulations, following (%): the AlCl of the stable content of acid waste liquid ingredient320.5-21.5；
FeCl33.9-4.2；TiCl20.001；CaCl20.4-0.48；NaCl 0.1-0.12；KCl 0.1-0.11.It does not observe and contains
The reduction of aluminium recovery in aluminum feedstock is 95.5%~97.5%.Every time after experiment, replaced with pure hydrochloric acid (20% concentration)
The waste liquid of 15% volume, to simulate through pyrohydrolysis or by (forming the low-solubility sulphur of respective metal with the processing of the concentrated sulfuric acid
Hydrochlorate) impurity is removed from circulation.
The average composition of the useless Si material of gained is as follows in terms of weight %: Al2O32.0；SiO290.5；Fe2O30.16；
Na2O 0.2；K2O < 0.15；TiO20.7；CaO 0.12；MgO < 0.025；P2O5；< 0.02；4.2.
After acid waste liquid composition is stablized, other 10 circulation experiments are carried out；As a result, creator, which produces, to be had with the following group
At the thick aluminium oxide of (weight %): Al2O386.0；SiO20.08；Fe2O32.9；Na2O 0.61；K2O < 0.15；<TiO2
0.05；CaO 0.3；MgO < 0.025；P2O5；0.06；Cl-3.5；7.0.
In order to pass through alkali process in Bayer recycles by thick alumina producing smelter grade alumina, the thick aluminium oxide of 500g is existed
2 hours: Al is dissolved in the alkaline green liquor with following composition (g/L) in 150 DEG C of autoclave2O3102.0；Na2O
174.0；NaCl 63.3.
The content of the filtered green liquor of gained is as follows in terms of g/L: Al2O3167.3；Na2O 149.2；NaCl 57.7.Root
Solution is precipitated according to Bayer technology, to isolate aluminium oxide, creator is after washing it with hot water (%), and 1,
It is calcined at 100 DEG C, produces the aluminium oxide with following chemical composition (%): Al2O398.7；；SiO20.004；Fe2O3
0.008；Na2O 0.15；K2O 0.01；TiO20.001；CaO 0.004；MgO 0.0025；P2O5；0.0007；V2O5
0.0002；Cr2O30.0003 0.02；Cl-0.013。
When measuring the physical and mechanical property of the aluminium oxide using standard method, creator has found following situations:
Although the content of chloride is very high in alkali circulation, the aluminium oxide of production, which is complied fully with, smelts grade oxygen for ' sand shape '
Change Russia's (GOST 30558-98 ' smelter grade alumina ') and the international requirement of aluminium.
Due to lacking the energy consumption data announced in similar approach, except similar method (Elsner D., Jenkins D.H.
With Sinha H.N.Alumina via hydrochloric acid leaching of high silica bauxites-
Process development.Light metals, page 1984,411-426) except, creator is to production 1kg aluminium oxide institute
The heat and electric energy of consumption are calculated, and compare all skills as a result, to mention more in the description of the present invention
The energy conservation of art.As a result as follows.
Obviously, in terms of the energy conservation when handling high silicon dioxide raw material, the method proposed is only second to patent family 1, however,
The latter cannot provide the production of smelter grade alumina.Other patent families need higher energy consumption.
When about 15% acid waste liquid carries out pyrohydrolysis, the chlorine ion concentration in intermediate alumina product is maintained at 0.2 weight
The level of the weight of %~5.0 % is measured, the chlorine ion concentration in alkaline waste liquor is maintained at the level of 40~90g/L, and will leave
Waste liquid (the 10 weight % of weight %~40 of the total flow) boiling down of settling zone until isolate to be removed during this containing chlorine
When compound crystal, energy conservation as defined in method claimed can be best accomplished.Bronsted lowry acids and bases bronsted lowry part based on this method
Gross mass balance mathematical model, calculate as defined in concentration and flow interval.In defined interval, in running parameter
Energy consumption is always calculated under any combination no more than 41.2kJ/kg.
Although specification refers to certain embodiments, for those skilled in the art, many modifications are answered
This is it will be apparent that and being not strictly limited to embodiment, description and process flow.
Claims (16)
1. smelter grade alumina production method comprising with the next stage:
Aluminum-containing raw material is ground, then it is used to hydrochloric acid extraction, the hydrochloric acid is acid waste liquid,
By resulting chloride pulp separation at useless precipitation of silica object and clear chloride solution,
Aluminium chloride hexahydrate is crystallized out from the clear chloride solution,
Aluminium chloride hexahydrate is thermally decomposed into aluminium oxide, is then calcined to produce thick aluminium oxide as intermediate product,
Thick alumina leaching is carried out with alkaline waste liquor and precipitates resulting aluminate solution, then forges isolated aluminium hydroxide
It burning, while about 15% acid waste liquid is subjected to pyrohydrolysis, the chlorine ion concentration in thick aluminium oxide is maintained at 0.2%~5.0%,
Chlorine ion concentration in alkaline waste liquor is maintained at the level of 40~90g/L, will measure 10 weight of weight %~40 % for total flow
Precipitating after alkaline waste liquor boiling down, until isolate the chlorine-containing compound crystal to remove during this.
2. according to the method described in claim 1, wherein, alkaline waste liquor boiling down in two stages, alkali carbonate is first
Stage crystallization, and alkali metal chloride is crystallized in second stage.
3. the alkali metal chloride of mainly sodium chloride and potassium chloride is purified according to the method described in claim 2, wherein,
And film or diaphragm electrolysis are carried out in form of an aqueous solutions.
4. according to the method described in claim 3, wherein, the shape during film of aqueous alkali metal chloride or diaphragm electrolysis
At chlorine and hydrogen be used to synthesize and be conveyed to extract the hydrochloric acid of initial aluminum-containing raw material, and will be in aqueous alkali metal chloride
Film or diaphragm electrolysis during formed partial alkaline-metal hydroxide aqueous solution with back to intermediate alumina product leach
The alkaline waste liquor in stage mixes.
It, will be by the film of aqueous alkali metal chloride or diaphragm electrolysis generation 5. according to the method described in claim 4, wherein
Partial alkaline-metal hydroxide solution, which is sent to, neutralizes precipitation of silica object.
6. smelter grade alumina production method comprising with the next stage:
Aluminum-containing raw material is ground, then leaches it with hydrochloride waste, the hydrochloride waste is acid waste liquid,
By resulting chloride pulp separation at useless precipitation of silica object and clear liquor alumini chloridi, the useless silica
Topple over after precipitate washed with water, wherein being supplied to the water for being used to wash purpose from the cigarette generated by calcining Aluminium chloride hexahydrate
Mist and by pyrohydrolysis process generate smog in adiabatic absorption hydrogen chloride region, and the amount of washing water by be used for adiabatic absorption
Water determine,
Aluminium chloride hexahydrate is crystallized out from clear liquor alumini chloridi；After separating crystal, resulting waste liquid is supplied to essence
Area is evaporated, is herein reduced the hydrogen cloride concentration in waste liquid to form hydrogen chloride gas, by the dry then confession of the hydrogen chloride gas
Area of saltouing should be arrived；The waste liquid being discharged from rectification zone is divided into two unequal parts: biggish part is directly supplied and is used to prepare
Waste liquid, another part supply to be applied to remove impurity by pyrohydrolysis,
Aluminium chloride hexahydrate is decomposed thermally to form aluminium oxide, is then calcined to produce thick aluminium oxide as intermediate product, simultaneously
Smog is calcined to be absorbed by the water for washing useless precipitation of silica object,
Thick alumina leaching is carried out with alkaline waste liquor according to Bayer process and precipitates resulting aluminate solution,
Isolated aluminium hydroxide wash and is then calcined, and
The waste liquid for having left settling zone and the boiling for having been used for washing aluminum hydroxide is dense, intermediate alumina will be returned to production
The alkaline waste liquor of product leaching stage, and
The waste liquid is mainly used for leaching aluminum-containing raw material, and only some is conveyed to for going to clean by pyrohydrolysis
Matter.
7. according to the method described in claim 6, wherein, the chlorine ion concentration in intermediate alumina product is maintained at 0.2 weight
The level for measuring the weight of %~5.0 %, the chlorine ion concentration in alkaline waste liquor are maintained at the level of 40~90g/L, and by from
The waste liquid boiling down of settling zone (the 10 weight % of weight %~40 of total flow) is opened, until isolating containing of removing during this
Chlorine compound crystal.
8. according to the method described in claim 6, wherein, the waste liquid being discharged from settling zone and the moisture two for having been used for washing purpose
A stage boiling down, alkali carbonate crystallize in the first stage, and alkali metal chloride is crystallized in second stage.
9. the alkali metal chloride of mainly sodium chloride and potassium chloride is purified according to the method described in claim 8, wherein,
And film or diaphragm electrolysis are carried out in form of an aqueous solutions.
10. according to the method described in claim 9, wherein, during the film of aqueous alkali metal chloride or diaphragm electrolysis
The chlorine and hydrogen of formation are used to synthesize the hydrochloric acid for being conveyed to leach initial aluminum-containing raw material, and will be water-soluble in alkali metal chloride
The partial alkaline-metal hydroxide aqueous solution formed during the film or diaphragm electrolysis of liquid is soaked with back to intermediate alumina product
The alkaline waste liquor mixing in stage out.
11. according to the method described in claim 10, wherein, will be generated by the film of aqueous alkali metal chloride or diaphragm electrolysis
Partial alkaline-metal hydroxide solution send to neutralize precipitation of silica object.
12. according to the method described in claim 6, wherein, the hydrogen cloride concentration in liquor alumini chloridi reaches about 17%~19%,
And in this case, due to the amount of heat discharged in HCl absorption process, liquor alumini chloridi is certainly in absorption process
Evaporation, and all water for washing useless precipitation of silica object supplied all are removed from circulation.
13. according to the method described in claim 6, wherein, liquor alumini chloridi is sent into crystallization and (is saltoutd) area, it herein will be by rectifying
The hydrogen chloride gas of generation is bubbled through the solution, and the concentration in the solution reaches about 32%, most of (~95%)
Aluminum precipitation is Aluminium chloride hexahydrate crystal.
14. according to the method described in claim 6, wherein, after separating crystal (crystalline particle), resulting waste liquid is sent to
Rectification zone herein reduces the hydrogen cloride concentration in waste liquid to form hydrogen chloride gas, and the hydrogen chloride gas is dry to containing
Water is about 5%, is then delivered to area of saltouing, wherein described by being carried out the temperature of gas cooling to about 35 DEG C with cooling water
It is dry.
15. according to the method described in claim 6, wherein, sending to the ratio (about 15%) for carrying out the waste liquid of pyrohydrolysis by sending to
The permission content of the impurity in waste liquid leached determines, and in pyrohydrolysis process, what is contained in waste liquid is all free
Acid and gas phase is all entered by the hydrogen chloride that hydrolyzes to form of chloride of the metal including Al, Fe, Ca, Mg；It is generated by pyrohydrolysis
Smog contains regenerated hydrogen chloride, and is sent to the region with the water absorbing hydrogen chloride for washing useless precipitation of silica object.
16. according to the method described in claim 6, wherein, producing the rank of thick aluminium oxide and the smog containing hydrogen chloride in calcining
Section is inhaled with the water for washing useless precipitation of silica object herein by the smoke delivery generated by calcination process to absorption region
Receive, at the same to supplied to leach area waste liquid in add it is fresh acid with compensate loss, and add fresh water with to by calcining and
The smog that pyrohydrolysis process generates carries out hygienic purification.
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| RU2016138762A RU2647041C1 (en) | 2016-09-30 | 2016-09-30 | Method of producing metallurgical alumina (variants) |
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| PCT/RU2017/000678 WO2018063029A1 (en) | 2016-09-30 | 2017-09-20 | Method for producing metallurgical alumina (variants) |
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| CN114341057A (en) * | 2019-06-07 | 2022-04-12 | 美卓奥图泰芬兰有限公司 | Method and apparatus for thermal decomposition of aluminium chloride hydrate to aluminium oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2705071C1 (en) * | 2018-11-07 | 2019-11-01 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of producing metallurgical alumina by an acid-alkaline method |
| CN110963662A (en) * | 2019-12-09 | 2020-04-07 | 上海净屹环保科技有限公司 | Method for recovering aluminum salt coagulant from aluminum-containing sludge |
| CN111186851B (en) * | 2020-03-05 | 2022-03-08 | 昆明冶金研究院有限公司 | Method for preparing modified aluminum-based catalyst by recycling electric dust collection powder of fluidized bed roaster |
| WO2024040302A1 (en) * | 2022-08-26 | 2024-02-29 | Alcoa Of Australia Limited | Process for preparing alumina |
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| CN114341057A (en) * | 2019-06-07 | 2022-04-12 | 美卓奥图泰芬兰有限公司 | Method and apparatus for thermal decomposition of aluminium chloride hydrate to aluminium oxide |
| CN114341057B (en) * | 2019-06-07 | 2023-11-10 | 美卓奥图泰芬兰有限公司 | Method and apparatus for thermal decomposition of aluminum chloride hydrate to aluminum oxide |
Also Published As
| Publication number | Publication date |
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| CA3118678A1 (en) | 2018-04-05 |
| CA3118678C (en) | 2024-05-14 |
| RU2647041C1 (en) | 2018-03-13 |
| MY186787A (en) | 2021-08-20 |
| CN109790045B (en) | 2022-06-17 |
| WO2018063029A1 (en) | 2018-04-05 |
| CA3032938A1 (en) | 2018-04-05 |
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