CN1281503C - Silicon slag treatment method in aluminium oxide production process - Google Patents
Silicon slag treatment method in aluminium oxide production process Download PDFInfo
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- CN1281503C CN1281503C CN 200410037942 CN200410037942A CN1281503C CN 1281503 C CN1281503 C CN 1281503C CN 200410037942 CN200410037942 CN 200410037942 CN 200410037942 A CN200410037942 A CN 200410037942A CN 1281503 C CN1281503 C CN 1281503C
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- dealkalize
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002893 slag Substances 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910052710 silicon Inorganic materials 0.000 title abstract description 7
- 239000010703 silicon Substances 0.000 title abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000004411 aluminium Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims description 38
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 18
- 230000007704 transition Effects 0.000 claims description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 239000003518 caustics Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 239000002699 waste material Substances 0.000 abstract description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 5
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 5
- 239000004571 lime Substances 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 4
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004131 Bayer process Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000000404 calcium aluminium silicate Substances 0.000 description 2
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 2
- WNCYAPRTYDMSFP-UHFFFAOYSA-N calcium aluminosilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WNCYAPRTYDMSFP-UHFFFAOYSA-N 0.000 description 2
- 229940078583 calcium aluminosilicate Drugs 0.000 description 2
- 229910001647 dawsonite Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- DEPUMLCRMAUJIS-UHFFFAOYSA-N dicalcium;disodium;dioxido(oxo)silane Chemical compound [Na+].[Na+].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DEPUMLCRMAUJIS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 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 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
Abstract
The present invention relates to a method for treating silicon slag during the process of producing aluminium oxide, which is characterized in that the treating process comprises: after solid-liquid separation, sodium silicon slag slurry is washed and then is mixed with lime milk, alkali is removed at 90 to 100 DEG C, and the reaction is kept for 2 to 4 hours; the surface of dealkalized slag is treated through ball milling, CO2 with the concentration of 8% to 100% is supplied and stirred, and transformation reaction is kept for 2 hours; alkali liquor is added into solution obtained after the solid-liquid separation of slurry after transformation and dealkalized slurry to dissolve aluminium; finally, aluminium dissolved slurry is obtained through solid-liquid separation and is put into a sintering red mud washing system to remove the slag phase. The dealkalizing rate of the method reaches more than 90%, A/S in waste slag is smaller than 0.7, and N/S is smaller than 0.2.
Description
Technical field
White residue treatment process in a kind of aluminum oxide production process relates to a kind of processing of adopting sintering process to produce the white residue that produces in the alumina process, particularly reclaims the method for aluminum oxide and sodium oxide from white residue.
Background technology
China's bauxite mostly is diaspore type, and based on medium grade, wherein, alumina silica ratio (A/S) is that 4～8 ore accounts for about 80% of total amount.Be that in existing its key of alkaline process production method of alumina aluminium, silicon separate.Hydrated aluminum silicate Na
2OAl
2O
31.7SiO
2NH
2O, i.e. sodium white residue is the reaction product of alkaline process most important silicon mine when handling bauxite.In the sodium white residue amount that forms, also contain a large amount of alkali and aluminum oxide.In medium grade ore of Bayer process high pressure stripping and process for desiliconizing crude liquid obtained by sinter process, reach 1000kg/t-Al respectively approximately
2O
3And 200kg/t-Al
2O
3Sintering process is all adopted in the processing of sodium white residue at present, is about to Bayer process red mud and sintering process white residue and delivers to respectively and turn back to that sintering system is prepared burden, sintering, makes process for making alumina complexity, production efficiency reduce.
Since last century the fifties, USSR (Union of Soviet Socialist Republics), Hungary and China are devoted to study the wet method aluminium silicon isolation technique of sodium white residue always, produce alumina technology to have formed high pressure water chemical method or Bayer-aquation method.Mainly contain: 1) USSR (Union of Soviet Socialist Republics) ripple Nuo Maliefu-Sa Ren etc. is by to Na
2O-Al
2O
3-SiO
2-CaO-H
2O be the balance solid phase researched and proposed the high pressure water chemical method, its principle is to make silicon generate the slag phase that does not contain or contain less aluminium or alkali under 260～350 ℃ higher temperature, as sodium calcium silicate, calcium silicate hydrate, molten iron fossil garnet etc., aluminum oxide then enters solution with the form of sodium aluminate.This method alkali recovery is greater than 80%, and the alumina recovery rate is 40%～70%.But the solution alkali concn is higher, causticity compares α
kUp to 10～30, and under high-temperature and high-pressure conditions, operate, equipment material is required harsh; 2) hydrothermal method of Czech, Hungary scholar proposition, its α
kBe about 4.0, loose slightly than the former condition, mainly reclaim the alkali in the red mud, but the alumina recovery rate is low, the red mud alumina silica ratio after the processing is still greater than 1, and is unreasonable economically.
Summary of the invention
The objective of the invention is to handle the deficiency that exists, provide a kind of and can realize effectively that sodium, aluminium, silicon in the sodium white residue separate, and reclaim the aluminum oxide in the sodium white residue, the white residue treatment process of sodium oxide at the existing above-mentioned silicic acid in producing alumina process.
The objective of the invention is to be achieved through the following technical solutions.
White residue treatment process in a kind of aluminum oxide production process is characterized in that treating processes is:
(1) the sodium white residue slurries behind the sodium aluminate solution desilicification are through the filter solid-liquid separation and after washing, and solution send the alumina producing flow process;
(2) isolated sodium white residue is pressed molecular ratio CaO/Na
2Mix with milk of lime O=3～4, and 90 ℃～100 ℃ of temperature, liquid-solid ratio is under the processing condition of 5-7, stirring reaction dealkalize in 2～4 hours;
(3) dealkalize slurries solid-liquid separation, the dealkalize slag by ball milling 20-30 minute, is carried out surface treatment to slag, at liquid-solid ratio 5-10,50 ± 10 ℃ of temperature are with the CO that feeds concentration 8%～100%
2Reaction 2 hours transition is carried out in stirring;
(4) slurries after will making the transition, the solution after the dealkalize slurries solid-liquid separation add alkali lye, make caustic sodium concentration reach 50～100g/L, liquid-solid ratio is 7～10, under the condition of 50 ℃ ± 10 ℃ of temperature molten aluminium 1-2 hour; Last solid-liquid separation goes out molten aluminium paste liquid and send the red mud from sintering process washing system, discards the slag phase.
Method of the present invention adopts the sodium white residue of normal temperature and pressure to add milk of lime dealkalize technology, and dealkalize slag technology transition and the slag modification technology that makes the transition are handled the sodium white residue, and its dealkalize rate is reached more than 90%, and A/S is less than 0.7 in the waste, and N/S is less than 0.2.
The inventive method sintering process white residue discards as waste residue after reclaiming wherein useful component, thus avoid a large amount of white residues later, batching forms inner invalid circulation, has excellent economy.
The purpose of sodium white residue dope filtration washing is to reduce the alumina content of solution in the white residue treating processes.In the white residue treating processes, if there is aluminum oxide to exist in the white residue attached liquid, after adding lime, the efficient oxidation calcium wherein at first with liquid phase in aluminum oxide react and enter solid phase, cause alumina loss, reduced the quantity of the efficient oxidation calcium that reacts with white residue simultaneously, made and take off the sodium deleterious.
The purpose of dealkalize slag transition is that aluminium in the calcium aluminosilicate hydrate that takes off in the sodium slag is transformed into easily by the aluminium hydroxide of alkali dissolution and dawsonite, and calcium changes calcium silicate hydrate in the calcium aluminosilicate hydrate.So that aluminium separates with silicon, calcium behind molten aluminium.
The purpose of ball milling is that the dealkalize slag is carried out surface modification in the transformation process, so that strengthen the kinetics diffusion process in transformation process, strengthens the conversion between silicon-containing compound, shortens white residue time transition.
The purpose that adds alkali in the molten aluminium process be with alkali under normal temperature, normal pressure with the aluminium hydroxide of indefinite form and dawsonite reaction, make aluminium enter solution with the sodium aluminate form so that calcium silicate hydrate separates, reach the isolating purpose of aluminium and silico-calcium.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
White residue treatment process in a kind of aluminum oxide production process, treating processes are that solution sent the alumina producing flow process after the sodium white residue slurries behind (1) sodium aluminate solution desilicification passed through filter solid-liquid separation and washing; (2) isolated sodium white residue is pressed (molecular ratio) CaO/Na
2Mix with milk of lime O=3～4, and 90 ℃～100 ℃ of temperature, liquid-solid ratio is under the processing condition of 5-7, stirring reaction dealkalize in 2～4 hours; (3) dealkalize slurries solid-liquid separation, the dealkalize slag was carried out surface treatment by ball milling 20-30 minute to slag, at liquid-solid ratio 5-10,50 ± 10 ℃ of temperature are with the CO that feeds concentration 8%～100%
2Reaction 2 hours transition is carried out in stirring; (4) slurries after will making the transition, the solution after the dealkalize slurries solid-liquid separation add alkali lye, make caustic sodium concentration reach 50～100g/L, liquid-solid ratio is 7～10, under the condition of 50 ± 10 ℃ of temperature molten aluminium 1-2 hour; Last solid-liquid separation goes out molten aluminium paste liquid and send the red mud from sintering process washing system, discards the slag phase.
Further specify as follows below by example to method of the present invention.
Embodiment 1
1, raw material:
(1) white residue:
High-pressure sodium white residue composition (%)
| SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | K 2O | Na 2O | TiO 2 |
| 23.74 | 24.04 | 13.01 | 3.52 | 11.67 |
(2), lime: CaO
T97%, f
CaO87%
(3), CO
2Concentration: 38%
(4), caustic sodium concentration: 50-100g/l
2, CONTROL PROCESS technical qualification:
1) dealkalize: 95 ℃ of temperature, CaO/Na
2O=3, liquid-solid ratio 5, reaction times 2h,
2) transition: liquid-solid ratio 5, about 50 ℃ of temperature, CO
2Concentration 38% makes the transition about time 2h; 20 minutes surface treatment time.
3) molten aluminium: 50 ℃ of temperature, 1 hour time, caustic sodium concentration 50g/L, liquid-solid ratio is 7.
3, technico-economical comparison;
(1), dealkalize rate 90%
(2), A/S is less than 0.7 in the waste, N/S is less than 0.2
Embodiment 2
1, raw material: (1) white residue:
High-pressure sodium white residue composition (%)
| SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | K 2O | Na 2O | TiO 2 |
| 23.74 | 24.04 | 13.01 | 3.52 | 11.67 |
(2), lime: CaO
T97%, f
CaO87%
(3), CO
2Concentration: 15%
(4), caustic sodium concentration: 50-100g/l
2, CONTROL PROCESS technical qualification:
1) dealkalize: 95 ℃ of temperature, CaO/Na
2O=4, liquid-solid ratio 5, reaction times 2h,
2) transition: liquid-solid ratio 5, about 50 ℃ of temperature, addition of C O
2Concentration 38%, time 2h makes the transition; 30 minutes surface treatment time.
3) molten aluminium: 50 ℃ of temperature, 1 hour time, caustic sodium concentration 100g/L, liquid-solid ratio is 7.
3, technico-economical comparison;
(1), dealkalize rate 92%
(2), A/S is less than 0.65 in the waste, N/S is less than 0.15
Embodiment 3:
1, raw material: (1) white residue:
High-pressure sodium white residue composition (%)
| SiO 2 | Fe 2O 3 | Al 2O 3 | CaO | K 2O | Na 2O | TiO 2 |
| 23.74 | 24.04 | 13.01 | 3.52 | 11.67 |
(2), lime: CaO
T97%, f
CaO87%
(3), CO
2Concentration: 8%
(4), caustic sodium concentration: 50-100g/l
2, CONTROL PROCESS technical qualification:
1) dealkalize: 95 ℃ of temperature, CaO/Na
2O=4, liquid-solid ratio 5, reaction times 2h,
2) transition: liquid-solid ratio 5,50 ℃ of temperature, addition of C O
2Concentration 38%, time 2h makes the transition; 20 minutes surface treatment time.
3) molten aluminium: 50 ℃ of temperature, 1 hour time, caustic sodium concentration 50g/L, liquid-solid ratio is 7.
3, technico-economical comparison;
(1), dealkalize rate 91%
(2), A/S is less than 0.75 in the waste, N/S is less than 0.17.
Claims (1)
1. the white residue treatment process in the aluminum oxide production process is characterized in that treating processes is:
(1) the sodium white residue slurries behind the sodium aluminate solution desilicification are through the filter solid-liquid separation and after washing, and solution send the alumina producing flow process;
(2) isolated sodium white residue is pressed molecular ratio CaO/Na
2Mix with milk of lime O=3～4, and 90 ℃～100 ℃ of temperature, liquid-solid ratio is under 5 the processing condition, stirring reaction dealkalize in 2～4 hours;
(3) dealkalize slurries solid-liquid separation, the dealkalize slag by ball milling 20-30 minute, is carried out surface treatment to slag, in liquid-solid ratio 5,50 ± 10 ℃ of temperature are with the CO that feeds concentration 8%～100%
2Reaction 2 hours transition is carried out in stirring;
(4) slurries after will making the transition, the solution after the dealkalize slurries solid-liquid separation add alkali lye, make caustic sodium concentration reach 50～100g/L, liquid-solid ratio is 7, under the condition of 50 ± 10 ℃ of temperature molten aluminium 1-2 hour; At last, the molten aluminium paste liquid that solid-liquid separation goes out send the red mud from sintering process washing system, discards the slag phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410037942 CN1281503C (en) | 2004-05-14 | 2004-05-14 | Silicon slag treatment method in aluminium oxide production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410037942 CN1281503C (en) | 2004-05-14 | 2004-05-14 | Silicon slag treatment method in aluminium oxide production process |
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| Publication Number | Publication Date |
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| CN1597529A CN1597529A (en) | 2005-03-23 |
| CN1281503C true CN1281503C (en) | 2006-10-25 |
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| CN 200410037942 Active CN1281503C (en) | 2004-05-14 | 2004-05-14 | Silicon slag treatment method in aluminium oxide production process |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100542960C (en) * | 2007-07-12 | 2009-09-23 | 中国铝业股份有限公司 | A kind of treatment process of white residue |
| CN101468866B (en) * | 2007-12-27 | 2011-04-20 | 中国科学院生态环境研究中心 | Normal atmosphere dealkalizing method by sintering |
| CN101565196B (en) * | 2009-06-05 | 2011-05-04 | 中国铝业股份有限公司 | Method for processing alumina process calcium silicone slag |
| CN103848452B (en) * | 2014-02-25 | 2015-10-07 | 湖南中大冶金设计有限公司 | The Simple treatment method of Bayer process red mud and silica residue in sinter process in producing alumina through series process |
| CN103964477B (en) * | 2014-04-30 | 2016-04-06 | 东北大学 | A kind of method being reduced red mud alumina silica ratio by multistage carbonation |
| CN105130142B (en) * | 2015-09-10 | 2018-01-05 | 中国科学院重庆绿色智能技术研究院 | A kind of method of non-Bayer process red mud depth dealkalize stage by stage |
| CN109809452A (en) * | 2019-03-29 | 2019-05-28 | 中南大学 | The recovery method of aluminium oxide in a kind of calcium aluminosilicate hydrate |
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