CN101397604B - Dense alkali liquid leaching pre-desiliconisation method for bauxite - Google Patents
Dense alkali liquid leaching pre-desiliconisation method for bauxite Download PDFInfo
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- CN101397604B CN101397604B CN2007101755032A CN200710175503A CN101397604B CN 101397604 B CN101397604 B CN 101397604B CN 2007101755032 A CN2007101755032 A CN 2007101755032A CN 200710175503 A CN200710175503 A CN 200710175503A CN 101397604 B CN101397604 B CN 101397604B
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- bauxite
- alumyte
- aluminium silicate
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- sodium
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- 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
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Abstract
The invention relates to a pre-desiliconization method by high-concentration alkaline liquor leaching of alumyte, which can improve alumyte grade obviously, and obtained beneficiated ore can be used for producing alumina technology by bayer process. The pre-desiliconization method comprises the following steps: at atmospheric pressure lower than 5 and normal pressure as selective preference, the alumyte is subjected to leaching reaction in the high-concentration alkaline liquor; conditions such as initial alkali concentration, temperature, alkali-ore ratio, reaction time and the like are controlled; by utilizing the dissolving characteristics of diasporite and kaolinite under different reaction conditions, the main impurity in the alumyte is removed in advance so as to realize the pre-desiliconization of the alumyte and improve the aluminum-silicon ratio (A/S) of the mid-low grade alumyte; serous fluid after reaction is subjected to liquid-solid separation to obtain high grade beneficiated alumyte, wherein, the A/S ratio of the obtained beneficiated alumyte can be up to over 10. A liquid phase is added with sodium-silicon slag or red mud waste slag seed crystal, stirred and crystallized for 1 to 20 hours, and then returned to the systems for recycling after most silicon dioxide thereof is removed.
Description
Technical field
The present invention relates to the high high alkali liquid leaching method for desilication of bauxite, can significantly improve bauxite grade with this method, the gained concentrate can be used for producing aluminium oxide by bayer technology.
Background technology
The industrial process of aluminum oxide mainly contains bayer's process, integrated process and sintering process.The grade difference of the bauxite that different production methods requires, the alumina silica ratio of bauxite (A/S) is a very important index in alumina producing, it is related to throughput, alumina recovery rate and the raw materials consumption amount etc. of equipment.Bayer's process requires the A/S of bauxite greater than 8~10, and integrated process requires 5~7, and it is 3.5~5.0 bauxite that the sintering rule can be handled A/S.China's bauxite is the high diaspore type bauxite of silicon content more than 98%, this bauxite of present domestic use carries out aluminum oxide industry production, general sintering process or the mixed combining method production technique of adopting, compare bayer's process, these technical process are long, energy consumption is big, cost is high, and the output red mud amount is many, and is more serious to the influence that environment causes.Therefore, remove part SiO in the ore in advance
2, the alumina silica ratio of raising bauxite not only can improve stripping and desiliconization condition, and help to save production cost.Compare with lime bayer's process or ore dressing bayer's process, Pre-desilicification for Bauxite-bayer's process has the raw material availability height, the characteristics of medium reusable edible.
But in traditional bayer's process flow process, the concentration of technology alkali lye is lower, and the effect that is used for pre-desiliconization is difficult to reach the requirement to the pre-desiliconization of middle-low bauxite.In the research of bauxite chemistry desiliconization, the dilute alkaline soln that the main NaOH of application concentration is lower than 20wt% is handled, common method has roasting-sodium hydroxide stripping desiliconization and the direct stripping of sodium hydroxide-sorting desiliconization method, energy consumption is bigger, and the existence of these factors has all proposed a difficult problem economically to industrial application.
Summary of the invention
The objective of the invention is to propose a kind of dense alkali liquid leaching pre-desiliconisation method for bauxite, remove sila matter in the bauxite at short notice, improve the bauxite aluminium-silicon ratio, effect is remarkable.Thereby improve raw material availability in the production of subsequent oxidation aluminium, shortened process reduces production energy consumption and reduces red mud quantity discharged etc.For the development and use of middle-low bauxite and solve present China alumina producing flow process complexity, the higher problem of energy consumption proposes a new way.
Dense alkali liquid leaching pre-desiliconisation method for bauxite of the present invention is to be lower than under 5 normal atmosphere, be preferably under the normal pressure, bauxite is leached reaction in high-concentration alkali liquor, control conditions such as initial alkali concn, temperature, alkali ore deposit ratio, reaction times, utilize diaspore and the kaolinite dissolution characteristics under the differential responses condition, remove the major impurity silicon-dioxide in the bauxite in advance, realize the pre-desiliconization of bauxite, improve the alumina silica ratio (A/S) of middle-low bauxite; The reaction rear slurry obtains the smart bauxite of higher-grade through liquid-solid separation, and the alumina silica ratio of the smart bauxite of gained can be up to more than 10.Liquid phase added sodium white residue or waste red mud residues crystal seed stirred crystallization 1~20 hour, slough wherein most of silicon-dioxide after, retrieval system recycles.
Dense alkali liquid leaching pre-desiliconisation method for bauxite of the present invention may further comprise the steps:
1) is being lower than under 5 atmospheric pressure, be preferably under the normal pressure, it is that 20%~50% NaOH solution leaches reaction that the bauxite of pulverizing is placed the weight percent concentration of reactor, wherein the weight part proportioning of bauxite and NaOH solution is 1: 2~1: 5, stir simultaneously, bauxite is fully contacted with NaOH solution; The temperature of control reaction system is 100~160 ℃; Reaction finishes, and obtains containing the alkaline solution and the smart bauxite of sodium aluminium silicate respectively through solid-liquid separation; By control reaction temperature, reaction times etc., realize the mineral target components stripping and with the separating of diaspore;
2) adding sodium white residue or waste red mud residues crystal seed carry out alkali liquor desiliconization in the alkaline solution that contains sodium aluminium silicate that step 1) obtains, form sodium silicoaluminate, wherein, sodium white residue or waste red mud residues crystal seed are 1: 10~3: 10 with the weight part proportioning that contains the alkaline solution of sodium aluminium silicate, in 50~160 ℃ of crystallizations, remove wherein and to make solution return step 1) behind the silica content to recycle, desilication product is a sodium silicoaluminate.
The weight percent concentration of described NaOH solution is preferably 30%~50%.
The particle diameter of the bauxite after the described pulverizing is 50~200 orders
The reaction times of step 1) system is 5~30 minutes.
Step 2) it is 1~20 hour in 50~160 ℃ of crystallization times.
The alumina silica ratio of the smart bauxite of gained can be up to more than 10, and preferred alumina silica ratio is 10~30.
Dense alkali liquid leaching pre-desiliconisation method for bauxite provided by the invention is compared with having the Pre-desilicification for Bauxite method both at home and abroad now, has following obvious superiority:
(1) the present invention compares with physical concentration desiliconization method, and it is low to have broken away from raw material availability, the problem that product grade is difficult to guarantee, and the alumina recovery rate reaches about 95%, and gained concentrate alumina silica ratio can be up to more than 10.
(2) the present invention compares with other chemical mineral processing method, does not establish roasting, assorting room, and the equipment input reduces, and energy consumption greatly reduces; And do not add any auxiliary material, bed drain purge reduces.
(3) the present invention is for being lower than under 5 normal atmosphere or normal pressure reaction down, and the steam energy consumption is low; And the reaction conditions gentleness, industrial implementation is workable.Handle the smart bauxite in back and can be directly used in bayer's process production bauxite technology.
(4) the present invention relates to the Pre-desilicification for Bauxite process reaction period only is 5~30 minutes, improve bauxite grade in short period of time rapidly at the utmost point, the alumina silica ratio of bauxite is brought up to more than 10 by 3~7, and the alumina recovery rate reaches about 95%, in desiliconization speed and be a quantum jump on the reaction times.
Embodiment
Embodiment 1.
Carry out the processing of Pre-desilicification for Bauxite with the comprehensive sample ore in Henan bauxite district as raw material, it is as follows that this Henan bauxite raw material is formed (wt%):
?Al 2O 3 | SiO 2 | Fe 2O 3 | CaO | TiO 2 | Moisture and other | A/S |
?63.67 | 11.63 | 4.72 | 2.30 | 2.74 | 14.94 | 5.47 |
Its treatment step is:
1, is that 40% NaOH solution is warming up to 120 ℃ with weight percent concentration in reactor, 120~200 purpose bauxite mixed with NaOH solution that its weight part proportioning is a bauxite: NaOH solution=1: 4.Reaction is 5 minutes under normal pressure, is mainly contained the mixed serum of alkali lye, sodium aluminium silicate and smart bauxite, 100 ℃ of insulation filtrations down, separates the alkaline solution and the smart bauxite that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 22.6g/L, SiO
2Content is 21.5g/L.
2, add waste red mud residues in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the red mud slag: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 20 hours under 60 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 7.5g/L, SiO
2Content is reduced to 6.5g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, add a small amount of dilute NaOH solution drip washing in the smart bauxite of step 1 gained, it is 20.2 that its alumina silica ratio is analyzed in oven dry, belongs to higher-grade bauxite.
Embodiment 2.
Carry out the processing of Pre-desilicification for Bauxite with Yangquan, Shanxi bauxite as raw material, the composition (wt%) of ore deposit, Yangquan, Shanxi raw material is as follows:
?Al 2O 3 | SiO 2 | Fe 2O 3 | CaO | TiO 2 | Moisture and other | A/S |
?60.34 | 17.16 | 5.61 | 1.0 | 2.15 | 13.74 | 3.5 |
Its treatment step is:
1, is that 40% NaOH solution is warming up to 120 ℃ with weight percent concentration in reactor, 120~200 purpose bauxite mixed with NaOH solution that its weight part proportioning is a bauxite: NaOH solution=1: 4.Reaction is 5 minutes under normal pressure, is mainly contained the mixed serum of alkali lye, sodium aluminium silicate and smart bauxite, 100 ℃ of insulation filtrations down, separates the alkaline solution and the smart bauxite that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 21.6g/L, SiO
2Content is 20.9g/L.
2, add waste red mud residues in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the red mud slag: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 20 hours under 60 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 5.0g/L, SiO
2Content is reduced to 4.1g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, step 1 gained concentrate is added a small amount of dilute NaOH solution drip washing, it is 15.7 that its alumina silica ratio is analyzed in oven dry, is the higher-grade concentrate.
Embodiment 3.
1, utilizes the resulting solution that removes behind the silica content of embodiment 2.The resulting solution that removes behind the silica content of embodiment 2 joined in the reactor recycle, mix with 120~200 purpose bauxite, its weight part proportioning is a bauxite: circulation NaOH solution (concentration is 36.3wt%)=1: 4.Temperature of reaction is risen to 120 ℃, and reaction is 5 minutes under normal pressure, is mainly contained the mixed serum of alkali lye, sodium aluminium silicate and smart bauxite, 100 ℃ of insulation filtrations down, separates the alkaline solution and the concentrate that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 22.7g/L, SiO
2Content is 25.2g/L.
2, add waste red mud residues in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the red mud slag: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 24 hours under 60 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 6.3g/L, SiO
2Content is reduced to 5.7g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, step 1 gained concentrate is added a small amount of dilute NaOH solution drip washing, its alumina silica ratio 12.9 is analyzed in oven dry, is the higher-grade concentrate.
Embodiment 4.
Carry out the processing of Pre-desilicification for Bauxite with ore deposit, Pingguo, Guangxi as raw material, it is as follows that this Used in Guangxi Pingguo Bauxite Project raw material is formed (wt%):
?Al 2O 3 | SiO 2 | ?Fe 2O 3 | CaO | TiO 2 | Moisture and other | A/S |
?59.2 | 7.93 | ?6.69 | 3.10 | 3.47 | 19.61 | 7.5 |
Its treatment step is:
1, is that 50% NaOH solution is warming up to 135 ℃ with weight percent concentration in reactor, 120~200 purpose bauxite mixed with NaOH solution that its weight part proportioning is a bauxite: NaOH solution=1: 5.Reaction is 8 minutes under normal pressure, is mainly contained the mixed serum of alkali lye, sodium aluminium silicate and smart bauxite, 100 ℃ of insulation filtrations down, separates the alkaline solution and the smart bauxite that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 17.6g/L, SiO
2Content is 16.5g/L.
2, add waste red mud residues in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the red mud slag: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 20 hours under 60 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 5.1g/L, SiO
2Content is reduced to 4.4g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, step 1 gained concentrate is added a small amount of dilute NaOH solution drip washing, it is 23.3 that its alumina silica ratio is analyzed in oven dry, belongs to higher-grade bauxite.
Embodiment 5.
Carry out the processing of Pre-desilicification for Bauxite with certain Shanxi bauxite as raw material, (wt%) is as follows for the composition of bauxitic feed materials:
?Al 2O 3 | SiO 2 | Fe 2O 3 | CaO | TiO 2 | Moisture and other | A/S |
?65.25 | 7.86 | 5.81 | 1.20 | 2.30 | 17.58 | 8.3 |
Its treatment step is:
1, be that 40% NaOH solution mixes in closed reactor with 50~100 purpose bauxite with weight percent concentration, its weight part proportioning is a bauxite: NaOH solution=1: 4.Be warming up to 160 ℃, be lower than under 4 normal atmosphere reaction 5 minutes, mainly contained the mixed serum of alkali lye, sodium aluminium silicate and concentrate, be cooled to then 100 ℃ down insulation filter, separate the alkaline solution and the smart bauxite that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 22.8g/L, SiO
2Content is 23.1g/L.
2, add the sodium white residue in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the sodium white residue: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 1 hour under 160 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 6.5g/L, SiO
2Content is reduced to 4.5g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, step 1 gained concentrate is added a small amount of dilute NaOH solution drip washing, its alumina silica ratio 30.7 is analyzed in oven dry, is the higher-grade concentrate.
Embodiment 6.
Carry out the processing of Pre-desilicification for Bauxite with Yangquan, Shanxi bauxite as raw material, the composition of raw material is with embodiment 2.
Its treatment step is:
1, be that 20% NaOH solution mixes with 120~200 purpose bauxite with weight percent concentration, be warming up to 140 ℃ in closed reactor, its weight part proportioning is a bauxite: NaOH solution=1: 5.Be lower than under 5 normal atmosphere reaction 30 minutes, mainly contained the mixed serum of alkali lye, sodium aluminium silicate and smart bauxite, 60 ℃ down insulation filter, separate the alkaline solution and the smart bauxite that obtain containing sodium aluminium silicate.This moment alkaline solution in Al
2O
3Content is 18.2g/L, SiO
2Content is 16.8g/L.
2, add waste red mud residues in the alkaline solution that contains sodium aluminium silicate, its weight part proportioning is the red mud slag: contain the alkaline solution of sodium aluminium silicate=1: 10, crystallization is 5 hours under 95 ℃ of conditions, this moment liquid phase Al
2O
3Content is reduced to 4.5g/L, SiO
2Content is reduced to 3.2g/L.Remove wherein and to make solution return step 1 behind the silica content to recycle, desilication product is a sodium silicoaluminate.
3, step 1 gained concentrate is added a small amount of dilute NaOH solution drip washing, it is 10.6 that its alumina silica ratio is analyzed in oven dry, is the higher-grade concentrate.
Claims (7)
1. a dense alkali liquid leaching pre-desiliconisation method for bauxite is characterized in that, this method may further comprise the steps:
1) is being lower than under 5 atmospheric pressure, it is that 20%~50% NaOH solution leaches reaction that bauxite after pulverizing is placed the weight percent concentration of reactor, wherein the weight part proportioning of bauxite and NaOH solution is 1: 2~1: 5, stir simultaneously, bauxite is fully contacted with NaOH solution; The temperature of control reaction system is 100~160 ℃; Reaction times is 5~30 minutes, obtains containing the alkaline solution and the smart bauxite of sodium aluminium silicate respectively through solid-liquid separation;
2) adding sodium white residue or waste red mud residues crystal seed carry out alkali liquor desiliconization in the alkaline solution that contains sodium aluminium silicate that step 1) obtains, wherein, sodium white residue or waste red mud residues crystal seed are 1~3: 10 with the weight part proportioning that contains the alkaline solution of sodium aluminium silicate, in 50~160 ℃ of crystallizations, remove wherein and to make solution return step 1) behind the silica content to recycle, desilication product is a sodium aluminium silicate.
2. method according to claim 1 is characterized in that: the weight percent concentration of described NaOH solution is 30%~50%.
3. method according to claim 1 is characterized in that: the particle diameter of the bauxite after the described pulverizing is 50~200 orders.
4. method according to claim 1 is characterized in that: described pressure is normal pressure.
5. method according to claim 1 is characterized in that: step 2) be 1~20 hour in 50~160 ℃ of crystallization times.
6. method according to claim 1 is characterized in that: the alumina silica ratio of the smart bauxite of gained is up to more than 10.
7. method according to claim 6 is characterized in that: described alumina silica ratio is 10~30.
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CN101857256B (en) * | 2009-04-13 | 2012-04-25 | 中国科学院过程工程研究所 | Method for removing silicon dioxide from low-grade diasporite type bauxite |
CN102951667B (en) * | 2012-11-26 | 2014-06-11 | 中国铝业股份有限公司 | Method for desilicating sodium aluminate solution |
CN105349797B (en) * | 2014-08-20 | 2018-05-22 | 中国科学院过程工程研究所 | A kind of method containing golden tailing or cyanidation tailings pretreatment desiliconization leaching gold |
CN113716577B (en) * | 2021-09-10 | 2023-04-18 | 湖南绿脉环保科技股份有限公司 | Desiliconization method of kaolin-containing silicon-aluminum-containing raw material |
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CN1320559A (en) * | 2000-04-26 | 2001-11-07 | 中南工业大学 | Process for desiliconizing crude liquid obtained by sinter method |
CN1565974A (en) * | 2003-06-24 | 2005-01-19 | 中国科学院过程工程研究所 | Normal pressure low temperature leaching production method for alumina |
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CN1320559A (en) * | 2000-04-26 | 2001-11-07 | 中南工业大学 | Process for desiliconizing crude liquid obtained by sinter method |
CN1565974A (en) * | 2003-06-24 | 2005-01-19 | 中国科学院过程工程研究所 | Normal pressure low temperature leaching production method for alumina |
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