CN101249976A - Technique for producing aluminum oxide by alkali dissolving carbonation method - Google Patents
Technique for producing aluminum oxide by alkali dissolving carbonation method Download PDFInfo
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- CN101249976A CN101249976A CNA2007101786702A CN200710178670A CN101249976A CN 101249976 A CN101249976 A CN 101249976A CN A2007101786702 A CNA2007101786702 A CN A2007101786702A CN 200710178670 A CN200710178670 A CN 200710178670A CN 101249976 A CN101249976 A CN 101249976A
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Abstract
A novel technique process which combines an alkali dissolution process, a carbon dioxide decomposition process and an electrolytic regeneration cycling process is employed in a producing process of alumina. The steps comprise employing sodium hydroxide solution to dissolve alumina in alumyte in form of sodium aluminate, adding sodium bicarbonate solution or carbon dioxide to completely decompose sodium aluminate, then transforming into aluminum hydroxide to separate out to obtain alumina products after roasting, employing electrolytic method to electrolyze sodium carbonate mother liquor and respectively obtaining NaOH solution and NaHCO3 solution in cathode region and anode region. And regenerating and recycling NaOH solution and NaHCO3 solution is realized.
Description
(1) technical field under
The invention belongs to technical field of alumina production.
(2) the technology of the present invention background
Metallic aluminium is the development of the national economy and the indispensable important raw and processed materials of uplifting the people's living standard.Along with the fast development of Chinese national economy, the output of China's metallic aluminium has also obtained increasing rapidly.The beginning of this century the first five years, the metallic aluminium annual growth rate surpasses 50%, reaches 935.84 ten thousand tons to 2006 annual production, output ranks first in the world.Aluminum oxide is a raw material of producing metallic aluminium, and the fast development of metallic aluminium has promoted the corresponding fast development of alumina producing, and China's aluminum oxide output had reached 1369.98 ten thousand tons in 2006, also ranked first in the world.
Metallic aluminium is that raw material makes by the fused salt electrolysis explained hereafter with the aluminum oxide.And aluminum oxide is produced with bauxitic feed materials.The production method of alumina mainly contains two kinds of Bayer process and sintering processs, and in fact produce now and go up the integrated process of using is exactly the process integration of Bayer process and two flow processs of sintering process.Bayer process is that relative energy consumption is low, the production technique that production cost is low.But it requires high to bauxitic feed materials, and aluminium content must be greater than 8 with the ratio of silicone content in the raw material, and promptly silicone content must be seldom.The raw material that is used for alumina producing abroad mainly is the siliceous few and easy molten gibbsite of alkali, is Bayer process greatly partly so produce the technology of aluminum oxide in the world.China's bauxite resource reserves are also abundanter, but main resource all is alkali diaspores than indissoluble.The diaspore silicon content generally is higher than gibbsite, and " rich ore " that the silicone content that wherein suitable Bayer process is produced is low is less.China is except that the bauxite of Guangxi, and other very big part bauxite resources all are siliceous high middle low grade ores.For many years, China aluminum oxide scientific worker is at the characteristics of China's bauxite resource, researched and developed successfully the process for making alumina of several suitable China different resource, they are the Bayer process that is applicable to diaspore, sintering process, Bayer-sintering integrated process, ore dressing-Bayer process or the like, thereby make China's aluminum oxide industry form production system with Chinese characteristics.In current actual production, pure sintering process technology is owing to relative energy consumption height, cost height, so its application rate gradually reduces.Integrated process technology is being undertaken important production task in current China aluminum oxide industry, integrated process output 70% by Bayer process system output.In recent years the resource predicament that reduces year by year at the low silicon bauxite " rich ore " of China and study successful ore dressing (desiliconization in advance)-bayer process and be actually pure Bayer process.High-quality resource raw materials such as Guangxi are produced with pure Bayer process.Find out that thus in China's alumina producing, bayer process is main production technique, its actual output accounts for about 80% of the whole nation.Therefore improvement, innovation and the innovation of studying bayer process are the main direction and the task of aluminum oxide industry technical progress.
Current, China's economic construction is advanced smoothly along the road of the Scientific Outlook on Development, and innovation is a state basic policy, and energy-saving and emission-reduction are industrial vital tasks.Aluminum oxide industry is as mineral processing industry, and the energy-saving and emission-reduction task is heavy.Spirit according to the Scientific Outlook on Development and innovation, can aluminum oxide industry be studied and create a production efficiency height, energy consumption is low, cost is low, pollute few novel process for making alumina with independent intellectual property right? by analysis, research to alumina producing principle and production technology, and by test, we have proposed of the present invention---the molten carbon branch of alkali alumina producing novel process.
Bayer process is that the J.K. Bayer was in invention in 1889～1892 years.The ultimate principle of Bayer process is the Bayer circulation, and this circulation comprises two patents of Bayer: the one, and, at Na
2O and Al
2O
3Mol ratio be in 1.8 the sodium aluminate solution, at normal temperatures, add aluminium hydroxide as crystal seed, the aluminum oxide in the solution just can progressively be separated out with the form of aluminium hydroxide, till both mol ratios reached 6 o'clock in solution.Kind in the alumina producing that Here it is is divided process; The 2nd,, separated out the solution of part aluminium hydroxide, when heating, the hydrated alumina in again can stripping bauxite.Use the process of seed precipitation solution stripping bauxite in the alumina producing that Here it is.Be used alternatingly this two processes, just formed the technical process of alumina producing Bayer process.
Though bayer process successfully used in industrial production more than 100 year, and be regarded as the best or even the most classical impassable technology of alumina producing always, but, a fatal weakness of Bayer process is exactly first invention of Bayer round-robin, promptly in kind of branch process, separate out the amount of aluminium hydroxide and be subjected to its theoretical basis---Na because sodium aluminate solution adds crystal seed
2O-Al
2O
3-H
2The restriction of O three-phase equilibrium concentration, cause the aluminium hydroxide in the sodium aluminate solution not separate out fully, in actual production, its rate of decomposition can only be below 50%, and for up to 30-70 hour, this not only causes half or has more spent the aluminum oxide of a large amount of energy and labor force's stripping can only continue to stay the next one circulation that enters production in the solution, cause significant wastage to the energy and labor force, and influence the speed that aluminum oxide in the bauxite continues stripping, productivity are low, the production unit utilization ratio is low, and energy dissipation seriously is the maximum deficiency and the defective of Bayer process.
Sintering process be applicable to siliceous high in low alumina silica ratio ore produce alumina technology.It is based on, and aluminum oxide can be combined into solid sodium aluminate with yellow soda ash in the mineral when high temperature (800 ℃), and solid sodium aluminate is dissolved in dilute alkaline soln, feeds CO again
2Separate out the principle of aluminium hydroxide.Because what sintering process was handled is high silicon mine, and need with the high equipment such as rotary kiln of energy consumption, thus relative energy consumption height, the cost height.But sintering process has an outstanding advantage, that is, it separates out aluminium hydroxide from sodium aluminate solution be to adopt to feed CO
2Method, i.e. the carbon method of dividing.The essence that carbon divides can be regarded the acid-base neutralisation reaction as, in theory, this reaction can thoroughly be carried through to the end fast, and promptly it can make sodium aluminate solution all resolve into aluminium hydroxide and yellow soda ash in 1-3 hour, and the rate of decomposition that carbon divides in the actual industrial production is about 90～92%.So the production efficiency and the plant factor of sintering process are much higher than Bayer process.
" alkali molten-carbon method produce aluminum oxide " novel process that present technique invention is proposed, what adopt is the basic combination of the carbon operation break-down of the alkali lye stripping operation of less energy-consumption and high de-agglomeration rate, and utilize electrolytic process to realize that the causticization again of yellow soda ash recycles, it neither contains the low kind operation break-down of rate of decomposition and does not also contain high evaporation of energy consumption and calcining process, thereby has high-level efficiency, less energy-consumption, low cost and eco-friendly characteristics.
(3) summary of the invention
The objective of the invention is to, at existing alumina-producing method Bayer process and the existing deficiency of sintering process, provide a kind of and can either significantly improve the alumina producing new process that alumina producing efficient can realize the less energy-consumption of alkali lye recycle again, the molten carbon method alumina producing of alkali promptly as described below novel process.
The molten carbon method alumina producing of alkali of the present invention new technological flow figure sees accompanying drawing 1 and accompanying drawing 2 explanations.
The main contents and the technological principle of the molten carbon method alumina producing of alkali of the present invention novel process are:
1, with the Al in the certain density NaOH solution dissolving bauxite
2O
3, obtain sodium aluminate solution:
Al
2O
3+ 2NaOH+aq==2NaAlO
2+ aq (formula 1)
2, use HCO
3 -Or CO
2Decomposition sodium aluminate liquid is separated out Al (OH)
3, and obtain Na
2CO
3Solution;
NaAlO
2+ NaHCO
3+ aq → Na
2CO
3+ Al (OH)
3+ aq (formula 2)
2NaAlO
2+ CO
2+ aq → Na
2CO
3+ 2Al (OH)
3+ aq (formula 3)
3, roasting Al (OH)
3Obtain Al
2O
3
4, electrolysis Na
2CO
3Solution obtains NaOH solution in the cathodic area, obtains NaHCO in the positive column
3Solution;
Positive column: 2Na
2CO
3+ H
2O+aq? 2e → 2NaHCO
3+ 1/2O
2+ 2Na
++ aq
Cathodic area: 2Na
++ 2H
2O+aq+2e → 2NaOH+H
2+ aq
Or 2Na
++ 1/2O
2+ aq+2e → 2NaOH+aq
Total reaction: Na
2CO
3+ aq → NaOH+NaHCO
3+ aq (formula 4)
5, the NaOH solution that electrolysis is obtained is used further to dissolve the Al in the bauxite
2O
3, the NaHCO that electrolysis is obtained
3Solution is used further to the decomposition of sodium aluminate, and then realizes NaOH solution and NaHCO
3The recycle of solution.
The present invention is characterized in: in process for making alumina, adopted the molten operation of alkali, carbon operation break-down to combine with three of electrolytic regeneration circulating process, that is, adopting alumina content to be lower than 1% sodium hydroxide solution in the molten operation of alkali is dissolved out the form of the aluminum oxide in the bauxite with sodium aluminate; Adopting interpolation sodium hydrogen carbonate solution or the logical method that adds carbonic acid gas to make the thorough decomposition and inversion of sodium aluminate in the carbon operation break-down is that aluminium hydroxide is separated out, and the sodium aluminate rates of decomposing and transforming reaches 92-99%; In the electrolytic regeneration circulating process, the yellow soda ash mother liquor electrolysis with remaining obtains mass percent concentration and can be reused for the molten operation of alkali up to the NaOH solution of 5-40% in the cathodic area, and obtaining mass percent concentration in the positive column can be up to the NaHCO of 5-15%
3Solution is reused for the carbon operation break-down, thereby realizes NaOH solution and NaHCO
3The recycling utilization of solution.
In the molten operation of alkali, the mass percent concentration of best sodium hydroxide solution is 15-40%.
In the carbon operation break-down, the mass percent concentration of best sodium hydrogen carbonate solution is 6-15%.
(4) description of drawings
For explanation more directly perceived feature of the present invention, the present invention describes in conjunction with Figure of description.Accompanying drawing 1 and accompanying drawing 2 are process flow sheets of the present invention.
(5) embodiment
The present invention is further illustrated below in conjunction with example.
Embodiment 1
Adopt 35%NaOH solution that the diaspore powder was carried out stripping 2 hours, obtain refining sodium aluminate dissolution fluid after the leaf filter; Sodium hydrogen carbonate solution by 1: 1.1 equivalence ratio interpolation 12-13% reacted 1.5 hours, the aluminium hydroxide and the yellow soda ash mother liquor of separating out was separated again; Roasting aluminium hydroxide obtains the aluminum oxide of purity＞98.5%; Residual aluminium hydroxide content＜0.2% in the yellow soda ash mother liquor, electrolysis carbonic acid mother liquid of sodium obtains 35-40%NaOH solution in the cathodic area, obtain the 14-15% sodium hydrogen carbonate solution in the positive column.
Embodiment 2
Adopt 30%NaOH solution that three diaspore powder were carried out stripping 2 hours, obtain refining sodium aluminate dissolution fluid after the leaf filter; The logical CO that adds
2PH is reduced to 8.9-9.2, react after 1.2 hours the aluminium hydroxide and the yellow soda ash mother liquor of separating out separated; Roasting aluminium hydroxide obtains the aluminum oxide of purity＞98.5%; Residual aluminium hydroxide content＜0.2% in the yellow soda ash mother liquor, electrolysis carbonic acid mother liquid of sodium obtains 30-35%NaOH solution in the cathodic area, obtain the 10-13% sodium hydrogen carbonate solution in the positive column.
Adopt 25%NaOH solution that boehmite powder was soaked stripping 3.5 hours, obtain refining sodium aluminate dissolution fluid after the leaf filter; Sodium hydrogen carbonate solution by 1: 1.1 equivalence ratio interpolation 8-10% reacted 2 hours, the aluminium hydroxide and the yellow soda ash mother liquor of separating out was separated again; Roasting aluminium hydroxide obtains the aluminum oxide of purity＞98.5%; Residual aluminium hydroxide content＜0.5% in the yellow soda ash mother liquor, electrolysis carbonic acid mother liquid of sodium obtains 33-35%NaOH solution in the cathodic area, obtain the 14-15% sodium hydrogen carbonate solution in the positive column.
Claims (2)
1, a kind of novel technique method of producing aluminum oxide, its principal character is: adopted the molten operation of alkali, carbon operation break-down and electrolytic regeneration circulating process three bonded integrated technologies in process for making alumina, promptly, adopting sodium hydroxide solution is dissolved out the aluminum oxide in the bauxite with the form of sodium aluminate after, adopting interpolation sodium hydrogen carbonate solution or the logical method that adds carbonic acid gas to make the thorough decomposition and inversion of sodium aluminate is that aluminium hydroxide is separated out, and then obtains NaOH solution and NaHCO in cathodic area and positive column respectively by the remaining yellow soda ash mother liquor of electrolysis again
3Solution is respectively applied for molten operation of alkali and carbon operation break-down again, realizes NaOH solution and NaHCO
3The recycling utilization of solution.
2, the aluminium hydroxide that obtains by claims 1 described method is used to produce alumina product.
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| CN2007101786702A CN101249976B (en) | 2007-12-04 | 2007-12-04 | Technique for producing aluminum oxide by alkali dissolving carbonation method |
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|---|---|---|---|
| CN2007101786702A CN101249976B (en) | 2007-12-04 | 2007-12-04 | Technique for producing aluminum oxide by alkali dissolving carbonation method |
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|---|---|
| CN101249976A true CN101249976A (en) | 2008-08-27 |
| CN101249976B CN101249976B (en) | 2010-12-22 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786644B (en) * | 2009-01-22 | 2012-06-27 | 中国科学院过程工程研究所 | Sandy alumina preparation method |
| CN102560521A (en) * | 2012-01-14 | 2012-07-11 | 新疆哥兰德新能源有限公司 | Method for electrochemically preparing high-purity aluminum oxide |
| CN102605383A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Method and device for hydrogen-circulating electrolysis and application of the method and device in production of aluminum oxide |
| CN101774618B (en) * | 2009-12-30 | 2013-02-13 | 中国科学院过程工程研究所 | Method for preparing ordered mesoporous aluminum oxide by using sodium bicarbonate to decompose sodium aluminate solution |
| CN103449486A (en) * | 2013-08-29 | 2013-12-18 | 中国科学院过程工程研究所 | Method for preparing boehmite by liquid phase carbonating decomposition of sodium aluminate solution and sodium bicarbonate |
| CN105197973A (en) * | 2015-09-09 | 2015-12-30 | 洛阳国兴矿业科技有限公司 | Method of utilizing low-quality bauxite to prepare aluminum oxide |
| CN105197959A (en) * | 2015-09-09 | 2015-12-30 | 洛阳国兴矿业科技有限公司 | Method of recovering fluorine resource in process of processing low-grade bauxite by chemical floatation method |
| CN105253907A (en) * | 2015-09-09 | 2016-01-20 | 洛阳国兴矿业科技有限公司 | Comprehensive utilization method for processing low-grade bauxite through chemical floating method |
| CN108745332A (en) * | 2018-07-03 | 2018-11-06 | 贵州大学 | A kind of method of ardealite and high-sulfur bauxite dechlorination catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4483830A (en) * | 1981-09-10 | 1984-11-20 | Comalco Limited | Production of alumina |
| CN1156399C (en) * | 2000-05-19 | 2004-07-07 | 郑州轻金属研究院 | Alumina producing process with hydraulic duralumin-type bauxite concentrate |
| CN100337921C (en) * | 2005-05-18 | 2007-09-19 | 中国铝业股份有限公司 | Method for preparing alumina |
-
2007
- 2007-12-04 CN CN2007101786702A patent/CN101249976B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786644B (en) * | 2009-01-22 | 2012-06-27 | 中国科学院过程工程研究所 | Sandy alumina preparation method |
| CN101774618B (en) * | 2009-12-30 | 2013-02-13 | 中国科学院过程工程研究所 | Method for preparing ordered mesoporous aluminum oxide by using sodium bicarbonate to decompose sodium aluminate solution |
| CN102560521A (en) * | 2012-01-14 | 2012-07-11 | 新疆哥兰德新能源有限公司 | Method for electrochemically preparing high-purity aluminum oxide |
| CN102605383A (en) * | 2012-03-26 | 2012-07-25 | 北京化工大学 | Method and device for hydrogen-circulating electrolysis and application of the method and device in production of aluminum oxide |
| CN102605383B (en) * | 2012-03-26 | 2015-04-01 | 北京化工大学 | Method and device for hydrogen-circulating electrolysis and application of the method and device in production of aluminum oxide |
| CN103449486A (en) * | 2013-08-29 | 2013-12-18 | 中国科学院过程工程研究所 | Method for preparing boehmite by liquid phase carbonating decomposition of sodium aluminate solution and sodium bicarbonate |
| CN103449486B (en) * | 2013-08-29 | 2015-05-06 | 中国科学院过程工程研究所 | Method for preparing boehmite by liquid phase carbonating decomposition of sodium aluminate solution and sodium bicarbonate |
| CN105197973A (en) * | 2015-09-09 | 2015-12-30 | 洛阳国兴矿业科技有限公司 | Method of utilizing low-quality bauxite to prepare aluminum oxide |
| CN105197959A (en) * | 2015-09-09 | 2015-12-30 | 洛阳国兴矿业科技有限公司 | Method of recovering fluorine resource in process of processing low-grade bauxite by chemical floatation method |
| CN105253907A (en) * | 2015-09-09 | 2016-01-20 | 洛阳国兴矿业科技有限公司 | Comprehensive utilization method for processing low-grade bauxite through chemical floating method |
| CN108745332A (en) * | 2018-07-03 | 2018-11-06 | 贵州大学 | A kind of method of ardealite and high-sulfur bauxite dechlorination catalyst |
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|---|---|
| CN101249976B (en) | 2010-12-22 |
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