CN101412616B - Method for processing red mud from Bayer process by block-making and lime sintering method - Google Patents
Method for processing red mud from Bayer process by block-making and lime sintering method Download PDFInfo
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- CN101412616B CN101412616B CN2007100779735A CN200710077973A CN101412616B CN 101412616 B CN101412616 B CN 101412616B CN 2007100779735 A CN2007100779735 A CN 2007100779735A CN 200710077973 A CN200710077973 A CN 200710077973A CN 101412616 B CN101412616 B CN 101412616B
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to a method for processing Bayer process red mud by a lump lime making sintering method, which is to make use of the lump lime making sintering method to process the Bayer process red mud so as to achieve the comprehensive utilization of the red mud. The method mainly comprises the following steps: preparing the Bayer process red mud and limestone according to a proportion; milling the materials and making blocks; cooling and crushing the blocks after the blocks are calcined at a temperature of between 1,100 and 1,300 DEG C for 3 to 5 hours; leaching the blocks in a sodium carbonate solution, and merging the leach liquor into the dilution working section of a Bayer process dissolved ore slurry; and washing the leaching residues which are used as cement raw materials.The method can extract 60 percent of aluminum oxide and more than 80 percent of alkali in the red mud which are returned to the process flow of the Bayer process so that the total extraction rate of bauxite by the Bayer process reaches more than 90 percent, the alkali consumption for producing one ton of the aluminum oxide is reduced to less than 20 kilograms, the silica alumina ratio range of the bauxite adaptive to the Bayer process is enlarged, and the problems of large area for piling up the red mud and the environmental pollution caused by corrosivity of the red mud are eliminated fundamentally.
Description
Technical field:
The present invention relates to the method for comprehensive utilization of the waste red mud residues of bayer's process, specifically utilize the clamp dog lime sinter process to handle Bayer process red mud, reach the comprehensive utilization of red mud.Belong to the calorize worker, environmental protection and industrial residue utilize the technology category.
Background technology:
The aluminum oxide and the aluminium hydroxide of produced worldwide have more than 90% and produce with bayer's process at present.So-called bayer's process, document 1 (" process for making alumina "; Professor Yang Chongyu of Zhongnan Polytechnic Univ chief editor, metallurgical industry press publishes, January nineteen eighty-two first version) be such report: bayer's process is necessarily to handle bauxite under high temperature and the pressure with caustic alkali, with stripping wherein aluminum oxide and obtain sodium aluminate solution, and with the method that adds decomposition of crystal seed, make aluminum oxide in the solution become crystalline aluminum hydroxide and separate out.Mother liquor returned after evaporation be used to leach bauxite and constitute bayer's process circulation.
The bayer's process flow process is simple, and energy consumption is low, good product quality, and product cost is low when handling high-quality bauxite.But along with the ore alumina silica ratio reduces, the alumina recovery rate descends, and alkaline consumption rises, and cost increases, so bayer's process is confined to handle high-quality bauxite, and its alumina silica ratio is not less than 7-8 at least, usually more than 10.In addition, bayer's process need consume the caustic alkali of price comparison costliness.
Producing aluminium oxide by bayer, the most basic obstacle are exactly the silicon-dioxide SiO in the bauxite
2Silicon-dioxide is the most deleterious impurity during bayer's process is produced, because silicon-dioxide is acidic oxide, when removing dissolved oxygen aluminium with caustic alkali NaOH, silicon-dioxide must react with sodium hydroxide, must consume a large amount of alkali, has not only lost alkali, but also to lose a large amount of aluminum oxide, throw out is 3Na in the slag because finally be lost to
2O3Al
2O
35SiO
2NH
2O, so must contain a considerable amount of alkali and aluminum oxide in the Bayer process red mud, even more serious when particularly handling low-grade bauxite.Produce one ton of aluminum oxide, output 0.5-1.5 ton red mud (different and different with bauxite grade and production method), red mud is the pollutent of alumina producer maximum, prevents that the basic outlet that red mud pollutes from being the problem of complex utilization that solves red mud.The present red mud of about hundred million tons of annual in the world outputs has only seldom that a part obtains utilizing, and many aluminium manufacturers have caused the serious environmental pollution because red mud is handled is not good at, and also take a large amount of soils and stack.This is the world-famous puzzle that exists in the alumina producing.The chemical constitution of Bayer process red mud is roughly:
SiO
2：5-20％； Al
2O
3：15-30％； Fe
2O
3：4-10％；
TiO
2：6-10％； Na
2O：4-10％； CaO：10-20％。
From the chemical constitution of Bayer process red mud, except Na
2O, TiO
2Outward, other chemical group Chengdu is the basic raw material that can produce cement, as long as incite somebody to action Na wherein
2O content is reduced to and just be can be used as the raw material of producing cement below 1%.China's cement products has reached more than 10 hundred million tons, other starting material of mass consumption, as the alkali in the Bayer process red mud is put forward, the alkali content of red mud is dropped to below 1%, can make cement raw material fully, turns waste into wealth, and this is the basic outlet that solves Bayer process red mud.
Processing and utilization for Bayer process red mud, report has two kinds of methods in the document 1: a kind of is the series process of Baeyer-sintering integrated process, this method is to handle with bayer's process earlier for the bauxite of medium grade, extract wherein most of aluminum oxide, and then use soda-lime sintering process, handle Bayer process red mud, further extract wherein aluminum oxide and alkali, the sodium aluminate solution of gained is incorporated the bayer's process system into.This method advantage is that aluminum ore is through twice processing, thereby the alumina extraction ratio height, gross investment simultaneously and process cost are lower, and shortcoming is that Bayer process red mud sintering in rotary kiln is relatively more difficult, reason is that sintering range is narrow, and fine or not being difficult to of the restive and clinker quality of sintering process guarantees.Bayer's process and sintering process two big systems also are difficult to balance simultaneously, and production stability is poor, and ordinary production is difficult to keep, and seldom adopt on the industrial production at present.Second method is the mixed combining method of Baeyer-sintering integrated process.For solving the not enough problem that series process occurs, proposed to add a part of low-grade aluminum ore and carry out sintering in Bayer process red mud, this method improves the grog alumina silica ratio, and the molten point of furnace charge is improved, firing range broadens, thereby having improved sintering process, also solved when handling low red bauxite ore deposit with pure series process and mended the insufficient problem of alkali, is the effective ways of handling high silicon and low iron bauxite, shortcoming is that flow process is very long, equipment is various, and investment is big, control complexity etc.
Two kinds of treatment processs for Bayer process red mud of report in the document 1, aluminum oxide in the red mud of bayer's process and alkali there is certain recovery, but no matter adopt which kind of integrated process, the red mud slag of last output, alkali content is still higher, and also difficulty is carried out its utilization, can not produce the raw material of cement, still environment is caused severe contamination, and still occupy a large amount of soils and stack.
Utilization for Bayer process red mud, document 2 (" a kind of new lime sintering-bayer's process combined production of hydrogen method of alumina ", patent of invention, application number 200710077821.5) reported method is that this is an important use of Bayer process red mud with the desiliconization agent of Bayer process red mud as the leach liquor in the lime sinter process production aluminium hydroxide.But consumption is very limited, and the Bayer process red mud slag processing and utilizing that can not will discharge is on a large scale fallen, and the more impossible Bayer process red mud slag that will stack is on a large scale disposed.
Other utilization for Bayer process red mud, some reports are arranged, for example useful Bayer process red mud makes building block brick, but all also there are many problems, all fail basic outlet is found in the reasonable utilization of Bayer process red mud, so far Bayer process red mud is still as serious pollutent, is emitted among the physical environment, and has taken a large amount of soils.
Summary of the invention:
The objective of the invention is to solve the problem of complex utilization of Bayer process red mud waste residue, the alkalescence of eliminating a large amount of landed properties stackings of red mud and red mud causes the deep-etching problem of environment pollution caused, the object of the present invention is achieved like this, promptly utilize a kind of clamp dog lime sinter process to handle the waste red mud residues of bayer's process, extract aluminum oxide and alkali in the red mud, and the recrement that will extract behind aluminum oxide and the alkali is used as cement raw material, thereby make bayer's process not have waste sludge discharge, fundamentally eliminated the severe contamination and the problem that take a large amount of soils stacking of Bayer process red mud to environment, the alumina silica ratio range extension of the bauxite that makes bayer's process simultaneously and adapted to, resource utilization is improved, accomplish to economize on resources and to the resource circulation utilization, economic benefit and social benefit are good.
Concrete grammar is: Bayer process red mud and Wingdale or lime and coal are prepared burden by a certain percentage, and distribution is: the ash with Bayer process red mud, Wingdale and coal carries out total analysis earlier, then with the chemical ingredients in the above-mentioned raw materials according to CaO and Al
2O
3Molecular ratio be 1: 1, CaO and SiO
2Molecular ratio be 2: 1, CaO and Fe
2O
3Molecular ratio be 3: 1, CaO and TiO
2Molecular ratio be that 1: 1 principle is prepared burden, by analyzing and calculate the concrete ratio of components of Bayer process red mud and Wingdale and coal, batching is after behind mixing and the grinding, add water and make bulk, with dry block (raw material piece) pile on the kiln car of tunnel furnace, push in the tunnel furnace and calcine, best tunnel furnace is the flat-top tunnel furnace, the high temperature section of tunnel furnace is controlled between 1100 ℃ to 1300 ℃, sintering time 2～5 hours, the grog piece that sintering goes out is after cooling off broken and grinding to 120～160 orders, leach down at 90-100 ℃ by 1: 3 proportioning of solid-to-liquid ratio with 80-150 grams per liter yellow soda ash alkali lye, extraction time is 1～5 hour, leaches after solid-liquid separation, the solution that contains sodium aluminate is integrated with the dilution workshop section of bayer's process dissolved mineral slurry, and recrement is sent to the cement mill and made cement producting material after three counter current water wash.Bath water is used to dispose sodium carbonate solution and is used for clamp dog.The also available carbon method of leach liquor is separated out aluminium hydroxide, and Recycling Mother Solution is used.
The present invention has following beneficial effect:
1, production technique of the present invention is with behind Bayer process red mud and the raw meal prepared from lime, make piece and be placed on sintering in the tunnel furnace, the firing temperature broad, production is easy to control, overcome in Baeyer in the document 1-sintering associating series process because firing temperature is narrow, the quality quality of sintered clinker is difficult to guarantee, and is restive, sticking kiln wall of grog and knot bulk often occur, cause phenomenons such as stopping production.
2, production technique of the present invention is simple, and flow process is short, less investment, and the Baeyer in the document 1-sintering integrated process long flow path, equipment is various, and control is complicated, and investment is big, and the present invention significantly is better than the Baeyer-sintering integrated process in the document 1.
3, the present invention's aluminum oxide that can extract in the Bayer process red mud reaches more than 60%, and alkali reaches more than 80%, can reach more than 90% the total extraction yield of bauxite, makes that producing one ton of aluminum oxide alkali consumption can drop to below 20 kilograms, and the alkaline consumption index is the advanced level in the world.The present invention handles Bayer process red mud not only good economic benefit, and main is to bring remarkable social benefit.
4, the most significant effective achievement of the present invention is after handling Bayer process red mud by method of the present invention, the alkali of Bayer process red mud is reduced to below 1%, thereby make processing back red mud can be used as cement raw material, turn waste into wealth, the fundamental way that has found Bayer process red mud to utilize in a large number, can reach the purpose of the zero release of Bayer process red mud, solve this global difficult problem of red mud contaminate environment of maximum during aluminum oxide industry is produced.
Embodiment:
The embodiments of the invention commerical test is to carry out in the test base, technique center of Guizhou Pingba Hongda Aluminum Chemical Co., Ltd., there is one in flat-top tunnel furnace empty wide 1.8 meters in long 60 meters the test base, be installed as the automatic coal powder injection machine of 12 usefulness of making a fire on the kiln, each one of dry grinding of φ 1.5 ball mills and wet-milling is arranged, various ore reduction equipment are arranged, the various device such as leaching, filtration, washing, conveying of wet method system is arranged.
The Bayer process red mud that embodiment adopted is the Bayer process red mud of alumina producing institute of grand calorize worker company limited output, and Wingdale is the local Wingdale in Pingba area.
Embodiment 1:
Implement the chemical composition of the Bayer process red mud of employing: Al
2O
3: 24.53%, SiO
2: 13.87%, Fe
2O
3: 7.48%; CaO:24.22%, TiO
2: 7.39%, Na
2O:5.2%.
Implement the chemical composition of the Wingdale of employing: CaO:53.34%, MgO:1.34%, SiO
2: 0.17%, Fe
2O
3: 0.02%, Al
2O
3: 0.50%, TiO
2Trace.
Batching: Bayer process red mud is 100: 42: 5 with the ingredients by weight ratio of Wingdale, coal, prepares burden with electronic scales.
After the biaxial rneader mixing is used in the batching back, enter the ball mill grinding, fineness reaches 120 orders, screen over-size is less than 5%, the raw material powder that comes out from ball mill, the water of adding 16% after twin shaft stirs, is sent into brick extruding machine and is made the bulk that size is 240 * 120 * 60 (mm) again, to expect that the piece pile is on tunnel kiln car, every kiln car is placed about 600, and the material piece of sign indicating number one car is sent in the tunnel furnace, and go-cart in per 40 minutes once, the tunnel kiln car of material piece is housed, in tunnel furnace, pass through arid zones, the preheating zone, the high temperature clinkering zone is again through cooling zone, per car is from advancing kiln to the other end kiln discharge, need 16 hours, the high temperature sintering temperature of tunnel furnace is 1200 ± 30 ℃, and the material piece is 4 hours in the thermal zone residence time.From tunnel furnace through incinerating grog piece through jaw crushing with after to the roller fragmentation, enter ball mill by wet process, leach with the sodium carbonate solution of 120 grams per liters, solid-to-liquid ratio is 1: 3, and extraction temperature is 95 ℃ ± 5 ℃, and the time is 1 hour, leach liquor is through sampling analysis, and the average data of analyzing for five times of taking a sample is: Na
2O:74.2g/L, Al
2O
355.07g/L.The slag that produces is after three water countercurrent washings, and after the oven dry, the total analysis chemical constitution is: Al
2O
3: 8.53%; SiO
2: 13.18%; Fe
2O
3: 6.59%; CaO:45.14%; TiO
2: 7.09%; Na
2O:0.80%.Leach liquor after filtering, filtrate joins the dilution workshop section of bayer's process dissolved mineral slurry.
Result of implementation: the alkaline extraction rate is 80%, the extraction rate reached 65% of aluminum oxide, and the slag alkalinity is lower than 1%, meets to make cement producting material.
Embodiment 2:
Operational path of implementing and working method are with embodiment 1, and only the chemical ingredients of the Bayer process red mud that uses is slightly different with ratio of components.
The chemical composition of Bayer process red mud: Al
2O
3: 20.84%, SiO
2: 13.65%, Fe
2O
3: 7.3%; CaO:23.5%, TiO
2: 7.5%, Na
2O:6.0%.
The Wingdale chemical composition is identical with embodiment 1.
Batching: Bayer process red mud is 100: 43: 5 with the ingredients by weight ratio of Wingdale, coal, prepares burden with electronic scales.
Working method and conditionally complete just leach the sodium carbonate solution concentration of using and change 100 grams per liters into embodiment 1.
Obtain leach liquor: Na
2O:75.1/L, Al
2O
3: 57.4g/L.
Result of implementation: the alkaline extraction rate is 80%, the extraction rate reached 65.5% of aluminum oxide.
Slag its chemical constitution after water washing is: Al
2O
3: 7.8%; SiO
2: 11.5%; Fe
2O
3: 6.5%; TiO
2: 7.25%; CaO:45.2%; Na
2O:0.85%.The slag alkalinity is lower than 1%, meets to make cement producting material.
Claims (6)
1. a clamp dog lime sinter process is handled the method for Bayer process red mud, it is characterized in that Bayer process red mud and Wingdale or lime and coal are prepared burden by a certain percentage, distribution is: earlier the ash with Bayer process red mud, Wingdale and coal carries out total analysis, then with the chemical ingredients in the above-mentioned raw materials according to CaO and Al
2O
3Molecular ratio be 1: 1, CaO and SiO
2Molecular ratio be 2: 1, CaO and Fe
2O
3Molecular ratio be 3: 1, CaO and TiO
2Molecular ratio be that 1: 1 principle is prepared burden, by analyzing and calculate the concrete ratio of components of Bayer process red mud and Wingdale and coal, batching back mixing grinding, add water and make bulk, with dry block 1100 ℃ to 1300 ℃ of controlled temperature in tunnel furnace, calcined 3～5 hours, cooling back crushing and grinding to 120～160 orders, press 1: 3 proportioning of solid-to-liquid ratio with 80-150 grams per liter yellow soda ash alkali lye, leached 0.5～2 hour down at 90-100 ℃, leach liquor is incorporated the dilution workshop section or the leach liquor of bayer's process dissolved mineral slurry into and is produced aluminium hydroxide with carbon method, soaks slag and make cement producting material after water washing.
2. a kind of clamp dog lime sinter process according to claim 1 is handled the method for Bayer process red mud, the granularity of mixing grinding must not be less than 120 orders after it is characterized in that preparing burden, cooling back properties of powder performace reaches 120 orders, and with 100～120 grams per liters, sodium carbonate solution was 95 ± 5 ℃ of extraction times 1 hour.
3. a kind of clamp dog lime sinter process according to claim 1 and 2 is handled the method for Bayer process red mud, it is characterized in that best tunnel furnace is the flat-top tunnel furnace.
4. a kind of clamp dog lime sinter process according to claim 3 is handled the method for Bayer process red mud, it is characterized in that adding the preferably brick-shaped thing of 240 * 120 * 60mm of block that water makes.
5. a kind of clamp dog lime sinter process according to claim 3 is handled the method for Bayer process red mud, and the high temperature sintering temperature that it is characterized in that tunnel furnace is 1200 ± 50 ℃, and the material piece is 2～4 hours in the thermal zone residence time.
6. a kind of clamp dog lime sinter process according to claim 1 is handled the method for Bayer process red mud, soaks slag through three water countercurrent washings after it is characterized in that leaching, and makes the alkali content in the slag be lower than 1%.
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|---|---|---|---|
| CN2007100779735A CN101412616B (en) | 2007-10-16 | 2007-10-16 | Method for processing red mud from Bayer process by block-making and lime sintering method |
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| CN2007100779735A CN101412616B (en) | 2007-10-16 | 2007-10-16 | Method for processing red mud from Bayer process by block-making and lime sintering method |
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| CN101412616B true CN101412616B (en) | 2011-06-08 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748848B (en) * | 2010-01-22 | 2011-09-28 | 贵州平坝宏大铝化工有限公司 | Bayer process red mud shale bricks and production method thereof |
| CN102500592A (en) * | 2011-09-16 | 2012-06-20 | 茌平县信发盛吉赤泥处理有限公司 | Method for comprehensively utilizing alumina red mud |
| CN102503371B (en) * | 2011-10-28 | 2013-07-10 | 河南华新奥建材股份有限公司 | Brick making method |
| CN102951665A (en) * | 2012-11-29 | 2013-03-06 | 中国铝业股份有限公司 | Converging method of sintering process dissolution rough liquid and bayer process slurry in alumina production |
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|---|---|---|---|---|
| CN1117945A (en) * | 1995-08-15 | 1996-03-06 | 贵州益华工业设计研究所 | Baeyer-synthesizing technology for processing bauxite |
| US6086771A (en) * | 1997-12-12 | 2000-07-11 | Nalco Chemical Company | Water continuous emulsion polymers for improving scale control in the bayer process |
| CN1405092A (en) * | 2002-11-12 | 2003-03-26 | 中国铝业股份有限公司 | Bayer combination production method for aluminium and calcium aluminate cement |
| CN1743472A (en) * | 2005-09-22 | 2006-03-08 | 贵阳铝镁设计研究院 | Method for recovering iron from red mud |
-
2007
- 2007-10-16 CN CN2007100779735A patent/CN101412616B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117945A (en) * | 1995-08-15 | 1996-03-06 | 贵州益华工业设计研究所 | Baeyer-synthesizing technology for processing bauxite |
| US6086771A (en) * | 1997-12-12 | 2000-07-11 | Nalco Chemical Company | Water continuous emulsion polymers for improving scale control in the bayer process |
| CN1405092A (en) * | 2002-11-12 | 2003-03-26 | 中国铝业股份有限公司 | Bayer combination production method for aluminium and calcium aluminate cement |
| CN1743472A (en) * | 2005-09-22 | 2006-03-08 | 贵阳铝镁设计研究院 | Method for recovering iron from red mud |
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