CN100404423C - Method of preparing aluminum oxide from fly ash - Google Patents

Method of preparing aluminum oxide from fly ash Download PDF

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CN100404423C
CN100404423C CNB2006100482955A CN200610048295A CN100404423C CN 100404423 C CN100404423 C CN 100404423C CN B2006100482955 A CNB2006100482955 A CN B2006100482955A CN 200610048295 A CN200610048295 A CN 200610048295A CN 100404423 C CN100404423 C CN 100404423C
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flyash
alumina
tai
ace
produce
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CN1923695A (en
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秦晋国
翟玉春
蒋训雄
白光辉
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PINGSHUO COAL INDUSTRY CORP
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PINGSHUO COAL INDUSTRY CORP
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Abstract

The invention discloses a preparing method of alumina through fly ash, which comprises the following steps: grinding fly ash; sintering; activating; stirring with H2SO4 evenly to sinter into dried slag; immersing through hot water; stripping aluminum sulfate; condensing; cooling to evolve aluminum sulfate; crystallizing; heating; dehydrating to obtain anhydrous aluminum sulfate; heating; decomposing to obtain gamma-Al2O3.

Description

A kind ofly produce method of alumina by flyash
Technical field
The invention belongs to the comprehensive utilization that becomes more meticulous of flyash, relate to and a kind ofly produce method of alumina, specifically relate to a kind of by flyash and dense H by flyash 2SO 4The mix direct roasting is produced method of alumina.
Background technology
A large amount of flyash of coal-burning power plant's discharging have caused serious pollution to agriculture production and living environment on every side, and comprehensive regulation flyash has become the environmental problem that an exigence solves.In China, the flyash amount of the annual discharging in coal-burning power plant is up to more than one hundred million tons, and volume of cargo in storage is very big.Al in the flyash 2O 3Content is higher, is about 20~40%, because volume of cargo in storage is big, is one and has the resource treasure-house that the comprehensive development and utilization that becomes more meticulous is worth.
From flyash, extract Al both at home and abroad 2O 3Method can be divided into alkaline process and acid system two big classes.In the sixties in last century, Poland just utilizes soda-lime sintering process to extract Al in flyash 2O 3, built up and produced 5000 tons of Al per year 2O 3And the pilot plant of 350,000 tons of cement.China Anhui Province Institute of Metallurgical Technology and Hefei cement research institute have declared with limestone sintering, yellow soda ash stripping in the eighties and extracted Al in flyash 2O 3, residue is used to produce the achievement of cement, in March nineteen eighty-two by expert statement.The soda-lime sintering process of building materials institute of Ningxia autonomous region research extracts Al in flyash 2O 3, residue produce cement industry in September, 1987 by the Ningxia State Scientific and Technological Commission of autonomous region tissue characterization.In December, 2004, Inner Mongolia Autonomous Region Science and Technology Department has held " flyash extracts the aluminum and coproducing cement industrialization technology " the project appraisal of scientific and technological achievements meeting of covering the research and development of western new and high technology Group Co.,Ltd, and this group has independently finished nearly 5000 tonnes pilot scale.Though extract Al about alkaline process 2O 3Report a lot, adopt above-mentioned processing method half industrialization and industrial continuous production report but have not yet to see to be.Its reason is to handle the numerous length of technology that this high silicon contains the aluminium powder coal ash with alkaline process, the inventory of running is big, facility investment is also big, the energy consumption height, the cost height, and also the level of residue that produces is the several times of flyash amount, limited with a large amount of cement market goods locallies that residue is made, overall economic efficiency is poor, and level of comprehensive utilization is low, thereby has hindered the application of alkaline process aspect comprehensive utilization flyash.
Compare with alkaline process, handle flyash with acid system and just have remarkable advantages.Acid system when the aluminum oxide that effectively extracts in the flyash, silicon-dioxide all can be refused outside liquid, can not produce new solid materials in process of production, level of residue is little, thereby the inventory of running is little, facility investment is little, energy consumption is low, product cost is also low.But the shortcoming of acid system is in leaching during aluminum oxide, has also brought into solution such as the many leachable impurity in the flyash such as iron, titanium, magnesium, must increase the postorder treatment process; The conversion unit manufacturing of Shi Yonging has certain degree of difficulty besides.But compare with alkaline process, use still the most promising method of acidic process fly ash, therefore, the research of carrying out this respect both at home and abroad is more.
Extract aluminum oxide with acidic process flyash and adopt sulfuric acid or saline and alkaline technology mostly.Owing to flyash is the tiny grit that forms through high temperature (1500 ℃) burning back, the glassy phase in the grit accounts for more than 90%, has had a strong impact on the activity of flyash and acid-respons, and therefore, the reactive behavior that need improve flyash and acid is to improve Al 2O 3Solubility rate.The more practice of data report is to add solubility promoter NH in the acidleach negate is answered 4F and CaF 2,, make Al thereby reach by the complexing Si oxide 2O 3The purpose of stripping.Adopt aforesaid method in flyash, to reclaim Al 2O 3, Al 2O 3Solubility rate all lower, generally have only 35~45%, resource utilization is low, and because of having added the fluorine element that environment is had pollution, has brought secondary pollution, has hindered the development and use that become more meticulous of flyash.
The CN1792802 patent disclosure a kind of method of alumina of from flyash, extracting, be flyash is ground and calcination activation after, with H 2SO 4The solution reacting by heating, the aluminum oxide of leaching with hot water boil molten after, the Tai-Ace S 150 crystallization is separated out in concentrated cooling, the dehydration that heats up obtains anhydrous slufuric acid aluminium, continues to heat up to decompose to obtain γ-Al 2O 3, and further prepare metallurgical-grade aluminum oxide.This method has adopted the flyash activating technology, has improved the reactive behavior of flyash with acid, makes Al 2O 3Solubility rate bring up to more than 85%.But, because this method is to adopt H 2SO 4The solution lixiviation process extracts aluminum oxide from flyash, need after reaction spent acid be separated with the lime-ash that contains Tai-Ace S 150, and the Tai-Ace S 150 in the filter residue also needs to boil the stripping of molten ability, technological process more complicated through superheated water.
Summary of the invention
The objective of the invention is the above-mentioned method of alumina of extracting from flyash is improved, provide a kind of by flyash and dense H 2SO 4The mix direct roasting is produced method of alumina.
The concrete grammar that the present invention produces aluminum oxide by flyash comprises:
Flyash is ground to-100 orders, in 200~760 ℃ of calcination activations 1~1.5 hour;
Flyash after weight ratio according to 1: 1~2 will activate and 〉=80% dense H 2SO 4Mix is even, becomes dried slag 200~400 ℃ of following roastings;
With the molten dried slag that soaks after the roasting of 80~90 ℃ hot water, stripping Tai-Ace S 150 wherein filters and obtains alum liquor;
With the alum liquor evaporation concentration, separate out the Tai-Ace S 150 crystallization;
The Tai-Ace S 150 crystallization heats up to dewater and obtains anhydrous slufuric acid aluminium;
Continue to heat up and make the decomposition of anhydrous slufuric acid aluminium obtain γ-Al 2O 3, and reclaim SO 3Flue gas.
Wherein, flyash and dense H 2SO 4Roasting time behind the mix is 20~40 minutes; The dried slag that obtains after the roasting is used molten the soaking of hot water that is equivalent to 2~4 times of its weight.
The processing of different methods is carried out in the Tai-Ace S 150 crystallization that the present invention separates out after evaporation concentration is cooled off, and can produce the aluminium salt and the aluminum oxide of many kinds, specifically:
The Tai-Ace S 150 crystallization being no more than dehydration fully under 400 ℃ the temperature, is generated anhydrous slufuric acid aluminium.
In calcining below 900 ℃, Tai-Ace S 150 is decomposed fully in anhydrous slufuric acid aluminium, all generate active strong γ-Al 2O 3
γ-the Al for preparing 2O 3Boil down moltenly at 120~190 ℃, make sodium aluminate solution with the NaOH solution of 150g/L~200g/L.Owing to impurity such as iron contained in the aluminum oxide, calcium, magnesium can not be present in the solid phase by alkali dissolution, can remove by filter, after the solid-liquid separation, form the high sodium aluminate solution of purity.Add aluminium hydroxide crystal seed in solution, the sodium aluminate in the solution is separated out with the form crystallization of aluminium hydroxide, the crystalline aluminum hydroxide that obtains can obtain metallurgical-grade aluminum oxide at 1100 ℃ of temperature lower calcinations.
Anhydrous slufuric acid aluminium decomposes preparation γ-Al 2O 3The time SO that produces 3Flue gas directly feeds and produces the vitriol oil in the sulphuric acid soln, produces the vitriol oil obtain and is used further to producing of aluminum oxide in the flyash, realizes that vitriolic recycles.
The present invention is with flyash and dense H 2SO 4Direct roasting is produced aluminum oxide, has saved H 2SO 4The acid sludge separation steps has been simplified production process in the solution lixiviation process, and the solubility rate of aluminum oxide is also brought up to more than 90%.
Any waste water, waste liquid, waste residue and obnoxious flavour are not discharged in all effectively recycles such as the spent acid that produces in the technological process of the present invention, waste water in the whole process.
Technological process of the present invention is simple, invests for a short time, and cost is low, and the added value of product height is a flyash that has the prospect comprehensive utilization industrialization method that becomes more meticulous.
Embodiment
Embodiment 1
Get salic 40% flyash 1t, grind to form-100 purpose fine powders, behind the iron removal by magnetic separation,, obtain activatory flyash in 400 ℃ of following roasting 1.5h.
Dense H with activating fly ash and 98% 2SO 41.1t mix is even, places on the load plate in the tunnel furnace, is warming up to 220 ℃ of roastings reaction 30min, comes out of the stove after burning till dried slag.
Use the molten dried slag that soaks after the roasting of 80 ℃ hot water 5t, stripping Tai-Ace S 150 wherein filters and obtains alum liquor.
With the filtrate evaporation concentration, return leaching prosess behind the water vapor condensation that steams, separate out the Tai-Ace S 150 crystallization after the concentrated solution cooling, filter, collect solid crystal 2400Kg.Filtrate adds filters in the alum liquor that obtains next time, and evaporation concentration is separated out the Tai-Ace S 150 crystallization once more.
The Tai-Ace S 150 solid crystal that obtains is warming up to 350 ℃ of dehydrations gradually, obtains 1600Kg anhydrous slufuric acid aluminium, returns leaching prosess behind the water vapor condensation of generation.
Anhydrous slufuric acid aluminium continues to be warming up to 453 ℃ and begins to decompose, and heats up until 870 ℃ again, and calcining 2h decomposes anhydrous slufuric acid aluminium fully, generates 380Kg γ-Al 2O 3
The SO that calcining produces 3Flue gas is passed into H 2SO 4In the solution, reclaim and produce dense H 2SO 4
Embodiment 2
Get salic 40% flyash 1t, grind to form-100 purpose fine powders, behind the iron removal by magnetic separation,, obtain activatory flyash in 600 ℃ of following roasting 1h.
Dense H with activating fly ash and 85% 2SO 4The 2t mix is even, places on the load plate in the tunnel furnace, is warming up to 200 ℃ of roastings reaction 30min, comes out of the stove after burning till dried slag.
Use the molten dried slag that soaks after the roasting of 90 ℃ hot water 3t, stripping Tai-Ace S 150 wherein filters and obtains alum liquor.
With the filtrate evaporation concentration, return leaching prosess behind the water vapor condensation that steams, separate out the Tai-Ace S 150 crystallization after the concentrated solution cooling, filter, collect solid crystal 2400Kg.Filtrate adds filters in the alum liquor that obtains next time, and evaporation concentration is separated out the Tai-Ace S 150 crystallization once more.
The Tai-Ace S 150 solid crystal that obtains is warming up to 400 ℃ of dehydrations gradually, obtains 1550Kg anhydrous slufuric acid aluminium, returns leaching prosess behind the water vapor condensation of generation.
Anhydrous slufuric acid aluminium continues to be warming up to 850 ℃, and calcining 2h decomposes anhydrous slufuric acid aluminium fully, generates 380Kg γ-Al 2O 3, the SO that calcining produces 3Flue gas is passed into H 2SO 4In the solution, reclaim and produce dense H 2SO 4
γ-Al 2O 3Join in the NaOH solution of 150g/L, be warming up to 150 ℃ and boil moltenly, remove by filter residue, add a spot of aluminium hydroxide crystal seed in the filtrate, the sodium aluminate in the filtrate is separated out with the form of crystalline aluminum hydroxide, filter, filtrate cycle is used.
The crystalline aluminum hydroxide that obtains is warming up to 1100 ℃ of calcinings obtains the 380Kg metallurgical-grade aluminum oxide.
Embodiment 3
Get salic 30% flyash 1t, grind to form-100 purpose fine powders, behind the iron removal by magnetic separation,, obtain activatory flyash in 700 ℃ of following roasting 1h.
Dense H with activating fly ash and 96% 2SO 41.35t mix is even, places on the load plate in the tunnel furnace, is warming up to 350 ℃ of roastings reaction 30min, comes out of the stove after burning till dried slag.
Use the molten dried slag that soaks after the roasting of 90 ℃ hot water 4t, stripping Tai-Ace S 150 wherein filters and obtains alum liquor.
With the filtrate evaporation concentration, return leaching prosess behind the water vapor condensation that steams, separate out the Tai-Ace S 150 crystallization after the concentrated solution cooling, filter, collect solid crystal 2000Kg.Filtrate adds filters in the alum liquor that obtains next time, and evaporation concentration is separated out the Tai-Ace S 150 crystallization once more.
The Tai-Ace S 150 solid crystal that obtains is warming up to 400 ℃ of dehydrations gradually, obtains 1050Kg anhydrous slufuric acid aluminium, returns leaching prosess behind the water vapor condensation of generation.
Anhydrous slufuric acid aluminium continues to be warming up to 850 ℃, and calcining 2h decomposes anhydrous slufuric acid aluminium fully, generates 280Kg γ-Al 2O 3, the SO that calcining produces 3Flue gas is passed into H 2SO 4In the solution, reclaim and produce dense H 2SO 4

Claims (6)

1. produce method of alumina by flyash for one kind, comprising:
Flyash is ground to-100 orders, in 200~760 ℃ of calcination activations 1~1.5 hour;
Flyash after weight ratio according to 1: 1~2 will activate and 〉=80% dense H 2SO 4Mix is even, becomes dried slag 200~400 ℃ of following roastings;
With the molten dried slag that soaks after the roasting of 80~90 ℃ hot water, stripping Tai-Ace S 150 wherein filters and obtains alum liquor;
With the alum liquor evaporation concentration, separate out the Tai-Ace S 150 crystallization;
The Tai-Ace S 150 crystallization heats up to dewater and obtains anhydrous slufuric acid aluminium;
Continue to heat up and make the decomposition of anhydrous slufuric acid aluminium obtain γ-Al 2O 3, and reclaim SO 3Flue gas.
2. produce method of alumina according to claim 1 is described by flyash, it is characterized in that flyash and dense H 2SO 4Behind the mix, roasting 20~40 minutes.
3. according to claim 1ly produce method of alumina, it is characterized in that with the molten dried slag that soaks after the roasting of the hot water that is equivalent to 2~4 times of dried slag weight by flyash.
4. according to claim 1ly produce method of alumina, it is characterized in that dehydration generates anhydrous slufuric acid aluminium under 400 ℃ the temperature being no more than with the Tai-Ace S 150 crystallization by flyash.
5. according to claim 1ly produce method of alumina, it is characterized in that anhydrous slufuric acid aluminium is prepared γ-Al at the temperature lower calcination that is no more than 900 ℃ by flyash 2O 3
6. according to claim 1ly produce method of alumina, it is characterized in that the SO that reclaims by flyash 3Flue gas is produced the vitriol oil with sulfuric acid absorption.
CNB2006100482955A 2006-09-15 2006-09-15 Method of preparing aluminum oxide from fly ash Active CN100404423C (en)

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Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100465096C (en) * 2007-05-08 2009-03-04 浙江大学 Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material
CN101811712A (en) 2010-04-27 2010-08-25 中国神华能源股份有限公司 Method for preparing metallurgical-grade aluminum oxide by using fluid-bed fly ash
EP2927199A4 (en) 2012-11-27 2016-10-05 Shenhua Group Corp Ltd Method for preparing soda-lime-silica glass basic formula and method for extracting aluminum from fly ash for co-production of glass
CN103342376B (en) * 2013-07-11 2015-07-01 中北大学 Process for extracting valuable metal from coal gangues
CN104445308A (en) * 2013-09-16 2015-03-25 贵阳铝镁设计研究院有限公司 Method for extracting alumina from fly ash in circulating fluidized bed
CN103738972B (en) * 2013-12-27 2015-12-02 中国神华能源股份有限公司 A kind of residue of aluminum-extracted pulverized fuel ash prepares the method for silicon powder
CN104787788B (en) * 2015-01-15 2016-03-02 北京矿冶研究总院 Aluminous fly-ash produces the method for aluminum oxide
CN104787789B (en) * 2015-01-15 2016-03-30 北京矿冶研究总院 Coal solid refuse is utilized to produce the method for aluminum oxide
CN104831074B (en) * 2015-05-19 2017-03-01 河北工程大学 A kind of method extracting aluminum from flyash
CN106115751B (en) * 2016-06-23 2017-08-25 中国神华能源股份有限公司 A kind of method that utilization two-part acid reaction method extracts aluminum oxide

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1792802A (en) * 2005-12-31 2006-06-28 朔州市人民政府 Process for extracting aluminium hydroxide from flyash

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1792802A (en) * 2005-12-31 2006-06-28 朔州市人民政府 Process for extracting aluminium hydroxide from flyash

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