CN101607259B - Method for activating fly ash at low temperature and application thereof - Google Patents
Method for activating fly ash at low temperature and application thereof Download PDFInfo
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- CN101607259B CN101607259B CN2009100550138A CN200910055013A CN101607259B CN 101607259 B CN101607259 B CN 101607259B CN 2009100550138 A CN2009100550138 A CN 2009100550138A CN 200910055013 A CN200910055013 A CN 200910055013A CN 101607259 B CN101607259 B CN 101607259B
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Abstract
The invention relates to a method for activating fly ash at low temperature and an application thereof, fly ash is subjected to grinding treatment till granularity is less than 30 microns, calcium content is added appropriately according to the contents of Ca and Al in fly ash and the reaction characteristic of the fly ash, the activation of fly ash is realized at lower calcining temperature by treatment under certain moisture content condition, and fly ash clinker which has high reaction activity and is suitable for alumina extraction is prepared and then leached with acid. The invention has the following advantages: batching is not influenced by the content of Si in fly ash, and the fly ash clinker can be prepared with alumina acid leaching ratio being over 75% by treatment of fly ash at lower temperature of 800-950 DEG C and shorter time of 30-60 minutes.
Description
[technical field]
The present invention relates to the flyash technical field, specifically, is a kind of method and application in extracting aluminium oxide thereof of activating fly ash at low temperature.
[background technology]
Flyash is a kind of solid waste that coal burning produces, and accounts for 10～40% of coal amount.At present Power Plant in China and the flyash of the annual discharging of other coal-burning boiler is up to 3.3 hundred million tons, is mainly used in building materials production, architectural engineering, builds the road, fertilizer production, improves the soil and backfill etc.The reason such as saturated and flyash activity owing to the market demand, China's flyash all has 100,000,000 tons accumulating in every year, and by 2008, China's flyash accumulative total was piled up above 2,700,000,000 tons.
China's aluminum oxide industry development in recent years is rapid, and 2006 annual productions leap to the No. 1 in the world, and 2008 annual productions account for 27.36% of Gross World Product.Aluminium oxide mainly passes through Bayer process production by the alum clay rich ore at present; Yet China's bauxite resource only accounts for 3.12% of world's gross reserves; And most of grade is lower; Therefore China mainly keeps the development of aluminum oxide industry at present through a large amount of import bauxite, and the bauxite import volume is from 25,790,000 tons of 880,000 tons of rapid growths to 2008 in 2004 year.The alternate resources of seeking bauxite is imperative in China.China's flyash alumina content average out to 27%, some areas are crucial bauxite resources up to 40～60%.Exploitation fly-ash Preparation aluminium oxide technology not only can effectively solve occupying cultivated land and problem of environmental pollution of flyash, also can solve the predicament of China's alumina producing scarcity of raw material, has great environment and economic implications.
Utilizing flyash mainly to be divided into acid system and alkaline process as the technology that bauxite resource prepares aluminium oxide, is with the flyash after the activation and acid or alkali reaction generation aluminium salt, makes aluminium oxide through the steps such as separation, drying, pyrolytic of purifying then.Relevant patent of invention and patent application are: a kind of of Mengxi Hi-Tech Group Corp., Ltd., Inner Mongolia's invention utilizes the method (patent No. ZL03131079.6) of fly-ash Preparation aluminum and coproducing cement grog and utilizes flyash and the method for lime stone Joint Production aluminium oxide and cement (number of patent application 200410090949.1); A kind of method of alumina (number of patent application 200510048274.9) of from flyash, extracting of Shuozhou City People's Goverment's invention; Extract the aluminium oxide method (number of patent application 200610012780.7) of co-producing white carbon black simultaneously in the flyash of Li Yu invention; Pingshuo Coal Industry Corp. invention a kind of by flyash produce method of alumina (number of patent application 200610048295.5) with a kind of from flyash method (number of patent application 200710062534.7) and a kind of flyash production silica and method of alumina 200710061662.X of utilizing of firstly extracting silicon and secondly extracting aluminum); A kind of method of alumina (number of patent application 200710118679.4) of from flyash, extracting of Chinese Aluminium Co., Ltd's invention; The a kind of of Chang An University invention extracts the method (number of patent application 200710017304.9) of aluminium oxide and producing cement from fag end thereof and from flyash, extracts aluminium oxide and utilize the method (number of patent application 200710017453.5) of producing cement from fag end from aluminous fly-ash; The aluminous fly-ash that utilizes of The Chinese Geology Univ.'s invention is produced aluminium oxide and white carbon process for cleanly preparing (number of patent application 200710087028.3); The a kind of of Zhejiang University's invention is the method (number of patent application 200710068433.0) of feedstock production tabular alumina with coal series kaolin rock or flyash; A kind of method (number of patent application 200710065366.7) of from aluminous fly-ash, extracting silica, aluminium oxide and gallium oxide of Tsing-Hua University's invention; A kind of fly-ash Preparation method of alumina (number of patent application 200710012997.2) of utilizing of Shenyang Aluminium Magnesium Design & Research Inst's invention; The novel aluminium oxide extraction process from coal ash (number of patent application 200710110423.9) of Neimonggol United Industry Co., Ltd.'s invention; Utilize carbide slag or the cyanogen ammonia slag of opening the invention of gram a word used in place name extract the method (number of patent application 200610092056.X) of aluminum and coproducing cement from flyash; What Huainan General Power Plant invented generates β-C 2S Binder Materials method (patent No. ZL87101461.0) simultaneously from the flyash extracting aluminum oxide; The method (number of patent application 200810017869.1) of from flyash, extracting high purity aluminium oxide and silica gel of Pan Aifang invention; A kind of method of alumina (number of patent application 200810302421.4) of from flyash, extracting of Guizhou University's invention; A kind of method (number of patent application 200810115355.X) of from flyash or slag, extracting metallurgical-grade aluminum oxide of Beijing Shijidihe Technology Co., Ltd.'s invention, the method (number of patent application 200710150915.0) of from flyash, extracting high-purity ultra-fine alumina of University Of Tianjin's invention.
The committed step of utilizing flyash to extract aluminium oxide is an activating fly ash; But present technology is in the flyash activating process, and the ubiquity calcining heat is high, and calcination time is long; High energy consumption, expensive problems such as the auxiliary agent volume is big; And because the auxiliary agent volume is big, and the waste residue amount is also corresponding huge, secondary pollution is serious.Therefore, restricted the large-scale industrialization application.
[summary of the invention]
The objective of the invention is to overcome the deficiency of prior art, a kind of method and application thereof of activating fly ash at low temperature are provided; Overcome the problem that the prior art calcining heat is high and calcination time is long, reduced energy consumption, existing environmental effect has economic implications again, for realizing flyash low-energy consumption extracting aluminium oxide method is provided.
Of the present invention being contemplated that: flyash through grinding handle to granularity less than 30 microns; According to Ca, Al content and response characteristic in the flyash; Suitably increase calcium content, and under certain moisture content condition, handle, adopt low temperature calcination; Can make the sintered clinker of qualified fly-ash Preparation aluminium oxide, adopt acidleach to get again.
The objective of the invention is to realize through following technical scheme:
A kind of method of activating fly ash at low temperature, its concrete steps are:
(1) adopt the grinding mode to control fineness of pulverized-coal ash less than 30 microns;
(2) calcium al proportion control: according to the response characteristic of flyash self, through increasing the mol ratio 0.5: 1～0.7: 1 that calcium makes Ca and Al in the flyash aggregate sample;
(3) moisture content control: according to the flyash response characteristic, the mass percent moisture content of compound is 5%～50% in the control step (2);
(4) material in the drying steps (3);
(5) low temperature calcination: under 800～950 ℃ to the compound calcining through above-mentioned steps (1), (2), (3), (4) preparation after 30～60 minutes, chilling makes sintered clinker.
Another object of the present invention provides a kind of application of method in extracting aluminium oxide of activating fly ash at low temperature, and concrete steps are:
(1) adopt the grinding mode to control fineness of pulverized-coal ash less than 30 microns;
(2) calcium al proportion control: according to the response characteristic of flyash self, through increasing the mol ratio 0.5: 1～0.7: 1 that calcium makes Ca and Al in the flyash aggregate sample;
(3) moisture content control: according to the flyash response characteristic, the mass percent moisture content of compound is 5%～50% in the control step (2);
(4) material in the drying steps (3);
(5) low temperature calcination: under 800～950 ℃ to the compound calcining through above-mentioned steps (1), (2), (3), (4) preparation after 30～60 minutes, chilling makes sintered clinker;
(6) aluminium element leaching: the sintered clinker that makes through step (5) leaches through watery hydrochloric acid or dilute sulfuric acid, and wherein, watery hydrochloric acid concentration is 0.4～0.7mol/l, and dilute sulfuric acid concentration is 0.2～0.7mol/l; 75～120 ℃ of leaching temperatures, leaching time 10～60 minutes obtains aluminium chloride or aluminum sulfate.
Compared with prior art, good effect of the present invention is:
Adopt 800～950 ℃ of lower temperatures and 30～60 minutes short periods that flyash is handled; And the efficient leaching of abraum salt acid capable of using and sulfur waste acid aluminium oxide in 75～120 ℃ of lower temperatures and short period 10～60 times realizations flyash; Reduced energy consumption, and residue of aluminum-extracted is few.
[specific embodiment]
The method of a kind of activating fly ash at low temperature of the present invention and the specific embodiment of application thereof below are provided.
Embodiment 1
With aluminium oxide quality percentage composition 31.47%, calcium oxide quality percentage composition be 2.75% flyash grinding to all through 30 microns, increase calcium by Ca and Al mol ratio 0.6; Control moisture content mass percent 20% mixes, and calcines 60 minutes down at 800 ℃ then; Chilling is pulverized, and the use mass percent concentration is 20% hydrochloric acid; 120 ℃ leached 10 minutes down, and alumina extraction ratio is 78%.
Embodiment 2
With aluminium oxide quality percentage composition 31.47%, calcium oxide quality percentage composition be 2.75% low calcium fly ash grinding to all through 20 microns, increase calcium by Ca and Al mol ratio 0.5; Control moisture content mass percent 10% mixes, and calcines 40 minutes down at 900 ℃ then; Chilling is pulverized, and the use mass percent concentration is 25% sulfuric acid; 120 ℃ leached 20 minutes down, and alumina extraction ratio is 84.70%.
Embodiment 3
With aluminium oxide quality percentage composition 31.47%, calcium oxide quality percentage composition be 2.75% low calcium fly ash grinding to all through 20 microns, increase calcium by Ca and Al mol ratio 0.7; Control moisture content mass percent 50% mixes, and calcines 30 minutes down at 950 ℃ then; Chilling is pulverized, and the use mass percent concentration is 25% hydrochloric acid; 75 ℃ leached 30 minutes down, and alumina extraction ratio is 87.13%.
Embodiment 4
With aluminium oxide quality percentage composition 53.26%, calcium oxide quality percentage composition be 3.41% low calcium fly ash grinding to all through 30 microns, increase calcium by Ca and Al mol ratio 0.6; Control moisture content mass percent 30% mixes, and calcines 60 minutes down at 900 ℃ then; Chilling is pulverized, and the use mass percent concentration is 20% hydrochloric acid; 120 ℃ leached 10 minutes down, and alumina extraction ratio is 92.80%.
Embodiment 5
With aluminium oxide quality percentage composition 19.99%, calcium oxide quality percentage composition be 18.75% flyash grinding to all through 30 microns, increase the calcium base auxiliary agent by Ca and Al mol ratio 0.5; Control moisture content mass percent 5% mixes, and calcines 30 minutes down at 800 ℃ then; Chilling is pulverized, and the use mass percent concentration is 20% hydrochloric acid; 100 ℃ leached 30 minutes down, and alumina extraction ratio is 93.55%.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the present invention's design; Can also make some improvement and retouching, these improvement and retouching also should be regarded as in protection scope of the present invention.
Claims (2)
1. the method for an activating fly ash at low temperature is characterized in that, concrete steps are:
(1) adopt the grinding mode to control fineness of pulverized-coal ash less than 30 microns;
(2) calcium al proportion control: according to the response characteristic of flyash self, through increasing the mol ratio 0.5: 1～0.7: 1 that calcium makes Ca and Al in the flyash aggregate sample;
(3) moisture content control: according to the flyash response characteristic, the mass percent moisture content of compound is 5%～50% in the control step (2);
(4) material in the drying steps (3);
(5) low temperature calcination: under 800～950 ℃ to the compound calcining through above-mentioned steps (1), (2), (3), (4) preparation after 30～60 minutes, chilling makes sintered clinker.
2. the application of the method for an activating fly ash at low temperature in extracting aluminium oxide is characterized in that concrete steps are:
(1) adopt the grinding mode to control fineness of pulverized-coal ash less than 30 microns;
(2) calcium al proportion control: according to the response characteristic of flyash self, through increasing the mol ratio 0.5: 1～0.7: 1 that calcium makes Ca and Al in the flyash aggregate sample;
(3) moisture content control: according to the flyash response characteristic, the mass percent moisture content of compound is 5%～50% in the control step (2);
(4) material in the drying steps (3);
(5) low temperature calcination: under 800～950 ℃ to the compound calcining through above-mentioned steps (1), (2), (3), (4) preparation after 30～60 minutes, chilling makes sintered clinker;
(6) aluminium element leaching: the sintered clinker that makes through step (5) leaches through watery hydrochloric acid or dilute sulfuric acid, and wherein, watery hydrochloric acid concentration is 0.4～0.7mol/l, and dilute sulfuric acid concentration is 0.2～0.7mol/l; 75～120 ℃ of leaching temperatures, leaching time 10～60 minutes obtains aluminium chloride or aluminum sulfate.
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| CN2009100550138A CN101607259B (en) | 2009-07-17 | 2009-07-17 | Method for activating fly ash at low temperature and application thereof |
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| CN2009100550138A CN101607259B (en) | 2009-07-17 | 2009-07-17 | Method for activating fly ash at low temperature and application thereof |
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| CN101607259B true CN101607259B (en) | 2012-01-25 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527692B (en) * | 2010-12-17 | 2014-01-29 | 华东理工大学 | Method for activating coal gangue without calcining |
| CN102432052B (en) * | 2011-09-26 | 2015-05-13 | 西安航天华威化工生物工程有限公司 | Method for extracting aluminum oxide from pulverized fuel ash by using potassium sulfate |
| CN103305686B (en) * | 2013-05-30 | 2016-05-25 | 华东理工大学 | Activated coal gasification lime-ash is realized the method that ferro-aluminum calcium separates |
| CN105776150A (en) * | 2014-12-23 | 2016-07-20 | 中国科学院过程工程研究所 | Method for cooperative activation of fly ash and decomposition of gypsum for recovery of sulfur resource |
| CN104831074B (en) * | 2015-05-19 | 2017-03-01 | 河北工程大学 | A kind of method extracting aluminum from flyash |
| CN108893612A (en) * | 2018-08-06 | 2018-11-27 | 昆明理工大学 | The recovery method of aluminium in a kind of flyash |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242313A (en) * | 1980-03-21 | 1980-12-30 | Extraction Research & Development, Inc. | Processes for the recovery of alumina from fly ash and production of cement constituents |
| CN1329301C (en) * | 2005-12-31 | 2007-08-01 | 朔州市人民政府 | Process for extracting aluminium hydroxide from flyash |
-
2009
- 2009-07-17 CN CN2009100550138A patent/CN101607259B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242313A (en) * | 1980-03-21 | 1980-12-30 | Extraction Research & Development, Inc. | Processes for the recovery of alumina from fly ash and production of cement constituents |
| CN1329301C (en) * | 2005-12-31 | 2007-08-01 | 朔州市人民政府 | Process for extracting aluminium hydroxide from flyash |
Non-Patent Citations (3)
| Title |
|---|
| JP特开平11-104591A 1999.04.20 |
| 唐云 等.碱石灰烧结法提取粉煤灰中的氧化铝.《矿冶工程》.2008,第28卷(第6期), * |
| 方荣利 等.提高粉煤灰活性方法研究.《水泥》.1999,(第6期),8-10. * |
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