CN102351451A - Dealkalization method of fly ash Al-extraction residues - Google Patents
Dealkalization method of fly ash Al-extraction residues Download PDFInfo
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- CN102351451A CN102351451A CN2011101683613A CN201110168361A CN102351451A CN 102351451 A CN102351451 A CN 102351451A CN 2011101683613 A CN2011101683613 A CN 2011101683613A CN 201110168361 A CN201110168361 A CN 201110168361A CN 102351451 A CN102351451 A CN 102351451A
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- alkali
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention discloses a dealkalization method of fly ash Al-extraction residues, comprising the following steps of: (1) adding water into the Al-extraction residues with stirring to prepare an Al-extraction residue slurry; (2) slowly adding calcium carbide slag into the Al-extraction residue slurry with stirring for a dealkalization reaction; (3) filtering the Al-extraction residue slurry which has undergone the dealkalization reaction, followed by washing to obtain the dealkalized Al-extraction residues. The invention is suitable for dealkalization of the Al-extraction residues by the fly ash alkali lime sintering method. After the dealkalization processing, the content of sodium oxide in the Al-extraction residues by the fly ash alkali lime sintering method is reduced from 1.3-2.0% to 0.4-0.6%, which can satisfy the requirement of mixing material addition material and cement clinker raw materials on the alkali content in the building material industry. The method provided by the invention has advantages of simple process, low energy consumption, less material consumption amount and low treatment cost, and is suitable for industrial popularization.
Description
Technical field
The present invention relates to the industrial solid castoff comprehensive utilization technique, relate in particular to a kind of dealkalization method of residue of aluminum-extracted pulverized fuel ash
Background technology
Along with the worsening shortages of China's bauxite resource, utilize industrial solid castoffs such as flyash, coal gangue to extract aluminum oxide and more and more receive people's attention.For example; Be rich in mineral such as boehmite and kaolinite in Neopaleozoic coal seam, basin, Erdos and the dirt band; Alumina content is up to about 50% in the flyash that burning back is produced, and is suitable with alumina content in the medium grade alumyte, is a kind of very valuable alumina producing raw material.According to statistics, the potential reserves of central and west regions, Inner Mongol aluminous fly-ash is up to 15,000,000,000 tons.Along with China's bauxite resource worsening shortages, contain from other that comprises aluminous fly-ash and to extract aluminum oxide the bauxite resource and more and more cause people's attention.Therefore the aluminium element silicon in these aluminous fly-ash resources of comprehensive development and utilization not only can ensure the strategic security that China's aluminium is industrial, also helps local environment protection and develops the recycling economy industry with its own strategic significance.
At present, aluminous fly-ash produce aluminum oxide comparatively rationally and maturation method be exactly preparatory desiliconization soda-lime sintering process, this preparatory desiliconization soda-lime sintering process can produce a large amount of residue of aluminum-extracted pulverized fuel ash.Because Na in the preparatory desiliconization soda-lime sintering process
2CO
3Introducing, the Na in the residue of aluminum-extracted pulverized fuel ash
2O content generally can't be utilized effectively up to 1.3-2.0%; Thereby brought bigger difficulty and challenge for this working method; Mean to have consumed another waste that a kind of waste produces basic equivalent again, and cause further environmental problem.
Therefore, this type residue of aluminum-extracted pulverized fuel ash will be expected utilization preferably, must carry out dealkalize to it and handle.Because red mud and silico-calcium dreg chemistry character and composition are comparatively similar, so the processing method of dealkalize has certain similarity.Red mud dealkalization research is comparatively deep; For example the number of applying for a patent is 200810231008.3 (denominations of invention: patent a kind of method of red mud dealkalization); Adopt first dilute sulphuric acid processing and then add milk of lime high pressure dealkalize bonded method, the alkali content in the red mud can be reduced to the technical requirements of accords with production cement building material.Though but the related method of this patent can be reduced to the alkali content in the red mud technical requirements of accords with production cement building material, processing cost is higher, is difficult to carry out large-scale industrialization promotion.
In addition; The patent No. is respectively 95110552.3 (publication numbers: CN1141264; Denomination of invention: sinter method for red mud dealkalization and processing technology for surface modification thereof) and 200410049747.2 (publication number: 1594093, denomination of invention: patent a kind of Bayer process red mud normal pressure dealkalization method) has adopted the method for adding the milk of lime dealkalize to sintering process and Bayer process red mud respectively.Above-mentioned two parts of patents, though treatment process is comparatively simple, cost is also relatively low, after these two kinds of methods are handled, R in the former red mud
2O (R represents alkali metal, mainly is Na and K) content is still up to 0.9-1.1%, and latter Geng Gao can't satisfy the technical requirements of building material industry to alkali content.
Though the chemical property of coal ash alkali lime sinter process residue of aluminum-extracted and composition are comparatively similar with red mud; But its thing phase composite and alkali metal occurrence status thereof are still pure bigger than big-difference with red mud; Therefore; Dealkalize mechanism and processing method also should have certain difference, and the dealkalize research about similar residue of aluminum-extracted does not at present appear in the newspapers as yet.
Summary of the invention
The present invention provides a kind of dealkalization method of residue of aluminum-extracted pulverized fuel ash; In order to solve defective of the prior art; Realize that technology is simple, energy consumption is low, the material consumption amount is few; Sodium oxide content can satisfy that blended material addition material and cement clinker raw material are suitable for industrialization promotion to the requirement of alkali content in the building material industry in the residue of aluminum after dealkalize is carried.
The dealkalization method of a kind of residue of aluminum-extracted pulverized fuel ash provided by the invention comprises the steps:
(1) residue of aluminum-extracted is added the water stirring and make the residue of aluminum-extracted slurries;
(2) under condition of stirring, in the residue of aluminum-extracted slurries, add carbide slag slowly, carry out de-alkali reaction; The purpose of dealkalize is will be with the non-free Na in the residue of aluminum-extracted
2O carries out the NaOH that washes that chemical reaction is replaced as free state through adding carbide slag, and through washing and liquid-solid the separation just realizing reducing Na content, main de-alkali reaction is following then:
Na
2OCaOSiO
3+ Ca (OH)
2(carbide slag main component)=2CaOSiO
2(C2S)+2NaOH
Na
2O-Al
2O
3-SiO
2n+Ca(OH)
2＝CaO-Al
2O
3-SiO
2+NaOH
(3) with residue of aluminum-extracted dope filtration, washing behind the de-alkali reaction, obtain the dealkalize residue of aluminum-extracted.
Further, residue of aluminum-extracted described in the step (1) is the residue of aluminum-extracted through three washings.
Further, new water is adopted once in washing in the step (3), and the wash water after step (3) washing is as the washing lotion recycle of three washings.Wash water in the step (3) recycles as the washing lotion of three washings of next batch residue of aluminum-extracted, and this will effectively improve the utilization ratio of water resources, reduces discharged waste water.
Further, residue of aluminum-extracted described in the step (1) is a coal ash alkali lime sinter process residue of aluminum-extracted, and sodium oxide quality percentage composition is 1.3～2.0% in the said residue of aluminum-extracted of step (1), and the quality percentage composition of water is 35～45%.
Further, the mass ratio of residue of aluminum-extracted butt and water is 1.5～3 described in the step (1).The mass ratio of residue of aluminum-extracted butt and carbide slag butt is 9～12: 1 described in the step (2).The effective Ca (OH) of carbide slag that is used for the residue of aluminum-extracted dealkalize
2Content is not less than 85%, Na
2O+0.66K
2O is no more than 0.1%; Water ratio is no more than 40%, and the 0.08mm screen over-size is no more than 12%.Na wherein
2O+0.66K
2O is the criterion calculation formula of cement industry to alkali metal oxide content control in cement clinker or the grog raw material, just Na in the silico-calcium slag
2The content of O adds 0.66 times K again
2The content sum of O must be lower than a certain limit value.K
2O content front takes advantage of 0.66 to be with K in the raw material
2The mass content of O is pressed Na
2O and K
2The ratio of O molecular weight is converted, unit mass K in cement raw material or the grog
2The harm of O is less than Na
2O.
Further, the temperature of reaction of said de-alkali reaction is 75～95 ℃, and the reaction times is 0.5～1.0h.
The dealkalization method of residue of aluminum-extracted pulverized fuel ash of the present invention, processing method is simple, science, reasonable, compares with prior art, mainly has following several respects advantage:
(1) utilizes carbide slag to handle the residue after the coal ash alkali lime sinter process is extracted aluminum oxide, reach the effect of waste recycling, realized the collaborative utilization of industrial solid castoff, reduced production cost, not only economically feasible, and obvious environment benefit.
(2) the method for the invention is the art breading of raw material through simple possible with the carbide slag of solid waste, with the Na in the residue of aluminum-extracted
2O content is reduced to 0.4-0.6% by 1.3-2.0%.(low alkali cement requires Na in the raw material to the requirement of alkali content to make it can satisfy blended material addition material and cement clinker raw material in the building material industry
2O+0.66K
2O≤0.6%), can be used as the high quality raw material of building material industry, make valuable resource obtain comprehensive utilization, increase economic efficiency.
Description of drawings
Accompanying drawing is used to provide further understanding of the present invention, and constitutes the part of specification sheets, is used to explain the present invention with embodiments of the invention, is not construed as limiting the invention.In the accompanying drawings:
The schema of the dealkalization method of the residue of aluminum-extracted pulverized fuel ash that Fig. 1 provides for the embodiment of the invention one.
Embodiment
For making the object of the invention, technical scheme and advantage clearer; To combine the accompanying drawing in the embodiment of the invention below, the technical scheme in the embodiment of the invention carried out clear, intactly description, obviously; Described embodiment is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
Embodiment one
The schema of the dealkalization method of the residue of aluminum-extracted pulverized fuel ash that Fig. 1 provides for the embodiment of the invention one.As the step of scheming the dealkalization method of visible residue of aluminum-extracted pulverized fuel ash is: at first; Will through three times the washing residue of aluminum-extracted (wherein the mass percentage content of sodium oxide is 2.0%; The mass percentage content of water is 35%); Main thing in the residue of aluminum-extracted has C2S (Dicalcium Phosphate (Feed Grade)) mutually; Account for the 70-80% of whole residue of aluminum-extracted; Scanning electron microscope study shows, the most of non-free Na in the residue of aluminum-extracted
2O is with Na
2OCaOSiO
3The form of (alkali formula Calucium Silicate powder) is composed and is deposited, and this is alkali metal is composed the situation of depositing in residue of aluminum-extracted and red mud a difference.The 3CaOAl that contains 5-10% in addition
2O
36H
2OnSiO
2(calcium aluminosilicate hydrate), the Al of 1-2% (OH)
3, 3-5% CaCO
3, the iron-bearing mineral of 3-6%, the uhligite (CaTiO of 2-3%
3), about 1% hydrated aluminum silicate (Na
2O
1.7Al
2O
3SiO
2NH
2O), be that 3 ratio adds new water (primary water) in the mass ratio of water and residue of aluminum-extracted butt, stir, make the residue of aluminum-extracted slurries.Then, under condition of stirring, in the residue of aluminum-extracted slurries, adding carbide slag slowly, carry out de-alkali reaction, is 9: 1 by residue of aluminum-extracted butt and carbide slag butt mass ratio, and temperature of reaction is 95 ℃, and the reaction times is 1.0h.At last; With the residue of aluminum-extracted dope filtration behind the above-mentioned de-alkali reaction; Adopt new water washing once; Obtain dealkalize residue of aluminum-extracted and wash water; Above-mentioned wash water is as three washing washing lotions recycle of next batch residue of aluminum-extracted; This will effectively improve the utilization ratio of water resources, reduce discharged waste water.
Main component contrast before and after the table 1 embodiment one residue of aluminum-extracted dealkalize, Na
2O and K
22.0% and 0.11% before by the dealkalize of the mass percent of O is reduced to 0.55% and 0.04% after the dealkalize.This shows through adopting the dealkalization method of the residue of aluminum-extracted pulverized fuel ash that the embodiment of the invention one provides, can effectively reduce the content of alkali in the residue of aluminum-extracted, and then satisfy in the building material industry blended material addition material and cement clinker raw material the requirement of alkali content.Loss on ignition (loss) is that chemical water and carbonic acid gas are overflowed and the mass loss that causes.
Main component contrast (mass percent %) before and after the table 1 embodiment one residue of aluminum-extracted dealkalize
Embodiment two
The step of the dealkalization method of the residue of aluminum-extracted pulverized fuel ash that embodiment two provides is: at first; Will through three times the washing coal ash alkali lime sinter process residue of aluminum-extracted (wherein the mass percentage content of sodium oxide is 1.4%; The mass percentage content of water is 45%); In the mass ratio of water and residue of aluminum-extracted butt is that 1.5 ratio adds new water; Stir, make the residue of aluminum-extracted slurries.Then, under condition of stirring, in the residue of aluminum-extracted slurries, add carbide slag slowly, carry out de-alkali reaction, press the residue of aluminum-extracted butt and calculate, with carbide slag butt mass ratio be 12: 1, temperature of reaction is 85 ℃, the reaction times is 0.5h.At last; With the residue of aluminum-extracted dope filtration behind the above-mentioned de-alkali reaction; Adopt new water washing once; Obtain dealkalize residue of aluminum-extracted and wash water; Above-mentioned wash water is as three washing washing lotions recycle of next batch residue of aluminum-extracted; This will effectively improve the utilization ratio of water resources, reduce discharged waste water.
Main component contrast before and after the table 2 embodiment two residue of aluminum-extracted dealkalizes, Na
2O and K
21.4% and 0.17% before by the dealkalize of the mass percent of O is reduced to 0.42% and 0.09% after the dealkalize.This shows the dealkalization method of the coal ash alkali lime sinter process residue of aluminum-extracted that provides through the employing embodiment of the invention two; The content of alkali in the residue of aluminum-extracted be can effectively reduce, and then blended material addition material and cement clinker raw material satisfied in the building material industry the requirement of alkali content.
Main component contrast (mass percent %) before and after the table 2 embodiment two residue of aluminum-extracted dealkalizes
| CaO | Na 2O | K 2O | SiO 2 | Al 2O 3 | MgO | TiO 2 | Fe 2O 3 | LOSS | |
| Before the dealkalize | 53.7 | 1.4 | 0.17 | 25.8 | 4.95 | 1.88 | 1.51 | 2.58 | 7.19 |
| After the dealkalize | 54.8 | 0.42 | 0.09 | 24.5 | 4.59 | 2.07 | 1.46 | 2.49 | 7.98 |
Embodiment three
The step of the dealkalization method of the residue of aluminum-extracted pulverized fuel ash that embodiment three provides is: at first; Will be through the coal ash alkali lime sinter process residue of aluminum-extracted (wherein the mass percentage content of sodium oxide is 1.73%) of three washings; In the mass ratio of water and residue of aluminum-extracted butt is that 2.0 ratio adds new water; Stir, make the residue of aluminum-extracted slurries.Then, under condition of stirring, in the residue of aluminum-extracted slurries, add carbide slag slowly, carry out de-alkali reaction, press the residue of aluminum-extracted butt and calculate, with carbide slag butt mass ratio be 10: 1, temperature of reaction is 90 ℃, the reaction times is 0.5h.At last; With the residue of aluminum-extracted dope filtration behind the above-mentioned de-alkali reaction; Adopt new water washing once; Obtain dealkalize residue of aluminum-extracted and wash water; Above-mentioned wash water is as three washing washing lotions recycle of next batch residue of aluminum-extracted; This will effectively improve the utilization ratio of water resources, reduce discharged waste water.
Main component contrast before and after the table 3 embodiment three residue of aluminum-extracted dealkalizes, Na
2O and K
21.73% and 0.13% before by the dealkalize of the mass percent of O is reduced to 0.48% and 0.06% after the dealkalize.This shows the dealkalization method of the coal ash alkali lime sinter process residue of aluminum-extracted that provides through the employing embodiment of the invention one; The content of alkali in the residue of aluminum-extracted be can effectively reduce, and then blended material addition material and cement clinker raw material satisfied in the building material industry the requirement of alkali content.
Main component contrast (mass percent %) before and after the table 3 embodiment three residue of aluminum-extracted dealkalizes
| CaO | Na 2O | K 2O | SiO 2 | Al 2O 3 | MgO | TiO 2 | Fe 2O 3 | LOSS | |
| Before the dealkalize | 53.9 | 1.73 | 0.13 | 25.2 | 5.17 | 1.84 | 1.46 | 2.70 | 7.87 |
| After the dealkalize | 56.5 | 0.48 | 0.06 | 23.5 | 4.62 | 2.01 | 1.49 | 2.88 | 8.46 |
What should illustrate at last is: above embodiment is only in order to illustrating technical scheme of the present invention, but not to its restriction; Although with reference to previous embodiment the present invention has been carried out detailed explanation, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these are revised or replacement, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of relevant art scheme.
Claims (9)
1. the dealkalization method of a residue of aluminum-extracted pulverized fuel ash is characterized in that, comprises the steps:
(1) residue of aluminum-extracted is added the water stirring and make the residue of aluminum-extracted slurries;
(2) under condition of stirring, in the residue of aluminum-extracted slurries, add carbide slag slowly, carry out de-alkali reaction;
(3) with residue of aluminum-extracted dope filtration, washing behind the de-alkali reaction, obtain the dealkalize residue of aluminum-extracted.
2. dealkalization method according to claim 1 is characterized in that, residue of aluminum-extracted described in the step (1) is the residue of aluminum-extracted through three washings.
3. dealkalization method according to claim 2 is characterized in that, new water is adopted once in washing in the step (3), and the wash water in the step (3) after the washing is as the washing lotion recycle of three washings.
4. dealkalization method according to claim 1 is characterized in that, residue of aluminum-extracted described in the step (1) is a coal ash alkali lime sinter process residue of aluminum-extracted.
5. according to claim 1 or 4 described dealkalization method, it is characterized in that sodium oxide quality percentage composition is 1.3～2.0% in the said residue of aluminum-extracted of step (1), the quality percentage composition of said water is 35～45%.
6. dealkalization method according to claim 1 is characterized in that, the mass ratio of residue of aluminum-extracted butt and water is 1.5～3 described in the step (1).
7. dealkalization method according to claim 1 is characterized in that, the mass ratio of residue of aluminum-extracted butt and carbide slag butt is 9～12: 1 described in the step (2).
8. dealkalization method according to claim 1 is characterized in that, the temperature of reaction of said de-alkali reaction is 75～95 ℃.
9. dealkalization method according to claim 1 is characterized in that, the reaction times of said de-alkali reaction is 0.5～1.0h.
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| CN104071995A (en) * | 2014-07-18 | 2014-10-01 | 河南理工大学 | Red mud on-line comprehensive treatment method |
| CN105271323A (en) * | 2014-06-06 | 2016-01-27 | 神华集团有限责任公司 | Aluminium dissolving-out method of fly-ash alkaline sintering clinker, aluminium dissolving-out reaction method, aluminium dissolving-out slurry separation method and fly-ahs aluminium extraction method |
| CN105293542A (en) * | 2014-06-06 | 2016-02-03 | 神华集团有限责任公司 | Pre-desilication method, leaching method, dealkalization method and separation method for coal fly ash, and method for extracting aluminum from coal fly ash |
| CN108275707A (en) * | 2018-01-22 | 2018-07-13 | 云南文山铝业有限公司 | The method of sodium oxide molybdena in efficient removal alumina producing Bayer process red mud |
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| CN105271323A (en) * | 2014-06-06 | 2016-01-27 | 神华集团有限责任公司 | Aluminium dissolving-out method of fly-ash alkaline sintering clinker, aluminium dissolving-out reaction method, aluminium dissolving-out slurry separation method and fly-ahs aluminium extraction method |
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| CN108275707A (en) * | 2018-01-22 | 2018-07-13 | 云南文山铝业有限公司 | The method of sodium oxide molybdena in efficient removal alumina producing Bayer process red mud |
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Application publication date: 20120215 |