CN104291539A - Method for dealkalizing Bayer process red mud by using CO2 and waste acid in combined way - Google Patents
Method for dealkalizing Bayer process red mud by using CO2 and waste acid in combined way Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a method for dealkalizing Bayer process red mud by using CO2 and waste acid in a combined way. The method comprises the following steps: smashing the Bayer process red mud, and mixing the smashed Bayer process red mud with water in the weight ratio of 1:(3-10); grinding the red mud till the granularity is 160-200 meshes to form a solid-liquid mixture, and introducing CO2 into the Bayer process red mud for performing an acidification reaction at the temperature of 60-80 DEG C for 0.5-2 hours, wherein the CO2 is introduced at the flow of 0.2-1L/min; adding 20 percent by mass waste hydrochloric acid into the solid-liquid mixture obtained in the first step for reacting at the temperature of 60-80 DEG C for 0.5-2 hours to obtain a solid-liquid mixture, wherein the mass ratio of the Bayer process red mud to the added waste hydrochloric acid is (2-4):1; and performing suction filtration separation on the obtained solid-liquid mixture, and separating treated residues to recover aluminum and iron. Through adoption of the method for treating the Bayer process red mud, a solution is provided for the application of the red mud to building materials.
Description
Technical field
The present invention relates to a kind for the treatment of process of Bayer process red mud dealkalize, belong to technical field of resource comprehensive utilization.
Background technology
China is the big producing country of aluminum oxide, and Bayer process red mud is that alumina producing is according to the waste in bayer process route production process.Often produce 1 ton of aluminum oxide by-product, 1.0 ~ 1.4 tons of red muds.Current China aluminum oxide output is about 3,000 ten thousand tons of red muds.
The red mud comprehensive utilization ratio of current China is lower.Along with China's aluminum oxide output increases the reduction gradually with bauxite grade year by year, the volume of cargo in storage of red mud also will constantly increase.Red mud comprehensive utilization still belongs to global problem, in the world red mud is mainly adopted to the disposal options of storing up earthing.At present, red mud is mostly carried stockyard by domestic and international alumina producer, and wet method of building a dam is stored up, and this method easily makes a large amount of waste lye penetrate into neighbouring farmland, causes alkalization of soils, paludification, polluted surface underground water source; Another kind of conventional method is stored up at dry method after red mud drying dehydration and evaporation, although this decreases volume of cargo in storage, processing cost increases, and still needs land occupation, simultaneously some local rainfall is plentiful, also easily cause soil to alkalize and the pollution of water system.
Large quantity research is carried out both at home and abroad according to the performance characteristics of red mud different aspect.Red mud is utilized to produce material of construction, as cement, concrete, novel wall material, vitrified brick, non-burning brick, environment-friendly type wall brick; Red mud is utilized to produce devitrified glass, plastic filler, impervious material, pavior, valuable metal is reclaimed from red mud, as Fe, Al, Ti, the application of red mud in environmental engineering, as red mud does siliceous fertilizer, improvement soil, administers containing waste water such as Cd, As, Cr, Cu, Pb, Zn, F, P, COD, ammonia nitrogens.
Especially, as production building materials aspect, because red mud alkali content is higher, there will be " scum " phenomenon for a long time, red mud is utilized and causes disadvantageous effect.Dealkalize process need be done to red mud, make alkali content be reduced to certain scope.
Patent No. US4668485, denomination of invention is that Recovery of sodium aluminate from Bayer process red mud utilizes SO
2process red mud dealkalization, red mud precipitation desiliconization after dealkalize, rear quaternization, sintering, obtains CaO, SO
2, CaO for the quaternization that circulates, SO
2circular treatment dealkalize.This invention process red mud dealkalization, red mud alkali content can be reduced to less than 1%, but complex process, pilot process needs sintering, high temperature service.
Publication number CN101423318A, the method for a kind of red mud dealkalization of denomination of invention, is divided into dilute sulphuric acid dealkalize stage and pressure oxidation calcium dealkalize stage.Add reaction dealkalize with a certain amount of sour red mud liquid-solid ratio, dealkalize red mud is at condition of high voltage, and temperature is 95-150 DEG C, reaction times 0.5h.Publication number CN1141264A, denomination of invention is sinter method for red mud dealkalization and processing technology for surface modification thereof, and invention describes one in atmospheric conditions, active calcium oxide is utilized to carry out dealkalize to red mud, after dealkalize, red mud alkali content is reduced to less than 1%, and above dealkalize needs the long period, and dealkalize cost is high.
Publication number CN101469966A, name is called a kind of normal atmosphere dealkalizing method by sintering, utilizes suspension and carbonation dealkalization method process red mud dealkalization, Na in red mud
2the content of O drops to less than 1%.According to pertinent literature, red mud is to CO
2specific absorption lower, the method, to high-alkali red mud dealkalization, takes time longer.
The present invention overcomes the imperfection of prior art, and technical problem to be solved provides the method for the process red mud dealkalization that a kind of starting material easily obtain, production cost is low.The present invention utilizes CO
2with spent acid combination treatment red mud dealkalization, utilize waste hydrochloric acid place red mud water soluble alkali, meanwhile, change red mud wherein crystalline texture, be convenient to lower step CO
2process red mud dealkalization.Utilize CO
2further process red mud dealkalization, reaches dealkalize effect, and dealkalize efficiency is more than 80%.
Summary of the invention
The problem that the present invention solves is to provide one and utilizes CO
2with the method for sour combination treatment red mud dealkalization.
The invention provides a kind of method utilizing flue gas and the dealkalize of spent acid combination treatment Bayer process red mud, the method comprises following detailed step:
The first step, pulverizes red mud, and after grinding, red mud granularity is at 160 ~ 200 orders, and mix with water, Bayer process red mud and water weight ratio example are 1:3 ~ 10; CO is passed in Bayer process red mud
2carry out acidification reaction and obtain solidliquid mixture (1); Pass into CO
2flow is 0.2 ~ 1L/min, and temperature of reaction is 60 DEG C ~ 80 DEG C, and the time is 0.5 ~ 2h;
Second step, to the solidliquid mixture (1) that the first step acidification reaction obtains, add mass concentration be 20% waste hydrochloric acid react, the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation is 2 ~ 4:1, temperature of reaction is 60 DEG C ~ 80 DEG C, time is 0.5 ~ 2h, obtains solidliquid mixture (2);
3rd step, the solidliquid mixture obtained after second step process (2) suction filtration is separated, and the residue after separating treatment, for reclaiming aluminium, iron.
The present invention compared with prior art has following beneficial effect.
Red mud is the waste of aluminum oxide industry, very large to environmental hazard, containing recyclable elements such as a large amount of Fe and Al in red mud.Meanwhile, consider in flue gas containing CO
2sour gas, for the treatment of red mud, can reach the effect of process Bayer process red mud dealkalize.Therefore, CO is utilized
2with the dealkalize of spent acid combination treatment Bayer process red mud, not only utilize application prospect in red mud dealkalization process and off-gas recovery, and there is very large potential age deduction.
Embodiment:
Following instance, for further illustrating the present invention, does not limit content of the present invention.
Example one:
The first step, pulverizes red mud, and after grinding, red mud granularity is at 160 orders, and mix with water, Bayer process red mud and water weight ratio example are 1:10; CO is passed in Bayer process red mud
2carry out acidification reaction and obtain solidliquid mixture (1); Pass into CO
2flow is 1L/min, and temperature of reaction is 80 DEG C, and the time is 0.5h; Second step, to the solidliquid mixture (1) that the first step acidification reaction obtains, add mass concentration be 20% waste hydrochloric acid react, the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation is 4:1, temperature of reaction is 80 DEG C, and the time is 2h, obtains solidliquid mixture (2); 3rd step, the solidliquid mixture obtained after second step process (2) suction filtration is separated, and the residue after separating treatment, for reclaiming aluminium, iron.Detect alkali content in low alkali red mud by ordinary method, analyzing alkali content in low alkali red mud is 1.8%.
Example two:
The first step, pulverizes red mud, and after grinding, red mud granularity is at 160 orders, and mix with water, Bayer process red mud and water weight ratio example are 1:9; CO is passed in Bayer process red mud
2carry out acidification reaction and obtain solidliquid mixture (1); Pass into CO
2flow is 1L/min, and temperature of reaction is 60 DEG C, and the time is 1h; Second step, to the solidliquid mixture (1) that the first step acidification reaction obtains, add mass concentration be 20% waste hydrochloric acid react, the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation is 3:1, temperature of reaction is 60 DEG C, and the time is 1h, obtains solidliquid mixture (2); 3rd step, the solidliquid mixture obtained after second step process (2) suction filtration is separated, and the residue after separating treatment, for reclaiming aluminium, iron.Detect alkali content in low alkali red mud by ordinary method, analyzing alkali content in low alkali red mud is 2.1%.
Example three;
The first step, pulverizes red mud, and after grinding, red mud granularity is at 180 orders, and mix with water, Bayer process red mud and water weight ratio example are 1:8; CO is passed in Bayer process red mud
2carry out acidification reaction and obtain solidliquid mixture (1); Pass into CO
2flow is 0.8L/min, and temperature of reaction is 70 DEG C, and the time is 1.5h; Second step, to the solidliquid mixture (1) that the first step acidification reaction obtains, add mass concentration be 20% waste hydrochloric acid react, the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation is 3:1, temperature of reaction is 60 DEG C, and the time is 1h, obtains solidliquid mixture (2); 3rd step, the solidliquid mixture obtained after second step process (2) suction filtration is separated, and the residue after separating treatment, for reclaiming aluminium, iron.Detect alkali content in low alkali red mud by ordinary method, analyzing alkali content in low alkali red mud is 1.6%.
Example four:
The first step, pulverizes red mud, and after grinding, red mud granularity is at 180 orders, and mix with water, Bayer process red mud and water weight ratio example are 1:8; CO is passed in Bayer process red mud
2carry out acidification reaction and obtain solidliquid mixture (1); Pass into CO
2flow is 0.8L/min, and temperature of reaction is 70 DEG C, and the time is 1.5h; Second step, to the solidliquid mixture (1) that the first step acidification reaction obtains, add mass concentration be 20% waste hydrochloric acid react, the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation is 3:1, temperature of reaction is 60 DEG C, and the time is 1h, obtains solidliquid mixture (2); 3rd step, the solidliquid mixture obtained after second step process (2) suction filtration is separated, and the residue after separating treatment, for reclaiming aluminium, iron.Detect alkali content in low alkali red mud by ordinary method, analyzing alkali content in low alkali red mud is 2.1%.
Claims (7)
1. one kind utilizes CO
2with the method for spent acid combination treatment Bayer process red mud dealkalize, it is characterized in that the step of its treating processes comprises:
(1), by Bayer process red mud pulverize, mix with water, pass into CO
2gas carries out acidification reaction, obtains solidliquid mixture 1.;
(2), to solidliquid mixture 1. in add mass concentration be 20% waste hydrochloric acid carry out reaction solidliquid mixture 2.;
(3) the solidliquid mixture 2. filtering separation, obtained after step (2) reaction; Residue after separating treatment, for reclaiming aluminium, iron.
2. the dealkalization method of a kind of Bayer process red mud according to claim 1, is characterized in that in step (1), Bayer process red mud grinding order number is 160 ~ 200.
3. the dealkalization method of a kind of Bayer process red mud according to claim 1, is characterized in that in step (1), Bayer process red mud and water weight ratio example are 1: 3 ~ 10.
4. the dealkalization method of a kind of Bayer process red mud according to claim 1, is characterized in that passing into CO in step (1)
2airshed is 0.2 ~ 1L/min.
5. the dealkalization method of a kind of Bayer process red mud according to claim 1, be that the temperature of reaction in step (1) is 60 DEG C ~ 80 DEG C, the time is 0.5 ~ 2h.
6. the dealkalization method of a kind of Bayer process red mud according to claim 1, is characterized in that the waste hydrochloric acid mass ratio of Bayer process red mud and interpolation in step (2) is 2 ~ 4: 1.
7. the dealkalization method of a kind of Bayer process red mud according to claim 1, be that the temperature of reaction in step (2) is 60 DEG C ~ 80 DEG C, the time is 0.5 ~ 2h.
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| CN201310295802.5A CN104291539B (en) | 2013-07-16 | 2013-07-16 | One utilizes CO2method with spent acid Combined Treatment Bayer process red mud dealkalize |
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| CN201310295802.5A CN104291539B (en) | 2013-07-16 | 2013-07-16 | One utilizes CO2method with spent acid Combined Treatment Bayer process red mud dealkalize |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130142A (en) * | 2015-09-10 | 2015-12-09 | 中国科学院重庆绿色智能技术研究院 | Non-bayer-process red mud staged deep dealkalization method |
| CN110354671A (en) * | 2019-07-30 | 2019-10-22 | 天津理工大学 | A kind of method of red mud and the processing of lime kiln exhaust gas common resourceization |
| CN111234350A (en) * | 2020-03-03 | 2020-06-05 | 中国地质大学（北京） | Composite board prepared from red mud, waste plastic and rice paper waste residues and preparation method thereof |
| CN112546529A (en) * | 2020-11-18 | 2021-03-26 | 洲际环境科学研究院(广州)有限公司 | Process for realizing dealkalization of high-alkalinity red mud by utilizing industrial waste residues and waste gases |
| CN114573253A (en) * | 2022-02-23 | 2022-06-03 | 山东大学 | Red mud activity improving method through physical activation, acidification and thermal activation |
| CN114573199A (en) * | 2022-03-17 | 2022-06-03 | 山东省科学院能源研究所 | Fenton iron mud dealkalization and carbon dioxide capture cooperative treatment system and method |
| CN117443914A (en) * | 2023-10-31 | 2024-01-26 | 广西大学 | Harmless treatment method of Bayer process red mud or papermaking white mud, catalytic liquid and preparation method of catalytic mechanical pulp |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668485A (en) * | 1984-12-21 | 1987-05-26 | Comalco Aluminum Limited | Recovery of sodium aluminate from Bayer process red mud |
| CN101468866A (en) * | 2007-12-27 | 2009-07-01 | 中国科学院生态环境研究中心 | Normal atmosphere dealkalizing method by sintering |
-
2013
- 2013-07-16 CN CN201310295802.5A patent/CN104291539B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668485A (en) * | 1984-12-21 | 1987-05-26 | Comalco Aluminum Limited | Recovery of sodium aluminate from Bayer process red mud |
| CN101468866A (en) * | 2007-12-27 | 2009-07-01 | 中国科学院生态环境研究中心 | Normal atmosphere dealkalizing method by sintering |
Non-Patent Citations (1)
| Title |
|---|
| 庞永刚等: "动力学因素对拜尔法赤泥使用CO2脱钠的影响", 《四川大学学报（工程科学版）》, vol. 44, 30 June 2012 (2012-06-30) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130142A (en) * | 2015-09-10 | 2015-12-09 | 中国科学院重庆绿色智能技术研究院 | Non-bayer-process red mud staged deep dealkalization method |
| CN110354671A (en) * | 2019-07-30 | 2019-10-22 | 天津理工大学 | A kind of method of red mud and the processing of lime kiln exhaust gas common resourceization |
| CN111234350A (en) * | 2020-03-03 | 2020-06-05 | 中国地质大学（北京） | Composite board prepared from red mud, waste plastic and rice paper waste residues and preparation method thereof |
| CN112546529A (en) * | 2020-11-18 | 2021-03-26 | 洲际环境科学研究院(广州)有限公司 | Process for realizing dealkalization of high-alkalinity red mud by utilizing industrial waste residues and waste gases |
| CN112546529B (en) * | 2020-11-18 | 2022-03-11 | 洲际环境科学研究院(广州)有限公司 | Process for realizing dealkalization of high-alkalinity red mud by utilizing industrial waste residues and waste gases |
| CN114573253A (en) * | 2022-02-23 | 2022-06-03 | 山东大学 | Red mud activity improving method through physical activation, acidification and thermal activation |
| CN114573199A (en) * | 2022-03-17 | 2022-06-03 | 山东省科学院能源研究所 | Fenton iron mud dealkalization and carbon dioxide capture cooperative treatment system and method |
| CN117443914A (en) * | 2023-10-31 | 2024-01-26 | 广西大学 | Harmless treatment method of Bayer process red mud or papermaking white mud, catalytic liquid and preparation method of catalytic mechanical pulp |
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| CN104291539B (en) | 2016-09-28 |
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