CN110841463A - Red mud dealkalization method coupled with calcium flue gas desulfurization process - Google Patents
Red mud dealkalization method coupled with calcium flue gas desulfurization process Download PDFInfo
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- CN110841463A CN110841463A CN201910932908.9A CN201910932908A CN110841463A CN 110841463 A CN110841463 A CN 110841463A CN 201910932908 A CN201910932908 A CN 201910932908A CN 110841463 A CN110841463 A CN 110841463A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/504—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific device
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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Abstract
The invention relates to a red mud dealkalization method coupled with a calcium flue gas desulfurization process, which comprises the steps of adding water into red mud in a red mud tank to prepare red mud slurry; introducing the red mud slurry into an inlet of a delivery pump on the uppermost 1-2 layers of the desulfurization tower, mixing the red mud slurry with limestone or lime slurry, spraying the mixture into the desulfurization tower, reversely contacting with flue gas to perform flue gas desulfurization, and introducing the desulfurized slurry into a desulfurization circulating tank to perform circulating desulfurization; fully mixing the red mud, the calcium-based desulfurizer and the desulfurized gypsum slurry in the desulfurization circulating tank to obtain desulfurized liquid slurry, leading a part of desulfurized liquid slurry out to a separation tank when the pH value of the desulfurized liquid slurry is reduced to a specific value, and separating calcium carbonate and calcium silicate solids through dehydration; and (4) inputting the supernatant obtained after the separation in the fifth step into a red mud tank, adding fresh red mud to adjust the pH value of the supernatant to a preset range, and continuously inputting the supernatant into a desulfurizing tower for circular desulfurization. Compared with the prior art, the method has wide environmental benefits and economic application value, and is suitable for red mud treatment and industrial flue gas desulfurization in the alumina industry.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a red mud dealkalization method coupled with a calcium flue gas desulfurization process.
Background
The production of raw aluminum in China is continuously positioned in the first place of the world for more than ten years. Alumina is the main raw material for producing primary aluminum. During the production of alumina, a large amount of red mud is produced. The reported annual red mud production in our country is about 3000 million tons. At present, the utilization rate of the red mud is very low, and the red mud can only be stockpiled and disposed generally, thereby occupying a large amount of land area. Moreover, the precipitation of alkaline components in red mud can cause the harm of salinization of soil. Red mud with pH values above 12 must be disposed of as hazardous waste, which in turn increases the cost of red mud treatment. With the increasing output of red mud, the environmental and economic problems are more and more serious, and a disposal method for the red mud needs to be developed urgently. The red mud contains CaO, MgO and Na2O and Al2O3And alkaline components are added, so that the possibility of flue gas desulfurization is realized. Meanwhile, the alkalinity of the red mud can be reduced by using the red mud flue gas desulfurization, so that the red mud is converted from dangerous waste into general waste, and the treatment difficulty and cost are reduced. Therefore, the red mud is utilized for desulfurization, and the method has good environmental protection benefit and economic benefit.
At present, research reports on the utilization of red mud are reported, such as red mud leachate desulfurization, red mud slurry desulfurization, dry red mud desulfurization and the like, but the large-scale industrial application of the methods is less. Chinese patents ZL200610200499.6 and ZL200610098706.1 adopt filler absorption towers respectively, and utilize red mud slurry to carry out flue gas desulfurization. However, the method has large pressure drop during operation, is easy to scale and block, is limited by the properties of the red mud, has low flue gas desulfurization efficiency, and cannot meet the requirement of ultralow emission of industrial flue gas at present. Therefore, how to reasonably and effectively utilize the red mud in the flue gas desulfurization and realize the recycling, reduction and harmless treatment of the red mud is still a difficult problem in the current red mud treatment process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a red mud dealkalization method coupled with a calcium flue gas desulfurization process.
The purpose of the invention can be realized by the following technical scheme: a red mud dealkalization method coupled with a calcium flue gas desulfurization process comprises the following steps of mixing and tempering red mud and partial calcium desulfurization slurry, removing oxysulfide in industrial flue gas by using the red mud and partial calcium desulfurization slurry as desulfurization slurry, dissolving out and neutralizing alkaline components in the red mud by using acidic desulfurization slurry generated in the desulfurization process, and finally realizing the purposes of flue gas desulfurization, red mud dealkalization and reutilization:
firstly, adding water into red mud in a red mud tank to prepare red mud slurry;
secondly, introducing the red mud slurry into an inlet of a delivery pump on the uppermost 1-2 layers of the desulfurization tower to be mixed with limestone or lime slurry;
thirdly, spraying the mixed solution of the red mud slurry and the limestone or lime slurry through the uppermost 1-2 spraying layers of the desulfurization tower, reversely contacting with the flue gas to carry out flue gas desulfurization, and introducing the desulfurized slurry into a desulfurization circulating tank to carry out circulating desulfurization;
fourthly, fully mixing the red mud in the desulfurization circulating tank with a calcium-based desulfurizer and desulfurized gypsum slurry to obtain desulfurized liquid slurry, and carrying out deep replacement and neutralization on sodium ions, combined alkali and other components in the red mud in circulating liquid with relatively low pH (the pH value is 5.5-7.0) under the combined action of calcium, sulfate radicals and sulfite radicals;
fifthly, when the pH value of the desulfurization slurry is reduced to a specific value, leading a part of the desulfurization slurry out to a separation tank, and dehydrating and separating calcium carbonate and calcium silicate solids;
and sixthly, inputting the supernatant obtained after the separation in the fifth step into a red mud tank, adding fresh red mud to adjust the pH value of the supernatant to a preset range, and continuously inputting the supernatant into a desulfurizing tower for circulating desulfurization.
The solid-to-liquid ratio of the red mud slurry in the first step is 1: 1-20.
The limestone or lime slurry in the second step is a raw material adopted by the flue gas desulfurization process by the calcium method.
The mass ratio of the red mud slurry to the limestone or lime slurry in the third step is 0.05-0.2: 1.
And fourthly, the desulfurization circulating tank is positioned at the bottom of the desulfurization tower.
And fourthly, the calcium-based desulfurizer and the desulfurized gypsum slurry in the desulfurization circulating pool are calcium agent desulfurized slurry (namely limestone or lime slurry) used for desulfurization in the existing calcium flue gas desulfurization process. The red mud is settled in a circulating pool and mixed with the circulating pool after being sprayed into the absorption tower, and the existing calcium flue gas desulfurization process is the conventional process in the field, such as the processes disclosed and reported in Chinese invention patents such as CN200610053076.6 and CN 201510428640.7.
And when the pH value of the circulating desulfurization slurry in the fifth step is reduced to 5.5, inputting 10-30% of the desulfurization circulating pool into a separation tank for solid-liquid separation, and conveying the supernatant into a red mud tank.
And adding fresh red mud into the red mud tank until the pH value of the red mud slurry is increased to 10.
The invention provides a red mud dealkalization method coupled with a calcium flue gas desulfurization process, aiming at the problems of a large amount of red mud which is difficult to dispose and is generated in the roasting process of alumina, low single-layer efficiency of calcium desulfurization and the like. The red mud slurry with high pH value is directly mixed with 1-2 layers of calcium-based spraying circulating liquid on the upper part of the desulfurizing tower, and free alkali in the red mud is utilized to improve the activity of the desulfurizing liquid and realize the ultralow emission effect. The red mud falls into a desulfurization circulating tank, and then is fully mixed with a calcium-based desulfurizer and desulfurization gypsum slurry, and sodium ions, combined alkali and other components in the red mud are deeply replaced and neutralized in circulating liquid with relatively low pH value under the combined action of calcium, sulfate radicals and sulfite radicals, so that the use of the calcium-based desulfurizer can be greatly reduced, and deep dealkalization and stabilization of the red mud can be realized. The red mud after the treatment can be used as a building material together with desulfurized gypsum. The method has wide environmental benefits and economic application value, and is suitable for red mud treatment in the alumina industry and industrial flue gas desulfurization application.
Compared with the prior art, the invention has the following advantages:
1. the invention can couple the red mud desulfurization and calcium desulfurization processes, improve the calcium desulfurization efficiency and reduce the consumption of limestone/lime and other desulfurizing agents;
2. the method utilizes the low-pH-value desulfurization slurry to promote the precipitation of alkaline substances in the red mud, thereby effectively reducing the alkalinity of the red mud;
3. the calcium silicate/calcium sulfate separated by the whole process can be used as a cement ingredient, and the aluminum hydroxide can be used as a raw material for roasting the aluminum oxide, so that the comprehensive utilization of solid wastes is realized.
Drawings
FIG. 1 is a schematic diagram of the process of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
In this embodiment, a pilot-scale desulfurization device for practical industrial flue gas was selected for verification. The smoke gas amount of the pilot test platform is 1500m3H, SO in flue gas2The concentration is 1000mg/m3The temperature of the flue gas is 80 ℃. Firstly, red mud slurry with a solid-to-liquid ratio of 1:10 is prepared and added into a limestone slurry input pipe in front of a spray pump at the uppermost layer according to a ratio of 0.1:1, and the pH value of the mixed slurry is 6.5. According to the gas-liquid ratio of 10L/m3The mixed red mud/limestone slurry is sprayed into the desulfurizing tower according to the proportion, and the result shows that the flue gas outlet SO2The concentration is 100mg/m3The flue gas desulfurization efficiency is about 90%.
Example 2
In this embodiment, the pilot-scale desulfurization device is also selected to perform a test study on the red mud-enhanced calcium flue gas desulfurization. Firstly, red mud slurry with a solid-to-liquid ratio of 1:5 is prepared and added into a limestone slurry input pipe in front of a spray pump at the uppermost layer according to a ratio of 0.2:1, and the pH value of the mixed slurry is 7.5. According to the gas-liquid ratio of 10L/m3The mixed red mud/limestone slurry is sprayed into the desulfurizing tower according to the proportion, and the result shows that the smoke is generatedGas outlet SO2The concentration is 40mg/m3The flue gas desulfurization efficiency is about 96%.
Example 3
A red mud dealkalization method coupled with a calcium flue gas desulfurization process specifically comprises the following steps:
firstly, adding red mud into water in a red mud tank to prepare red mud slurry with a solid-to-liquid ratio of 1: 1;
secondly, introducing the red mud slurry into an inlet of a delivery pump on the uppermost 1-2 layers of the desulfurization tower to be mixed with limestone or lime slurry; the mass ratio of the red mud slurry to the limestone or lime slurry is 0.05: 1;
thirdly, spraying the mixed solution of the red mud slurry and the limestone or lime slurry through the uppermost 1-2 spraying layers of the desulfurization tower, reversely contacting with the flue gas to perform flue gas desulfurization, and introducing the desulfurized slurry into a desulfurization circulating tank positioned at the bottom of the desulfurization tower to perform circulating desulfurization;
fourthly, fully mixing the red mud in the desulfurization circulating tank with a calcium-based desulfurizer and desulfurized gypsum slurry to obtain desulfurized liquid slurry, and carrying out deep replacement and neutralization on sodium ions, combined alkali and other components in the red mud in circulating liquid with relatively low pH (the pH value is 5.5-7.0) under the combined action of calcium, sulfate radicals and sulfite radicals;
fifthly, when the pH value of the desulfurization liquid slurry is reduced to 5.5, 10 percent of the desulfurization liquid slurry is input into a separation tank for solid-liquid separation, calcium carbonate and calcium silicate solids are separated through dehydration, and the supernatant is conveyed into a red mud tank.
And sixthly, adding a certain amount of fresh red mud into the red mud tank, adjusting the pH value of the supernatant to 10, continuously inputting the supernatant into a pulping tank, mixing the supernatant with limestone or lime slurry, and inputting the mixture into a desulfurizing tower for circulating desulfurization.
Example 4
A red mud dealkalization method coupled with a calcium flue gas desulfurization process specifically comprises the following steps:
firstly, adding red mud into water in a red mud tank to prepare red mud slurry with a solid-to-liquid ratio of 1: 20;
secondly, introducing the red mud slurry into an inlet of a delivery pump on the uppermost 1-2 layers of the desulfurization tower to be mixed with limestone or lime slurry; the mass ratio of the red mud slurry to the limestone or lime slurry is 0.2: 1;
thirdly, spraying the mixed solution of the red mud slurry and the limestone or lime slurry through the uppermost 1-2 spraying layers of the desulfurization tower, reversely contacting with the flue gas to perform flue gas desulfurization, and introducing the desulfurized slurry into a desulfurization circulating tank positioned at the bottom of the desulfurization tower to perform circulating desulfurization;
fourthly, fully mixing the red mud in the desulfurization circulating tank with a calcium-based desulfurizer and desulfurized gypsum slurry to obtain desulfurized liquid slurry, and carrying out deep replacement and neutralization on sodium ions, combined alkali and other components in the red mud in circulating liquid with relatively low pH (the pH value is 5.5-7.0) under the combined action of calcium, sulfate radicals and sulfite radicals;
fifthly, when the pH value of the desulfurization liquid slurry is reduced to 5.5, 30 percent of the desulfurization liquid slurry in the desulfurization circulating pool is input into a separation tank for solid-liquid separation, calcium carbonate and calcium silicate solids are separated through dehydration, and supernatant is conveyed into a red mud tank.
And sixthly, adding a certain amount of fresh red mud into the red mud tank, adjusting the pH value of the supernatant to 10, continuously inputting the supernatant into a pulping tank, mixing the supernatant with limestone or lime slurry, and inputting the mixture into a desulfurizing tower for circulating desulfurization.
Claims (8)
1. A red mud dealkalization method coupled with a calcium flue gas desulfurization process is characterized by comprising the following steps:
firstly, adding water into red mud in a red mud tank to prepare red mud slurry;
secondly, introducing the red mud slurry into an inlet of a delivery pump on the uppermost 1-2 layers of the desulfurization tower to be mixed with limestone or lime slurry;
thirdly, spraying the mixed solution of the red mud slurry and the limestone or lime slurry through the uppermost 1-2 spraying layers of the desulfurization tower, reversely contacting with the flue gas to carry out flue gas desulfurization, and introducing the desulfurized slurry into a desulfurization circulating tank to carry out circulating desulfurization;
fourthly, fully mixing the red mud in the desulfurization circulating tank with a calcium-based desulfurizer and desulfurized gypsum slurry to obtain desulfurized liquid slurry, and performing deep replacement and neutralization on sodium ions, combined alkali and other components in the red mud under the combined action of calcium, sulfate radicals and sulfite radicals;
fifthly, when the pH value of the desulfurization slurry is reduced to a specific value, leading a part of the desulfurization slurry out to a separation tank, and dehydrating and separating calcium carbonate and calcium silicate solids;
and sixthly, inputting the supernatant obtained after the separation in the fifth step into a red mud tank, adding fresh red mud to adjust the pH value of the supernatant to a preset range, and continuously inputting the supernatant into a desulfurizing tower for circulating desulfurization.
2. The red mud dealkalization method coupled with the calcium flue gas desulfurization process according to claim 1, characterized in that the solid-to-liquid ratio of the red mud slurry in the first step is in the range of 1: 1-20.
3. The red mud dealkalization method coupled with the calcium flue gas desulfurization process according to claim 1, characterized in that the limestone or lime slurry in the second step is a raw material adopted in the calcium flue gas desulfurization process.
4. The red mud dealkalization method coupled with the calcium flue gas desulfurization process according to claim 1, characterized in that the mass ratio of the red mud slurry and limestone or lime slurry in the third step is 0.05-0.2: 1.
5. The red mud dealkalization method coupled with the calcium flue gas desulfurization process as recited in claim 1, wherein the fourth step is that the desulfurization circulation tank is positioned at the bottom of the desulfurization tower.
6. The red mud dealkalization method coupled with the calcium flue gas desulfurization process according to claim 1, wherein the pH value of the desulfurization liquid slurry in the desulfurization circulating tank in the fourth step is 5.5 to 7.0.
7. The red mud dealkalization method coupled with the calcium flue gas desulfurization process as recited in claim 6, wherein when the pH value of the circulating desulfurization slurry in the fifth step is reduced to 5.5, 10-30% of the desulfurization slurry in the desulfurization circulating tank is fed into the separation tank for solid-liquid separation, and the supernatant is fed into the red mud tank.
8. The red mud dealkalization method coupled with the calcium flue gas desulfurization process according to claim 1, characterized in that fresh red mud is added into the red mud tank until the pH value of the red mud slurry is increased to 10.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845138A (en) * | 2021-08-06 | 2021-12-28 | 昆明理工大学 | Method for deep desulfurization and full-scale utilization of red mud |
| CN114100360A (en) * | 2021-11-15 | 2022-03-01 | 中国铝业股份有限公司 | Desulfurizing agent and preparation method thereof |
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| US4222992A (en) * | 1978-02-27 | 1980-09-16 | Sumitomo Aluminium Smelting Company, Limited | Process for the removal of sulfur oxides from exhaust gases using slurry of red mud containing calcium ion |
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| CN106882932A (en) * | 2017-02-07 | 2017-06-23 | 郑州大学 | A kind of method of comprehensive utilization of red mud |
| CN108722143A (en) * | 2018-07-19 | 2018-11-02 | 中冶节能环保有限责任公司 | A kind of dry cleaning device that can realize flue gas minimum discharge and technique |
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2019
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Patent Citations (6)
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| US4222992A (en) * | 1978-02-27 | 1980-09-16 | Sumitomo Aluminium Smelting Company, Limited | Process for the removal of sulfur oxides from exhaust gases using slurry of red mud containing calcium ion |
| CN101480577A (en) * | 2008-11-17 | 2009-07-15 | 北京博奇电力科技有限公司 | Desulfuration technique with jet bubble process using red mud as absorbing agent |
| CN101700461A (en) * | 2009-10-16 | 2010-05-05 | 中国铝业股份有限公司 | Aluminum oxide production self-owned power plant boiler smoke desulfuration method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113845138A (en) * | 2021-08-06 | 2021-12-28 | 昆明理工大学 | Method for deep desulfurization and full-scale utilization of red mud |
| CN113845138B (en) * | 2021-08-06 | 2023-11-24 | 昆明理工大学 | Method for deep desulfurization and full quantitative utilization of red mud |
| CN114100360A (en) * | 2021-11-15 | 2022-03-01 | 中国铝业股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN114100360B (en) * | 2021-11-15 | 2023-08-15 | 中国铝业股份有限公司 | Desulfurizing agent and preparation method thereof |
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