CN103408204A - Method for performing dealkalization on Bayer process red mud by using fluorgypsum - Google Patents
Method for performing dealkalization on Bayer process red mud by using fluorgypsum Download PDFInfo
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- CN103408204A CN103408204A CN201310316423XA CN201310316423A CN103408204A CN 103408204 A CN103408204 A CN 103408204A CN 201310316423X A CN201310316423X A CN 201310316423XA CN 201310316423 A CN201310316423 A CN 201310316423A CN 103408204 A CN103408204 A CN 103408204A
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Abstract
The invention discloses a method for performing dealkalization on bayer process red mud by using fluorgypsum. The method comprises the following steps: step 1, adding crushed fluorgypsum in red mud slurry produced in a bayer process technological process proportionally, wherein the mass fraction of the fluorgypsum is 35-50 percent, and the liquid-solid ratio of the red mud slurry is 5 to 10; step 2, stirring the mixture in a reaction vessel, and pressurizing and heating the mixture for 40-120 minutes, wherein the mixing speed is 100-200 rpm, the pressure is 1.0-1.6 MPa, and the reaction temperature is 40-100 DEG C; step 3, filtering out liquid reactant, namely completing the dealkalization process. The method has the characteristics that the process is simple, the cost is low, the dealkalization rate is high, and the dealkalized red mud can be recycled, so that not only is the environment pollution caused by red mud and the fluorgypsum avoided to create good social benefits, but also an excellent economic effect is provided.
Description
Technical field
The present invention relates to relate to a kind of red mud dealkalization method, be specifically related to a kind of fluorgypsum that utilizes and Bayer process red mud carried out to the method for dealkalize.
Background technology
Bayer process red mud is that in aluminum oxide production process, 1 ton of commercial alumina of every production will produce solid waste---the red mud of 0.8-1.5 ton from bauxite, adopting bayer process to extract the waste residue produced after aluminum oxide.Building a dam, to store up be the disposal options generally adopted both at home and abroad.But to have an alkali content high because of it, the characteristic such as quantity is large, store up red mud not only will take a large amount of soils, and can cause severe contamination to the environment such as water body, atmosphere on every side.Alkali content in red mud is more, and pH value is 10.30～11.88, and the pH value of its leach liquor is 12.1～13.0, exceed " non-ferrous metals industry solid waste pollution control criterion ", so red mud belongs to strongly alkaline soil.Because alkalescence is larger, when stacking, red mud can infiltrate contaminated soil and underground water in soil in the open, and its airborne dust can cause topsoil; During discharge into sea, can pollute to seawater again the harm marine organisms.And alkalescence is excessive also makes its recycling also be subject to very large restriction, is difficult to realize recycling.Thereby how these red muds are carried out to effective dealkalize processing, be a problem demanding prompt solution.
The red mud dealkalization method of report is nearly following several both at home and abroad at present: lime hydrothermal method, normal pressure lime method, lime soda ash sintering process, salt lixiviation process, acid leaching process, Industrial " three Waste " neutralisation, Bioleaching method and film take off the sodium technology, but these methods are complex process, complex operation not only, and cost is high, be unfavorable for the large-scale promotion use.
Fluorgypsum is the byproduct in preparing hydrogen fluoric acid production process, is that the sulfur acid calcium of take that is reacted output by sulfuric acid with fluorite is main waste residue, and main source is inorganic or organic fluoride factory and other Acid of Hydrofluoric Acid Production factories.Every production 1t hydrofluoric acid approximately produces fluorgypsum 3.6t left and right, so output is huge especially, and the accumulating amount of China's waste slag of fluorine gypsum ranks first in the world.New fluorgypsum main component of discharging is anhydrous calciumsulphate, SO
3Content is 40%-42%, and impurity is mainly CaF
2, total CaF
2Content can reach 2%-4%.Fluorgypsum is insoluble in water, and hydration rate is extremely slow, can not directly make gelling material and use.In the past, most of fluorgypsum is just being stored up as a kind of solid waste after work and processing a little, not only landed property; also contaminated soil and groundwater environment, fully utilize chemical by-product gypsum, both has been conducive to protection of the environment; can economize on resources again, tool is of great significance.
Utilizing main patent documentation aspect the red mud dealkalization processing to have:
In Chinese patent literature " a kind of method of red mud dealkalization " (publication number CN 101423318 A, open day on May 6th, 2009), introduced a kind ofly under condition of high voltage, utilized active calcium oxide to carry out the dealkalize processing to its red mud.Under condition of normal pressure, utilize active calcium oxide to carry out dealkalize to its red mud, after dealkalize in red mud alkali content lower, still, the method dealkalize overlong time of high-pressure oxidation calcium red mud dealkalization, operate more loaded down with trivial detailsly, and the dealkalize cost is high.
Chinese patent literature " a kind of method of the Bayer process red mud of dissolving " (publication number CN 102757060 A, open day on October 31st, 2012) in, at first Bayer process red mud and white lime are carried out to calcification dealkalize transition, then calcification is made the transition to Bayer process red mud after dealkalize with clear water or lower concentration sodium aluminate solution mix in encloses container after, carry out the compressive reaction dealkalize to passing into carbonic acid gas in container.This invention dealkalize complex process, overlong time, and the dealkalize cost is high.
Chinese patent literature " with phosphogypsum, red mud being carried out the method for quick dealkalize " (publication number CN 102206024 A, open day on October 5th, 2011) in, pulverize, smash phosphogypsum loose, then it is mixed with red mud and water, after reciprocating vibration, stirring reaction, obtain the red mud after dealkalize.The phosphogypsum that this invention is used is the byproduct of phosphoric acid industry, is acid, except main component is calcium sulfate, also contains a small amount of phosphoric acid, silicon, magnesium, iron, aluminium, fluorine and organic matter etc.Although this invention technique is simple, dealkalize technique has only adopted type of heating, and the content of red mud dealkalization rear oxidation sodium is still higher, and the dealkalize effect is undesirable, and the dealkalize time is longer.
Chinese patent literature " a kind of normal atmosphere dealkalizing method by sintering " (publication number CN 101468866A, open day on July 1st, 2009) in, the red mud produced in the sintering process technological process is carried out to roasting, pulverizing, the red mud particle is mixed to the gas-liquid-solid reaction container of putting into stirring with water, pass into CO to red mud slurry
2Gas carries out de-alkali reaction.Adopt the suspension and carbonation dealkalization method of this invention, in red mud, the clearance of alkali can reach more than 85%, but the dealkalize overlong time, complicated operation, and the dealkalize cost is also higher.
Summary of the invention
The object of the present invention is to provide a kind of fluorgypsum that utilizes Bayer process red mud to be carried out to the method for dealkalize, the defect existed when processing red mud for above-mentioned existing dealkalize technology, aim to provide a kind ofly have that technique is simple, with low cost, the dealkalize rate is high, method that the red mud after dealkalize can be done the Bayer process red mud dealkalize of the characteristics such as recycling, this method has not only been avoided the pollution to environment of red mud, fluorgypsum, produce good social benefit, also had good economic benefit.
To achieve these goals, the present invention is by the following technical solutions:
A kind of fluorgypsum that utilizes carries out the method for dealkalize to Bayer process red mud, comprise the steps:
Step 1, in the red mud mud that the bayer process process is produced by than row, adding the fluorgypsum of pulverizing; The massfraction of described fluorgypsum is 35%-50%, and the liquid-solid ratio of red mud mud is 5-10;
Step 2, stir and pressurized, heated 40-120 minute in reaction vessel, stirring velocity is 100-200rpm, and pressure is 1.0-1.6MPa, and temperature of reaction is 40-90 ℃;
Step 3, be press-filtered out reaction solution with pressure filter, namely completes the dealkalize process.
What particularly point out is that the reaction solution be press-filtered out in the technical solution used in the present invention can enter in the technological process of alumina producing, as the secondary washing liquid use of red mud.
As preferably, in described step 2, in described reaction vessel, pass into steam and heat.
As preferably, described reaction vessel is autoclave.
As preferably, described fluorgypsum derives from the waste residue of producing hydrofluoric acid, and its main component is terra alba, content >=93%.
As preferably, in described red mud mud, the particle diameter of red mud particle is between 150-200um.
As preferably, complete alkali content≤1% in the red mud of dealkalize process.
As preferably, the red mud alkali content that described bayer process process produces is 4-8%.
As preferably, in described step 3, adopt the liquid compressor filtering reacting liquid.
Beneficial effect of the present invention is:
Main purpose of the present invention is to provide a kind of method that technique is simple, with low cost, increase substantially red mud resource utilization.Adopt the massfraction of sodium oxide in the Bayer process red mud after dealkalization method of the present invention is processed can be down to 1% left and right, not only alkali has obtained effectively removing, and the industrial residue that acid industry is discharged is utilized effectively, thereby reach the effect of doulbe-sides' victory, really realize changing waste into resources and environmental friendliness, met China's energy-saving and emission-reduction, the strategy of sustainable development.
With existing red mud dealkalization technology, compare, the present invention utilizes the acid waste slag of fluorine gypsum of the by-product of acid industry to be raw material, carry out the dealkalize of Bayer process red mud, not only successfully solved the problem of two kinds of maximum discharge trade wastes to environment, the Bayer process red mud that dealkalize is processed is widely used in the production of the building material products such as cement.Simultaneously, the alkali lye filtered out and other useful component be recoverable also, has realized to greatest extent the comprehensive utilization of resource.Application the technology of the present invention can solve the difficult problem that industrial residue is difficult to process effectively, improves the level of comprehensive utilization of trade waste, is conducive to the Sustainable development of China's material of construction, and can significantly improves economic results in society.
The accompanying drawing explanation
Fig. 1 is method process flow sheet of the present invention.
Embodiment
As shown in Figure 1, main process step of the present invention is as follows:
In the red mud mud that the bayer process process is produced by than row, adding the fluorgypsum of pulverizing; Then in reaction vessel, stir and pressurized, heated, can adopt the steam-heated mode that passes into.After filter filters, after washing, drying, then hang down the alkali red mud.In following examples, can adopt Filter Press, reaction vessel can adopt autoclave.
Embodiment 1:
Bayer process red mud alkali content 4.66%, grain diameter is 180um, take the be made into red mud slurry of liquid-solid ratio as 8, adds 35% fluorgypsum gypsum, in autoclave, passes into steam and heats de-alkali reaction.Temperature of reaction is 90 ℃, and reaction pressure 1.2MPa stirs 90min, and stir speed (S.S.) is 200rpm.Red mud slurry after filtration, after washing, drying, the content of analyzing alkali in red mud from sintering process is 0.96%.
Embodiment 2:
Bayer process red mud alkali content 4.28%, grain diameter is 200um, take the be made into red mud slurry of liquid-solid ratio (ml/g) as 9, adds 40% fluorgypsum, in autoclave, passes into steam and heats de-alkali reaction.Temperature of reaction is 100 ℃, and reaction pressure 1.6MPa stirs 90min, and stir speed (S.S.) is 180rpm.Red mud slurry after filtration, after washing, drying, the content of analyzing alkali in red mud from sintering process is 0.86%.
Embodiment 3:
Bayer process red mud alkali content 6.28%, grain diameter is 180um, take the be made into red mud slurry of liquid-solid ratio as 8.5, adds 35% fluorgypsum, in reaction vessel, passes into steam and heats de-alkali reaction.Temperature of reaction is 70 ℃, and reaction pressure 1.0MPa stirs 80min, and stir speed (S.S.) is 180rpm.Red mud slurry after filtration, after washing, drying, the content of analyzing alkali in red mud from sintering process is 0.96%.
Embodiment 4:
Bayer process red mud alkali content 3.45%, grain diameter is 200um, take the be made into red mud slurry of liquid-solid ratio as 7.5, adds 45% fluorgypsum, in reaction vessel, passes into steam and heats de-alkali reaction.Temperature of reaction is 80 ℃, and reaction pressure 1.6MPa stirs 70min, and stir speed (S.S.) is 200rpm.Red mud slurry after filtration, after washing, drying, the content of analyzing alkali in red mud from sintering process is 0.89%.
Embodiment 5:
Bayer process red mud alkali content 7.23%, grain diameter is 180um, take the be made into red mud slurry of liquid-solid ratio as 6, adds 47% fluorgypsum, in reaction vessel, passes into steam and heats de-alkali reaction.Temperature of reaction is 90 ℃, and reaction pressure 1.3MPa stirs 50min, and stir speed (S.S.) is 180rpm.Red mud slurry after filtration, after washing, drying, the content of analyzing alkali in red mud from sintering process is 0.98%.
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise break away from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of claim scope of the present invention.
Claims (8)
1. one kind is utilized fluorgypsum Bayer process red mud to be carried out to the method for dealkalize, it is characterized in that: comprise the steps:
Step 1, in the red mud mud that the bayer process process is produced by than row, adding the fluorgypsum of pulverizing; The massfraction of described fluorgypsum is 35%-50%, and the liquid-solid ratio of red mud mud is 5-10;
Step 2, stir and pressurized, heated 40-120 minute in reaction vessel, stirring velocity is 100-200rpm, and pressure is 1.0-1.6MPa, and temperature of reaction is 40-100 ℃;
Step 3, filter out reaction solution, namely completes the dealkalize process.
2. a kind of fluorgypsum that utilizes according to claim 1 carries out the method for dealkalize to Bayer process red mud, it is characterized in that: in described step 2, in described reaction vessel, pass into steam and heat.
3. a kind of fluorgypsum that utilizes according to claim 1 and 2 carries out the method for dealkalize to Bayer process red mud, and it is characterized in that: described reaction vessel is autoclave.
4. a kind of fluorgypsum that utilizes according to claim 1 and 2 carries out the method for dealkalize to Bayer process red mud, it is characterized in that: described fluorgypsum derives from the waste residue of producing hydrofluoric acid, and its main component is terra alba, content >=93%.
5. a kind of fluorgypsum that utilizes according to claim 1 and 2 carries out the method for dealkalize to Bayer process red mud, and it is characterized in that: in described red mud mud, the particle diameter of red mud particle is between 150-200um.
6. a kind of fluorgypsum that utilizes according to claim 1 carries out the method for dealkalize to Bayer process red mud, it is characterized in that: complete alkali content≤1% in the red mud of dealkalize process.
7. a kind of fluorgypsum that utilizes according to claim 1 carries out the method for dealkalize to Bayer process red mud, it is characterized in that: the red mud alkali content that described bayer process process produces is 4-8%.
8. a kind of fluorgypsum that utilizes according to claim 1 carries out the method for dealkalize to Bayer process red mud, it is characterized in that: in described step 3, adopt the liquid compressor filtering reacting liquid.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170307A (en) * | 2015-09-29 | 2015-12-23 | 河南理工大学 | Red-mud citric acid dealkalizing technique |
| CN105665425A (en) * | 2016-04-11 | 2016-06-15 | 贵州晨辉达矿业工程设计有限公司 | Harmless disposing method for red mud and ardealite |
| CN108975364A (en) * | 2018-07-30 | 2018-12-11 | 中南大学 | A kind of method that the processing of Bayer process red mud acid removes alkali collection sodium |
| 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 |
| CN113061011A (en) * | 2021-04-19 | 2021-07-02 | 贵州理工学院 | Method for manufacturing red mud-modified phosphogypsum mine filling material |
| CN113929418A (en) * | 2021-10-25 | 2022-01-14 | 杭州瑞鼎建材有限公司 | Aerated concrete and preparation method thereof |
| CN114853295A (en) * | 2022-05-19 | 2022-08-05 | 北京工业大学 | Method for dealkalizing red mud by utilizing waste incineration fly ash |
| CN114873881A (en) * | 2022-06-17 | 2022-08-09 | 山东大学 | Red mud resource utilization process based on gypsum hydrothermal dealkalization and titanium dioxide waste acid iron extraction |
| CN116622415A (en) * | 2023-05-15 | 2023-08-22 | 华中农业大学 | Method for preparing hydrogen-rich gas by grading conversion of rubber and plastic solid waste by utilizing red mud |
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| CN1673129A (en) * | 2005-02-06 | 2005-09-28 | 中国铝业股份有限公司 | Bayer process red mud matrix improvement technology |
Non-Patent Citations (1)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170307A (en) * | 2015-09-29 | 2015-12-23 | 河南理工大学 | Red-mud citric acid dealkalizing technique |
| CN105665425A (en) * | 2016-04-11 | 2016-06-15 | 贵州晨辉达矿业工程设计有限公司 | Harmless disposing method for red mud and ardealite |
| CN108975364A (en) * | 2018-07-30 | 2018-12-11 | 中南大学 | A kind of method that the processing of Bayer process red mud acid removes alkali collection sodium |
| 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 |
| CN113061011A (en) * | 2021-04-19 | 2021-07-02 | 贵州理工学院 | Method for manufacturing red mud-modified phosphogypsum mine filling material |
| CN113929418A (en) * | 2021-10-25 | 2022-01-14 | 杭州瑞鼎建材有限公司 | Aerated concrete and preparation method thereof |
| CN113929418B (en) * | 2021-10-25 | 2022-06-17 | 杭州瑞鼎建材有限公司 | Aerated concrete and preparation method thereof |
| CN114853295A (en) * | 2022-05-19 | 2022-08-05 | 北京工业大学 | Method for dealkalizing red mud by utilizing waste incineration fly ash |
| CN114873881A (en) * | 2022-06-17 | 2022-08-09 | 山东大学 | Red mud resource utilization process based on gypsum hydrothermal dealkalization and titanium dioxide waste acid iron extraction |
| CN116622415A (en) * | 2023-05-15 | 2023-08-22 | 华中农业大学 | Method for preparing hydrogen-rich gas by grading conversion of rubber and plastic solid waste by utilizing red mud |
| CN116622415B (en) * | 2023-05-15 | 2024-01-26 | 华中农业大学 | Method for preparing hydrogen-rich gas by grading conversion of rubber and plastic solid waste by utilizing red mud |
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Application publication date: 20131127 |