CN101423318A - Red mud dealkalization method - Google Patents
Red mud dealkalization method Download PDFInfo
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- CN101423318A CN101423318A CNA2008102310083A CN200810231008A CN101423318A CN 101423318 A CN101423318 A CN 101423318A CN A2008102310083 A CNA2008102310083 A CN A2008102310083A CN 200810231008 A CN200810231008 A CN 200810231008A CN 101423318 A CN101423318 A CN 101423318A
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- red mud
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- filter cake
- slip
- calcium oxide
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Abstract
The invention discloses a dealkalization method for red mud. The method comprises a dilute sulphuric acid dealkalization step and a pressure calcium oxide dealkalization step. Red mud is prepared into slurry and introduced into a grinder to be ground; according to the content of alkaline in the red mud, the slurry is slowly added with required dilute sulphuric acid to be ground, filtered and washed to obtain a filter cake and the content of alkaline in the filter cake is analyzed; according to the analyzed content of alkaline in the filter cake, the filter cake is added with calcium oxide and uniformly mixed to be introduced to a high pressure reaction kettle and heated for reaction, and after reaction, the mixture is cooled, filtered and washed; and the obtained filter cake is dried and content of alkaline in the dried filter cake is analyzed. The invention can use only the pressure calcium oxide method to carry out dealkalization of the red mud. Red mud subjected to dealalization treatment of the method has low alkaline content and can be used more in fields such as concrete production, high quality brick and transformed brickproduction. The method solves the problem of the red mud of severe pollution and achieves remarkable economic and social benefits.
Description
One, technical field:
The present invention relates to the treatment process of the solid, powdery waste-red mud of discharging in a kind of aluminum oxide metallurgy industry production process, particularly relate to a kind of method of utilizing dilute sulphuric acid-pressure oxidation calcium integrated processes and pressure oxidation calcium method thereof red mud to be carried out dealkalize.
Two, background technology:
Red mud is the solid, powdery waste of discharging in the aluminum oxide metallurgy industry production process, because the bauxite iron content is higher, makes this type of waste appearance color similar to redness of the skin or complexion earth and gain the name.Red mud mainly is made up of fine grain mud and coarse grained sand, and its chemical ingredients is because of the different differences to some extent of the bauxite place of production and alumina-producing method.It is Dicalcium Phosphate (Feed Grade), calcium aluminosilicate hydrate, diaspore that the red mud essential mineral that produces in the domestic aluminum oxide metallurgy industry is formed, and secondly is aquation tricalcium aluminate, moisture Calucium Silicate powder, cancrinite, rhombohedral iron ore, sodalite, calcium iron ore.Red mud is the synthetic material of complex chemical composition, it has glued porous frame hollow structure, porosity is strong, tightness is low, gluing connects, crystallization connects, characteristics such as hole is big, light weight, consolidation structure is stable, compressibility is low, perviousness is weak, the performance that red mud itself is had can make it obtain good engineering and use.The research worker has carried out a large amount of red mud comprehensive utilizating research according to the performance characteristics of red mud different aspect both at home and abroad.As with red mud as one of raw material of producing cement produce cement, utilize red mud make the high-quality brick and transition brick, red mud as plastic filler, red mud handle waste water, from red mud, extract valuable metal, red mud is made devitrified glass etc., and all there has been bigger progress aspects.But,, can't be applied directly to and produce in cement, making high-quality brick and the productions such as the brick that makes the transition, making devitrified glass owing to alkalinity in the red mud of directly discharge is too high.For a large amount of waste-red muds is utilized again, minimizing is to the severe contamination of environment, must earlier red mud be carried out dealkalize handles, make the alkali content in its red mud be reduced to certain limit, just it can better be used for producing in cement, making high-quality brick and the productions such as the brick that makes the transition, making devitrified glass.
At present, red mud being carried out the method for dealkalize processing normally utilizes calcium oxide to carry out dealkalize under condition of normal pressure, for example: application number is 95110552.3, denomination of invention is sinter method for red mud dealkalization and processing technology for surface modification thereof, the present invention has introduced a kind of under condition of normal pressure, utilizes active calcium oxide that its red mud is carried out dealkalize and handles.Under the condition of normal pressure, utilize active calcium oxide that its red mud is carried out dealkalize, after the dealkalize in the red mud alkali content be reduced to below 1%, still, the method dealkalize overlong time of atmospheric pressure oxidation calcium red mud dealkalization, operate more loaded down with trivial details, and dealkalize cost height.
Three, summary of the invention:
The technical problem to be solved in the present invention provides a kind of method or pressure oxidation calcium method of dilute sulphuric acid-pressure oxidation calcium associating utilized red mud is carried out dealkalize, i.e. a kind of method of red mud dealkalization.
Address the above problem, the technical solution used in the present invention is:
The invention provides a kind of method of red mud dealkalization, this method comprises following detailed step:
A, dilute sulphuric acid dealkalize: the content of at first analyzing alkali in the red mud, red mud is mixed with slip, the solid content of slip is less than 65%, the slip for preparing is imported shredder to be ground, according to the content of alkali in the red mud desired concn is lower than 10% dilute sulphuric acid and slowly joins in the slip, the vitriolic add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
40.5～2 times of required sulfuric acid amount, the granularity of grinding the back red mud is less than 10 microns, and the red mud after grinding is filtered, washs and obtain filter cake, utilizes ordinary method to analyze the content of alkali in the filter cake;
B, pressure oxidation calcium dealkalize: according to the content of alkali in the gained filter cake after the dealkalize of step a dilute sulphuric acid, adding calcium oxide and water are made slip in its filter cake, the add-on of calcium oxide is 0.5～6.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR (annotate: R represents the negatively charged ion in the red mud constituent in the formula), the solid content of slip is less than 65%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 95～150 ℃, reacted 5～30 minutes, after the reaction it is cooled to below 80 ℃, filter then, washing obtains filter cake, the gained filter cake is dry under 100～200 ℃ of conditions, be dried to water ratio in the filter cake less than 5%, utilize ordinary method to analyze the content of alkali in the gained oven dry filter cake at last, promptly get the content that alkali in the red mud of back is handled in dealkalize.
According to the method for described red mud dealkalization, the preferable add-on of vitriolic described in the step a is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41～1.3 times of required sulfuric acid amount; The preferred speed muller of described shredder, milling time are 30～60min.
According to the method for described red mud dealkalization, the sulfuric acid after will diluting among the step a adds red mud in batches, repeats slurrying, grinding, filtration and washing 2～5 times, and best multiplicity is 3 times.
According to the method for described red mud dealkalization, among the step a in the gained filter cake content of alkali be sodium oxide content less than 1.0%, potassium oxide content is less than 0.5%.
According to the method for described red mud dealkalization, the preferable add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 3～4.5 times among the step b.
According to the method for described red mud dealkalization, among the step b in the gained oven dry filter cake content of alkali be sodium oxide content less than 0.3%, the content of potassium oxide is less than 0.2%.
A kind of method of pressure oxidation calcium red mud dealkalization:
At first analyze the content of alkali in the red mud, add required calcium oxide and water is mixed with slip according to the content of alkali in the red mud, the add-on of calcium oxide is 0.5～6.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR (annotate: R represents the negatively charged ion in the red mud constituent in the formula), the solid content of slip is less than 65%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 95～150 ℃, reacted 5～30 minutes, after the reaction it is cooled to below 80 ℃, filter then, washing obtains filter cake, and the gained filter cake is dry under 100～200 ℃ of conditions, is dried to water ratio in the filter cake less than 5%, utilize ordinary method to analyze the content of alkali in the gained oven dry filter cake at last, promptly get the content that alkali in the red mud of back is handled in dealkalize.
According to the method for described pressure oxidation calcium red mud dealkalization, the preferable add-on of described calcium oxide is 3～4.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR.
According to the method for described pressure oxidation calcium red mud dealkalization, the content that alkali in the red mud of back is handled in described dealkalize be sodium oxide content less than 0.3%, the content of potassium oxide is less than 0.2%.
For the method for top whole described red mud dealkalizations, described red mud is the solid, powdery waste that Bayer process, sintering process or integrated process are smelted the aluminum oxide gained; In described dry employing air stream drying method, the desiccating method of drifting along, kiln desiccating method or the cylinder drier any.
The present invention carries out dealkalize to red mud, can adopt the pressure oxidation calcium dealkalization method described in dilute sulphuric acid dealkalization method described in the step a and the step b separately, wherein the pressure oxidation calcium method described in the step b can realize the degree of depth dealkalize to red mud, and the total content that makes after the dealkalize sodium oxide and potassium oxide in the red mud is less than 0.5%.
Positive beneficial effect of the present invention:
1, the present invention adopts dilute sulphuric acid that red mud is carried out dealkalize earlier in the process that red mud dealkalization is handled, and can effectively reduce the alkali content in the red mud, and dilute sulphuric acid takes off sodium effect highly significant to sodium oxide in the red mud, and is comparatively remarkable to the removal effect of potassium oxide.Wherein the decreasing ratio of sodium oxide can reach 50～70%, and the decreasing ratio of potassium oxide can reach 40～50% approximately.After the dilute sulphuric acid dealkalize, sodium oxide content is less than 1.0% in the red mud, and potassium oxide content is less than 0.5%.
2, the present invention is by great deal of experimental, determined to adopt concentration to be lower than 10% dilute sulphuric acid red mud is carried out dealkalize, and the dealkalize effect is more remarkable.Because other composition in the high more easy more decomposition red mud of vitriolic concentration not only increases the vitriolic consumption, also can make the mineral structure of red mud that bigger variation takes place, be unfavorable for the utilization again of red mud after the dealkalize.
3, the present invention adopts in the process of red mud dealkalization under the condition of pressurization, utilizes calcium oxide to remove alkali in the red mud, and is not only simple to operate, compares with the dealkalize of atmospheric pressure oxidation calcium, shortened the dealkalize time greatly, and the dealkalize time is minimum can to shorten 80%.
4, adopt dilute sulphuric acid-pressure oxidation calcium integrated process that red mud is carried out dealkalize and handle, simple to operate, removal effect is better, and red mud dealkalization rear oxidation sodium content is less than 0.3%, and the content of potassium oxide is less than 0.2%.Red mud after its dealkalize is used in manufacture of cement, high-quality brick and the courses of processing such as brick making transition, devitrified glass making greatly.
5, utilize the red mud of gained after the inventive method dealkalize, can be applied to widely in manufacture of cement, high-quality brick and the courses of processing such as brick making transition, devitrified glass making, solved the severe contamination problem of a large amount of red mud wastes, and make it obtain using greatly, obtained remarkable economic efficiency; From environmental angle, the present invention has remarkable social benefit.
6, the present invention adopts pressure oxidation calcium method that red mud is carried out dealkalize separately, can realize the degree of depth dealkalize to red mud, and the total content that makes after the dealkalize sodium oxide and potassium oxide in the red mud is less than 0.5%.With atmospheric pressure oxidation calcium method to red mud dealkalization, save time.
Four, embodiment:
Following examples only in order to further specify the present invention, do not limit content of the present invention.
Red mud is the solid, powdery waste that Bayer process, sintering process or integrated process are smelted the aluminum oxide gained.
Embodiment one: a kind of method of red mud dealkalization
This method comprises calcium oxide dealkalize operation under dilute sulphuric acid dealkalize operation and the pressurized conditions, and its detailed step is as follows:
A, dilute sulphuric acid dealkalize: the content of at first analyzing alkali in the red mud, it is mixed with slip, the solid content of slip is 50%, the slip for preparing is imported speed muller to be ground, be that 8% sulfuric acid slowly joins in the slip according to the content of alkali with desired concn then, described vitriolic add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.3 times of required sulfuric acid amount, the granularity of grinding red mud after 45 minutes are less than 10 microns, and the red mud after grinding is filtered, washs and obtain filter cake, utilize ordinary method to analyze the content of alkali in the gained filter cake;
B, pressure oxidation calcium dealkalize: according to the content of alkali in the gained filter cake after the dealkalize of step a dilute sulphuric acid, adding calcium oxide and water are made slip in its filter cake, the add-on of calcium oxide is 4.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR (annotate: R represents the negatively charged ion in the red mud constituent in the formula), the solid content of slip is 45%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 100 ℃, reacted 25 minutes, after the reaction it is cooled to below 80 ℃, filter then, washing obtains filter cake, adopt kiln dry under 130 ℃ of conditions the gained filter cake, the water ratio of dry back filter cake utilizes ordinary method to analyze the content of alkali in the gained oven dry filter cake less than 5% at last, promptly gets the content that alkali in the red mud of back is handled in dealkalize, sodium oxide content is less than 0.3% in the red mud that finally obtains, and the content of potassium oxide is less than 0.2%.
Embodiment two: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 6% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
42 times of required sulfuric acid amount, the slip solid content that is mixed with is 45%, importing the time that speed muller grinds is 50 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 4 times among the step b, the solid content of slurry is 60%, temperature of reaction in autoclave is 120 ℃, reaction times is 20 minutes, adopt the cylinder dryer to carry out drying the gained filter cake, drying temperature is 150 ℃.
Embodiment three: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 9% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
40.5 times of required sulfuric acid amount, the slip solid content that is mixed with is 30%, importing the time that speed muller grinds is 30 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 6 times among the step b, the solid content of slurry is 35%, temperature of reaction in autoclave is 150 ℃, reaction times is 5 minutes, adopts the air stream drying method dry under 180 ℃ of conditions the gained filter cake.
Embodiment four: same embodiment-basic identical, and something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 5% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.8 times of required sulfuric acid amount, the slip solid content that is mixed with is 60%, importing the time that speed muller grinds is 60 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 1 times among the step b, the solid content of slurry is 25%, temperature of reaction in autoclave is 95 ℃, and the reaction times is 30 minutes, is 200 ℃ with the temperature of filtration cakes torrefaction.
Embodiment five: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 6% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
40.8 times of required sulfuric acid amount, the slip solid content that is mixed with is 25%, importing the time that speed muller grinds is 30 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 0.5 times among the step b, the solid content of slurry is 50%, temperature of reaction in autoclave is 130 ℃, and the reaction times is 20 minutes, is 110 ℃ with the temperature of filtration cakes torrefaction.
Embodiment six: basic identical with embodiment three, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 5% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.2 times of required sulfuric acid amount, the slip solid content that is mixed with is 45%, importing the time that speed muller grinds is 45 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 3 times among the step b, the solid content of slurry is 40%, temperature of reaction in autoclave is 120 ℃, and the reaction times is 20 minutes, is 160 ℃ with the temperature of filtration cakes torrefaction.
Embodiment seven: basic identical with embodiment two, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 8% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.5 times of required sulfuric acid amount, the slip solid content that is mixed with is 38%, importing the time that speed muller grinds is 50 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 6.5 times among the step b, the solid content of slurry is 38%, temperature of reaction in autoclave is 140 ℃, and the reaction times is 10 minutes, is 150 ℃ with the temperature of filtration cakes torrefaction.
Embodiment eight: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 6% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.6 times of required sulfuric acid amount, the slip solid content that is mixed with is 28%, importing the time that speed muller grinds is 40 minutes;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 5 times among the step b, the solid content of slurry is 40%, temperature of reaction in autoclave is 120 ℃, and the reaction times is 20 minutes, is 130 ℃ with the temperature of filtration cakes torrefaction.
Embodiment nine: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 8% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.3 times of required sulfuric acid amount, the slip solid content that is mixed with is 28%, importing the time that speed muller grinds is 40 minutes, divides three addings at this stage dilute sulphuric acid, repeats to make slip, grinding, filtration and washing three times;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 3.5 times among the step b, the solid content of slurry is 35%, temperature of reaction in autoclave is 120 ℃, and the reaction times is 20 minutes, is 130 ℃ with the temperature of filtration cakes torrefaction.
Embodiment ten: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 8% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.1 times of required sulfuric acid amount, the slip solid content that is mixed with is 38%, importing the time that speed muller grinds is 50 minutes, divides three addings at this stage dilute sulphuric acid, repeats to make slip, grinding, filtration and washing three times;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 4.5 times among the step b, the solid content of slurry is 38%, temperature of reaction in autoclave is 140 ℃, and the reaction times is 10 minutes, is 150 ℃ with the temperature of filtration cakes torrefaction.
Embodiment 11: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 5% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41.2 times of required sulfuric acid amount, the slip solid content that is mixed with is 45%, importing the time that speed muller grinds is 45 minutes, adds at twice at this stage dilute sulphuric acid, repeats to make slip, grinding, filtration and washed twice;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 3.8 times among the step b, the solid content of slurry is 40%, temperature of reaction in autoclave is 120 ℃, and the reaction times is 20 minutes, is 160 ℃ with the temperature of filtration cakes torrefaction.
Embodiment 12: basic identical with embodiment one, something in common is no longer narrated, and difference is:
The concentration of dilute sulphuric acid is 9% among the step a, and its add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41 times of required sulfuric acid amount, the slip solid content that is mixed with is 30%, importing the time that speed muller grinds is 30 minutes, divides four addings at this stage dilute sulphuric acid, repeats to make slip, grinding, filtration and washing four times;
The add-on of calcium oxide is according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR 4.2 times among the step b, the solid content of slurry is 35%, temperature of reaction in autoclave is 150 ℃, reaction times is 5 minutes, adopt the air stream drying method to carry out drying the gained filter cake, drying temperature is 180 ℃.
Embodiment 13: a kind of method of pressure oxidation calcium red mud dealkalization
The detailed step of this method is: the content of at first analyzing alkali in the red mud, add the required calcium oxide of people and water is mixed with slip according to the content of alkali in the red mud, the add-on of calcium oxide is 4.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR (annotate: R represents the negatively charged ion in the red mud constituent in the formula), the solid content of slip is 35%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 100 ℃, reacted 25 minutes, after the reaction it is cooled to below 80 ℃, filter then, washing obtains filter cake, adopt kiln to carry out drying the gained filter cake, drying temperature is 130 ℃, be dried to water ratio in the filter cake less than 5%, utilize ordinary method to analyze the content of alkali in the gained oven dry filter cake at last, promptly get the content that alkali in the back red mud is handled in dealkalize.
The content that alkali in the red mud of back is handled in the gained dealkalize be sodium oxide content less than 0.3%, the content of potassium oxide is less than 0.2%.
Embodiment 14: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 4 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 45%, temperature of reaction in autoclave is 130 ℃, reaction times is 15 minutes, will filter the gained filter cake and adopt the cylinder dryer to dry under 180 ℃ of conditions.
Embodiment 15: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 6.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 30%, temperature of reaction in autoclave is 150 ℃, reaction times is 5 minutes, will filter the gained filter cake and adopt the cylinder dryer to dry under 200 ℃ of conditions.
Embodiment 16: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 3 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 55%, temperature of reaction in autoclave is 95 ℃, and the reaction times is 30 minutes, will filter the gained filter cake and adopt kiln to carry out drying under 100 ℃ of conditions.
Embodiment 17: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 2 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 28%, temperature of reaction in autoclave is 120 ℃, reaction times is 20 minutes, will filter the gained filter cake and adopt the air stream drying method to carry out drying under 150 ℃ of conditions.
Embodiment 18: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 1 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 28%, temperature of reaction in autoclave is 140 ℃, and the reaction times is 10 minutes, will filter the gained filter cake and adopt kiln to dry under 120 ℃ of conditions.
Embodiment 19: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 0.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 38%, temperature of reaction in autoclave is 125 ℃, reaction times is 15 minutes, will filter the gained filter cake and adopt the cylinder dryer to dry under 150 ℃ of conditions.
Embodiment 20: originally identical with the embodiment tridecyl, something in common is no longer narrated, and difference is:
The add-on of calcium oxide is 3.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is 45%, temperature of reaction in autoclave is 130 ℃, and the reaction times is 15 minutes, will filter the gained filter cake and adopt kiln to dry under 140 ℃ of conditions.
Claims (10)
1, a kind of method of red mud dealkalization is characterized in that said method comprising the steps of:
A, dilute sulphuric acid dealkalize: the content of at first analyzing alkali in the red mud, red mud is mixed with slip, the solid content of slip is less than 65%, the slip for preparing is imported shredder to be ground, according to the content of alkali in the red mud desired concn is lower than 10% dilute sulphuric acid and slowly joins in the slip, the vitriolic add-on is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
40.5～2 times of required sulfuric acid amount, the granularity of grinding the back red mud is less than 10 microns, and the red mud after grinding is filtered, washs and obtain filter cake, utilizes ordinary method to analyze the content of alkali in the filter cake;
B, pressure oxidation calcium dealkalize: according to the content of alkali in the gained filter cake after the dealkalize of step a dilute sulphuric acid, adding calcium oxide and water are made slip in its filter cake, the add-on of calcium oxide is 0.5～6.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is less than 65%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 95～150 ℃, reacted 5～30 minutes, after the reaction it is cooled to below 80 ℃, filter then, washing obtains filter cake, and the gained filter cake is dry under 100～200 ℃ of conditions, is dried to water ratio in the filter cake less than 5%, utilize ordinary method to analyze the content of alkali in the gained oven dry filter cake at last, promptly get the content that alkali in the red mud of back is handled in dealkalize.
2, the method for red mud dealkalization according to claim 1 is characterized in that: the add-on of vitriolic described in the step a is according to chemical reaction 2K
++ 2Na
++ 2SO
4 2-=Na
2SO
4+ K
2SO
41～1.3 times of required sulfuric acid amount; Described shredder adopts speed muller, and milling time is 30～60min.
3, the method for red mud dealkalization according to claim 1 is characterized in that: the sulfuric acid after will diluting among the step a adds red mud in batches, repeats slurrying, grinding, filtration and washing 2～5 times.
4, the method for red mud dealkalization according to claim 1 is characterized in that: among the step a in the gained filter cake content of alkali be sodium oxide content less than 1.0%, potassium oxide content is less than 0.5%.
5, the method for red mud dealkalization according to claim 1 is characterized in that: the add-on of calcium oxide is 3～4.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR among the step b.
6, the method for red mud dealkalization according to claim 1 is characterized in that: among the step b in the gained oven dry filter cake content of alkali be sodium oxide content less than 0.3%, the content of potassium oxide is less than 0.2%.
7, a kind of method of pressure oxidation calcium red mud dealkalization, it is characterized in that: the content of at first analyzing alkali in the red mud, add required calcium oxide and water is mixed with slip according to the content of alkali in the red mud, the add-on of calcium oxide is 0.5～6.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR, the solid content of slip is less than 65%, slip is imported in the shredder, it is mixed, the slip that mixes is imported stirring heating in the autoclave, temperature rises to 95～150 ℃, reacted 5～30 minutes, and after the reaction it was cooled to below 80 ℃, filter then, washing obtains filter cake, the gained filter cake is dry under 100～200 ℃ of conditions, be dried to water ratio in the filter cake less than 5%, utilize ordinary method to analyze the content of alkali in the gained oven dry filter cake at last, promptly get the content that alkali in the back red mud is handled in dealkalize.
8, the method for red mud dealkalization according to claim 7 is characterized in that: the add-on of described calcium oxide is 3～4.5 times according to the required calcium oxide content of chemical reaction KNaR+CaO=KNaO+CaR.
9, the method for red mud dealkalization according to claim 7 is characterized in that: the content that alkali in the red mud of back is handled in described dealkalize be sodium oxide content less than 0.3%, the content of potassium oxide is less than 0.2%.
10, according to the method for each described red mud dealkalization of claim 1～9, it is characterized in that: described red mud is the solid, powdery waste that Bayer process, sintering process or integrated process are smelted the aluminum oxide gained; In described dry employing air stream drying method, the desiccating method of drifting along, kiln desiccating method or the cylinder drier any.
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