CN1235802C - Bayer process stripping additive and its preparation and using method - Google Patents
Bayer process stripping additive and its preparation and using method Download PDFInfo
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- CN1235802C CN1235802C CN 03121955 CN03121955A CN1235802C CN 1235802 C CN1235802 C CN 1235802C CN 03121955 CN03121955 CN 03121955 CN 03121955 A CN03121955 A CN 03121955A CN 1235802 C CN1235802 C CN 1235802C
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Abstract
The present invention discloses a dissolution additive through a Bayer method, which relates to a dissolution additive used for decreasing the alumina silica ratio and the sodium silica ratio in dissolution red mud and a preparation and use method thereof. The present invention is characterized in that hydrated calcium ferrite is used as the dissolution additive. A preparation process comprises the steps in sequence that (1) calcium carbonate is uniformly mixed with hematite according to the proportion of 2 to 1, the burning temperature in a burning furnace is controlled between 1000 and 1300 DEG C, and burning is carried out for 30 to 120 minutes; burnt calcium ferrite materials are milled; (2) the burnt calcium ferrite is mixed with calcium oxide according to the ratio of 1 to 1 between 2CaO. Fe2O3 and CaO; the reaction temperature ranges from 25 to 60 DEG C, and the reaction time ranges from 4 to 10 hours; limewater is added to carry out hydration so as to prepare hydrated calcium ferrite 3CaO. Fe2O3.6H2O; an adding dissolution process is calculated when n in 3CaO. Fe2O3. nSiO2. (6-2n)H2O as the chemical formula of molten iron garnet generated by a dissolution reaction ranges from 1.5 to 2. In dissolution red mud, the alumina silica ratio ranges from 0.5 to 1.0, and the sodium silica ratio ranges from 0.15 to 0.20. The purpose of the direct outwards discharge of red mud through a Bayer method and the treatment of medium and low grade diaspore through the direct use of a pure Bayer method can be realized.
Description
Technical Field
A Bayer process stripping method relates to a stripping method which is used for reducing the ratio of aluminum to silicon and the ratio of sodium to silicon in red mud in the Bayer process stripping process by adopting diasporic bauxite and is added with a stripping additive.
Technical Field
In the mixed combination process or the pure Bayer process digestion process for treating diasporic bauxite, lime is generally added according to 5-8% of the dry ore amount as a digestion additive in order to eliminate the harmful effect of titanium minerals, and the addition of the lime can improve the digestion speed of alumina and reduce alkali consumption, but in general, the aluminum-silicon ratio of the digested red mud is 1.5-2.0, and the sodium-silicon ratio is about 1.3. If the red mud is not recycled, a large amount of alkali is lost, and the utilization rate of ores is reduced; if the recovery is carried out, a sintering method with higher energy consumption is adopted for treatment, so that the energy consumption of the whole production process is increased. The method is characterized in that lime is replaced by a novel stripping additive which has the effect of reducing the aluminum-silicon ratio and the sodium-silicon ratio of red mud to be stripped, so that red mud in a Bayer process can be directly discharged, a sintering process part for producing alumina by a hybrid process is eliminated, the problem that middle-grade and low-grade diaspore bauxite cannot be treated by a pure Bayer process is effectively solved, and the method is a technical difficulty which is concerned by people in the prior art for producing alumina by adopting middle-grade and low-grade diaspore bauxite.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a method for leaching by adding a leaching agent to a diasporic bauxite bayer process, which can effectively reduce the ratio of aluminum to silicon and the ratio of sodium to silicon in red mud to be leached.
The purpose of the invention is realized by the following technical scheme.
A Bayer process for dissolving out the calcium ferrite particles features that the hydrated calcium ferrite 3 CaO-Fe is used as dissolving-out additive2O3·6H2O, adding the hydrated calcium ferrite into the Bayer process dissolution process, wherein the adding amount of the hydrated calcium ferrite is determined according to the molten iron fossil garnet 3 CaO. Fe generated by dissolution reaction2O3·nSiO2·(6-2n)H2And (3) calculating n in O to be 1.5-2 for dissolution.
In the process of producing alumina by Bayer process, the additive hydrated calcium ferrite is added, so that the silicon dioxide in the dissolving process continuously enters the hydrated calcium ferrite molecules, the generated iron fossil garnet becomes the main component in the red mud, thereby reducing the aluminum-silicon ratio and the sodium-silicon ratio in the red mud,improving the recovery rate of alumina in the production process of Bayer process, reducing the alkali consumption, and finally enabling the alumina industry in China to utilize medium-low grade diaspore ore and adopt the pure Bayer process for production.
In the Bayer process, hydrated calcium ferrite is added as a dissolution additive, so that silicon minerals in the ore are dissolved out in the form of hydrated garnet instead of the conventional hydrated sodium aluminate. The additive is not existed in nature, so it needs to be synthesized under certain conditions. The Bayer process dissolution additive is used for Bayer process dissolution, the aluminum-silicon ratio of red mud dissolved out is 0.5-1.0, the sodium-silicon ratio is 0.15-0.20, direct discharge of the Bayer process red mud can be realized, a sintering process part is eliminated, and the aim of treating low-grade diaspore bauxite by a pure Bayer process is fulfilled.
Detailed Description
A Bayer process for dissolving out the hydrated calcium ferrite 3 CaO-Fe as additive2O3·6H2And O. The preparation process comprises the following steps:1) calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2: 1, the firing temperature is controlled to be 1000-1300 ℃ in a firing furnace, the firing is carried out for 30-120 minutes, the fired calcium ferrite material is ground, and the main chemical reaction is that (ii) a 2) Iron to be firedCalcium carbonate is prepared from CaO and calcium ferrite 2 CaO. Fe2O31 to 1 ratio of materials are mixed, the reaction temperature is 25 to 60 ℃, the reaction time is 4 to 10 hours, and lime water is added for hydration to prepare hydrated calcium ferrite 3 CaO. Fe2O3·6H2O; the main chemical reaction is 。
Adding hydrated calcium ferrite into the Bayer process for dissolution, wherein the adding amount of the hydrated calcium ferrite is determined according to the generated molten iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2And (3) in O, n is 1.5-2, and the Bayer process dissolution is carried out under certain dissolution conditions, wherein the aluminum-silicon ratio of red mud dissolved out is 0.5-1.0, and the sodium-silicon ratio is 0.15-0.20. The additive hydrated calcium ferrite is synthesized by firstly adopting calcium carbonate and hematite to be mixed and evenly mixed according to the proportion of 2 to 1, controlling the firing temperature to be 1000-1300 ℃ in a firing furnace, and firing for 30-120 minutes to prepare the calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is added with CaO and 2CaO&Fe according to the hydration condition2And (3) mixing the materials with the ratio of 1 to 1, reacting at the temperature of 25-60 ℃ for 4-10 hours, and adding lime water for hydration to obtain hydrated calcium ferrite. The application method of Bayer process stripping additive is characterized by that the calcium ferrite hydrate is added in the course of Bayer process stripping process, and its added quantity is according to molten iron fossil garnet 3 CaO. Fe produced by stripping reaction2O3·nSiO2·(6-2n)H2And (3) calculating n in O to be 1.5-2 for dissolution. The aluminum-silicon ratio of the leached red mud is 0.5-1.0, the sodium-silicon ratio is 0.15-0.20, and the direct discharge of the Bayer process red mud can be realized, so that the sintering process part is eliminated, and the aim of treating the middle-low grade diaspore bauxite by using a pure Bayer process is fulfilled.
The present invention will be further described with reference to the following examples.
Example 1
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled to be 1000 ℃ in a firing furnace, and the mixture is baked for 120 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O3Mixing materials in a ratio of 1: 1, reacting at 25 deg.C for 4 hr, adding lime waterHydration to obtain hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 2, and the red mud is eluted at 260 ℃ for 90 minutes, wherein the ratio of aluminum to silicon and the ratio of sodium to silicon in the eluted red mud are 0.5 and 0.20, respectively.
Example 2
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled at 1100 ℃ in a firing furnace, and the mixture is baked for 90 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 45 ℃, the reaction time is 6 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, the red mud was eluted at 260 ℃ for 90 minutes with an Al-Si ratio of 0.7 and a Na-Si ratio of 0.20, where n is 2.
Example 3
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2: 1, the firing temperature is controlled to be 1200 in a firing furnace, and the mixture is fired for 60 minutes to prepare the calcium ferrite 2 CaO. Fe2O3The sintered calcium ferrite is pressed into a piece of CaO and 2CaO&Fe2O31 to 1 ratio of materials are mixed, the reaction temperature is 60 ℃, the reaction time is 8 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 1.8, and the red mud is eluted at 260 ℃ for 90 minutes at an Al-Si ratio of 1.0 and a Na-Si ratio of 0.15.
Example 4
By using carbonMixing calcium carbonate and hematite at a ratio of 2: 1, calcining at 1300 deg.C for 30 min in a calcining furnace to obtain calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 40 ℃, the reaction time is 4 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 1.5, and the red mud is eluted at 260 ℃ for 90 minutes at an Al-Si ratio of 1.0 and a Na-Si ratio of 0.18.
Example 5
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2: 1, the firing temperature is controlled at 1200 ℃ in a firing furnace, and the mixture is baked for 80 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 50 ℃, the reaction time is 6 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 1.5, and the red mud is eluted at 260 ℃ for 90 minutes at an Al-Si ratio of 0.6 and a Na-Si ratio of 0.16.
Example 6
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled at 1100 ℃ in a firing furnace, and the mixture is baked for 120 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 60 ℃, the reaction time is 6 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for digestion with caustic alkali concentration of 220g/l and caustic ratio of about 3.0, adding hydrated calcium ferrite according to the amount of the generated molten iron fossil garnet3CaO·Fe2O3·nSiO2·(6-2n)H2In O, n is 1.8, and the red mud is eluted at 260 ℃ for 90 minutes, wherein the ratio of aluminum to silicon and the ratio of sodium to silicon in the eluted red mud are 0.5 and 0.15, respectively.
Example 7
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled to be 1300 ℃ in a firing furnace, and the mixture is baked for 90 minutes to prepare the calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 45, the reaction time is 10 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, the red mud was eluted at 260 ℃ for 90 minutes with an Al-Si ratio of 0.5 and a Na-Si ratio of 0.18, where n is 2.
Example 8
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled to be 1000 ℃ in a firing furnace, and the mixture is baked for 30 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O3The 1 to 1 proportioning is carried out,the reaction temperature is 60 ℃, the reaction timeis 10 hours, and the hydrated calcium ferrite is prepared by adding lime water for hydration.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 2, and the red mud is eluted at 260 ℃ for 90 minutes, wherein the ratio of aluminum to silicon and the ratio of sodium to silicon in the eluted red mud are 1.0 and 0.20, respectively.
Example 9
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled to be 1300 ℃ in a firing furnace, and the mixture is baked for 90 minutes to prepare the calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 60 ℃, the reaction time is 8 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, the red mud was eluted at 260 ℃ for 90 minutes with an Al-Si ratio of 0.6 and a Na-Si ratio of 0.15, where n is 2.
Example 10
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled at 1200 ℃ in a firing furnace, and the mixture is baked for 60 minutes to prepare the calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 60 ℃, the reaction time is 10 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 1.8, and the red mud is eluted at 260 ℃ for 90 minutes at an Al-Si ratio of 0.8 and a Na-Si ratio of 0.18.
Example 11
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled at 1100 ℃ in a firing furnace, and the mixture is baked for 120 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 45 ℃, the reaction time is 4 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, the red mud was eluted at 260 ℃ for 90 minutes with an Al-Si ratio of 0.8 and a Na-Si ratio of 0.20, where n is 2.
Example 12
Calcium carbonate and hematite are mixed and evenly mixed according to the proportion of 2 to 1, the firing temperature is controlled at 1200 ℃ in a firing furnace, and the mixture isbaked for 90 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 25 ℃, the reaction time is 10 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 1.8, and the red mud is eluted at 260 ℃ for 90 minutes at an Al-Si ratio of 1.0 and a Na-Si ratio of 0.15.
Example 13
Calcium carbonate and hematite are mixed and mixed according to the proportion of 2: 1, the firing temperature is controlled to be 1000 ℃ in a firing furnace, and the mixture is bakedBurning for 120 minutes to prepare calcium ferrite 2 CaO. Fe2O3The calcined calcium ferrite is mixed with 2 CaO. Fe according to CaO2O31 to 1 ratio of materials are mixed, the reaction temperature is 60 ℃, the reaction time is 8 hours, and lime water is added for hydration to prepare hydrated calcium ferrite.
Adopting a solution for dissolving with the caustic alkali concentration of 220g/l and the caustic ratio of about 3.0, and adding the hydrated calcium ferrite according to the amount of the generated iron fossil garnet 3 CaO. Fe2O3·nSiO2·(6-2n)H2In O, n is 2, and the red mud is eluted at 260 ℃ for 90 minutes, wherein the ratio of aluminum to silicon and the ratio of sodium to silicon in the eluted red mud are 0.5 and 0.15, respectively.
Claims (1)
1. A Bayer process for dissolving out the calcium ferrite particles features that the hydrated calcium ferrite 3 CaO-Fe is used as dissolving-out additive2O3·6H2O, adding the hydrated calcium ferrite into the Bayer process dissolution process, wherein the adding amount of the hydrated calcium ferrite is determined according to the molten iron fossil garnet 3 CaO. Fe generated by dissolution reaction2O3·nSiO2·(6-2n)H2N in O is 1.5-2The process is carried out.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390307C (en) * | 2006-07-18 | 2008-05-28 | 中国铝业股份有限公司 | Prepn process of Bayer process leaching additive |
| CN100441708C (en) * | 2007-05-31 | 2008-12-10 | 中国铝业股份有限公司 | Stripping method for diasporite type bauxite |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173463A (en) * | 2011-03-14 | 2011-09-07 | 陕西科技大学 | Method for preparing iron-based composite oxide Ca2Fe2O5 |
| CN107298452A (en) * | 2017-06-23 | 2017-10-27 | 东北大学 | The method that the hot method of the step alkali of andradite one handles Bayer process red mud production metallurgy grade aluminum oxide |
| CN107188209A (en) * | 2017-06-23 | 2017-09-22 | 东北大学 | The method that the hot method of the step alkali of andradite one handles middle-low bauxite production metallurgy grade aluminum oxide |
| CN111570491B (en) * | 2020-05-14 | 2020-12-01 | 生态环境部环境规划院 | Preparation method of modified red mud composite polymer gel Cr (VI) removing filler |
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2003
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390307C (en) * | 2006-07-18 | 2008-05-28 | 中国铝业股份有限公司 | Prepn process of Bayer process leaching additive |
| CN100441708C (en) * | 2007-05-31 | 2008-12-10 | 中国铝业股份有限公司 | Stripping method for diasporite type bauxite |
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