CN111302394B - Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method - Google Patents
Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/04—Halides
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P10/20—Recycling
Abstract
The invention provides a regeneration method of a deep purification medicament used in the production of aluminum oxide by a one-step acid dissolution method, which comprises the following steps: (1) drying the purified impurity-removed filter cake; (2) mixing the purified impurity-removed filter cake treated in the step (1) with solid alkali, and roasting to obtain a roasted product; (3) adding the roasted product obtained in the step (3) into water for leaching, filtering, and washing a filter cake to obtain a washing liquid and a solid substance; (4) adding the solid matter obtained in the step (3) into hydrochloric acid for a dissolution reaction to obtain slurry; (5) and (4) filtering the slurry obtained in the step (4), and concentrating and crystallizing the filtrate to obtain crystals, namely the regenerated deep purification medicament. The regeneration rate of the regeneration method is more than 90 wt%, and the purification effect of the regeneration medicament is consistent with that of the original medicament; the regeneration method can greatly reduce the deep purification cost, is beneficial to improving the economic benefit, and is simple and easy to operate.
Description
Technical Field
The invention belongs to the field of fly ash, and particularly relates to a regeneration method of a deep purification agent used in the production of alumina by a one-step acid dissolution method.
Background
The one-step acid dissolution process for extracting alumina from fly ash is a process for producing alumina by using high-alumina fly ash as a raw material by using a circulating fluidized bed. Compared with the general alkaline extraction technology in the alumina industry, the technology has the advantages of wide technical conditions, short process flow, acid recycling, reduction, safety, environmental protection, low production cost and the like, and can extract rare metals such as gallium, lithium and the like while extracting alumina. Through independent research and development of Shenhua Bingquan company for over ten years and seven industrialized pilot test research studies (pilot scale 4000 ton/year) of quasi-capital company, the one-step acid dissolution method technology has great success in the aspects of equipment and material development, cooperative dissolution, separation, refined impurity removal, environmental protection and other technologies, and the construction of 30 ten thousand ton/year high-alumina fly ash comprehensive utilization industrialized demonstration plants is currently carried out.
In the process of generating alumina by the one-step acid dissolution method, in order to improve the purity of the prepared alumina, the pickle liquor generated by acid dissolution of the fly ash needs to be purified and purified, and then is evaporated and crystallized to prepare the alumina. The purification and impurity removal process mainly comprises the steps of sequentially removing Fe and Ca impurity ions in the pickle liquor through resin adsorption and separation, and removing P and Si non-metal impurities in the pickle liquor through a chemical precipitation method by using a deep purification medicament. The purity of an alumina product can be improved by deep purification and impurity removal, the discharge amount of the scale steaming liquid (namely, the liquid which has to be discharged in the evaporation crystallization process due to accumulation of impurity ions) in the evaporation crystallization process can be reduced, and the discharge amount of the scale steaming liquid after deep purification is reduced to about 3% from 15% of the alumina production capacity. However, the addition amount of the deep purification agent is 1.0-2.0kg/m3, the market price is 16000-. Therefore, the development of a regeneration method of a deep purification agent suitable for the process of producing alumina by using fly ash through a one-step acid dissolution method is urgently needed.
Disclosure of Invention
The invention aims to provide a regeneration method of a deep purification medicament used in the production of alumina by a one-step acid dissolution method, which is economical and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a regeneration method of a deep purification medicament used in the production of aluminum oxide by a one-step acid dissolution method comprises the following steps:
(1) pretreatment of
Drying the purified impurity-removed filter cake; the purification impurity-removal filter cake is a filter cake obtained by filtering acid leaching solution in the process of producing alumina by a fly ash one-step acid dissolution method after adsorption impurity removal by resin and chemical precipitation impurity removal by an advanced purification medicament; the deep purification agent comprises any one or combination of more of zirconium chloride, zirconium hydroxide, zirconium oxychloride octahydrate, zirconium sulfate and zirconium carbonate;
(2) roasting
Mixing the purified impurity-removed filter cake treated in the step (1) with solid alkali, and then roasting to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into water for leaching, filtering, and washing a filter cake to obtain a washing liquid and a solid substance;
(4) acid leaching dissolution
Adding the solid matter obtained in the step (3) into hydrochloric acid for a dissolution reaction to obtain slurry;
(5) concentration crystallization
And (5) filtering the slurry obtained in the step (4), and concentrating and crystallizing the filtrate to obtain crystals, namely the regenerated deep purification medicament.
The step (1) of removing impurities from the pickle liquor in the process of producing alumina by using the fly ash one-step acid dissolution method through resin adsorption refers to the step of removing iron and calcium from the pickle liquor in the process of producing alumina by using the fly ash one-step acid dissolution method through resin (iron removal resin and calcium removal resin) adsorption, wherein the obtained product is refined calcium removal liquid after the removal of impurities through resin adsorption, the content of calcium ions is not higher than 60mg/L by using calcium oxide, and the content of iron ions is Fe 3+ Not more than 10mg/L, mainly contains Al 3+ P and Si (wherein Al 3+ The content of (1) is 40000-60000mg/L, P content of 150-250mg/L, Si content of 15-30mg/L), and the balance is lower K + And Na + There is substantially no effect on the regeneration process of the present invention.
The filter cake for purifying and impurity removing is obtained by adding a deep purification medicament into the calcium-removing refined liquid to carry out chemical precipitation and impurity removal (non-metallic impurities of silicon and phosphorus) and then filtering. The deep purification agent comprises any one or more of zirconium chloride, zirconium hydroxide, zirconium oxychloride octahydrate, zirconium sulfate and zirconium carbonate.
The process for extracting alumina from fly ash by the "one-step acid dissolution method" can be found in patent document CN 102145905 a, which is incorporated by reference in the present application. Specifically, the preparation method of the pickle liquor comprises the following steps:
1) magnetic separation and iron removal of the fly ash: crushing the fly ash to be below 100 meshes, adding water to prepare slurry with the solid content of 20-40 wt%, and carrying out magnetic separation on a vertical ring type magnetic separator, wherein the magnetic separation field strength is 1.0-2.0 ten thousand GS; carrying out solid-liquid separation on the slurry subjected to magnetic separation to obtain a filter cake with the solid content of 25-50 wt%;
2) acid dissolution: placing the filter cake after magnetic separation in an acid-proof reaction kettle for hydrochloric acid dissolution, wherein the concentration of hydrochloric acid is 20-37 wt%, the molar ratio of HCl in hydrochloric acid to alumina in fly ash is 4:1-9:1, the dissolution temperature is 100-; carrying out solid-liquid separation on the acid-dissolved product to obtain the pickle liquor;
and (3) adsorbing the pickle liquor by resin to remove impurities, namely removing iron from the pickle liquor by a macroporous cation resin column with single column/double columns connected in series at the speed of 1-4 times the volume of the resin per hour at the temperature of 20-90 ℃ to obtain the refined aluminum chloride iron-removing liquor.
The calcium-removing refined liquid is obtained by removing calcium from the aluminum chloride iron-removing refined liquid by calcium-removing resin; in one embodiment, the resin and method for calcium removal can be found in patent document CN 107758717 a, which is incorporated by reference into the present application. Specifically, the calcium removal resin contains amine groups, hydroxyl groups and sulfur, and is prepared by the following method: 1) reacting resin dry white balls with a chloromethylation reagent to obtain chlorine balls; 2) reacting the chlorine balls obtained in the step 1) with an organic amine solution containing hydroxyl according to a mass ratio of 1: 4-1: 6, and drying to obtain the organic amine solution containing amino and hydroxylA resin; 3) mixing the resin containing the amino and the hydroxyl obtained in the step 2) with a swelling agent and swelling to obtain a swelling product; 4) reacting the swelling product obtained in the step 3) with an alkaline substance and a sulfur-containing compound to obtain calcium-removing resin; the calcium removal method comprises the following steps: adding AlCl containing calcium ions 3 Passing the solution (equivalent to the refined solution for removing iron from aluminum chloride) through a resin column filled with the calcium-removing resin, and collecting the effluent to obtain the calcium-removed AlCl 3 And (5) obtaining the calcium-removing refined solution.
The method for regenerating the deep purification medicament used in the production of the alumina by the one-step acid dissolution method can regenerate the deep purification medicament to obtain the regenerated deep purification medicament which is the zirconium oxychloride octahydrate (ZrOCl) 2 .8H 2 O), thereby reducing the cost of the deep purification agent, further reducing the cost of the alumina generated by the acid dissolution method, improving the purity of the obtained alumina and contributing to improving the economic benefit.
In one embodiment, in the step (1), the liquid obtained by removing impurities from the pickle liquor in the process of producing alumina by using the fly ash one-step acid dissolution method is a calcium-removed refined liquid; when the calcium removal refining solution is subjected to chemical precipitation and impurity removal by a deep purification medicament, the addition amount of the deep purification medicament is 0.0031-0.0062mol/L (calculated by zirconium ions), such as 0.0035mol/L, 0.0040mol/L, 0.0043mol/L, 0.0050mol/L and 0.0055 mol/L. That is, the molar amount of the chemical for deep purification added to 1L of the calcium-depleted purified solution is 0.0031 to 0.0062mol based on zirconium ions.
In one embodiment, Al in the calcium-removed refined liquid obtained by removing impurities from the pickle liquor in the process of producing alumina by using fly ash one-step acid dissolution method through resin adsorption 3+ The content of (b) is 40000-60000mg/L, such as 42500mg/L, 45000mg/L, 47500mg/L, 50000mg/L, 52500mg/L, 55000mg/L and 57500 mg/L; the P content is 150-250mg/L, such as 175mg/L, 200mg/L and 225 mg/L; the Si content is 15-30mg/L, such as 20mg/L and 25 mg/L.
In one embodiment, the drying temperature in step (1) is 100 ℃ to 300 ℃, such as 150 ℃, 200 ℃ and 250 ℃.
Those skilled in the art will appreciate that the drying means is drying means commonly used in the art, such as drying. In the step (1), the water content of the purified impurity-removed filter cake is about 50 wt%, and after drying treatment, the water content can be reduced to less than 1 wt%.
In the step (2), the purified impurity-removed filter cake and solid alkali are mixed and roasted, so that zirconium in the purified impurity-removed filter cake can be converted into water-insoluble zirconate and exists in a roasted product. Preferably, in the step (2), the roasting temperature is 600-1200 ℃, such as 700 ℃, 800 ℃, 900 ℃, 1000 ℃ and 1100 ℃; the calcination time is 30-120min, such as 45min, 60min, 75min, 90min and 105 min.
Preferably, the mass ratio of the purified filter cake treated in the step (1) to the solid alkali is 1 (1.1-2), such as 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8 and 1:1.9, so as to convert zirconium in the purified filter cake as completely as possible into zirconate.
Preferably, the solid base is any one or more of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
As will be understood by those skilled in the art, the firing treatment of step (2) is carried out in a firing furnace.
In the step (3), the roasted product is subjected to water leaching to remove impurities, so that unreacted solid alkali can be removed along with the washing liquid (phosphorus and part of soluble silicon in the solid alkali can be removed along with the washing liquid at the same time), and the zirconate with higher purity is obtained and exists in the solid matter. In one embodiment, in the step (3), the leaching time is 30-60min, such as 40min and 50 min. As understood by those skilled in the art, the leaching is to soak the roasted product with deionized water or purified water to dissolve out substances capable of being dissolved in water in the roasted product so as to remove the substances during subsequent washing to obtain zirconate with higher purity; the amount of soaking water is such that the roast product is submerged, and it is preferable that the volume ratio of the soaking water to the roast product is (1-5):1, such as 2:1, 3:1 and 4: 1.
In one embodiment, in the step (3), the washing is performed by multistage countercurrent washing; preferably 3-5 stages. Those skilled in the art understand that the washing is with deionized or purified water.
Countercurrent washing refers to: after the filtration operation, the filter cake is washed in a countercurrent manner with a solvent, called detergent. Some suspensions are subjected to filtration operations to effect solid-liquid separation followed by counter current washing in order to recover valuable filtrate remaining in the filter cake or to further remove soluble impurities from the filter cake to increase the purity of the solid product. Countercurrent washing is typically carried out in a multi-stage (e.g., three-stage) continuous countercurrent washing system. The countercurrent washing is adopted, and a relatively satisfactory washing effect can be achieved by using a small amount of detergent. The present invention prefers 3-5 stages of counter current washing.
As understood by those skilled in the art, the scrubbing liquid obtained in step (3) contains mainly non-metallic impurities of silicon and phosphorus (P and Si), as well as unreacted solid base. In one embodiment, the washing liquid is sent to a resource recycling unit for recycling or sent to a wastewater treatment unit for treatment.
In the step (4), the solid substance and hydrochloric acid are subjected to dissolution reaction, so that zirconate in the solid substance and hydrochloric acid can react to generate water-soluble ZrOCl 2 Is present in the slurry. Preferably, in the step (4), the dissolution temperature is 60 to 110 ℃, such as 70 ℃, 80 ℃, 90 ℃ and 100 ℃; the dissolution time is 15-60min, such as 30min and 45min, to convert the zirconate in the solid matter to ZrOCl as completely as possible 2 。
Preferably, in the step (4), the concentration of the hydrochloric acid is 24 to 31 wt%, such as 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, and 30 wt%. When the concentration of hydrochloric acid is within this range, the dissolution effect in step (4) is good.
In one embodiment, in the step (5), the treatment temperature of the concentrated crystallization is 95 to 110 ℃, such as 100 ℃ and 105 ℃.
In the present invention, it is understood by those skilled in the art that the filtration may be a filtration method commonly used in the art, such as suction filtration, plate-and-frame filter pressing, etc., and preferably, the plate-and-frame filter pressing is adopted to enhance the filtration effect and reduce the water content in the filter cake.
The regenerated deep purification medicament obtained by concentration and crystallization in the step (5) is dichloro-oxydichloride octahydrateZirconium ZrOCl 2 .8H 2 And O. In one embodiment, in the step (5), the filter cake obtained by the filtration is neutralized with lime for harmless treatment.
The invention has the beneficial effects that:
(1) the regeneration method of the deep purification medicament used in the production of the alumina by the fly ash one-step acid dissolution method has the regeneration rate of more than 90wt percent, and the purification effect of the regenerated deep purification medicament is not much different from that of the original deep purification medicament, thereby almost reaching the purification effect of the original deep purification medicament;
(2) the regeneration method can greatly reduce the deep purification cost, thereby reducing the production cost of producing the alumina by the fly ash one-step acid dissolution method, being beneficial to improving the economic benefit, and being simple and easy to operate.
Detailed Description
The technical solution and effects of the present invention will be further described below by way of specific embodiments. The following embodiments are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The raw materials of the following examples of the invention are from the following sources:
calcium removal refining liquid: the decalcification refined liquid is a process liquid of a one-step acid dissolution method, and is prepared by performing solid-liquid separation on fly ash after acid leaching, and sequentially removing iron and impurities of iron and calcium from acid leaching liquid obtained by separation by using an iron removal resin and a decalcification resin; wherein, Al 3+ The content of (A) is 53260mg/L, the content of P is 194.7mg/L, and the content of Si is 21.30 mg/L;
purifying and impurity removing filter cake a 1: zirconium oxychloride octahydrate (ZrOCl) 2 .8H 2 O) is added into the calcium-removing refined liquid, the adding amount is 0.005mol/L, and after stirring and reacting for 30min at 55 ℃, the mixture is subjected to plate-and-frame filter pressing to obtain a purified impurity-removing filter cake a1 with the water content of 50 wt%;
purifying and impurity removing filter cake a 2: zirconium carbonate (ZrC) 2 O 5 ) Adding into the calcium-removing refined liquid at 0.0043mol/L, stirring at 60 deg.C for 50min, and making into platePerforming frame pressure filtration to obtain a purified impurity-removed filter cake a2 with the water content of 50 wt%;
purifying and impurity removing filter cake a 3: zirconium oxychloride octahydrate (ZrOCl) 2 .8H 2 O) is added into the calcium-removing refined liquid, the adding amount is 0.0062mol/L, and after stirring and reacting for 30min at 55 ℃, plate-and-frame filter pressing is carried out, so as to obtain a purification impurity-removing filter cake a3 with the water content of 50 wt%;
purifying and impurity removing filter cake a 4: zirconium carbonate (ZrC) 2 O 5 ) Adding the calcium-removing refined liquid into the calcium-removing refined liquid, wherein the adding amount is 0.0031mol/L, stirring and reacting at 60 ℃ for 30min, and performing plate-frame filter pressing to obtain a purification impurity-removing filter cake a4 with the water content of 50 wt%;
zirconium oxychloride octahydrate (ZrOCl) 2 .8H 2 O), zirconium carbonate (ZrC) 2 O 5 ) All the samples are analytically pure and purchased from Jiangxi Nanchang Jingan high-tech company Limited;
sodium hydroxide, sodium carbonate and hydrochloric acid, all being analytical reagents, national drug group chemical reagents limited.
Detection of P and Si removal rates:
detecting the sample liquid by using an inductively coupled plasma emission spectrometer (ICP-OES), wherein the detection conditions are as follows: diluting the sample solution by 10 times and detecting at room temperature; the detection process is shown in Standard inductively coupled plasma emission spectrometry (ICP-OES) for detecting impurity elements of inorganic chemical products (GB/T30902-2014), and particularly in a standard curve method of a quantitative analysis part.
Example 1 (i.e., S1)
(1) Pretreatment of
Drying 2.0g of the purified impurity-removed filter cake a1 in a muffle furnace at 200 ℃ for 45min until the water content is less than 1 wt%;
(2) roasting
Uniformly mixing the purified impurity-removed filter cake treated in the step (1) with 1.3g of sodium hydroxide, and then feeding the mixture into a roasting furnace to be roasted at 800 ℃ for 120min to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into 150mL of deionized water, soaking for 40min, carrying out suction filtration, and carrying out 3-stage countercurrent washing on a filter cake obtained by suction filtration by using the deionized water until the pH of a washing liquid is about 7 to obtain a washing liquid and a solid substance;
(4) acid leaching and dissolving out
Adding the solid matter obtained in the step (4) into 100mL of hydrochloric acid with the concentration of 24 wt%, and carrying out dissolution reaction at 100 ℃ for 30min to obtain slurry;
(5) concentrated crystallization
And (5) cooling the slurry obtained in the step (4), filtering, evaporating and concentrating the filtrate at 100 ℃ to crystallize to obtain 0.83g of crystals, namely 0.83g of regenerated deep purification agent A1. The regeneration rate was 93.4 wt%.
As a result:
adding the regenerated deep purification agent A1 prepared in example 1 into the calcium-removing refined liquid, wherein the adding amount is 0.005mol/L (about 1.6g/L), the reaction temperature is 55 ℃, the stirring reaction time is 30min, and the content of P and Si in the liquid after the reaction is detected, namely the removal rate of the regenerated deep purification agent A1 to P and Si is detected;
taking the same molar amount of the deep purification medicament octahydrate dichlorozirconium oxide, wherein the addition amount (in mol/L) and the reaction condition are completely consistent with those of the regenerated deep purification medicament A1, and detecting the removal rate of P and Si of the original deep purification medicament octahydrate dichlorozirconium oxide;
the effect of the regenerated deep purification agent A1 and the original deep purification agent zirconium oxychloride octahydrate on removing P and Si in the calcium-removing refined solution is compared, and the effect is shown in Table 1.
Removal effects of P and Si in S1 of Table 1
| Composition of | Al 3+ | P | Si |
| Calcium-removing refined liquid/mg/L | 53260 | 194.7 | 21.30 |
| Deep purification medicament of zirconium oxychloride octahydrate/mg/L | 53210 | 2.127 | 9.244 |
| Adding regenerated deep purifying agent A1 at a concentration of mg/L | 53218 | 2.152 | 9.230 |
Example 2 (i.e., S2)
(1) Pretreatment of
Drying 2.0g of the purified impurity-removed filter cake a2 in a muffle furnace at 200 ℃ for 30min until the water content is less than 1 wt%;
(2) roasting
Uniformly mixing the purified impurity-removed filter cake treated in the step (1) with 1.5g of sodium carbonate, and then feeding the mixture into a roasting furnace to roast at 1200 ℃ for 30min to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into 200mL of deionized water, soaking for 30min, then carrying out suction filtration, and then carrying out 5-stage countercurrent washing on a filter cake obtained by suction filtration by using the deionized water until the pH of a washing liquid is about 7 to obtain a washing liquid and a solid substance;
(4) acid leaching and dissolving out
Adding the solid matter obtained in the step (4) into 100mL of 31 wt% hydrochloric acid, and carrying out dissolution reaction at 100 ℃ for 30min to obtain slurry;
(5) concentrated crystallization
And (4) cooling the slurry obtained in the step (4), performing suction filtration, and performing evaporation concentration on the filtrate at 100 ℃ to crystallize to obtain 0.84g of crystals, namely 0.84g of regenerated deep purification agent A2. The regeneration rate was 93.4 wt%.
As a result:
adding the regenerated deep purification agent A2 prepared in example 2 into the calcium-removal refined liquid, wherein the adding amount is 0.005mol/L (about 1.6g/L), the reaction temperature is 60 ℃, the stirring reaction time is 45min, and the content of P and Si in the liquid after the reaction is detected, namely the removal rate of the regenerated deep purification agent A2 to P and Si is detected;
taking the same molar amount of zirconium carbonate (namely, the same molar amount of zirconium carbonate as the regenerated deep purification agent A2 prepared in example 2), wherein the addition amount (in mol/L) and the reaction conditions are completely consistent with those of the regenerated deep purification agent A2, and detecting the removal rate of P and Si by the original deep purification agent zirconium carbonate;
the effect of the regenerated deep purification agent A2 on removing P and Si in the calcium-removing refined solution is compared with that of the original deep purification agent zirconium carbonate, and the effect is shown in Table 2.
Removal effects of P and Si in S2 of Table 2
Example 3 (i.e., S3)
(1) Pretreatment of
Drying 2.0g of the purified impurity-removed filter cake a3 in a muffle furnace at 100 ℃ for 45min until the water content is less than 1 wt%;
(2) roasting
Uniformly mixing the purified impurity-removed filter cake treated in the step (1) with 2.0 potassium hydroxide, and then feeding the mixture into a roasting furnace to roast at 600 ℃ for 120min to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into 500mL of deionized water, soaking for 60min, carrying out suction filtration, and then washing a filter cake obtained by suction filtration with deionized water until the pH of a washing liquid is about 7 to obtain a washing liquid and a solid substance;
(4) acid leaching and dissolving out
Adding the solid matter obtained in the step (4) into 150mL of hydrochloric acid with the concentration of 26 wt%, and carrying out dissolution reaction for 20min at 110 ℃ to obtain slurry;
(5) concentrated crystallization
And (4) cooling the slurry obtained in the step (4), performing suction filtration, and evaporating and concentrating the filtrate at 110 ℃ to crystallize to obtain 0.86g of crystals, namely 0.86g of regenerated deep purification agent A3. The regeneration rate was 95.6 wt%.
As a result:
adding the regenerated deep purification agent A3 prepared in example 3 into the calcium-removal refined liquid, wherein the adding amount is 0.0031mol/L (about 1.0g/L), the reaction temperature is 55 ℃, the stirring reaction time is 60min, and the content of P and Si in the liquid after the reaction is detected, namely the removal rate of the regenerated deep purification agent A3 to P and Si is detected;
taking the same molar amount of the deep purification medicament namely octahydrate zirconium oxychloride, wherein the addition amount (in mol/L) and the reaction condition are completely consistent with those of the regenerated deep purification medicament A3, and detecting the removal rate of the original deep purification medicament zirconium oxychloride on P and Si;
the effect of the regenerated deep purification agent A3 and the original deep purification agent zirconium oxychloride octahydrate on removing P and Si in the calcium-removing refined solution is compared, and the effect is shown in Table 3.
Removal effects of P and Si in S3 of Table 3
| Make up of | Al 3+ | P | Si |
| Calcium-removing refined liquid/mg/L | 53243 | 194.5 | 21.28 |
| Deep purification medicament of zirconium oxychloride octahydrate/mg/L | 53217 | 2.085 | 8.934 |
| Adding regenerated deep purifying agent A3 at a concentration of mg/L | 53225 | 2.090 | 8.951 |
Example 4 (i.e., S4)
(1) Pretreatment of
Drying 2.0g of the purified impurity-removed filter cake a4 in a muffle furnace at 250 ℃ for 20min until the water content is less than 1 wt%;
(2) roasting
Uniformly mixing the purified impurity-removed filter cake treated in the step (1) with 2.0 potassium carbonate, and then feeding the mixture into a roasting furnace for roasting treatment at 1100 ℃ for 105min to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into 300mL of deionized water, soaking for 50min, carrying out suction filtration, and carrying out 3-stage countercurrent washing on a filter cake obtained by suction filtration by using the deionized water until the pH of a washing liquid is about 7 to obtain a washing liquid and a solid substance;
(4) acid leaching dissolution
Adding the solid matter obtained in the step (4) into 180mL of 31 wt% hydrochloric acid, and carrying out dissolution reaction at 60 ℃ for 60min to obtain slurry;
(5) concentrated crystallization
And (4) cooling the slurry obtained in the step (4), performing suction filtration, and evaporating and concentrating the filtrate at 110 ℃ to crystallize to obtain 0.87g of crystals, namely 0.87g of regenerated deep purification agent A4. The regeneration rate was 96.7 wt%.
As a result:
adding the regenerated deep purification agent A4 prepared in example 4 into the calcium-removing refined liquid, wherein the addition amount is 0.005mol/L (about 1.6g/L), the reaction temperature is 60 ℃, the stirring reaction time is 30min, and the content of P and Si in the liquid after the reaction is detected, namely the removal rate of the regenerated deep purification agent A4 on P and Si is detected;
taking the same molar amount of zirconium carbonate as the deep purification agent (namely, taking the same molar amount of zirconium carbonate as the regenerated deep purification agent A4 prepared in example 4), adding the zirconium carbonate (in mol/L) and reaction conditions completely consistent with the regenerated deep purification agent A4, and detecting the removal rate of P and Si by the original zirconium carbonate as the deep purification agent;
the effect of the regenerated deep purification agent A4 on the removal of P and Si in the calcium-removing refined solution is compared with that of the original deep purification agent zirconium carbonate, and the specific effect is shown in Table 4.
Removal effects of P and Si in S4 of Table 4
| Composition of | Al 3+ | P | Si |
| Calcium-removing refining liquid/mgL | 53259 | 194.2 | 21.30 |
| Deep purification medicament zirconium carbonate/mg/L | 53248 | 2.131 | 9.240 |
| Adding regenerated deep purifying agent A4 at a concentration of mg/L | 53255 | 2.044 | 8.538 |
As can be seen from examples 1-4 and tables 1-4, the regeneration method of the present invention has a regeneration rate of the deep purification agent of > 90 wt% (less than 10 wt% of the deep purification agent remained in the washing solution); the obtained regenerated deep purification medicament and the original deep purification medicament have basically the same removal effect on P and Si in the calcium removal refining liquid. Wherein, the regeneration rate is the percentage of the mass of the regenerated deep purification agent (zirconium oxychloride octahydrate) obtained by regenerating a certain mass of the purification and impurity removal filter cake and the mass of the deep purification agent added when the purification and impurity removal filter cake with the mass is obtained (the mass of the deep purification agent is calculated by the mass of the zirconium oxychloride octahydrate with the same molar quantity as the mass of the deep purification agent), for example, in example 1, the regeneration rate is (the mass of the regenerated deep purification agent a1 obtained by regenerating 2g of the purification and impurity removal filter cake a 1)/(the mass of the zirconium oxychloride octahydrate added when 2g of the purification and impurity removal filter cake a 1) x 100 wt%; for example, in example 2, the regeneration rate is (the mass of the regenerated deep purification agent a1 obtained by regenerating 2g of the purification and impurity removal filter cake a 2)/(the mass of zirconium oxychloride octahydrate having the same molar amount as that of zirconium carbonate serving as the deep purification agent added when 2g of the purification and impurity removal filter cake a1 was obtained) × 100 wt%.
According to the preliminary calculation of the experimental result, about 1.5-1.6 tons of NaOH or Na are consumed for one ton of deep purification medicament product regeneration 2 CO 3 1.7-1.8 tons, about 2 tons of hydrochloric acid with the concentration of 31 wt%, and the drying and roasting cost, the complete cost of regeneration of the ton deep purification agent is about 8000 yuan less, and the deep purification cost can be reduced by at least 50%. After industrial scale-up production, the economic benefit is more obvious.
Claims (13)
1. The regeneration method of the deep purification medicament used in the production of the alumina by the one-step acid dissolution method is characterized by comprising the following steps:
(1) pretreatment of
Drying the purified impurity-removed filter cake; the purification impurity-removal filter cake is a filter cake obtained by filtering acid leaching solution in the process of producing alumina by a fly ash one-step acid dissolution method after adsorption impurity removal by resin and chemical precipitation impurity removal by an advanced purification medicament; the deep purification agent comprises any one or combination of more of zirconium chloride, zirconium hydroxide, zirconium oxychloride octahydrate, zirconium sulfate and zirconium carbonate;
(2) roasting
Mixing the purified impurity-removed filter cake treated in the step (1) with solid alkali, and roasting to obtain a roasted product;
(3) removing impurities by water immersion
Adding the roasted product obtained in the step (3) into water for leaching, filtering, and washing a filter cake to obtain a washing liquid and a solid substance;
(4) acid leaching dissolution
Adding the solid matter obtained in the step (3) into hydrochloric acid for a dissolution reaction to obtain slurry;
(5) concentrated crystallization
Filtering the slurry obtained in the step (4), and concentrating and crystallizing the filtrate to obtain crystals, namely the regenerated deep purification medicament; wherein the content of the first and second substances,
in the step (2), the roasting time is 30-105 min;
the step (1) of removing impurities from the pickle liquor in the process of producing alumina by using the fly ash one-step acid dissolution method through resin adsorption refers to the step of removing iron and calcium from the pickle liquor in the process of producing alumina by using the fly ash one-step acid dissolution method through iron removal resin and calcium removal resin, wherein the liquid obtained after removing impurities through resin adsorption is a calcium removal refined liquid.
2. The method according to claim 1, wherein in the step (1), when the calcium removal refined solution is subjected to chemical precipitation and impurity removal by a deep purification agent, the addition amount of the deep purification agent is 0.0031-0.0062mol/L based on zirconium ions.
3. The method as claimed in claim 1, wherein the calcination temperature in step (2) is 600-1200 ℃.
4. The method according to any one of claims 1 to 3, wherein in the step (2), the mass ratio of the purified impurity-removed filter cake after the treatment of the step (1) to the solid alkali is 1 (1.1-2).
5. The method according to claim 4, wherein in the step (2), the solid base is any one or more of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
6. The method according to any one of claims 1 to 3 and 5, wherein in the step (3), the leaching time is 30 to 60 min.
7. The method according to claim 6, wherein in the step (3), the leaching is performed with deionized water or purified water.
8. The method according to any one of claims 1 to 3, 5 and 7, wherein in the step (3), the washing employs a multistage counter-current washing.
9. The method according to claim 8, wherein in the step (3), the washing is washing with deionized water or purified water.
10. The method according to any one of claims 1 to 3, 5, 7 and 9, wherein in the step (4), the dissolution temperature is 60 to 110 ℃ and the dissolution time is 15 to 60 min.
11. The method according to any one of claims 1 to 3, 5, 7 and 9, wherein the concentration of the hydrochloric acid in the step (4) is 24 to 31 wt%.
12. The method according to any one of claims 1 to 3, 5, 7 and 9, wherein the treatment temperature of the concentrated crystallization in the step (5) is 95 to 110 ℃.
13. The method according to any one of claims 1 to 3, 5, 7 and 9, wherein in the step (5), the filtration is performed by plate-and-frame pressure filtration.
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