CN113307298B - Method for producing high-purity scandium oxide from scandium oxide concentrate - Google Patents
Method for producing high-purity scandium oxide from scandium oxide concentrate Download PDFInfo
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- CN113307298B CN113307298B CN202110772539.9A CN202110772539A CN113307298B CN 113307298 B CN113307298 B CN 113307298B CN 202110772539 A CN202110772539 A CN 202110772539A CN 113307298 B CN113307298 B CN 113307298B
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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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/212—Scandium oxides or hydroxides
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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
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for producing high-purity scandium oxide from scandium oxide concentrate, which belongs to the technical field of preparation methods of high-purity metal scandium, and comprises the steps of dissolving scandium oxide concentrate by sulfuric acid, adjusting pH value by sodium hydroxide, hydrolyzing to remove impurities, adding mandelic acid, precipitating double salt of sulfate, back extracting by potassium hydroxide, dissolving by hydrochloric acid and precipitating by oxalic acid, and finally roasting to obtain high-purity scandium oxide. Has positive influence on improving the purity of scandium oxide.
Description
Technical Field
The invention belongs to the technical field of preparation methods of high-purity metal scandium, and relates to a method for producing high-purity scandium oxide from a scandium oxide concentrate.
Background
Scandium is known as a strategic element in the new century, is widely applied to the fields of national defense, aerospace, nuclear technology, laser, electronics, metallurgy, chemical engineering, glass, computer power supply, superconduction, medicine and the like, and has limited scandium resources on the earth.
The compounds used today for the purification of scandium have a rather well established process scheme. Since scandium is the least basic of the hydroxide than yttrium and lanthanides, the rare earth element mischmetal containing scandium, when transferred into solution after treatment and treated with ammonia, will precipitate scandium hydroxide first, so that it can be separated from the rare earth element relatively easily using the "fractional precipitation" method. The other method is to separate by using 'fractional decomposition' of nitrate, and scandium nitrate is most easily decomposed, so that the purpose of separating scandium can be achieved. Further, the comprehensive recovery of associated scandium from uranium, thorium, tungsten, tin, and other deposits is one of the important sources of scandium. The raw materials adopted in the existing preparation method of high-purity scandium metal need high-purity raw materials, so that the prepared scandium metal has high purity, the cost of the raw materials is high, the step precipitation method comprises more and more complicated steps, and the loss in the process is serious, so that a method for efficiently and economically producing high-purity scandium oxide by using a scandium oxide concentrate needs to be developed.
Disclosure of Invention
The invention aims to provide a method for producing high-purity scandium oxide from a scandium oxide concentrate, and solves the technical problems mentioned in the background technology.
The purpose of the invention can be realized by the following technical scheme:
a process for producing high purity scandium oxide from a scandium oxide concentrate, comprising the steps of:
step A1, adding 75-80% by mass of sulfuric acid into the scandium oxide concentrate, stirring and dissolving, adding deionized water and a modified flocculant, standing for 1-2h, filtering, adding sodium hydroxide into the filtrate to adjust the pH value to 1.5-3, adding mandelic acid, boiling, and performing suction filtration to obtain clear liquid a;
step A2, adding sulfate into the clear liquid a, stirring uniformly, standing, filtering to obtain a precipitate a, adding 2-3mol/L NaOH solution into the precipitate a, mixing for 35-45min, and filtering to obtain a precipitate b;
and step A3, adding 6mol/L hydrochloric acid solution into the precipitate b, stirring for dissolving, adjusting the pH value to 1.5-2.5, heating to 60-90 ℃, adding oxalic acid, reacting for 30-60min, filtering, drying a filter cake, and calcining in an electric heating furnace at 800-900 ℃ for 3.5-4h to obtain the high-purity scandium oxide.
Further, in the step A1, the using amount ratio of the scandium oxide concentrate, the sulfuric acid and the deionized water is 10-12 g: 5-8 mL: 10-15mL, the dosage of the modified flocculant is 10-15% of the scandium oxide enrichment substance, and the dosage of the mandelic acid is 5-10% of the scandium oxide enrichment substance.
Further, in the step A2, the sulfate is one or more of sodium sulfate, potassium sulfate and aluminum sulfate, and is mixed according to any proportion.
Furthermore, the dosage of the sulfate in the step A2 is 15-20% of the mass of the clear liquid a, and the dosage of the NaOH solution is 10.5-13.5 times of the mass of the precipitate a.
Further, the amount of oxalic acid used in the step A3 is 70-80% of the mass of the precipitate b.
The modified flocculant is prepared by the following steps:
step S1, adding acrylamide and epoxy chloropropane into a three-neck flask, heating to 60 ℃ and reacting for 5-6h to obtain an intermediate 1;
the reaction process is as follows:
step S2, adding concentrated sulfuric acid with the mass fraction of 98% into a three-neck flask, adding 4- (4-methylphenyl) phenol under the ice bath condition, heating to 60 ℃ for reaction for 1 hour, heating to 80 ℃ for reaction for 3 hours, heating to 90 ℃ for reaction for 3 hours, cooling to room temperature, sequentially adding acetonitrile and dichloromethane, filtering, and discarding the filtrate to obtain an intermediate 2;
the reaction process is as follows:
step S3, adding the intermediate 2, sodium hydroxide and deionized water into a three-neck flask, heating to 70 ℃, uniformly stirring, adding potassium permanganate, heating to 90 ℃, reacting for 9 hours, cooling to room temperature, adding 12mol/L hydrochloric acid solution, reacting for 30-50min, performing suction filtration, and drying a filter cake at 60-70 ℃ to constant weight to obtain an intermediate 3;
the reaction process is as follows:
step S4, adding the intermediate 3 and an isopropanol solution of sodium hydroxide into a three-neck flask, heating to 40-45 ℃, reacting for 3-4h, and carrying out reduced pressure distillation to obtain an intermediate 4;
the reaction process is as follows:
step S5, adding the intermediate 4, absolute ethyl alcohol and sodium hydroxide into a three-neck flask, stirring and dissolving, adding the intermediate 1, heating to 80-90 ℃, reacting for 13-15h, cooling to room temperature, performing suction filtration, washing a filter cake with deionized water for 2-3 times, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 5;
the reaction process is as follows:
and step S6, adding acrylamide, the intermediate 5 and deionized water into a three-neck flask, stirring and dissolving, adding ammonia water with the mass fraction of 30% to adjust the pH value to 7.8-8, adding azobisisobutyronitrile, Span-20 and EDTA, and carrying out polymerization reaction at the temperature of 8-10 ℃ for 6-7h to obtain the modified flocculant.
The reaction process is as follows:
further, in step S1, the molar ratio of acrylamide to epichlorohydrin is 1: 1.
further, the using amount ratio of the concentrated sulfuric acid to the 4- (4-methylphenyl) phenol in the step S2 is 30.3-31.2 mL: 9.7-9.9 g.
Further, in the step S3, the dosage ratio of the intermediate 2, sodium hydroxide, deionized water, potassium permanganate, and hydrochloric acid solution is 7.2-7.4 g: 0.7-0.9 g: 73.3-75.4 mL: 12.2-12.5 g: 34.5-35.6 mL.
Further, the dosage ratio of the intermediate 3 and the isopropanol solution of sodium hydroxide in the step S4 is 5.7-5.9 g: 47.6-48.2mL, wherein the dosage ratio of the sodium hydroxide to the isopropanol in the isopropanol solution of the sodium hydroxide is 0.5-0.8 g: 45 mL.
Further, the dosage ratio of the intermediate 4, the absolute ethyl alcohol, the sodium hydroxide and the intermediate 1 in the step S5 is 0.15-0.17 mol: 80-85 mL: 0.11-0.12 mol: 0.15-0.17 mol.
Further, in step S6, the dosage ratio of acrylamide, intermediate 5, deionized water, azobisisobutyronitrile, Span-20, and EDTA is 2.3-2.5 g: 2.1-2.4 g: 10-12 mL: 0.07-0.09 g: 0.12-0.14 g: 0.21-0.24 g.
The invention has the beneficial effects that:
the invention provides a method for producing high-purity scandium oxide from a scandium oxide concentrate, which comprises the steps of dissolving the scandium oxide concentrate by sulfuric acid, adjusting pH value by sodium hydroxide to hydrolyze and remove impurities, adding mandelic acid and double salt precipitation of sulfate, performing back extraction by potassium hydroxide, dissolving by hydrochloric acid and precipitating by oxalic acid, and finally roasting to obtain high-purity scandium oxide.
Secondly, the invention adopts a pure chemical method, avoids adopting oxygen-containing organic matters (P350) and nitrogen-containing organic matters (N235), thereby reducing the cost of environmental protection treatment, and is more environment-friendly, wherein both P350 and N235 are expensive extracting agents, the cost of the traditional production method is higher, and particularly the price of P350 reaches 35 ten thousand yuan/ton. The chemical reagents adopted by the method are common chemical reagents and are low in price.
Thirdly, the core of the invention is the double-salt precipitation of sulfate, because scandium ions and sulfate can generate the double-salt precipitation of sulfate, monovalent ions, divalent ions such as calcium, manganese, ferrous iron and the like can not generate precipitation, and most trivalent ions such as Ti3+、Fe3+Quadrivalent ions, anions and the like do not generate double-salt precipitation with sulfate, thereby effectively realizing the separation of scandium and other impurities.
Fourthly, the other core technology of the invention is sulfuric acid dissolution and sodium hydroxide pH value adjustment for hydrolysis for impurity removal, compared with the traditional hydrochloric acid dissolution for impurity removal, the invention contains a large amount of sodium sulfate, the sodium sulfate and rare earth ion impurities form complex salt precipitation, and scandium sulfate ions and sodium sulfate are difficult to form scandium sulfate sodium precipitation, thereby achieving the purpose of effectively removing the rare earth impurities, and the invention can also remove most of zirconium ions due to the addition of mandelic acid.
Fifth, the present invention is lower in cost than the conventional method, and only has a half of the purification cost of the conventional method.
And sixthly, adding a modified flocculant to carry out primary treatment on the acid solution of the scandium oxide concentrate, wherein compared with an inorganic flocculant, the modified flocculant belongs to an organic polymer flocculant, and inorganic impurities are not introduced actually, wherein effective functional groups can strongly adsorb fine particles, a bridging effect is formed between the fine particles, and the fine particles in the solution are effectively condensed, so that the flocculation purpose is achieved, and importantly, hydrophilic group sulfonic groups are introduced to freely form chain, annular and other structures, so that the adsorption surface area is increased, and the excellent flocculation purpose is realized.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The modified flocculant is prepared by the following steps:
step S1, adding acrylamide and epichlorohydrin into a three-neck flask, heating to 60 ℃ and reacting for 5h to obtain an intermediate 1, wherein the molar ratio of the acrylamide to the epichlorohydrin is 1: 1;
step S2, adding 30.3mL of 98 mass percent concentrated sulfuric acid into a three-neck flask, adding 9.7g of 4- (4-methylphenyl) phenol under an ice bath condition, heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 3h, heating to 90 ℃ for reaction for 3h, cooling to room temperature, sequentially adding acetonitrile and dichloromethane, filtering, and discarding filtrate to obtain an intermediate 2;
step S3, adding 7.2g of intermediate 2, 0.7g of sodium hydroxide and 73.3mL of deionized water into a three-neck flask, heating to 70 ℃, uniformly stirring, adding 12.2g of potassium permanganate, heating to 90 ℃, reacting for 9 hours, cooling to room temperature, adding 34.5mL of 12mol/L hydrochloric acid solution, reacting for 30 minutes, carrying out suction filtration, and drying a filter cake at 60 ℃ to constant weight to obtain an intermediate 3;
step S4, adding 5.7g of intermediate 3 and 47.6mL of isopropanol solution of sodium hydroxide into a three-neck flask, heating to 40 ℃ for reaction for 3h, and carrying out reduced pressure distillation to obtain an intermediate 4, wherein the dosage ratio of sodium hydroxide to isopropanol in the isopropanol solution of sodium hydroxide is 0.5 g: 45 mL;
step S5, adding 0.15mol of intermediate 4, 80mL of absolute ethyl alcohol and 0.11mol of sodium hydroxide into a three-neck flask, stirring and dissolving, adding 0.15mol of intermediate 1, heating to 80 ℃, reacting for 13h, cooling to room temperature, performing suction filtration, washing a filter cake with deionized water for 2 times, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 5;
step S6, adding 2.3g of acrylamide, 2.1g of intermediate 5 and 10mL of deionized water into a three-neck flask, stirring and dissolving, adding ammonia water with the mass fraction of 30% to adjust the pH value to 7.8, adding 0.07g of azobisisobutyronitrile, 0.12g of Span-20 and 0.21g of EDTA, and carrying out polymerization reaction at 8 ℃ for 6h to obtain the modified flocculant.
Example 2
The modified flocculant is prepared by the following steps:
step S1, adding acrylamide and epichlorohydrin into a three-neck flask, heating to 60 ℃ and reacting for 5h to obtain an intermediate 1, wherein the molar ratio of the acrylamide to the epichlorohydrin is 1: 1;
step S2, adding 30.8mL of 98 mass percent concentrated sulfuric acid into a three-neck flask, adding 9.8g of 4- (4-methylphenyl) phenol under an ice bath condition, heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 3h, heating to 90 ℃ for reaction for 3h, cooling to room temperature, sequentially adding acetonitrile and dichloromethane, filtering, and discarding filtrate to obtain an intermediate 2;
step S3, adding 7.3g of intermediate 2, 0.8g of sodium hydroxide and 74.1mL of deionized water into a three-neck flask, heating to 70 ℃, uniformly stirring, adding 12.4g of potassium permanganate, heating to 90 ℃, reacting for 9 hours, cooling to room temperature, adding 34.9mL of 12mol/L hydrochloric acid solution, reacting for 40 minutes, performing suction filtration, and drying a filter cake at 65 ℃ to constant weight to obtain an intermediate 3;
step S4, adding 5.8g of intermediate 3 and 47.9mL of isopropanol solution of sodium hydroxide into a three-neck flask, heating to 43 ℃ for reaction for 3h, and carrying out reduced pressure distillation to obtain an intermediate 4, wherein the dosage ratio of sodium hydroxide to isopropanol in the isopropanol solution of sodium hydroxide is 0.65 g: 45 mL;
step S5, adding 0.16mol of intermediate 4, 83mL of absolute ethyl alcohol and 0.11mol of sodium hydroxide into a three-neck flask, stirring and dissolving, adding 0.16mol of intermediate 1, heating to 85 ℃, reacting for 14h, cooling to room temperature, performing suction filtration, washing a filter cake with deionized water for 2 times, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 5;
step S6, adding 2.4g of acrylamide, 2.2g of intermediate 5 and 11mL of deionized water into a three-neck flask, stirring and dissolving, adding ammonia water with the mass fraction of 30% to adjust the pH value to 7.9, adding 0.08g of azobisisobutyronitrile, 0.13g of Span-20 and 0.22g of EDTA, and carrying out polymerization reaction at 9 ℃ for 6h to obtain the modified flocculant.
Example 3
The modified flocculant is prepared by the following steps:
step S1, adding acrylamide and epichlorohydrin into a three-neck flask, heating to 60 ℃ and reacting for 6h to obtain an intermediate 1, wherein the molar ratio of the acrylamide to the epichlorohydrin is 1: 1;
step S2, adding 31.2mL of 98 mass percent concentrated sulfuric acid into a three-neck flask, adding 9.9g of 4- (4-methylphenyl) phenol under an ice bath condition, heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 3h, heating to 90 ℃ for reaction for 3h, cooling to room temperature, sequentially adding acetonitrile and dichloromethane, filtering, and discarding filtrate to obtain an intermediate 2;
step S3, adding 7.4g of intermediate 2, 0.9g of sodium hydroxide and 75.4mL of deionized water into a three-neck flask, heating to 70 ℃, uniformly stirring, adding 12.5g of potassium permanganate, heating to 90 ℃, reacting for 9 hours, cooling to room temperature, adding 35.6mL of 12mol/L hydrochloric acid solution, reacting for 50 minutes, carrying out suction filtration, and drying a filter cake at 70 ℃ to constant weight to obtain an intermediate 3;
step S4, adding 5.9g of intermediate 3 and 48.2mL of isopropanol solution of sodium hydroxide into a three-neck flask, heating to 45 ℃ for reaction for 4h, and carrying out reduced pressure distillation to obtain an intermediate 4, wherein the dosage ratio of sodium hydroxide to isopropanol in the isopropanol solution of sodium hydroxide is 0.8 g: 45 mL;
step S5, adding 0.17mol of intermediate 4, 85mL of absolute ethyl alcohol and 0.12mol of sodium hydroxide into a three-neck flask, stirring and dissolving, adding 0.17mol of intermediate 1, heating to 90 ℃, reacting for 15h, cooling to room temperature, performing suction filtration, washing a filter cake with deionized water for 3 times, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 5;
step S6, adding 2.5g of acrylamide, 2.4g of intermediate 5 and 12mL of deionized water into a three-neck flask, stirring and dissolving, adding ammonia water with the mass fraction of 30% to adjust the pH value to 8, adding 0.09g of azodiisobutyronitrile, 0.14g of Span-20 and 0.24g of EDTA, and carrying out polymerization reaction at 10 ℃ for 7h to obtain the modified flocculant.
Example 4
A process for producing high purity scandium oxide from a scandium oxide concentrate, comprising the steps of:
step A1, adding 5mL of sulfuric acid with the mass fraction of 75% into 10g of scandium oxide concentrate, stirring and dissolving, adding 10mL of deionized water and the modified flocculant prepared in the embodiment 1, standing for 1h, filtering, adding sodium hydroxide into filtrate to adjust the pH value to 1.5, adding mandelic acid, boiling, and performing suction filtration to obtain clear liquid a, wherein the dosage of the modified flocculant is 10% of the mass of the scandium oxide concentrate, and the dosage of the mandelic acid is 5% of the mass of the scandium oxide concentrate;
step A2, adding sulfate into the clear liquid a, stirring uniformly, standing, filtering to obtain a precipitate a, adding 2mol/L NaOH solution into the precipitate a, mixing for 35min, and filtering to obtain a precipitate b, wherein the use amount of the sulfate is 15% of the mass of the clear liquid a, the use amount of the NaOH solution is 10.5 times of the mass of the precipitate a, and the sulfate is sodium sulfate and potassium sulfate in a mass ratio of 1: 1, mixing to obtain the product;
and step A3, adding 6mol/L hydrochloric acid solution into the precipitate b, stirring for dissolving, adjusting the pH to 1.5, heating to 60 ℃, adding oxalic acid, reacting for 30min, filtering, drying a filter cake, and calcining in an electric heating furnace at 800 ℃ for 3.5h to obtain high-purity scandium oxide, wherein the using amount of the oxalic acid is 70% of the mass of the precipitate b.
Example 5
A process for producing high purity scandium oxide from a scandium oxide concentrate, comprising the steps of:
step A1, adding 6mL of sulfuric acid with the mass fraction of 78% into 11g of scandium oxide concentrate, stirring and dissolving, adding 12mL of deionized water and the modified flocculant prepared in the embodiment 2, standing for 1h, filtering, adding sodium hydroxide into the filtrate to adjust the pH value to 2, adding mandelic acid, and boiling to obtain clear liquid a, wherein the dosage of the modified flocculant is 13% of the mass of the scandium oxide concentrate, and the dosage of the mandelic acid is 6% of the mass of the scandium oxide concentrate;
step A2, adding sulfate into the clear liquid a, stirring uniformly, standing, filtering to obtain a precipitate a, adding 2mol/L NaOH solution into the precipitate a, mixing for 40min, and filtering to obtain a precipitate b, wherein the use amount of the sulfate is 17% of the mass of the clear liquid a, the use amount of the NaOH solution is 12.6 times of the mass of the precipitate a, and the sulfate is sodium sulfate and aluminum sulfate in a mass ratio of 2: 1, mixing to obtain the product;
and step A3, adding 6mol/L hydrochloric acid solution into the precipitate b, stirring for dissolving, adjusting the pH to 2, heating to 75 ℃, adding oxalic acid, reacting for 40min, filtering, drying a filter cake, and calcining in an electric heating furnace at 850 ℃ for 3.5h to obtain high-purity scandium oxide, wherein the using amount of the oxalic acid is 75% of the mass of the precipitate b.
Example 6
A process for producing high purity scandium oxide from a scandium oxide concentrate, comprising the steps of:
step A1, adding 8mL of sulfuric acid with the mass fraction of 80% into 12g of scandium oxide concentrate, stirring and dissolving, adding 15mL of deionized water and the modified flocculant prepared in the embodiment 3, standing for 2h, filtering, adding sodium hydroxide into filtrate to adjust the pH value to 3, adding mandelic acid, boiling, and performing suction filtration to obtain clear liquid a, wherein the dosage of the modified flocculant is 15% of the mass of the scandium oxide concentrate, and the dosage of the mandelic acid is 10% of the mass of the scandium oxide concentrate;
step A2, adding sulfate into the clear liquid a, stirring uniformly, standing, filtering to obtain a precipitate a, adding a 3mol/L NaOH solution into the precipitate a, mixing for 45min, and filtering to obtain a precipitate b, wherein the use amount of the sulfate is 20% of the mass of the clear liquid a, the use amount of the NaOH solution is 13.5 times of the mass of the precipitate a, and the sulfate is sodium sulfate and potassium sulfate in a mass ratio of 3: 1, mixing to obtain the product;
and step A3, adding 6mol/L hydrochloric acid solution into the precipitate b, stirring for dissolving, adjusting the pH to 2.5, heating to 90 ℃, adding oxalic acid, reacting for 60min, filtering, drying a filter cake, and calcining in an electrothermal furnace at 900 ℃ for 4h to obtain high-purity scandium oxide, wherein the using amount of the oxalic acid is 80% of the mass of the precipitate b.
Comparative example 1
The high temperature acid leaching disclosed in chinese patent CN104120267A relates to example 1 in the method of extracting high purity scandium oxide from titanium white waste acid and bayer process red mud.
Comparative example 2
Comparative example 2 process for producing high purity scandium oxide referring to example 4, except that no modified flocculant was added.
Comparative example 3
Comparative example 3 process for producing high purity scandium oxide referring to example 4, except that the modified flocculant was replaced with a polyacrylamide flocculant.
The scandium oxide purity of examples 4 to 6 and comparative examples 1 to 3 and the flocculation effect of the modified flocculant on the acid solution of the scandium oxide concentrate were evaluated by first adding an equal amount of flocculant sample to the acid solution of the scandium oxide concentrate, stirring at a rotation speed of 300r/min for 30s, standing for 10min, observing the size of the formed flocs, measuring the transmittance of the supernatant at a distance of 3cm from the liquid surface, measuring the transmittance with a type 722 spectrophotometer, measuring the transmittance at a measurement wavelength of 660nm using a 1.0cm cuvette and deionized water as a reference, and finding the results in table 1:
TABLE 1
As can be seen from Table 1, compared with comparative examples 1-3, the scandium oxide prepared in examples 4-6 has better purity, and the modified flocculant has good flocculation performance, plays a role of 'adsorption bridging', rapidly enlarges flocs to be beneficial to flocculation and sedimentation, and has a positive effect on improving the purity of the scandium oxide.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. A method for producing high purity scandium oxide from a scandium oxide concentrate, comprising the steps of:
step A1, adding sulfuric acid into the scandium oxide concentrate, stirring and dissolving, adding deionized water and a modified flocculant, standing for 1-2h, filtering, adding sodium hydroxide into the filtrate to adjust the pH value to 1.5-3, adding mandelic acid, boiling, and performing suction filtration to obtain clear liquid a;
step A2, adding sulfate into the clear liquid a, stirring uniformly, standing, filtering to obtain a precipitate a, adding NaOH solution into the precipitate a, mixing for 35-45min, and filtering to obtain a precipitate b;
step A3, adding a hydrochloric acid solution into the precipitate b, stirring for dissolving, adjusting the pH value to 1.5-2.5, heating to 60-90 ℃, adding oxalic acid, reacting for 30-60min, filtering, drying a filter cake, and then putting the filter cake into an electric heating furnace for calcining for 3.5-4h to obtain high-purity scandium oxide;
the modified flocculant is prepared by the following steps:
step S1, mixing acrylamide and epichlorohydrin, heating to 60 ℃ and reacting for 5-6h to obtain an intermediate 1;
step S2, adding concentrated sulfuric acid into a three-neck flask, adding 4- (4-methylphenyl) phenol under an ice bath condition, heating to 60 ℃ for reaction for 1h, heating to 80 ℃ for reaction for 3h, heating to 90 ℃ for reaction for 3h, cooling to room temperature, adding acetonitrile and dichloromethane, filtering, and discarding the filtrate to obtain an intermediate 2;
step S3, adding the intermediate 2, sodium hydroxide and deionized water into a three-neck flask, heating to 70 ℃, uniformly stirring, adding potassium permanganate, heating to 90 ℃, reacting for 9 hours, cooling to room temperature, adding a hydrochloric acid solution, reacting for 30-50min, performing suction filtration, and drying a filter cake at 60-70 ℃ to constant weight to obtain an intermediate 3;
step S4, adding the intermediate 3 and an isopropanol solution of sodium hydroxide into a three-neck flask, heating to 40-45 ℃, reacting for 3-4h, and carrying out reduced pressure distillation to obtain an intermediate 4;
step S5, stirring and dissolving the intermediate 4, absolute ethyl alcohol and sodium hydroxide, adding the intermediate 1, heating to 80-90 ℃, reacting for 13-15h, cooling to room temperature, performing suction filtration, washing and recrystallizing a filter cake to obtain an intermediate 5;
and step S6, stirring and dissolving acrylamide, the intermediate 5 and deionized water, adding ammonia water to adjust the pH value to 7.8-8, adding azobisisobutyronitrile, Span-20 and EDTA, and carrying out polymerization reaction at the temperature of 8-10 ℃ for 6-7h to obtain the modified flocculant.
2. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: in the step A2, the sulfate is one or more of sodium sulfate, potassium sulfate and aluminum sulfate which are mixed according to any proportion.
3. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: in the step S1, the mol ratio of the acrylamide to the epichlorohydrin is 1: 1.
4. a method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: the dosage ratio of the concentrated sulfuric acid to the 4- (4-methylphenyl) phenol in the step S2 is 30.3-31.2 mL: 9.7-9.9 g.
5. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: in the step S3, the dosage ratio of the intermediate 2, sodium hydroxide, deionized water, potassium permanganate and hydrochloric acid solution is 7.2-7.4 g: 0.7-0.9 g: 73.3-75.4 mL: 12.2-12.5 g: 34.5-35.6 mL.
6. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: the dosage ratio of the intermediate 3 to the isopropanol solution of the sodium hydroxide in the step S4 is 5.7-5.9 g: 47.6-48.2mL, wherein the dosage ratio of the sodium hydroxide to the isopropanol in the isopropanol solution of the sodium hydroxide is 0.5-0.8 g: 45 mL.
7. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: the dosage ratio of the intermediate 4, the absolute ethyl alcohol, the sodium hydroxide and the intermediate 1 in the step S5 is 0.15-0.17 mol: 80-85 mL: 0.11-0.12 mol: 0.15-0.17 mol.
8. A method for producing high purity scandium oxide from a scandium oxide concentrate according to claim 1, further including: in the step S6, the dosage ratio of the acrylamide, the intermediate 5, the deionized water, the azobisisobutyronitrile, the Span-20 and the EDTA is 2.3-2.5 g: 2.1-2.4 g: 10-12 mL: 0.07-0.09 g: 0.12-0.14 g: 0.21-0.24 g.
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