CN109179486B - Preparation method of thallium chloride based on interface effect - Google Patents
Preparation method of thallium chloride based on interface effect Download PDFInfo
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- CN109179486B CN109179486B CN201811049605.4A CN201811049605A CN109179486B CN 109179486 B CN109179486 B CN 109179486B CN 201811049605 A CN201811049605 A CN 201811049605A CN 109179486 B CN109179486 B CN 109179486B
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Abstract
The invention discloses a preparation method of thallium chloride based on interface effect, belonging to the technical field of metal compound preparation‑Extracting Tl from the diluted acid+Adding Tl to bromine water+Oxidation to Tl3+(ii) a Hydrochloric acid modified activated carbon adsorption Tl3+The ammonium oxalate solution is reduced from the hydrochloric acid modified activated carbon and the Tl is eluted+To obtain Tl+Eluting the solution; to Tl+Chloride is added into the eluent, and the mixture is stirred and heated to precipitate TlCl crystals. The preparation method can shorten the extraction time and prepare purer thallium chloride.
Description
Technical Field
The invention belongs to the technical field of metal compound preparation, and particularly relates to a preparation method of thallium chloride based on an interface effect.
Background
The wide valence band (4eV) of the thallium chloride crystal is about 2-4 times of that of a common insulating crystal (1-2eV), the band gap (3eV) is only 1/3 of that of the common insulating crystal (about 10eV), and the thallium chloride crystal is a good semiconductor material and is widely used in the fields of safety detection and imaging. Thallium chloride is also a chemical raw material for preparing thallium reagents, and various thallium reagents with higher purity can be prepared by taking thallium chloride as the raw material.
The Chinese invention patent 'a method for preparing thallium chloride by using lead-zinc ore smelting wastewater as a raw material' (the application number is 201410023981.1, and the application date is 2014, 1, 18): the method comprises the following steps of 1: stirring at a ratio of 500, adding lime for precipitation, adsorption and coprecipitation to prepare bottom mud, and extracting thallium from wastewater to prepare thallium chloride, but the method has some defects: lead-zinc ore is produced from multi-metal ore, the heavy metal content in the lead-zinc ore waste residue and smelting wastewater is high, the obtained thallium chloride has more impurities, and the purification is complex.
Therefore, it is necessary to design a highly efficient method for preparing thallium chloride, which can shorten the extraction time and prepare more pure thallium chloride.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of thallium chloride based on interface effect, which can shorten extraction time and prepare more pure thallium chloride.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing thallium chloride based on interface action includes using sulfuric acid ash, dilute acid and F-Extracting Tl from the diluted acid+Adding Tl to bromine water+Oxidation to Tl3+(ii) a Hydrochloric acid modified activated carbon adsorption Tl3+The ammonium oxalate solution is reduced from the hydrochloric acid modified activated carbon and the Tl is eluted+To obtain Tl+Eluting the solution; to Tl+Adding chloride into the eluent, stirring and heating to separate out TlCl crystals; the sulfuric acid ash contains Fe2O3、Fe3O4、TlF、TlF3、Tl2F4、Tl4F6、Tl3F5And Tl3F7The pH value of the dilute acid is 3-4; wherein Tl represents thallium, F represents fluorine, Fe represents iron, O represents oxygen, and Cl represents chlorine.
As an improvement of the technical scheme, the preparation method sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, adding dilute acid into the sulfuric acid ash, stirring and oscillating for 4-6h, and filtering to obtain a filtrate I and a filter residue I;
s2) adding dilute acid into the filter residue I, and repeating the operation of the step S1) for at least 3 times to obtain a filtrate II and a filter residue II;
s3) adding F into the filter residue II-Stirring and standing the dilute acid, and filtering to obtain filtrate III;
s4) combining the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 30-60min, and filtering to obtain an activated carbon mixture;
s6) rinsing the activated carbon with a heated ammonium oxalate solution in several portionsCollecting the eluate to obtain Tl+Eluting the solution;
s7) to the Tl+Adding chloride into the eluent, stirring, heating and concentrating to obtain a thallium extracting solution II; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
At step S1), dilute acid (such as HCl, HNO) with pH value of 3.0-4.0 is added into the sulphuric acid ash3And H2SO4) Stirring and oscillating, and hydrolyzing the iron oxide:
3Fe2O3+2H2O+7H+→Fe(OH)2++5Fe(OH)2 + (1)
2Fe3O4+H2O+7H+→2Fe(OH)++2Fe(OH)2 0+Fe(OH)2++Fe(OH)2 + (2)
TlF、TlF3and the intermediate product is a heterogeneous system, and TlF is easy to dissolve (80g/100g H)2O)，TlF3Poorly soluble (deliquescent/H)2O), intermediate Tl2F4(Tl+Tl3+F4)、Tl4F6(Tl3 +Tl3+F6)、Tl3F5(Tl2 +Tl3+F5) And Tl3F7(Tl+Tl2 3+F7) Containing non-coordinating Tl+And Tl3+There is a spontaneous thermodynamic process (Tl)3+/Tl+＝1.25V，Fe3+/Fe2+0.77V); thus, at the solid-liquid interface sulfuric acid ash-solution, solution (liquid phase) -hydrolysate (gel phase), intermediate (solid phase) -hydrolysate (gel phase), and solution (liquid phase) -TlF and TlF are contained3(solid phase) and the like. The interphase interface region has special interfacial reaction activity due to special physicochemical and biochemical properties, and the mass transmission and transformation of the interphase interface region are often the key steps of the whole reaction.
Repeating S1) for at least 3 times, preferably repeating S1) for 3 times in step S2), strengthening the interface process, and further extracting thallium from the sulfuric acid ash;at this time, Fe is present at the interface of solution (liquid phase) -hydrolyzate (gel phase)2+And Fe3+Further hydrolysis:
Fe(OH)++OH-→Fe(OH)2 0 (3)
Fe(OH)2++OH-→Fe(OH)2 + (4)；
at the intermediate (solid phase) -hydrolysate (gel phase) interface: on the one hand, Tl3+/Tl+And Fe3+/Fe2+The couple can spontaneously generate oxidation-reduction reaction; in another aspect, Fe (OH)2 0Two OH of (2)-Reverse drawing to zero charge, Fe2+The electron cloud obviously shifts to two sides, the reaction activity is obviously enhanced, and the electron cloud and an intermediate product quickly generate an oxidation reaction:
Tl2F4(+2e)+2Fe(OH)2 0→2TlF2 -+2Fe(OH)2 + (5)
Tl4F6(+2e)+2Fe(OH)2 0→2TlF2 -+2TlF0+2Fe(OH)2 + (6)
Tl3F5(+2e)+2Fe(OH)2 0→2TlF2 -+TlF3 2-+2Fe(OH)2 + (7)
Tl3F7(+4e)+4Fe(OH)2 0→2TlF3 2-+TlF0+4Fe(OH)2 + (8)；
(5) - (8) formation of Fe (OH)2 +And can continue to perform reduction reaction with the intermediate product to cause Fe (OH)2 0Regeneration (intermediate product fraction Tl+Oxidized):
Tl2F4(-2e)+2Fe(OH)2 +→2TlF3 0+2Fe(OH)2 0 (9)
Tl4F6(-2e)+2Fe(OH)2 +→2TlF3 0+2Tl++2Fe(OH)2 0 (10)
Tl3F5(-2e)+2Fe(OH)2 +→2TlF2 ++TlF0+2Fe(OH)2 0 (11)
Tl3F7(-2e)+2Fe(OH)2 +→2TlF3 0+TlF0+2Fe(OH)2 0 (12)
TlF3 0sensitive to moisture TlF3 0+H2O→Tl(OH)3+HF (13)；
(9) - (13) formation of Fe (OH)2 0The series of reactions (5) to (8) above, followed by the series of reactions (9) to (13) above, continues until the intermediate of the ash is completely dissolved in the form of fluorine-thallium complex.
Fluorine-thallium complex ion dissociation:
TlF0→Tl++F- (14)
TlF2 -→Tl++2F- (15)
TlF3 2-→Tl++3F- (16)
TlF2 +→Tl3++2F- (17)；
tl after dissociation3+Hydrolyzing Tl in the adsorption solution+：
Tl3++OH-→Tl(OH)3 (18)
Tl(OH)3+Tl+→Tl(OH)3-Tl+ (19)；
As is clear from the reactions (13), (18) and (19), Tl in the solution+Is Tl (OH)3Adsorption, as is apparent from reactions (5) to (8), (11) to (12) and (14) to (17), a large amount of F-Entering a solution; thus, in solution (liquid phase) -TlF and TlF3(solid phase) interface, TlF and TlF3Soluble in the form of fluorine-thallium complex:
3TlF+6F-→TlF2 -+TlF3 2-+TlF4 3- (20)
TlF3+F-→TlF4 -(K＝1.3×10-2) (21)；
the fluorine-thallium complex ion formed dissociates again:
TlF4 3-→Tl3++4F- (22)
TlF2 -and TlF3 2-See (15) and (16);
thus far, TlF of heterogeneous system3And intermediates thereof can enter the solution through interfacial reactions.
The Chinese patent application of 'a preparation method of thallium iodide' (application number is 201810264009.1, application date is 2018, 3 and 28 days), the preparation method is carried out by taking sulfuric acid ash, sulfuric acid wastewater and iodide as raw materials, no intermediate product is found at the moment, and the extraction scheme mainly aims at that the sulfuric acid ash contains TlF and TlF3Designed by containing F-Tl of ash slag precipitated by strong acid dissolution and alkali liquor+(ii) a Later researches show that TlF-TlF exists in the sulfuric acid ash3And TlCl-TlCl3The two heterogeneous systems participate in the redox reaction when the strong acid is dissolved, so that the yield is relatively high; however, when the strong acid dissolves, the iron oxide becomes Fe3+And Fe2+In which Fe is dissolved2+Has a reactivity lower than that of Fe (OH)2 0Therefore, the extraction time is long. This point is related to Fe (OH) in the Fenton reaction2 0And H2O2The reaction is very similar, in the Fenton reaction, when the pH is higher<At 3, the ferrous species is mainly Fe2+There are:
Fe2++H2O2→Fe3++OH-+.OH (23)
Fe3++H2O2→Fe2++H++HO2 . (24)
Fe3++HO2 .→Fe2++O2+H+ (25)；
at pH 3-4, ferrousThe hydrolyzed form of the seed is Fe (OH)+And Fe (OH)2 0Wherein Fe (OH)2 0The reactivity of (A) is Fe2+Approximately 10 times of so that.OH and Fe (OH)2 +Can be generated in large quantity, the oxidation capability of the system is obviously enhanced (Lulai and Huchun, 2017), and the reactions (5) to (12) of the invention are isogeny; therefore, the essence of the invention is to utilize: 1) TlF-TlF3Intermediate products of heterogeneous systems with Fe (OH)2 0Fenton-like effect of 2) TlF-TlF3TlF and TlF of heterogeneous system3The thallium of the sulfuric acid ash is extracted by the interface reaction, and the reaction time can be obviously shortened. Because the solubility of TlF is high, the TlF is easy to enter the environment to cause pollution in the ash weathering process, and the invention tries to extract the TlF-TlF to the maximum extent by means of Fenton-like reaction3Thallium in a heterogeneous system prevents the thallium from polluting the environment.
In step S3), adding dilute acid containing fluoride ions to the filter residue ii, desorbing thallium in the filter residue ii, filtering, and keeping filtrate iii:
Tl++F-→TlF0(ΔGf＝-311.8kJmol-1) (26)
TlF0(lgK＝0.1)→Tl++F- (27)。
in step S5), bromine water is added dropwise to the thallium extract I to a slight yellow color, and Tl is added+Total oxidation to Tl3+(ii) a Adding activated carbon modified by hydrochloric acid to enrich thallium in the thallium extracting solution I, and separating and purifying the thallium extracting solution I from a complex matrix:
Tl++Br2→Tl3++2Br- (28)
Tl3++4Cl-→TlCl4 - (29)；
the hydrochloric acid modified activated carbon is prepared by the following method: the activated carbon needs to be dried in a 105 ℃ oven for 2 hours before use, and is rinsed for more than 10 times by 1.5-3.5mol/L hydrochloric acid.
In step S5), bromine water is added dropwise to the thallium extract I to a slight yellow color, and Tl is added+Total oxidation to Tl3+(ii) a Adding activated carbon modified by hydrochloric acid to enrich thallium in the thallium extract ISeparation from complex matrix and purification:
Tl++Br2→Tl3++2Br- (30)
Tl3++4Cl-→TlCl4 - (31)。
in step S6), the activated carbon mixture is repeatedly rinsed with the hot ammonium oxalate solution to elute thallium:
(NH4)2C2O4+TlCl4 -→2(NH4)Cl+2CO2↑+TlCl2 - (32)
in step S7), chlorides (such as NaCl and KCl) are added to the thallium extraction solution ii:
Tl++Cl-→TlCl (33)。
the invention firstly extracts the Tl generated by Fenton-like reaction of sulfuric acid ash+And Tl in sulfuric acid ash+Then oxidized into Tl by bromine water3+Hydrochloric acid modified activated carbon adsorption of Tl3+Eluting with ammonium oxalate solution and eluting with Tl3+Reduction to Tl+To prepare purer TlCl.
As a further improvement of the above technical scheme, in step S1), the weight ratio of the sulfuric acid ash and the dilute acid is 1/15-1/6; in the step S2), the weight ratio of the filter residue I to the dilute acid is 1/15-1/6, and the repetition times are 3 times; the pH value of the dilute acid is 3-4.
As a further improvement of the above technical solution, in step S3), the filter residue ii contains F-The weight ratio of the diluted acid is 1: 1, containing F-In dilute acid of (2) F-Has a concentration of 0.15-0.3mg/L and contains F-The pH value of the diluted acid is 3-4.
As a further improvement of the technical scheme, in the step S5), the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1/150000-1/40000.
As a further improvement of the above technical solution, in step S6), the concentration of ammonium oxalate in the ammonium oxalate solution is 40-60g/L, and the temperature of the ammonium oxalate solution after heating is 50-60 ℃.
As a further improvement of the above technical solution, in step S7), the chloride is potassium chloride, the concentration of potassium chloride in the thallium extract ii is 0.14-0.22mg/ml, and the thallium extract ii and the Tl are+The volume ratio of the eluent is 1/16-1/10.
As a further improvement of the above technical solution, in step S1), the weight ratio of the sulfuric acid ash to the dilute acid is 1/10, and the pH of the dilute acid is 3 to 4;
in the step S2), the weight ratio of the filter residue I to the dilute acid is that the repeated times are 3 times;
in step S3), the filter residue II contains F-Has a weight ratio of 1/10 and contains F-In dilute acid of (2) F-Has a concentration of 0.20mg/L and contains F-The pH value of the diluted acid is 3-4;
in step S5), the weight ratio of the hydrochloric acid-modified activated carbon to the thallium extract i is 1: 80000;
in step S6), the concentration of ammonium oxalate in the ammonium oxalate solution is 50g/L, and the temperature of the ammonium oxalate solution after heating is 50 ℃;
in step S7), the chloride is potassium chloride, and the Tl+The concentration of potassium chloride in the eluent is 0.17mg/ml, and the thallium extract II and the Tl+The volume ratio of the eluent 1/15.
The invention has the beneficial effects that: the invention provides a preparation method of thallium chloride with interface effect, and the invention finds that TlF-TlF3Fenton-like reaction of heterogeneous system for extracting Tl in sulfuric acid ash+Greatly shorten Tl+The extraction time of (3); then oxidizing the mixture into Tl by using bromine water3+Hydrochloric acid modified activated carbon adsorption of Tl3+Eluting with ammonium oxalate solution and eluting with Tl3+Reduction to Tl+To prepare purer TlCl; the raw materials adopted in the preparation method of the thallium chloride are harmful waste and conventional reagents in the sulfuric acid production process, the preparation method is simple, the cost is low, and the method has the beneficial effect of treating waste by waste.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
It should be understood that the terms "reject i", "reject ii", "filtrate i", "filtrate ii" and "filtrate iii", "thallium extract i", "thallium extract ii", etc. are used to describe various information in the present invention, but the information should not be limited to these terms, and these terms are only used to distinguish one type of information from another.
Example 1
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, adding dilute acid into the sulfuric acid ash, stirring and oscillating for 4-6h, and filtering to obtain a filtrate I and a filter residue I;
s2) adding dilute acid into the filter residue I, and repeating the operation of the step S1) for at least 3 times to obtain a filtrate II and a filter residue II;
s3) adding F into the filter residue II-Stirring and standing the dilute acid, and filtering to obtain filtrate III;
s4) combining the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 30-60min, and filtering to obtain an activated carbon mixture;
s6) leaching the activated carbon mixture for multiple times by using heated ammonium oxalate solution, and collecting eluent to obtain Tl+Eluting the solution;
s7) to Tl+Adding chloride into the eluent, stirring, heating and concentrating to obtain a thallium extracting solution II; cooling and drying the thallium extracting solution II to obtain a TlCl crystal;
in the step S1), the weight ratio of the sulfuric acid ash to the dilute acid is 1/15-1/6; in the step S2), the weight ratio of the filter residue I to the dilute acid is 1/15-1/6, and the repetition times are 3 times; the pH value of the diluted acid is 3-4; in step S3), filter residue II is mixed withWith F-The weight ratio of the diluted acid is 1: 1, containing F-In dilute acid of (2) F-Has a concentration of 0.15 to 0.30mg/L and contains F-The pH value of the diluted acid is 3-4; in the step S5), the mass ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1/40000-1/150000; in step S6), the concentration of ammonium oxalate in the ammonium oxalate solution is 40-60g/L, and the temperature of the heated ammonium oxalate solution is 50-60 ℃; in step S7), thallium extract II and Tl+The volume ratio of the eluent is 1/16-1/10.
Preferably, the chloride is potassium chloride, and the concentration of the potassium chloride in the thallium extracting solution II is 0.14-0.22 mg/ml.
Example 2
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, and sieving with a 200-mesh sieve (the particle size of the crushed sulfuric acid ash is less than or equal to 0.08 mm); taking 10kg of crushed sulfuric acid ash, and mixing the following raw materials: liquid weight ratio 1: 6, adding hydrochloric acid with the pH value of 3, stirring and oscillating for 6 hours, and filtering to obtain a filtrate I and a filter residue I;
s2) pressing: liquid weight ratio 1: 6, continuously adding hydrochloric acid with the pH value of 3 into the filter residue I, and repeating the operation of the step S1) for 3 times to obtain a filtrate II and a filter residue II;
s3) pressing: liquid weight ratio 1: 1 adding 0.3mg/L F into filter residue II-And the hydrochloric acid with the pH value of 3 is stirred, kept stand and filtered to obtain filtrate III;
s4) mixing the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 50min, and filtering to obtain an activated carbon mixture; the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1: 90000;
s6) leaching the activated carbon mixture for multiple times by using ammonium oxalate solution with the temperature of 53 ℃, and collecting eluent to obtain Tl+Eluting the solution; the concentration of ammonium oxalate in the ammonium oxalate solution is 52 g/L;
s7) to Tl+Adding potassium chloride and Tl into the eluent+In the eluentThe concentration of potassium chloride is 0.2 mg/mL; stirring, heating and concentrating to obtain thallium extract II, thallium extract II and Tl+The volume ratio of the eluent is 1/10; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
Example 3
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, and sieving with a 200-mesh sieve (the particle size of the crushed sulfuric acid ash is less than or equal to 0.08 mm); taking 10kg of crushed sulfuric acid ash, and mixing the following raw materials: liquid weight ratio 1: 12.5 adding sulfuric acid with the pH value of 3, stirring and oscillating for 6 hours, and filtering to obtain filtrate I and filter residue I;
s2) pressing: liquid specific weight is 1: 12.5, continuously adding sulfuric acid with the pH value of 3 into the filter residue I, and repeating the operation of the step S1) for 3 times to obtain a filtrate II and a filter residue II;
s3) pressing: liquid weight ratio 1: 1 adding 0.15mg/L F into filter residue II-Stirring and standing sulfuric acid with the pH value of 3, and filtering to obtain filtrate III;
s4) mixing the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 50min, and filtering to obtain an activated carbon mixture; the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1: 100000;
s6) leaching the activated carbon mixture for multiple times by using ammonium oxalate solution with the temperature of 50 ℃, and collecting eluent to obtain Tl+Eluting the solution; the concentration of ammonium oxalate in the ammonium oxalate solution is 45 g/L;
s7) to Tl+Adding potassium chloride and Tl into the eluent+The concentration of potassium chloride in the eluent is 0.22 mg/mL; stirring, heating and concentrating to obtain thallium extract II, thallium extract II and Tl+The volume ratio of the eluent is 1/12; and cooling and drying the thallium extracting solution III to obtain the TlCl crystal.
Comparative example 1
This comparative example provides a method for producing thallium chloride, which is different from the production method of example 3 in that: in step S1), 10kg of crushed sulfuric acid ash is taken, and the ratio of solid: liquid weight ratio 1: 5, adding sulfuric acid wastewater with the pH value of 1-2, stirring for 24 hours, and filtering to obtain a thallium extracting solution I; the remaining steps employed example 2 preparation method steps S5) -S7).
In the raw materials adopted in example 3 and comparative example 1, the sulfuric acid ash and the sulfuric acid wastewater come from a cloud floating sulfuric acid plant, the content of thallium in the sulfuric acid wastewater is 0.28mg/kg, the content of thallium in the sulfuric acid ash is 49mg/kg, and the sulfuric acid ash comprises the following components in percentage by weight: fe2O3 38％、Fe3O448% and SiO213 percent. Yield and purity were measured for the thallium chloride crystals prepared in example 3 and comparative example 1, and example 3 prepared 53mg of TlCl crystals and 94% of TlCl crystals, comparative example 1 prepared 27mg of TlCl crystals and 93% of TlCl crystals, and less TlCl crystals were extracted in a short time.
Comparative example 1 adopted in the invention patent of "a method for producing thallium iodide" (application No. 201810264009.1, application date 3/28/2018) of China+Although a small amount of thallium can be introduced into the sulfuric acid wastewater used in the preparation method of comparative example 1, when the pH of the dilute acid in the preparation method of example 3 is 3, the ferrous species of the sulfuric acid ash is Fe (OH)+And Fe (OH)2 0Hydrolyzing and adsorbing F with strong electronegativity-The ferrous species is Fe when the reaction activity is 1-2 compared with the pH value2+The dissolution is obviously enhanced; in addition, in the preparation method of the comparative example 1, when the sulfuric acid waste water is subjected to acidolysis, more coexisting ions are introduced into the sulfuric acid ash and the sulfuric acid waste water, and the thallium chloride with lower purity is prepared in the comparative example 1.
Example 4
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, and sieving with a 200-mesh sieve (the particle size of the crushed sulfuric acid ash is less than or equal to 0.08 mm); taking 10kg of crushed sulfuric acid ash, and mixing the following raw materials: liquid weight ratio 1: 10 adding nitric acid with the pH value of 3.5, stirring and oscillating for 4 hours, and filtering to obtain filtrate I and filter residue I;
s2) pressing: liquid weight ratio 1: 10, continuously adding nitric acid with the pH value of 3.5 into the filter residue I, and repeating the operation of the step S1) for 3 times to obtain a filtrate II and a filter residue II;
s3) pressing: liquid weight ratio 1: 1 adding 0.20mg/L F into filter residue II-Stirring and standing nitric acid with the pH value of 3.5, and filtering to obtain filtrate III;
s4) mixing the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 40min, and filtering to obtain an activated carbon mixture; the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1: 80000;
s6) leaching the activated carbon mixture for multiple times by using ammonium oxalate solution with the temperature of 50 ℃, and collecting eluent to obtain Tl+Eluting the solution; the concentration of ammonium oxalate in the ammonium oxalate solution is 50 g/L;
s7) to Tl+Adding potassium chloride and Tl into the eluent+The concentration of potassium chloride in the eluent is 0.17 mg/mL; stirring, heating and concentrating to obtain thallium extract II, thallium extract II and Tl+The volume ratio of the eluent is 1/15; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
Comparative example 2
This comparative example provides a method for producing thallium chloride, which is different from example production method 5 in that: in step S1), 10kg of crushed sulfuric acid ash is taken, and the ratio of solid: liquid weight ratio 1: 3, adding sulfuric acid wastewater with the pH value of 1-2, stirring for 16h, and filtering to obtain a thallium extracting solution I; the remaining steps employed example 4 preparation method steps S5) to S7).
In the raw materials adopted in example 4 and comparative example 2, the sulfuric acid ash and the sulfuric acid wastewater come from a cloud floating sulfuric acid plant, the content of thallium in the sulfuric acid wastewater is 0.29mg/kg, the content of thallium in the sulfuric acid ash is 40mg/kg, and the sulfuric acid ash comprises the following components in percentage by weight: fe2O3 49％、Fe3O441% and SiO29.5 percent. Yield and purity were measured for the thallium chloride crystals prepared in example 5 and comparative example 2, and example 4 prepared TlCl crystals of49mg of TlCl with a purity of 94%, 9mg of TlCl crystals prepared in comparative example 2 and 93% of TlCl.
Example 5
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, and sieving with a 200-mesh sieve (the particle size of the crushed sulfuric acid ash is less than or equal to 0.08 mm); taking 10kg of crushed sulfuric acid ash, and mixing the following raw materials: liquid ratio is 1: 15 adding sulfuric acid with the pH value of 4, stirring and oscillating for 5 hours, and filtering to obtain filtrate I and filter residue I;
s2) pressing: liquid weight ratio 1: 15, continuously adding sulfuric acid with the pH value of 4 into the filter residue I, and repeating the operation of the step S1) for 3 times to obtain a filtrate II and a filter residue II;
s3) pressing: liquid weight ratio 1: 1 adding 0.25mg/L F into filter residue II-Stirring and standing sulfuric acid with the pH value of 4, and filtering to obtain filtrate III;
s4) mixing the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 40min, and filtering to obtain an activated carbon mixture; the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1: 150000;
s6) leaching the activated carbon mixture for multiple times by using ammonium oxalate solution with the temperature of 60 ℃, and collecting eluent to obtain Tl+Eluting the solution; the concentration of ammonium oxalate in the ammonium oxalate solution is 40 g/L;
s7) to Tl+Adding potassium chloride and Tl into the eluent+The concentration of potassium chloride in the eluent is 0.14 mg/mL; stirring, heating and concentrating to obtain thallium extract II, thallium extract II and Tl+The volume ratio of the eluent is 1/16; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
Comparative example 3
This comparative example provides a method for producing thallium chloride, which is different from example production method 5 in that: in step S1), 10kg of crushed sulfuric acid ash is taken, and the ratio of solid: liquid weight ratio 1: 6, adding sulfuric acid wastewater with the pH value of 1-2, stirring for 20 hours, and filtering to obtain a thallium extracting solution I; the remaining steps employed steps S5) through S7) of the preparation method of example 5.
In the raw materials adopted in example 5 and comparative example 3, the sulfuric acid ash and the sulfuric acid wastewater come from a cloud floating sulfuric acid plant, the content of thallium in the sulfuric acid wastewater is 0.32mg/kg, the content of thallium in the sulfuric acid ash is 51mg/kg, and the sulfuric acid ash comprises the following components in percentage by weight: fe2O3 30％、Fe3O440% and SiO220 percent. Yield and purity were measured for the thallium chloride crystals prepared in example 5 and comparative example 3, and example 5 prepared 39mg of TlCl crystals with a TlCl purity of 93%, and comparative example 3 prepared 27mg of TlCl crystals with a TlCl purity of 92.5%.
Example 6
This example provides a method for preparing interface-based thallium chloride, which sequentially comprises the following steps:
s1) grinding and crushing the sulfuric acid ash, and sieving with a 200-mesh sieve (the particle size of the crushed sulfuric acid ash is less than or equal to 0.08 mm); taking 10kg of crushed sulfuric acid ash, and mixing the following raw materials: liquid weight ratio 1: 10 adding nitric acid with the pH value of 3.5, stirring and oscillating for 4.5h, and filtering to obtain filtrate I and filter residue I;
s2) pressing: liquid weight ratio 1: 10, continuously adding nitric acid with the pH value of 3.5 into the filter residue I, and repeating the operation of the step S1) for 3 times to obtain a filtrate II and a filter residue II;
s3) pressing: liquid weight ratio 1: 1 adding 0.25mg/L F into filter residue II-Stirring and standing nitric acid with the pH value of 3.5, and filtering to obtain filtrate III;
s4) mixing the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding activated carbon modified by hydrochloric acid, stirring for 30min, and filtering to obtain an activated carbon mixture; the weight ratio of the activated carbon modified by hydrochloric acid to the thallium extracting solution I is 1: 40000;
s6) leaching the activated carbon mixture for multiple times by using ammonium oxalate solution with the temperature of 50 ℃, and collecting eluent to obtain Tl+Eluting the solution; the concentration of ammonium oxalate in the ammonium oxalate solution is 60 g/L;
s7) to Tl+Adding potassium chloride and Tl into the eluent+Adding potassium chloride into the eluent to the concentration of 0.16 mg/mL; stirring, heating and concentrating to obtain thallium extract II, thallium extract II and Tl+The volume ratio of the eluent 1/16; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
Comparative example 4
This comparative example provides a method for producing thallium chloride, which is different from example production method 6 in that: in step S1), 10kg of crushed sulfuric acid ash is taken, and the ratio of solid: liquid weight ratio 1: 2, adding sulfuric acid wastewater with the pH value of 1-2, stirring for 18h, and filtering to obtain a thallium extracting solution I; the remaining steps employed steps S5) to S7) of the preparation method of example 6.
In the raw materials adopted in example 6 and comparative example 4, the sulfuric acid ash and the sulfuric acid wastewater come from a cloud floating sulfuric acid plant, the content of thallium in the sulfuric acid wastewater is 0.34mg/kg, the content of thallium in the sulfuric acid ash is 57mg/kg, and the sulfuric acid ash comprises the following components in percentage by weight: fe2O3 33％、Fe3O435% and SiO220 percent. Yield and purity were measured for the thallium chloride crystals prepared in example 6 and comparative example 4, and example 6 prepared 49mg of TlCl crystals with a TlCl purity of 95%, and comparative example 1 prepared 12.5mg of TlCl crystals with a TlCl purity of 93%.
As can be seen from the above, the inventive examples and comparative examples have the same amount of sulfated ash and the same extraction time, since Tl is the same+Due to the difference of the extraction methods, the amount and the purity of the thallium chloride obtained by the method are superior to those of a comparative example.
The invention only shows the yield and purity of the TlCl crystal prepared in the examples 3-6, and other examples of the invention can also achieve the experimental effect similar to the examples 3-6.
Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The preparation method of thallium chloride based on interface action is characterized in that firstly sulfuric acid ash, dilute acid and F-containing-Extracting Tl from the diluted acid+Adding Tl to bromine water+Oxidation to Tl3+(ii) a Hydrochloric acid modified activated carbon adsorption Tl3+The ammonium oxalate solution is reduced from the hydrochloric acid modified activated carbon and the Tl is eluted+To obtain Tl+Eluting the solution; to Tl+Adding chloride into the eluent, stirring and heating to separate out TlCl crystals; the sulfuric acid ash contains Fe2O3、Fe3O4、TlF、TlF3、Tl2F4、Tl4F6、Tl3F5And Tl3F7Said dilute acid and containing F-The pH value of the diluted acid is 3-4; wherein Tl represents thallium, F represents fluorine, Fe represents iron, O represents oxygen, and Cl represents chlorine.
2. The method of claim 1, comprising the steps of, in order:
s1) grinding and crushing the sulfuric acid ash, adding dilute acid into the sulfuric acid ash, stirring and oscillating for 4-6h, and filtering to obtain a filtrate I and a filter residue I;
s2) adding dilute acid into the filter residue I, and repeating the operation of the step S1) for at least 3 times to obtain a filtrate II and a filter residue II;
s3) adding F into the filter residue II-Stirring and standing the dilute acid, and filtering to obtain filtrate III;
s4) combining the filtrate I, the filtrate II and the filtrate III to obtain a thallium extracting solution I;
s5) adding bromine water dropwise into the thallium extracting solution I to be yellowish, adding hydrochloric acid modified activated carbon, stirring for 30-60min, and filtering to obtain an activated carbon mixture;
s6) leaching the activated carbon mixture for multiple times by using heated ammonium oxalate solution, and collecting eluent to obtain Tl+Eluting the solution;
s7) to the Tl+Adding chloride into the eluent, stirring, heating and concentrating to obtain a thallium extracting solution II; and cooling and drying the thallium extracting solution II to obtain the TlCl crystal.
3. The method of claim 2, wherein in step S1), the weight ratio of the sulfuric acid ash to the dilute acid is 1/15-1/6; in the step S2), the weight ratio of the filter residue I to the dilute acid is 1/15-1/6, and the repetition times are 3 times; the pH value of the diluted acid is 3-4.
4. The method according to claim 2, wherein in step S3), the residue II is mixed with the residue F-The weight ratio of the diluted acid is 1: 1, containing F-In dilute acid of (2) F-Has a concentration of 0.15-0.3mg/L and contains F-The pH value of the diluted acid is 3-4.
5. The production method according to claim 2, wherein in step S5), the weight ratio of the hydrochloric acid-modified activated carbon to the thallium extracted solution i is 1/150000 to 1/40000.
6. The method according to claim 2, wherein in step S6), the concentration of ammonium oxalate in the ammonium oxalate solution is 40-60g/L, and the temperature of the ammonium oxalate solution after heating is 50-60 ℃.
7. The method according to claim 2, wherein in step S7), the chloride is potassium chloride, and the Tl is+The concentration of potassium chloride in the eluent is 0.14-0.22mg/ml, and the thallium extract II and the Tl+The volume ratio of the eluent is 1/16-1/10.
8. The method of claim 2, wherein in step S1), the weight ratio of the sulfuric acid ash to the dilute acid is 1/10, and the pH of the dilute acid is 3 to 4;
in the step S2), the weight ratio of the filter residue I to the dilute acid is 1/12.5, and the repetition times are 3 times;
in step S3), the filter residue II contains F-Has a weight ratio of 1/10 and contains F-In dilute acid of (2) F-Has a concentration of 0.20mg/L and contains F-The pH value of the diluted acid is 3-4;
in step S5), the weight ratio of the hydrochloric acid-modified activated carbon to the thallium extract i is 1: 80000;
in step S6), the concentration of ammonium oxalate in the ammonium oxalate solution is 50g/L, and the temperature of the ammonium oxalate solution after heating is 50 ℃;
in step S7), the chloride is potassium chloride, and the Tl+The concentration of potassium chloride in the eluent is 0.17mg/ml, and the thallium extract II and the Tl+The volume ratio of the eluent 1/15.
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