CN112919801B - A method for preparing arsenic-containing borosilicate glass by treating arsenic solid waste - Google Patents
A method for preparing arsenic-containing borosilicate glass by treating arsenic solid waste Download PDFInfo
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The invention relates to a method for preparing arsenic-containing borosilicate glass by treating arsenic-containing solid waste, which is to prepare the arsenic-containing solid waste into mixed-valence arsenate by a purification process, take the mixed-valence arsenate and silicon dioxide as main glass raw materials, uniformly mix the raw materials, heat and melt the raw materials together, and then cool and solidify the raw materials to prepare the arsenic-containing borosilicate glass of transparent or milky glass; in the glass raw material, the content of silicon dioxide is 60-80% and the content of mixed-valence arsenate is 2-20% by mass fraction. The precipitation amount of the prepared arsenic-containing borosilicate glass is detected according to the GB19778-2005 standard, and the precipitation amount of arsenic is less than or equal to 0.02mg/dm2(ii) a Detecting the arsenic precipitation amount to be less than or equal to 0.24mg/L according to a GB/T5086.1 standard method; the method can effectively treat the solid waste of the nonferrous metal, realizes recycling, reduces the influence on the environment, is more environment-friendly and has low cost, and compared with other borosilicate glasses containing arsenic, the prepared borosilicate glass containing arsenic has the advantages of transparency, good heat resistance, excellent chemical stability and extremely low arsenic precipitation amount.
Description
Technical Field
The invention belongs to the technical field of arsenic-containing solid waste treatment, and relates to a method for preparing arsenic-containing borosilicate glass by treating arsenic-containing solid waste.
Background
A large amount of arsenic-containing residue is produced in mining, smelting, chemical engineering and other processes. Arsenic slag generated in non-ferrous metal industry per year in China is more than 300 million tons/year, and original arsenic can be recovered As2O3The sodium antimonate is used as the glass clarifying agent for removing bubbles, and the sodium antimonate is used as the glass clarifying agent instead based on the toxicity, so most of the arsenic-containing residues generated at present are disposed in a stacking or simple curing landfill mode, have great environmental risk and cause the waste of arsenic resources. At present, arsenic in the smelting industry is almost not used as a metal arsenic product, but the metal arsenic is very limited in utilization and is very easy to oxidize into a virulent arsenic oxide, so that the arsenic oxide is difficult to store. The glass ampoule is filled with argon or vacuumized for sale, which is also the main reason that the arsenic-containing solid waste is difficult to treat at present.
At present, relevant researches on arsenic include solidification of ceramics such as cement and sludge, the solidification measure hardly reaches the national standard of HJ298, and researches or reports on glass solidification are related, but ferrite or phosphate and the like are adopted, for example, in patent 201680073830.4, glass containing 13.2-26.9% of Fe by mass fraction is disclosed. Because the glass is boron-free and contains iron, the glass is dark black glass, has large expansion coefficient and is easy to crystallize, on one hand, the precipitation amount of arsenic is difficult to reduce, and only solid waste burying can be carried out; patent 201811448997.1 discloses a glass containing 30-50% arsenic, which is a dark black glass because arsenic is easily phase-separated in silicate glass, and only 20-40% of silica can be added when the content is so high, and 5-15% of iron oxide is introduced, and the silica content is low, the chemical stability is poor, and the solid waste precipitation amount is relatively high.
Therefore, the research on the arsenic-containing borosilicate glass which has high chemical stability, lower arsenic precipitation amount, high transparency and good heat resistance and can be secondarily applied has very important significance.
Disclosure of Invention
Aiming at the problems in the prior art, in particular to the technical problems that the arsenic precipitation amount is high after the arsenic-containing solid waste is treated and the arsenic is only buried but not reused in the prior art, the method for preparing the arsenic-containing borosilicate glass by treating the arsenic-containing solid waste is provided. The invention provides a method for preparing arsenic-containing borosilicate glass from arsenic in arsenic-containing smelting residue, which solves the problem of recovering arsenic in the smelting residue.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing borosilicate glass containing arsenic by treating arsenic solid waste comprises the steps of preparing arsenic-containing solid waste into mixed-valence arsenate by a purification process, uniformly mixing the mixed-valence arsenate and silicon dioxide serving as main glass raw materials, heating, melting uniformly, cooling and solidifying to obtain the borosilicate glass containing arsenic of transparent or milky glass;
the mixed-valence arsenate is arsenate and/or arsenite;
in the glass raw material, the content of silicon dioxide is 60-80% and the content of mixed-valence arsenate is 2-20% by mass fraction.
As a preferred technical scheme:
the method for preparing the borosilicate glass containing arsenic by treating the arsenic solid waste comprises the steps of preparing a mixed-valence arsenate from sodium arsenate and/or sodium arsenite or potassium arsenate and/or potassium arsenite;
the mixed-valence arsenate is prepared by separating and purifying arsenic-containing nonferrous metal solid waste, and the specific steps are as follows:
a: according to the difference of arsenic content of solid waste containing arsenic non-ferrous metal, carrying out alkaline leaching on the solid waste containing arsenic non-ferrous metal for 3-8 hours at normal temperature-50 ℃ by using a sodium hydroxide solution or a potassium hydroxide solution with the mass concentration of 5-20%, adding an oxidant (hydrogen peroxide, potassium permanganate and the like), and proportionally adding a transition liquid according to theoretical conversion demand to control the valence state of arsenic so as to obtain a soaking liquid;
b: filtering the soaking solution to obtain a transition solution and insoluble recyclable nonferrous metal residues;
c: evaporating and crystallizing the transition liquid to obtain mixed-valence arsenate;
the method for preparing the arsenic-containing borosilicate glass by treating the arsenic solid waste comprises the steps of mixing a valence arsenate with a valence of calcium arsenate and/or calcium arsenite, or magnesium arsenate and/or magnesium arsenite, or barium arsenate and/or barium arsenite;
the mixed-valence arsenate is prepared by separating and purifying arsenic-containing nonferrous metal solid waste, and the specific steps are as follows:
s1: according to the difference of arsenic content of solid waste containing arsenic non-ferrous metal, carrying out alkaline leaching on the solid waste containing arsenic non-ferrous metal for 3-8 hours at normal temperature-50 ℃ by using a sodium hydroxide solution with the mass concentration of 5-20%, adding an oxidant (hydrogen peroxide, potassium permanganate and the like), and proportionally adding the oxidant into a transition liquid according to theoretical conversion demand to control the valence state of arsenic so as to obtain a soaking liquid;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable nonferrous metal residues;
s3: adding a saturated alkaline hydroxide solution into the transition liquid, treating for 3-6 hours at 60-70 ℃, filtering and separating to obtain a mixed-valence arsenate precipitate and a mixed solution of the mixed-valence arsenate precipitate and sodium hydroxide, filtering, and recovering to obtain a mixed-valence arsenate and a sodium hydroxide filtrate; the hydroxide solution is calcium hydroxide solution, magnesium hydroxide solution or barium hydroxide solution. Preferably, calcium arsenate/calcium arsenite is used as the arsenic enrichment carrier, and compared with sodium arsenate, calcium arsenate and calcium arsenite have lower water solubility, lower volatility and lower corresponding toxicity. Meanwhile, the calcium carbonate is obtained by enriching with slaked lime water, and the corresponding preparation cost is lower. Compared with magnesium arsenate, the magnesium arsenate has high preparation difficulty and high cost, and is not beneficial to industrial production.
The method for preparing the borosilicate glass containing arsenic by treating the arsenic solid waste has the advantages that As in the mixed-valence arsenate2O3And/or As2O5The content of (A) is 30-72%.
In the method for preparing the arsenic-containing borosilicate glass by arsenic solid waste treatment, the sodium hydroxide filtrate can be returned to S1 for reuse.
According to the method for preparing the borosilicate glass containing arsenic by treating the arsenic solid waste, the process of cooling and solidifying after heating and melting uniformly comprises the following steps: melting the alloy at 1400-1550 ℃ for 2-3 hours, and annealing at 500-580 ℃ for 2-10 hours.
According to the method for preparing the arsenic-containing borosilicate glass by treating the arsenic solid waste, considering the volatilization of the arsenate with mixed valence, when the glass is heated and melted, the cold top melting process of the all-electric furnace is adopted, the tin dioxide electrode is used for heating the glass internally, the temperature at the top of the glass melting furnace is controlled to be not higher than 200 ℃, and the volatilization of the arsenic-containing material is prevented.
The arsenic-containing borosilicate glass is matched with the full electric furnace cold top process to be prepared, so that the arsenic-containing borosilicate glass has better benefits.
According to the invention, the adopted heating equipment is a glass all-electric melting furnace, the corresponding tin dioxide ceramic electrode is used as a heating body and is arranged at the bottom or the side part of the furnace body, the material is heated by directly utilizing the Joule heat generated by the resistance of high-temperature glass liquid, so that the temperature in the furnace is up to 1350-1500 ℃, the arsenic oxide is solidified in the glass after the corresponding raw material is melted in a heating temperature range, the material descends along with the melting top of the material, and the newly added material enables the charge level temperature to be stably controlled to fluctuate in a 100-200 ℃ range, the charge level temperature is low, arsenate is not volatilized, no combustion waste gas is generated, and the environment is completely up to the standard. Compared with other conventional glass melting furnaces, the material surface flame heating mode is carried out by adopting fuel oil or natural gas and the like, when the material is heated to the temperature, the arsenic-containing material is extremely easy to volatilize, the problem of flying of powder is easily caused, and the environment is not facilitated.
According to the method for preparing the arsenic-containing borosilicate glass by arsenic solid waste treatment, the glass raw materials comprise the following components in percentage by mass: 60-80% of silicon dioxide, 0.1-20% of boric acid, 5-20% of soda ash, 0-10% of potassium carbonate, 0-3% of aluminum hydroxide and 2-20% of mixed-valence arsenate.
According to the method for preparing the arsenic-containing borosilicate glass by arsenic solid waste treatment, the arsenic-containing borosilicate glass is detected according to the GB19778-2(ii) a According to GBThe arsenic precipitation amount detected by the standard method of/T5086.1 is less than or equal to 0.24mg/L and is far lower than 5mg/L of national standard HJ 298.
The method for preparing the arsenic-containing borosilicate glass by arsenic solid waste treatment has the thermal shock resistance>110 ℃ (GB 35598--6～75×10-6/° c; the transmittance of the arsenic-containing borosilicate glass reaches 90%, and the acid and alkali resistance is good.
The principle of the invention is as follows:
the mixed-valence arsenate adopted by the invention is directly obtained by separating and enriching the arsenic-containing non-ferrous metal solid waste, and can effectively solve the recovery problem in smelting non-ferrous metals. Meanwhile, in the step of separating mixed-valence arsenate from the arsenic-containing non-ferrous metal solid waste, the arsenic is dissolved in the corresponding soaking solution by using a dilute sodium hydroxide/potassium solution, and then the non-ferrous metal solid waste and the transition solution are obtained through solid-liquid separation, so that the corresponding non-ferrous metal can be recovered; meanwhile, saturated hydroxide solution such as hydrated lime and the like is added into corresponding transition liquid to replace mixed-valence arsenate precipitate, and the mixed-valence arsenate precipitate is filtered and then conveyed to vitrification production for solidification. In this way, the transition liquid is regenerated after being added with the saturated hydroxide solution such as slaked lime and the like, so as to obtain the sodium hydroxide solution, the sodium hydroxide solution can be recycled to the step S1, the saturated hydroxide solution such as slaked lime and the like is adopted, and the sodium hydroxide can be recycled, so that the whole process is low in cost, the corresponding non-ferrous metals and mixed-valence arsenate can be recycled, and the solid waste of the non-ferrous metals can be effectively treated.
Moreover, the invention adopts a glass component system with good chemical stability, particularly the silicon dioxide content is high, the chemical stability is good, on one hand, the arsenic-containing borosilicate glass of the invention has high chemical stability, and on the other hand, higher arsenic content can be fixed, because the arsenic belongs to the fifth main group element, the solubility is lower in a silicate glass system, and the phase separation is easy. According to the invention, by introducing elements such as boron, sodium and the like and through the structural recombination of the glass network intermediate and the modifying body, the arsenic concentration can be improved, the structure of the glass network body is very stable, and the arsenic is difficult to migrate out of the silicon-oxygen tetrahedral structure of the glass, so that the arsenic precipitation amount of the arsenic-containing borosilicate glass is low;
meanwhile, ions with crystallization and coloring, such as metal oxides of iron, manganese, copper and the like, are avoided from being used in the glass raw materials, so that the prepared arsenic-containing borosilicate glass has high transparency, and a borosilicate system glass component is adopted, so that on one hand, the high-boron borosilicate glass has very good heat resistance and very good chemical stability;
the arsenic-containing borosilicate glass in the prior art has high arsenic precipitation amount, and the precipitation amount of more than 5mg/L is harmful solid waste according to the related solid waste requirements, so that secondary application cannot be carried out.
Advantageous effects
(1) According to the preparation method of the arsenic-containing borosilicate glass, the mixed-valence arsenate is adopted, and the mixed-valence arsenate is separated from the residues of the nonferrous metals for preparation, so that the solid waste of the nonferrous metals can be effectively treated, the recycling is realized, the influence on the environment is reduced, and the preparation method is more environment-friendly and has low cost;
(2) compared with other arsenic-containing borosilicate glasses, the arsenic-containing borosilicate glass has the advantages of transparency, good heat resistance, excellent chemical stability and extremely low arsenic precipitation amount, can be treated as common solid waste like common glass, and is preferably used in decorative glass.
Drawings
FIG. 1 is an SEM photograph of an arsenic-containing borosilicate glass produced in example 3.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparation of calcium arsenate and calcium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 7%) containing the arsenic non-ferrous metal by using a sodium hydroxide solution with the mass concentration of 5% at 25 ℃ for 6 hours, and adding hydrogen peroxide with the concentration of 50% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: adding saturated calcium hydroxide solution into the transition liquid, treating at 60 deg.C for 6 hr, filtering and separating to obtain precipitate of calcium arsenate and calcium arsenite and its mixed solution with sodium hydroxide, filtering, and recovering to obtain precipitate and sodium hydroxide filtrate.
The obtained precipitate is calcium arsenate and calcium arsenite, wherein, As2O3And As2O5The sum of the contents of (A) and (B) is 52% (As)2O3/(As2O3+As2O5) 0.95) and the mass concentration of the sodium hydroxide filtrate is 0.2 wt%, the concentration can be increased by evaporating water and then returned to S1 for reuse.
(2) Uniformly mixing 5% of the precipitate prepared in the step (1), 80% of silicon dioxide, 8% of boric acid, 5% of soda ash, 1% of potassium carbonate and 1% of aluminum hydroxide by mass fraction, melting at 1550 ℃ for 2 hours by adopting an all-electric furnace cold top melting process, and annealing at 580 ℃ for 10 hours to prepare the arsenic-containing borosilicate glass, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is utilized to internally heat, and the top temperature of a glass melting furnace is controlled to be 150 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>120 ℃ (GB 35598--6The arsenic-containing borosilicate glass has the transmittance of 90.3 percent and good acid and alkali resistance, can be used in decorative glass, and has the arsenic precipitation amount of 0.02mg/dm according to the detection of the GB19778-2005 standard2(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.6 according to the detection of the GB/T5086.1 standard method45mg/L。
Example 2
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparation of barium arsenate and barium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 11%) containing the arsenic non-ferrous metal by using a sodium hydroxide solution with the mass concentration of 6% at 35 ℃ for 6 hours, and adding hydrogen peroxide with the concentration of 35% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: and adding a saturated barium hydroxide solution into the transition liquid, treating for 6 hours at 65 ℃, filtering and separating to obtain precipitates of barium arsenate and barium arsenite and a mixed solution of the precipitates and the sodium hydroxide, filtering, and recovering to obtain a precipitate and a sodium hydroxide filtrate.
The obtained precipitate is barium arsenate and barium arsenite, wherein, As2O3And As2O5The sum of the contents of (A) and (B) is 30% (As)2O3/(As2O3+As2O5) 0.82) and the mass concentration of the sodium hydroxide filtrate is 0.5 wt%, the concentration can be increased by evaporating water and then returned to S1 for reuse.
(2) Uniformly mixing 10% of the precipitate prepared in the step (1), 60% of silicon dioxide, 8% of boric acid, 12% of soda ash and 10% of potassium carbonate by mass, melting at 1400 ℃ for 3 hours by adopting an all-electric furnace cold top melting process, and annealing at 500 ℃ for 3 hours to prepare the borosilicate glass containing arsenic, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is used for heating internally, and the top temperature of a glass melting furnace is controlled to be 160 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>110 ℃ (GB 35598--6The arsenic-containing borosilicate glass has the transmittance of 90.5 percent and good acid and alkali resistance, can be used in decorative glass, and has the arsenic precipitation amount of 0 when detected according to the GB19778-2005 standard.02mg/dm2(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.81mg/L according to the detection of a GB/T5086.1 standard method.
Example 3
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparation of calcium arsenate and calcium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 13%) containing the arsenic non-ferrous metal by using a sodium hydroxide solution with the mass concentration of 9% at 45 ℃ for 3 hours, and adding hydrogen peroxide with the concentration of 10% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: adding saturated calcium hydroxide solution into the transition liquid, treating at 68 deg.C for 3 hr, filtering to obtain precipitate of calcium arsenate and calcium arsenite and its mixed solution with sodium hydroxide, filtering, and recovering to obtain precipitate and sodium hydroxide filtrate.
The obtained precipitate is calcium arsenate and calcium arsenite, wherein, As2O3And As2O5The sum of the contents of (A) is 54% (As)2O3/(As2O3+As2O5) 0.43) and the mass concentration of the sodium hydroxide filtrate was 0.8 wt%, the concentration was increased by evaporating water and the filtrate was returned to S1 for reuse.
(2) Uniformly mixing 12% of the precipitate prepared in the step (1), 62% of silicon dioxide, 0.1% of boric acid, 20% of soda ash, 5% of potassium carbonate and 0.9% of aluminum hydroxide by mass fraction, melting at 1450 ℃ for 3 hours by adopting an all-electric furnace cold top melting process, and annealing at 520 ℃ for 5 hours to prepare the arsenic-containing borosilicate glass, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is used for internal heating, and the top temperature of a glass melting furnace is controlled to be 180 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>110 ℃ (GB 35598--6Per DEG C, the transmittance of the arsenic-containing borosilicate glass is 90.8 percent, and the glass is resistant to acid and alkaliIs good, can be used in decorative glass, and has an arsenic precipitation amount of 0.01mg/dm according to the detection of GB19778-20052(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.56mg/L according to the detection of a GB/T5086.1 standard method. When the borosilicate glass containing arsenic is subjected to microscope test, as shown in figure 1, the phase separation of arsenic oxide in the glass is very small and is only 10-20 nm as seen from the microstructure of the glass, the glass has good transparency, and the formed glass has very good stability.
Example 4
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparing sodium arsenate and sodium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 18%) containing the arsenic non-ferrous metal by using a sodium hydroxide solution with the mass concentration of 12% at 45 ℃ for 6 hours, and adding hydrogen peroxide with the concentration of 30% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: directly heating, evaporating and crystallizing in the transition liquid to obtain the precipitate of sodium arsenate and sodium arsenite.
In the obtained precipitate of sodium arsenate and sodium arsenite, As2O3And As2O5The sum of the contents of (A) is 72% (As)2O3/(As2O3+As2O5) 0.6).
(2) Uniformly mixing 10% of the precipitate of the sodium arsenate and the sodium arsenite prepared in the step (1), 62% of silicon dioxide, 20% of boric acid, 4% of soda ash, 3% of potassium carbonate and 1% of aluminum hydroxide by mass, then adopting an all-electric furnace cold top melting process, melting at 1480 ℃ for 3 hours, and annealing at 560 ℃ for 6 hours to prepare the arsenic-containing glass, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is used for internal heating, and the top temperature of a glass melting furnace is controlled to be 185 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>130 ℃ (GB 35598-Has an expansion coefficient of 65X 10-6The arsenic-containing borosilicate glass has the transmittance of 90.5 percent and good acid and alkali resistance, can be used in decorative glass, and has the arsenic precipitation amount of 0.004mg/dm according to the detection of the GB19778-2005 standard2(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.31mg/L according to the detection of a GB/T5086.1 standard method.
Example 5
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparation of potassium arsenate and potassium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 20%) containing the arsenic non-ferrous metal by using a potassium hydroxide solution with the mass concentration of 15% at 45 ℃ for 8 hours, and adding potassium permanganate with the concentration of 15% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: evaporating and crystallizing the transition liquid to obtain the precipitate of potassium arsenate and potassium arsenite.
In the obtained precipitate of potassium arsenate and potassium arsenite, As2O3And As2O5The sum of the contents of (A) is 67% (As)2O3/(As2O3+As2O5) 0.96).
(2) Uniformly mixing 15% of the precipitate of the potassium arsenate and the potassium arsenite prepared in the step (1), 65.5% of silicon dioxide, 10% of boric acid, 8% of soda ash, 1% of potassium carbonate and 0.5% of aluminum hydroxide by mass, adopting an all-electric furnace cold top melting process, melting at 1520 ℃ for 3 hours, and annealing at 570 ℃ for 3 hours to prepare the borosilicate glass containing arsenic, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is used for internal heating, and the top temperature of a glass melting furnace is controlled to be 190 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>120 ℃ (GB 35598--6The glass has a permeability of 90.1% at/° C, is good in acid and alkali resistance, and can be used for decorative glassIn the method, the arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.003mg/dm according to the detection of GB19778-20052(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.05mg/L according to the detection of a GB/T5086.1 standard method.
Example 6
A method for preparing arsenic-containing borosilicate glass by arsenic solid waste treatment comprises the following steps:
(1) preparation of magnesium arsenate and magnesium arsenite:
s1: performing alkaline leaching on solid waste (with arsenic content of 32%) containing the arsenic non-ferrous metal by using a sodium hydroxide solution with the mass concentration of 50% at 50 ℃ for 10 hours, and adding potassium permanganate with the concentration of 5% for oxidation treatment to obtain a soaking solution;
s2: filtering the soaking solution to obtain a transition solution and insoluble recyclable non-ferrous metal solid waste;
s3: adding saturated magnesium hydroxide solution into the transition liquid, treating at 70 deg.C for 3 hr, filtering, separating to obtain precipitate of magnesium arsenate and magnesium arsenite and mixed solution of the precipitate and sodium hydroxide, filtering, recovering to obtain precipitate, and filtering with sodium hydroxide.
The obtained precipitate is magnesium arsenate and magnesium arsenite, wherein, As2O3And As2O5The sum of the contents of (A) is 62% (As)2O3/(As2O3+As2O5) 0.16) and the sodium hydroxide filtrate has a mass concentration of 3 wt%, and the concentration can be increased by evaporating water and then returned to S1 for reuse.
(2) Uniformly mixing 20% of the precipitate prepared in the step (1), 60% of silicon dioxide, 8% of boric acid, 10% of soda ash and 2% of aluminum hydroxide by mass, melting at 1520 ℃ for 2 hours by adopting an all-electric furnace cold top melting process, and annealing at 580 ℃ for 9 hours to prepare the arsenic-containing borosilicate glass, wherein in the all-electric furnace cold top melting process, a tin dioxide electrode is utilized to internally heat, and the top temperature of a glass melting furnace is controlled to be 185 ℃;
thermal shock resistance of the prepared arsenic-containing borosilicate glass>110 ℃ (GB 35598--6The arsenic-containing borosilicate glass has the transmittance of 90.2 percent and good acid and alkali resistance, can be used in decorative glass, and has the arsenic precipitation amount of 0.002mg/dm according to the detection of the GB19778-2005 standard2(ii) a The arsenic precipitation amount of the arsenic-containing borosilicate glass is 0.24mg/L according to the detection of a GB/T5086.1 standard method.
In the preparation of arsenate and/or arsenite in the invention, because the valence states of arsenate and arsenite are easy to be mutually converted, the invention can also adopt the situation that all arsenate or all arsenite is used on the premise of not changing the content of the main raw material of the invention, and the corresponding technical effect is still within the scope claimed by the invention.
Claims (8)
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| CN102247967A (en) * | 2010-05-18 | 2011-11-23 | 上海复拓环境技术有限公司 | Harmless treatment process for arsenic-containing waste dangerous chemicals |
| CN102965517A (en) * | 2012-12-03 | 2013-03-13 | 中南大学 | Treatment method for vitrifying arsenic-alkali residue |
| CN108368564A (en) * | 2015-12-23 | 2018-08-03 | 三菱综合材料株式会社 | The fixing means and firming body containing arsenic glass of arsenic |
| CN110282640A (en) * | 2019-07-05 | 2019-09-27 | 长沙紫宸科技开发有限公司 | A method of by arsenic alkaline slag extraction and separation resource utilization |
| CN110938742A (en) * | 2019-10-25 | 2020-03-31 | 江苏理工学院 | Method for recovering and preparing sodium arsenate and metal gallium from gallium arsenide waste residues |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060217585A1 (en) * | 2005-03-28 | 2006-09-28 | Forrester Keith E | Method for stabilization of arsenic bearing waste or material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102247967A (en) * | 2010-05-18 | 2011-11-23 | 上海复拓环境技术有限公司 | Harmless treatment process for arsenic-containing waste dangerous chemicals |
| CN102965517A (en) * | 2012-12-03 | 2013-03-13 | 中南大学 | Treatment method for vitrifying arsenic-alkali residue |
| CN108368564A (en) * | 2015-12-23 | 2018-08-03 | 三菱综合材料株式会社 | The fixing means and firming body containing arsenic glass of arsenic |
| CN110282640A (en) * | 2019-07-05 | 2019-09-27 | 长沙紫宸科技开发有限公司 | A method of by arsenic alkaline slag extraction and separation resource utilization |
| CN110938742A (en) * | 2019-10-25 | 2020-03-31 | 江苏理工学院 | Method for recovering and preparing sodium arsenate and metal gallium from gallium arsenide waste residues |
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