CN110482853B - Method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass and obtained glass - Google Patents
Method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass and obtained glass Download PDFInfo
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- CN110482853B CN110482853B CN201910873324.9A CN201910873324A CN110482853B CN 110482853 B CN110482853 B CN 110482853B CN 201910873324 A CN201910873324 A CN 201910873324A CN 110482853 B CN110482853 B CN 110482853B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Abstract
The invention discloses a method for solidifying toxic metal ions in electroplating wastewater, a method for preparing soda-lime-aluminosilicate glass from gel obtained by the method, and the glass obtained by the method. The method uses electroplating wastewater to provide an acid environment for a reaction system, calcium oxide to adjust the pH value of the reaction system and provide calcium element required for glass preparation, sodium silicate and sodium metaaluminate are subjected to sol-gel reaction to obtain xerogel, and the gel is used for preparing sodium-calcium-aluminosilicate glass, so that toxic metal ions in the electroplating wastewater are solidified. The reaction system is simple, and is carried out at normal temperature, so that the cost is low; xerogel generated by treating wastewater can be used for preparing soda-lime-aluminosilicate glass; the ion leaching amount of the prepared soda-lime-aluminosilicate glass is detected by using the Product Consistency (PCT), and the result shows that the leaching rate of all elements in 7 days is less than 0.0002 g.m‑2·d‑1The effective solidification of the toxic metal ions is realized; the xerogel is recycled, so that solid waste and secondary pollution are avoided.
Description
Technical Field
The invention relates to a method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass and the obtained glass, belonging to the technical field of environment.
Background
Electroplating is widely used in industries such as corrosion prevention and decoration. However, a large amount of waste water is generated by electroplating, wherein toxic metal ions seriously harm water bodies and organisms in the water bodies after being discharged along with the waste water, and can enter human bodies through water circulation and food chains, so that the method brings great harm to the environment and human beings.
After being treated by methods such as precipitation, adsorption and the like, most of the electroplating wastewater is transferred to solid waste, which becomes a secondary pollution source. The solid waste can be used as raw material after being treated by dehydration, drying, crushing and the like, and then is mixed with other raw materials to prepare materials such as glass or ceramics and the like through a high-temperature process, which is one of the ways of avoiding secondary pollution. However, the method is complex in process and limited by the influence of the water treatment process, the composition of the used solid waste generally does not meet the material preparation requirement, a large amount of other raw materials are required to be added, the utilization rate is low, and the practical popularization and application are difficult.
There have been few attempts to recover and convert metal ions in electroplating wastewater into useful resources. For example, patent CN104817272A discloses a method for concentrating metal ions in electroplating wastewater into an adsorbent by using a specially designed adsorbent, and using the adsorbent together with a waste adsorbent as a glass colorant. However, new wastewater is generated again in the preparation process of the adsorbent, the adsorption process is long, the adsorption of metal ions is incomplete, acid radical ions, organic pollutants and the like in the wastewater are difficult to remove, and the wastewater still remains and needs to be further treated.
Disclosure of Invention
In order to solve the technical defects, the invention provides a method for solidifying metal ions in electroplating wastewater into glass.
The invention is realized by the following measures:
the method comprises the steps of firstly removing sulfate radicals in electroplating wastewater, then sequentially adding calcium oxide, sodium metaaluminate and a water glass solution, and completely gelatinizing the wastewater through a sol-gel reaction; the obtained wet gel is simply dried and then directly used as a raw material to prepare the soda-lime-aluminosilicate glass, and toxic metal ions in the waste water can be completely solidified in the glass with high chemical stability.
The method comprises the following specific operation steps:
(1) adding barium nitrate into the electroplating wastewater, and stirring for reaction to remove sulfate radicals in the wastewater;
(2) filtering the precipitate in the step (1) to obtain the primary treated wastewater;
(3) adding calcium oxide into the primarily treated wastewater, and uniformly stirring;
(4) sequentially adding sodium metaaluminate and water glass into the mixed solution obtained in the step (3), and uniformly stirring;
(5) standing until the mixed solution in the step (4) is completely gelatinized to form gel;
(6) aging the gel;
(7) drying to obtain dry gel;
(8) ball milling the dried gel to obtain gel powder;
(9) and heating the gel powder, melting the gel powder at a high temperature under a heat preservation condition, forming and annealing to obtain a glass sample.
The barium nitrate is added in the step (1) until no turbidity is generated after the barium nitrate is added into the wastewater. Taking the copper electroplating wastewater as an example, the sulfur content measured by ICP is 3583.9mg/L, and the addition amount of barium nitrate in each liter of wastewater is 52 g.
The stirring reaction time in the step (1) is 0.5 h.
The addition amount of the calcium oxide in the step (3) is 50 g per liter of wastewater.
The sodium metaaluminate and the water glass in the step (4) are both commercial products, wherein the modulus of the sodium metaaluminate is 3.8; the modulus of the water glass is 3.3, and the volume ratio of the wastewater to the water glass to the sodium metaaluminate is 3:2: 0.08-0.16.
And (4) uniformly stirring in the steps (3) and (4), wherein the time is 10s and 30s respectively.
In the step (5), the standing time is 30-80 min.
The aging time in the step (6) is 1 hour.
The drying temperature in the above step (7) is 100 deg.CoAnd C, drying for 6 h.
In the step (8), the powder granularity after ball milling meets the preparation requirement of the conventional glass; preferably, the powder is sieved through a 100 mesh sieve;
in the above step (9), the temperature increase rate is 5oC/min, temperature 1400oC, the heat preservation time is 2 hours, the annealing temperature is 500oC. The time is 1 h.
Experiments show that when the volume ratio of the wastewater to the sodium metaaluminate is 3: 0-5.49, the wastewater can be completely gelatinized through the steps (1) - (5); wherein, when the volume ratio of the wastewater to the sodium metaaluminate is 3: 0.8-1.6, the obtained xerogel can meet the component requirements of the preparation of the soda-lime-aluminosilicate glass. However, when the volume ratio of the wastewater to the sodium metaaluminate is less than 3:5.49 (i.e., when the amount of the sodium metaaluminate added is increased), the wastewater cannot be completely gelled;
the electroplating wastewater contains acid radical, iron ions, other metal ions and organic matters. For example, the electrolytic copper plating wastewater mainly contains sulfate radicals, iron, copper, sodium, calcium, magnesium ions and the like. After the electroplating wastewater is treated in the steps (1) to (7), toxic ions are all solidified into the xerogel.
The main component of the xerogel powder is SiO by XRF analysis2（48~52%）、Na2O（20~28%）、CaO（16~17%）、Fe2O3(5-6%) and Al2O3(4-7%) by weight. The gel powder can be melted at a lower temperature without adding any other components to obtain the soda-lime-alumina-silica glass. And the gel powder is converted into glass, and simultaneously, all metal ions in the wastewater are solidified in the glass. The ion leaching rate of the glass sample is detected by using the Product Consistency (PCT), and the result shows that the ion leaching rate is less than 0.0002 g.m-2·d-1And the stability is good.
The obtained glass is a brown yellow transparent sample, and the color of the glass is mainly caused by main metal ions (such as iron ions and copper ions) in electroplating wastewater; the density of the glass is 2.6546-2.6568 g/cm3Since the addition of sodium metaaluminate introduces alumina to increase the density of the glass and the introduced sodium oxide causes the density of the glass to decrease, the increase in the addition amount of sodium metaaluminate causes the density of the glass to increase first and then decrease.
The glass obtained is at 5oHeating to 600-976 at C/min rateoC, under the condition of keeping the temperature for 2h, the material has the surface crystallization characteristic, can be used as a sintered glass ceramics and ceramic enamel raw material, and the precipitated crystal is the caldum chabazite (Na)4Ca4（Si6O18)). Therefore, the obtained soda-lime-aluminosilicate glass is also within the protection scope of the invention.
Has the advantages that: the whole process of the invention is carried out at room temperature; the electroplating wastewater is completely gelatinized by adjusting the dosage of the additive, and the obtained gel can be vitrified at a low temperature directly without adding other substances to form high-stability soda-lime-aluminosilicate glass, so that toxic and harmful substances in the wastewater are cured, and the generation of solid wastes is avoided.
Drawings
FIG. 1 surface crystallization photograph of sample of example 2
FIG. 2 is an XRD pattern of surface devitrification of the sample of example 2.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments, which are only used to more clearly illustrate the technical solutions of the present patent, but not to limit the scope of the present invention.
The density of the soda-lime-aluminosilicate glass is detected by adopting a drainage method, and the ion leaching performance of the glass is detected by using a PCT method.
The following are specific examples:
example 1
(1) Adding 52g of barium nitrate into 1L of copper electroplating wastewater, and stirring for reaction for 0.5h to remove sulfate radicals in the wastewater;
(2) filtering the precipitate in the step (1) to obtain the primary treated wastewater;
(3) adding 50 g of calcium oxide into 1L of the wastewater subjected to primary treatment, and stirring for 10 s;
(4) adding 26.7 ml of sodium metaaluminate and 667 ml of water glass into the mixed solution obtained in the step (3) in sequence, and stirring for 30 s;
(5) standing the mixed solution in the step (4) for 80 min, and completely gelatinizing the mixed solution to form gel;
(6) aging the gel for 1 h;
(7)100 oc, drying for 6 hours to obtain xerogel
(8) Ball-milling the xerogel sample, and then sieving the xerogel sample by a 100-mesh sieve to obtain gel powder;
(9) gel powder 5oThe temperature rises to 1400 ℃ at the rate of C/minoC, the heat preservation time is 2 hours, the annealing temperature is 500oAnd C, preserving the heat for 1h to obtain a glass sample.
The gel powder obtained by the above preparation process contains SiO as main ingredient2（48%）、Na2O（24%）、CaO（17%）、Fe2O3(5%) and Al2O3(4%) (weight ratio). The density of the prepared glass sample is 2.6546 g/cm3The leaching amount of the Na-Si-Al-K-Fe element is 1.88 multiplied by 10 respectively through PCT detection-4 g·m-2·d-1、0.15×10-4 g·m-2·d-1、0.61×10-4 g·m-2·d-1、1.80×10-4 g·m-2·d-1、6.27×10-8 g·m-2·d-1。
Example 2
(1) - (3) the same as in example 1;
(4) adding 40 ml of sodium metaaluminate and 667 ml of water glass into the mixed solution obtained in the step (3) in sequence, and stirring for 30 s;
(5) standing the mixed solution in the step (4) for 60 min, and completely gelatinizing the mixed solution to form gel;
(6) examples (9) are the same as in example 1.
The gel powder obtained by the above preparation process has SiO as the main component2（52%）、Na2O（20%）、CaO（16%）、Fe2O3(5%) and Al2O3(6%) (weight ratio), a glass sample was prepared having a density of 2.6568 g/cm3The leaching amount of the Na-Si-Al-K-Fe element is 2.16 multiplied by 10 respectively through PCT detection-4 g·m-2·d-1、0.12×10-4 g·m-2·d-1、0.47×10-4 g·m-2·d-1、0.13×10-4 g·m-2·d-1、1.79×10-8 g·m-2·d-1. Glass warp 600-830oC degree heat treatment, surface crystallization occurs (see fig. 1); precipitating the main crystal phase of the aragonite (Na)4Ca4（Si6O18) (see FIG. 2).
Example 3
(1) - (3) the same as in example 1;
(4) adding 53.3 ml of sodium metaaluminate and 667 ml of water glass into the mixed solution obtained in the step (3) in sequence, and stirring for 30 s;
(5) standing the mixed solution in the step (4) for 30 min, and completely gelatinizing the mixed solution to form gel;
(6) examples (9) are the same as in example 1.
The gel powder obtained by the above preparation process has SiO as the main component2（49%）、Na2O（28%）、CaO（17%）、Fe2O3(6%) and Al2O3(7%) (weight ratio), the density of the prepared glass sample was 2.6547 g/cm3The leaching amount of the Na-Si-Al-K elements is 1.42 multiplied by 10 respectively through PCT detection-4 g·m-2·d-1、0.13×10-4 g·m-2·d-1、0.40×10-4g·m-2·d-1、0.31×10-4 g·m-2·d-1。
Comparative example
(1) - (3) the same as in example 1;
(4) adding 200 ml of sodium metaaluminate and 667 ml of water glass into the mixed solution obtained in the step (3) in sequence, and stirring for 30 s;
(5) standing, wherein the mixed solution cannot be completely gelatinized, the sample contains a large amount of aqueous solution, and metal ions in the wastewater cannot be solidified in gel and glass.
Claims (7)
1. A method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass is characterized by comprising the following steps:
adding barium nitrate into the electroplating wastewater, and stirring for reaction to remove sulfate radicals in the wastewater;
filtering the precipitate in the step (1) to obtain the primary treated wastewater;
adding calcium oxide into the primarily treated wastewater, and uniformly stirring; wherein, the amount of calcium oxide added in each liter of the primarily treated wastewater is 50 g;
sequentially adding sodium metaaluminate and water glass into the mixed solution obtained in the step (3), and uniformly stirring; wherein the volume ratio of the primarily treated wastewater to the water glass is 3:2, and the volume ratio of the primarily treated wastewater to the sodium metaaluminate is 3: 0.08-0.16;
standing until the mixed solution in the step (4) is completely gelatinized to form gel;
aging the gel;
drying to obtain dry gel;
ball milling the dried gel and then sieving the dried gel by a 100-mesh sieve to obtain gel powder;
and heating the gel powder, melting the gel powder at a high temperature under a heat preservation condition, forming and annealing to obtain a glass sample.
2. The method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass according to claim 1, wherein the method comprises the following steps: the barium nitrate is added in the step (1) until no turbidity is generated after the barium nitrate is added into the wastewater.
3. The method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass according to claim 1, wherein the method comprises the following steps: in the step (5), the standing time is 30-80 min.
4. The method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass according to claim 1, wherein the method comprises the following steps: the aging time in the step (6) is 1 h.
5. The method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass according to claim 1, wherein the method comprises the following steps: the drying temperature in the step (7) is 100 ℃, and the time is 6 hours.
6. The method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass according to claim 1, wherein the method comprises the following steps: the temperature increase rate in step (8) was 5oAnd C/min, the temperature is 1400 ℃, the heat preservation time is 2 hours, the annealing temperature is 500 ℃, and the heat preservation time is 1 hour, so that the soda-lime-aluminosilicate glass sample can be obtained.
7. A soda-lime-aluminosilicate glass produced by the method according to any one of claims 1 to 6.
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