CN110590014A - Method for purifying electroplating wastewater and application of obtained xerogel in glass - Google Patents
Method for purifying electroplating wastewater and application of obtained xerogel in glass Download PDFInfo
- Publication number
- CN110590014A CN110590014A CN201910873323.4A CN201910873323A CN110590014A CN 110590014 A CN110590014 A CN 110590014A CN 201910873323 A CN201910873323 A CN 201910873323A CN 110590014 A CN110590014 A CN 110590014A
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- wastewater
- glass
- water
- electroplating wastewater
- xerogel
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C03C1/004—Refining agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
Abstract
The invention discloses a method for treating electroplating wastewater. Firstly, calcium oxide is added into the electroplating wastewater, the pH value is adjusted to a proper range, and then water glass is added to completely gelatinize the wastewater. A large amount of bound water is fixed by the gel, and partial water is recovered during drying of the gel, so that the volume of the waste water is greatly reduced; meanwhile, the pH value and the metal ion content of the recovered water can meet the emission standard; the obtained dry gel can be used as clarifier for colored plate glass and bottle glass.
Description
Technical Field
The invention relates to a treatment method of electroplating wastewater and application of xerogel obtained after treatment in glass, belonging to the technical field of environment.
Background
The main sources of the electroplating wastewater are as follows: cleaning wastewater of a plated part, filtering water for plating solution, waste plating solution and wastewater generated by 'running, overflowing, dripping and leaking' in equipment and production processes; waste water generated by washing plants, workshops and equipment, and the like. The waste water discharged from electroplating plant features many kinds, complex water quality, containing surfactant, additive, cyanide and metal ions of Cu, Zn, Cr, Ni, Pb and Cd.
Electroplating wastewater is an important component of water pollution and has great influence on water quality, aquatic organisms and human health. The purification of electroplating wastewater is a problem which is difficult and urgently needed to be solved in the electroplating industry. The current electroplating wastewater treatment methods comprise an electrolysis method, a precipitation method, an adsorption method, a membrane separation method and the like. The problems of electroplating wastewater treatment include that the wastewater is often subjected to primary treatment in an electroplating plant and then is concentrated in a sewage treatment plant for treatment, so that the wastewater cannot be treated in place at one time; organic pollutants, metal ions, acid radical ions and pH value in the electroplating wastewater can not be treated in one step so that the electroplating wastewater can completely meet the requirements of wastewater treatment, thereby realizing wastewater purification and reaching the standard for discharge or recycling.
Waste residues generated after electroplating wastewater treatment are also a difficult problem in the current wastewater treatment, and generally, the waste residues contain toxic ions and are easy to cause secondary pollution when stored.
Disclosure of Invention
The invention provides a method for treating electroplating wastewater by gelation purification, aiming at solving the defects of the prior art.
The invention is realized by the following measures:
firstly, adding calcium oxide into electroplating wastewater to adjust the pH value of a system to a proper range, and then adding water glass; in a liquid phase system with proper pH, the water glass generates sol-gel reaction, and the wastewater is completely gelatinized. After the gel is dried, a large amount of bound water is fixed, and the discharge of waste water is reduced; meanwhile, impurity ions and the pH value in water evaporated and recovered in the drying process both meet the requirement of direct discharge.
The specific operation steps of the purification method of the acid electroplating wastewater provided by the invention are as follows:
(1) adding a proper amount of calcium oxide into the electroplating wastewater, and uniformly stirring;
(2) adding water glass into the mixed solution and stirring;
(3) standing for a certain time, and completely gelatinizing the mixed solution;
(4) aging the gel;
(5) heating and drying, and recovering water volatilized during drying and residual xerogel.
Further, in the step (1), 0 ~ 20g of calcium oxide was added per liter of wastewater.
Further, the volume ratio of the wastewater to the added water glass in the step (2) is 3:2 ~ 2: 3.
Furthermore, the stirring time in the steps (1) and (2) is only required to be uniformly distributed by calcium oxide and water glass, and the practical stirring time is respectively 10s and 30 s.
Further, the standing time in the step (3) was 4 ~ 50 hours.
Further, the aging time in the step (4) is 1 h.
Further, the drying temperature in the step (5) is 100 DEGoC, drying for 6 h.
Experiments show that as the addition amount of calcium oxide increases, the pH value of the wastewater increases, and the gel time is firstly reduced and then increased. Taking the copper electroplating wastewater as an example, when the calcium oxide is increased from 0 to 10g, the pH of the system is increased from 2.15 to 3.11, and the gel time is shortened from 6 h to 4 h; when the addition amount of calcium oxide is continuously increased to 20g, the pH of the system is increased from 3.11 to 7.59, and the gel time is increased from 4h to 7 h. The amount of water glass added affects the gel time, which increases with increasing water glass addition. Taking the copper electroplating wastewater as an example, when the volume ratio of the copper electroplating wastewater to the water glass is 3:2, the gel time is 6 h, when the volume ratio is 1:1, the gel time is increased to 24 h, and when the addition amount of the water glass is continuously increased until the volume ratio of the copper electroplating wastewater to the water glass is 2:3, the gel time is 50 h.
The electroplating wastewater contains acid radicals, iron ions, other metal ions and organic matters, and the solution is highly acidic. For example, the electrolytic copper plating wastewater mainly contains sulfate radical (10737.17 mg/L), iron (4549.3 mg/L), copper (153.8 mg/L), sodium (163.5 mg/L), calcium (170.1 mg/L), magnesium ion (84.16 mg/L) and the like, and the pH value is 2.15; after the treatment of the steps, most ions are fixed in the gel, and a small amount of harmless ions (such as calcium ions) enter the water recovered after drying.
The water recovered in the gel drying process is detected by ICP, and does not contain acid radical ions, and only contains a small amount of alkali metal and alkaline earth metal ions, so that the pH value of the recovered water is alkalescent, and the content of the metal ions meets the regulation of the comprehensive sewage discharge standard.
The resulting dried gel was analyzed by XRD diffraction at 20 ~ 40oA broad diffraction peak in the range, which is typical of SiO as the sample bulk2An amorphous structure. In addition, Na in the sample appears in the map2SO4Diffraction peaks of the crystalline phase. When less CaO is added, the crystal phase is relatively weak at lower pH values (e.g., 2.15); as the amount of CaO added increases, the pH increases, and the diffraction peak increases, changing significantly with increasing pH. Wherein Na+The sulfur comes from the water glass added in the experimental process and the electroplating wastewater. When calcium oxide is not added, the main components of the xerogel are sodium oxide and silicon oxide; when calcium oxide is added, the main components of the xerogel are calcium oxide, sodium oxide and silicon oxide, and the content of the xerogel is increased along with the increase of the addition amount of the calcium oxide and the water glass. Since the xerogel contains Na2SO4And metal ions from the electroplating wastewater (such as iron and copper ions which are main in the electroplating wastewater) can be used as a clarifying agent for daily glass including colored flat glass and colored bottles and cans, so that the xerogel produced by the electroplating wastewater treatment method is also within the protection scope of the invention.
When the xerogel is used as a clarifying agent for colored glass, the dosage of the xerogel is the same as that of Na required by conventional glass2SO4The amount of calcium oxide, sodium oxide and silica carried by the added xerogel is subtracted from the glass batch (typically about 1 ~ 1.5.5% of the amount of sand in the glass batch).
Has the advantages that: the method provided by the invention can completely gelatinize the wastewater, the volume of the wastewater recovered after drying is greatly reduced, the pH value and the metal ion content of the wastewater meet the discharge requirement, and a new thought is provided for the treatment of electroplating wastewater. The whole wastewater treatment process is simple and efficient, no special equipment such as an adsorption tower is needed, the investment is low, and the cost is low. The waste residue after the wastewater treatment can be fully utilized, thereby saving resources and protecting the environment.
Drawings
FIG. 1 is an XRD pattern of the gel material prepared in example 1.
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.
Analyzing the crystalline phase in the xerogel sample by XRD diffraction; the composition of the xerogel was analyzed by XRF; the moisture content was recovered by ICP analysis.
The following are specific examples:
example 1
(1) 667 ml of water glass is added into 1L of the copper electroplating wastewater and stirred for 30 s;
(2) standing for 6 h, and completely gelatinizing the mixed solution;
(3) aging the gel for 1 h;
（4）100 oand C, heating and drying, and recovering water volatilized during drying and residual xerogel.
The pH value of the water recovered by the process is 8.35, and the water only contains a small amount of sodium calcium silicon barium (1.6729, 1.3186, 0.4251 and 0.4017 mg/L) plasma through ICP detection, thereby meeting the regulation of the comprehensive sewage discharge standard.
The XRD pattern of the xerogel obtained in example 1 is shown in figure 1, and the result shows that the main crystal phase of the sample is Na2SO4Crystalline phase also at 20 ~ 40oIn the range of one SiO2An amorphous diffraction peak; the specific component is SiO2（51.62 %）、Na2O（29.86 %）、SO3（11.06 %）、Fe2O3(6.23%) can be used as a clarifying agent of colored glass according to the conventional glass process.
Example 2
(1) Adding 10g of calcium oxide into 1L of copper electroplating wastewater, and stirring for 10 s;
(2) adding 667 ml of water glass into the mixed solution and stirring for 30 s;
(3) standing for 4h, and completely gelatinizing the mixed solution;
(4) aging the gel for 1 h;
（5）100 oc plusHeat drying and recovering the water evaporated during drying and the remaining xerogel.
The recovered xerogel has a composition of SiO2（62.28 %）、Na2O（20.31 %）、CaO（2.51 %）、Fe2O3（5.01 %）、SO3(7.52%) and can be used as a clarifying agent of colored glass according to the conventional glass process.
Example 3
(1) Adding 20g of calcium oxide into 1L of copper electroplating wastewater, and stirring for 10 s;
(2) adding 667 ml of water glass into the mixed solution and stirring for 30 s;
(3) standing for 7 h, and completely gelatinizing the mixed solution;
(4) aging the gel for 1 h;
（5）100 oand C, heating and drying, and recovering water volatilized during drying and residual xerogel.
Example 4
(1) Adding 1L of water glass into 1L of copper electroplating wastewater, and stirring for 30 s;
(2) standing for 24 h, and completely gelatinizing the mixed solution;
(3) aging the gel for 1 h;
（4）100 oand C, heating and drying, and recovering water volatilized during drying and residual xerogel.
Example 5
(1) Adding 1.5L of water glass into 1L of electroplating wastewater, and stirring for 30 s;
(2) standing for 50 h, and completely gelatinizing the mixed solution;
(3) aging the gel for 1 h;
（4）100 oc, heating and drying, and recovering water volatilized during drying and the remaining xerogel.
Comparative example
(1) Adding 23.33 g of calcium oxide into 1L of copper electroplating wastewater, and stirring for 10 s;
(2) adding 667 ml of water glass into the mixed solution and stirring for 30 s;
(3) and standing, and no gel reaction is generated.
Claims (8)
1. A method for purifying acid electroplating wastewater is characterized by comprising the following steps:
(1) adding a proper amount of calcium oxide into the electroplating wastewater, and uniformly stirring;
(2) adding water glass into the mixed solution, and continuously stirring;
(3) standing for a certain time, and completely gelatinizing the mixed solution;
(4) aging the gel;
(5) heating and drying, and recovering water volatilized during drying and residual xerogel.
2. The method as set forth in claim 1, wherein the amount of calcium oxide added in step (1) is 0 ~ 20g per liter of wastewater.
3. The method as set forth in claim 1, wherein the volume ratio of the wastewater to the added water glass in the step (2) is 3:2 ~ 2: 3.
4. The method according to claim 1, wherein the standing time in the step (3) is 4 ~ 50 hours.
5. The method of claim 1, further comprising: the aging time in the step (4) is 1 h.
6. The method of claim 1, further comprising: the drying temperature in the step (5) is 100 ℃ and the drying time is 10 h.
7. A xerogel obtainable by the process of any one of claims 1 to 6, wherein: the main components are calcium oxide, sodium oxide and silicon oxide, or sodium oxide and silicon oxide; the main crystal phase is Na2SO 4.
8. Use of a xerogel as claimed in claim 7 as a fining agent in a colored glass.
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Application publication date: 20191220 |