CN110482853A - It is a kind of that toxic metal ions in electroplating wastewater are solidified to method and gained glass in sodium calcium aluminium silicate glass - Google Patents
It is a kind of that toxic metal ions in electroplating wastewater are solidified to method and gained glass in sodium calcium aluminium silicate glass Download PDFInfo
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- CN110482853A CN110482853A CN201910873324.9A CN201910873324A CN110482853A CN 110482853 A CN110482853 A CN 110482853A CN 201910873324 A CN201910873324 A CN 201910873324A CN 110482853 A CN110482853 A CN 110482853A
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- electroplating wastewater
- waste water
- glass
- silicate glass
- sodium
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Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B1/00—Preparing the batches
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a kind of methods and gained glass for solidifying the method for toxic metal ions and its gained gel in electroplating wastewater and preparing sodium calcium aluminium silicate glass.This method provides acidic environment using electroplating wastewater for reaction system, calcium oxide adjusts pH value of reaction system and provides required calcium constituent for glass preparation, waterglass and sodium metaaluminate occur solgel reaction and obtain xerogel, sodium calcium aluminium silicate glass is prepared using the gel, to solidify toxic metal ions in electroplating wastewater.Reaction system of the present invention is simple, carries out at normal temperature, at low cost；The xerogel that processing waste water generates can prepare sodium calcium aluminium silicate glass；The ion leaching content of prepared sodium calcium aluminium silicate glass is detected using homogeneity of product (PCT), the leaching rate of the 7 of all elements day is less than 0.0002gm as the result is shown‑2·d‑1, realize effective solidification of toxic metal ions；The recycling of xerogel avoids the generation of solid waste and secondary pollution.
Description
Technical field
The present invention relates to it is a kind of by toxic metal ions in electroplating wastewater solidify in sodium calcium aluminium silicate glass method and
Its resulting glass, belongs to field of environmental technology.
Background technique
Plating is widely used in the industries such as anti-corrosion, decoration.But plating generates a large amount of waste water, and wherein toxic metal ions are with waste water
Water body and biology therein will be seriously endangered after discharge, and can be recycled by water and food chain enter human body, thus to environment and
The mankind bring great harm.
Electroplating wastewater is transferred in solid waste mostly after the methods of being precipitated, being adsorbed processing, becomes pollution source.
Solid waste can be used as raw material after the processing such as dehydration, drying, broken, then be equipped with after other raw materials are mixed, through high temperature mistake
It is to avoid one of approach of secondary pollution that journey, which prepares the materials such as glass or ceramics,.But this method process is complicated, and is limited to water process
The influence of process, solid waste composition used are not inconsistent condensation material preparation usually and require, need to add other a large amount of raw materials, lead to benefit
It is low with rate, it is practical to promote and apply hardly possible.
There is trial few in number, useful resources will be converted into after the metal ion recycling in electroplating wastewater.Such as patent
Metal ion in electroplating wastewater is enriched in adsorbent by CN104817272A by using the adsorbent of special designing, then
It is used together with spent sorbents together as glass colorant.But adsorbent preparation process generates new waste water again, and adsorbs
The journey time is long, and adsorption of metal ions is not thorough, and acid ion and organic pollutant etc. are difficult to remove clean in waste water, still there is waste water
Residual, need to be further processed.
Summary of the invention
The present invention in order to solve the deficiency of the above technology, provide it is a kind of by metal ion solidification in electroplating wastewater in glass
In method.
The present invention is achieved by the following measures:
This method removes the sulfate radical in electroplating wastewater first, sequentially adds calcium oxide, sodium metaaluminate and water glass solution, leads to
Sol gel reaction is crossed, waste water is able to whole gelations；Sodium calcium is prepared directly as raw material after gained wet gel is simply dry
Alumina silicate glass, toxic metal ions are able to all solidify in the high glass of chemical stability in waste water.
The method of the present invention specific steps are as follows:
(1) barium nitrate is added in electroplating wastewater, is stirred to react, to remove the sulfate radical in waste water；
(2) precipitating in (1) is filtered out, the waste water of preliminary treatment is obtained；
(3) calcium oxide is added in the waste water of preliminary treatment, and stirred evenly；
(4) sodium metaaluminate, waterglass are sequentially added into mixed solution obtained by step (3), and stirred evenly；
(5) the mixed solution whole gelation into (4) is stood, gel is formed；
(6) gel aging；
(7) dry, obtain xerogel；
(8) by xerogel ball milling, gel powder is obtained；
(9) gel powder melts and is formed through heating, soak, annealed, and obtains glass sample.
The additional amount of barium nitrate should be in above-mentioned steps (1) no longer to generate research of chaotic phenomenon after addition barium nitrate in waste water
Only.For copper waste water is electroplated, the sulfur content that wherein ICP is measured is 3583.9mg/L, and barium nitrate additive amount is in every liter of waste water
52g。
The time being stirred to react in above-mentioned steps (1) is 0.5h.
The additional amount of calcium oxide is to add 50 g in every liter of waste water in above-mentioned steps (3).
Sodium metaaluminate and waterglass in above-mentioned steps (4) are commercial goods, and wherein sodium metaaluminate modulus is 3.8；Water
Glass modulus is 3.3, and waste water and waterglass and sodium metaaluminate volume ratio are 3:2:0.08 ~ 0.16.
It is stirred evenly in above-mentioned steps (3) and (4), the time is respectively 10s and 30s.
In above-mentioned steps (5), time of repose is 30 ~ 80 min.
Ageing time in above-mentioned steps (6) is 1h.
Drying temperature in above-mentioned steps (7) is 100oC, drying time 6h.
In above-mentioned steps (8), powder size meets Conventional glass preparation and requires after ball milling；Preferably, powder crosses 100 mesh
Sieve；
In above-mentioned steps (9), heating rate 5oC/min, temperature 1400oC, soaking time 2h, annealing temperature 500oC, time 1h.
When the volume ratio of experiment discovery, waste water and sodium metaaluminate is 3:0 ~ 5.49, waste water can be made through above-mentioned steps (1) ~ (5)
Whole gelations；Wherein, when the volume ratio of waste water and sodium metaaluminate is 3:0.8 ~ 1.6, gained xerogel can meet sodium calcium aluminium
The component requirements of silicate glass preparation.But (sodium metaaluminate adds when the volume ratio of waste water and sodium metaaluminate is lower than 3:5.49
When entering amount increase), waste water cannot whole gelations；
Contain acid group, iron ion and other metal ions and organic matter in electroplating wastewater.It is such as electroplated in copper waste water and mainly contains sulphur
Acid group, iron, copper, sodium, calcium and magnesium ion etc..Electroplating wastewater is after above-mentioned steps (1) ~ (7) are handled, wherein toxic ion is consolidated
Change into xerogel.
Through XRF analysis, the main component of dry gel powder is SiO2(48 ~ 52%), Na2O(20 ~ 28%), CaO(16 ~ 17%),
Fe2O3(5 ~ 6%) and Al2O3(4 ~ 7%) (weight ratio).Gel powder, can be in lower temperature without adding any other component
Lower thawing obtains sodium calcium aluminosilicate glass.While gel powder is changed into glass, the metal ion in waste water all solidifies in glass
In glass.Using the ion leaching rate of homogeneity of product (PCT) detection glass sample, ion leaching rate is less than as the result is shown
0.0002g·m-2·d-1, stability is good.
Gained glass be brown color transparent sample, color mainly due to the primary metal ion in electroplating wastewater (such as
Iron ion and copper ion) caused by；The density of glass is 2.6546 ~ 2.6568 g/cm3, since the addition of sodium metaaluminate introduces
Aluminium oxide, increases the density of glass, and the sodium oxide molybdena introduced leads to the reduction of the density of glass, therefore sodium metaaluminate additive amount
Increase the density first increases and then decreases for leading to glass.
Gained glass is 5oC/min rate is warming up to 600 ~ 976oC under conditions of keeping the temperature 2 h, has Surface Crystallization special
Property, it can be used as sintered glass-ceramics and ceramic enamel raw material, precipitate crystal as combeite (Na4Ca4(Si6O18)).Cause
This, gained sodium calcium aluminosilicate glass is also in the scope of the present invention.
The utility model has the advantages that all processes of the present invention carry out at room temperature；It is by adjusting the dosage of additive, plating is useless
Water whole gelation, gained gel without adding other materials, can directly vitrifying at a lower temperature, form high stability sodium
Calcium aluminium silicate glass had both had cured poisonous and harmful substance in waste water, in turn avoided the generation of solid waste.
Detailed description of the invention
The Surface Crystallization photo of 2 sample of Fig. 1 embodiment
Fig. 2 is the XRD spectrum of 2 sample surfaces crystallization of embodiment.
Specific embodiment
Invention is further described in detail for specific embodiment with reference to the accompanying drawing, and following embodiment is only used for more clear
Illustrate to Chu the technical solution of this patent, and not intended to limit the protection scope of the present invention.
Using the density of drainage detection sodium calcium aluminium silicate glass, the ion leachability of PCT method detection glass is used
Energy.
The following are specific embodiments:
Example 1
(1) 52 g barium nitrates are added in 1 L plating copper waste water, 0.5 h are stirred to react, to remove the sulfate radical in waste water；
(2) filter out in (1) precipitate preliminary treatment waste water；
(3) 50 g calcium oxide are added in the waste water of 1 L preliminary treatment, and stir 10 s；
(4) 26.7 ml sodium metaaluminates, 667 ml waterglass are sequentially added into mixed solution obtained by step (3), and stir 30
s；
(5) 80 min of mixed solution in (4) is stood, mixed solution whole gelation forms gel；
(6) 1 h of gel aging；
(7)100 oC dries 6 h, obtains xerogel
(8) it will be sieved with 100 mesh sieve after xerogel sample ball milling, obtain gel powder；
(9) gel powder is through 5oC/min rate is warming up to 1400oC, soaking time 2h, annealing temperature 500oC, heat preservation
Glass sample can be obtained in 1h.
The main component of the above-mentioned resulting gel powder of preparation process is SiO2(48%), Na2O(24%), CaO(17%),
Fe2O3(5%) and Al2O3(4%) (weight ratio).Its density of the glass sample of preparation is 2.6546 g/cm3, sodium sial is detected through PCT
The leaching content of potassium ferro element is respectively 1.88 × 10-4 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) are the same as embodiment 1；
(4) 40 ml sodium metaaluminates, 667 ml waterglass are sequentially added into mixed solution obtained by step (3), and stir 30 s；
(5) 60 min of mixed solution in (4) is stood, mixed solution whole gelation forms gel；
(6) ~ (9) are the same as embodiment 1.
The main component group of the above-mentioned resulting gel powder of preparation process becomes SiO2(52%), Na2O(20%), CaO
(16%), Fe2O3(5%) and Al2O3(6%) (weight ratio), its density of the glass sample of preparation are 2.6568 g/cm3, detected through PCT
The leaching content of sodium Si-Al-K ferro element is respectively 2.16 × 10-4 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 is through 600 ~ 830oC degree heat
Surface Crystallization (see figure 1) occurs for processing；Precipitation principal crystalline phase is combeite (Na4Ca4(Si6O18)) (see figure 2).
Embodiment 3
(1) ~ (3) are the same as embodiment 1；
(4) 53.3 ml sodium metaaluminates, 667 ml waterglass are sequentially added into mixed solution obtained by step (3), and stir 30
s；
(5) 30 min of mixed solution in (4) is stood, mixed solution whole gelation forms gel；
(6) ~ (9) are the same as embodiment 1.
The main component group of the above-mentioned resulting gel powder of preparation process becomes SiO2(49%), Na2O(28%), CaO
(17%), Fe2O3(6%) and Al2O3(7%) (weight ratio), its density of the hyaloid of preparation are 2.6547 g/cm3, sodium is detected through PCT
The leaching content of sial potassium element is respectively 1.42 × 10-4 g·m-2·d-1、0.13×10-4 g·m-2·d-1、0.40×10-4
g·m-2·d-1、0.31×10-4 g·m-2·d-1。
Comparative example
(1) ~ (3) are the same as embodiment 1；
(4) 200 ml sodium metaaluminates, 667 ml waterglass are sequentially added into mixed solution obtained by step (3), and stir 30
s；
(5) stand, mixed solution cannot whole gelations, sample contains a large amount of aqueous solutions, and metal ion cannot be consolidated in waste water
Change in gel and glass.
Claims (9)
1. a kind of method for solidifying toxic metal ions in electroplating wastewater in sodium calcium aluminium silicate glass, it is characterized in that including
Following steps:
(1) barium nitrate is added in electroplating wastewater, is stirred to react, to remove the sulfate radical in waste water；
(2) precipitating in (1) is filtered out, the waste water of preliminary treatment is obtained；
(3) calcium oxide is added in the waste water of preliminary treatment, and stirred evenly；
(4) sodium metaaluminate, waterglass are sequentially added into mixed solution obtained by step (3), and stirred evenly；
(5) the mixed solution whole gelation into (4) is stood, gel is formed；
(6) gel aging；
(7) dry, obtain xerogel；
(8) it will be sieved with 100 mesh sieve after xerogel ball milling, obtain gel powder；
(9) gel powder melts and is formed through heating, soak, annealed, and obtains glass sample.
2. the method according to claim 1 for solidifying metal ion in electroplating wastewater, it is characterized in that: above-mentioned steps (1)
The additional amount of middle barium nitrate should be until no longer generating research of chaotic phenomenon after barium nitrate is added in waste water.
3. the method according to claim 1 for solidifying metal ion in electroplating wastewater, it is characterized in that: in above-mentioned steps (3)
The amount that calcium oxide is added in the waste water of every liter of preliminary treatment is 50 g.
4. metal ion method in solidification electroplating wastewater according to claim 1, it is characterized in that: being mixed in above-mentioned steps (4)
It closes in solution in terms of the waste water of every liter of preliminary treatment, is 3:2:0.8 ~ 1.6 with the volume ratio of waterglass and sodium metaaluminate.
5. metal ion method in solidification electroplating wastewater according to claim 1, it is characterized in that: in above-mentioned steps (5),
Time of repose is 30 ~ 80 min.
6. metal ion method in solidification electroplating wastewater according to claim 1, it is characterized in that: the aging in step (6)
Time is 1h.
7. metal ion method in solidification electroplating wastewater according to claim 1, it is characterized in that: the drying in step (7)
Temperature is 100 oC, and the time is 6 h.
8. metal ion method in solidification electroplating wastewater according to claim 1, it is characterized in that: the heating in step (8)
Rate is 5 oC/min, and temperature is 1400 oC, and soaking time 2h, annealing temperature is 500 oC, and sodium calcium can be obtained in heat preservation 1h
Alumina silicate glass sample.
9. preparing sodium calcium aluminium silicate glass made from the method according to claim 1 ~ any one of 8.
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| CN201910873324.9A CN110482853B (en) | 2019-09-17 | 2019-09-17 | Method for solidifying toxic metal ions in electroplating wastewater in soda-lime-aluminosilicate glass and obtained glass |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590014A (en) * | 2019-09-17 | 2019-12-20 | 济南大学 | Method for purifying electroplating wastewater and application of obtained xerogel in glass |
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| WO1994002410A1 (en) * | 1992-07-24 | 1994-02-03 | Nalco Fuel Tech | BOILER OPERATION WITH DECREASED NOx AND WASTE WATER DISCHARGE |
| WO1995002086A2 (en) * | 1993-07-09 | 1995-01-19 | The Dow Chemical Company | Process for removing metal ions from liquids |
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| CN110590014A (en) * | 2019-09-17 | 2019-12-20 | 济南大学 | Method for purifying electroplating wastewater and application of obtained xerogel in glass |
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