CN112661425A - Method for dechlorinating aluminum ash - Google Patents
Method for dechlorinating aluminum ash Download PDFInfo
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- CN112661425A CN112661425A CN202011593669.8A CN202011593669A CN112661425A CN 112661425 A CN112661425 A CN 112661425A CN 202011593669 A CN202011593669 A CN 202011593669A CN 112661425 A CN112661425 A CN 112661425A
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Abstract
The invention discloses a dechlorination method for aluminum ash, which realizes efficient dechlorination of the aluminum ash through three continuous links of high-temperature water vapor denitrification, silicate stabilization of heavy metal and washing dechlorination, and simultaneously the leaching concentration of the heavy metal in a washing liquid is obviously reduced, and the process is simple. The chlorine removal rate can be realized by 96-99%, the leaching concentration of zinc, copper and chromium is reduced by 97-99%, and the leaching concentration of nickel, lead and cadmium is reduced by 99-100%.
Description
Technical Field
The invention relates to a dechlorination method of aluminum ash, belonging to the field of harmless treatment of solid waste.
Background
A large amount of aluminum ash is easily generated in the aluminum electrolysis, casting and waste aluminum recovery and regeneration processes. And each ton of aluminum-based products is accompanied by the output of 10-30 kg of aluminum ash. At present, the annual yield of the aluminum ash in China exceeds 100 ten thousand tons, however, no effective resource utilization way for consuming the aluminum ash is found up to now. If the aluminum ash is randomly buried, soil salinization and heavy metal pollution are easily caused. The aluminum ash is generally composed of 10% -80% of metallic aluminum, 40% -70% of aluminum oxide, 10% -30% of aluminum nitride, 3% -15% of chlorine salt and other impurity components.
At present, two main ways of recycling the aluminum ash are available, namely, recycling the aluminum in the aluminum ash, and preparing a cementing material by using the aluminum ash, such as preparing a geopolymer material and firing cement. However, the large amount of aluminum nitride, chloride and other impurity components in the aluminum ash limit the effective development of the existing resource utilization approach of the aluminum ash. The aluminum ash is used as a raw material to be burnt into cement, and pre-dechlorination treatment needs to be carried out on the aluminum ash. However, aluminum nitride in the aluminum ash can be slowly decomposed in water to release ammonia gas, which limits the development of wet dechlorination of the aluminum ash. Meanwhile, heavy metals in the aluminum ash can be transferred to the washing liquid in the washing process, so that the treatment cost of the washing liquid is increased.
Therefore, in order to realize effective resource utilization of the aluminum ash, a treatment technology for efficient dechlorination of the aluminum ash needs to be developed.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a high-efficiency aluminum ash dechlorination method.
The technical scheme is as follows: the invention relates to a method for dechlorinating aluminum ash, which comprises the following steps:
(1) mechanically grinding the aluminum ash to obtain activated aluminum ash;
(2) placing the activated aluminum ash in a high-temperature steam generator for treatment to obtain denitrified aluminum ash;
(3) dissolving sodium silicate in water to obtain a sodium silicate aqueous solution;
(4) mixing the sodium silicate aqueous solution and the denitrified aluminum ash, stirring, standing and aging to obtain stable aluminum ash slurry;
(5) mixing the aluminum ash stable slurry with water, continuously stirring, and performing centrifugal separation to obtain dechlorinated aluminum mortar and washing waste liquid;
(6) and drying the dechlorinated aluminum ash slurry, and mechanically grinding to obtain dechlorinated aluminum ash.
Further, in the step (1), the mechanical grinding time is 0.5-4.5 h.
Further, in the step (2), the temperature of air in the high-temperature steam generator is 100-300 ℃, the relative humidity of the air is 90-100%, and the treatment time is 0.5-4.5 h.
Further, in the step (3), the mass concentration of the sodium silicate aqueous solution is 0.05-0.5 mol/L.
Further, in the step (4), the solid-to-solid ratio of the sodium silicate aqueous solution to the denitrified aluminum ash is 0.4-0.8: 1(mL/mg), the stirring time is 2-10 hours, and the standing and aging time is 6-24 hours.
Further, in the step (5), the volume ratio of the water to the stable aluminum ash slurry is 1-3: 1, and the continuous stirring time is 1-5 hours.
Further, in the step (6), the mechanical grinding time is 0.5-4.5 h.
The reaction mechanism is as follows: the aluminum ash is mechanically ground, the particle size of the aluminum ash can be further reduced through the shearing friction effect, the specific surface area of the aluminum ash is increased, and meanwhile, the solubility of soluble salts in the aluminum ash is further increased through mechanical activation. And (2) placing the aluminum ash in a high-temperature steam generator, wherein high-temperature steam is contacted with aluminum nitride in the aluminum ash in the treatment process and then reacts to generate aluminum hydroxide and ammonia, part of the ammonia is discharged along with the steam, and part of the ammonia is dissolved in water to form ammonium salt on the surface of the aluminum ash. After the sodium silicate aqueous solution and the denitrified aluminum ash are mixed, part of sodium silicate reacts with heavy metal ions to generate heavy metal silicate precipitates in the stirring process, part of sodium silicate reacts with aluminum oxide or aluminum hydroxide to generate aluminosilicate, and the aluminosilicate can precipitate and further wrap the heavy metal silicate, so that the leachability and the mobility of heavy metals in the denitrified aluminum ash are obviously reduced. The water and the stable aluminum ash slurry are mixed, the chlorine and the ammonium salt in the stable aluminum ash slurry are dissolved in the water body in the stirring process, and the heavy metal is stabilized in the silicate, so that the efficient dechlorination of the aluminum ash is realized on the premise of remarkably reducing the leaching concentration of the heavy metal.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the method for dechlorinating the aluminum ash is simple in process, high-efficiency dechlorination of the aluminum ash is realized through three continuous links of high-temperature steam denitrification, silicate stabilization of heavy metals and washing dechlorination, and the leaching concentration of the heavy metals in a washing liquid is obviously reduced. The chlorine removal rate can be realized by 96-99%, the leaching concentration of zinc, copper and chromium is reduced by 97-99%, and the leaching concentration of nickel, lead and cadmium is reduced by 99-100%.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The aluminum ash mainly comprises 65.87 percent of Al2O3、5.56％SiO2、0.64％Fe2O3、2.46％CaO、3.72％MgO、6.74％Na2O、1.86％TiO2、8.34％Cl、2.24％S、0.06％F、1.16％BaO、1.22％PbO、0.03％ZnO、0.02％CdO、0.04％Cr2O3、0.02％NiO、0.02％CuO。
Example 1 Effect of mechanical grinding time of aluminum Ash on dechlorination efficiency of aluminum Ash
And mechanically grinding the aluminum ash for 0.5h, 1.5h, 2.5h, 3.5h and 4.5h respectively to obtain five groups of activated aluminum ash. And (3) placing the activated aluminum ash in a high-temperature steam generator for treatment for 0.5h to obtain five groups of denitrified aluminum ash, wherein the air temperature in the high-temperature steam generator is 100 ℃, and the relative humidity of the air is 90%. Sodium silicate is dissolved in water to prepare a sodium silicate aqueous solution with the concentration of 0.05 mol/L. Respectively weighing the sodium silicate aqueous solution and the denitrified aluminum ash according to the liquid-solid ratio of 0.4:1(mL: mg), mixing, stirring for 2h, and standing and aging for 6h to obtain five groups of stable aluminum ash slurry. Respectively weighing water and the aluminum ash stable slurry according to the volume ratio of 1:1 of the water to the aluminum ash stable slurry, mixing, continuously stirring for 1h, and then centrifugally separating the mixed slurry to obtain five groups of dechlorinated aluminum mortar and washing waste liquid. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 0.5h to obtain five groups of dechlorinated aluminum ash.
And (3) comparison test: and respectively mechanically grinding the aluminum ash for 4.5 hours to obtain activated aluminum ash. Respectively weighing water and activated aluminum ash according to the volume ratio of 1:1 of the water to the activated aluminum ash, mixing, continuously stirring for 1h, and then centrifugally separating the mixed slurry to obtain the dechlorinated aluminum mortar and the washing waste liquid. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 0.5h to obtain dechlorinated aluminum ash.
Zinc, copper, chromium, nickel, lead, cadmium concentration: the concentration of zinc, copper, nickel, lead and cadmium in the washing waste liquid is measured according to the inductively coupled plasma emission spectrometry (HJ776-2015) for measuring 32 elements in water quality, and the concentration of Cr (VI) pollutants is measured according to the flow injection-dibenzoyl dihydrazide photometry (HJ908-2017) for measuring hexavalent chromium in water quality.
The leaching reduction percentage of zinc, copper, chromium, nickel, lead and cadmium is as follows: the leaching reduction percentage of zinc, copper, chromium, nickel, lead and cadmium is calculated according to the formula (1), wherein RMThe leaching percentage of zinc, copper, chromium, nickel, lead and cadmium is reduced (M is zinc, copper, chromium, nickel, lead and cadmium), cM0Concentrations (mg/L) of zinc, copper, chromium, nickel, lead and cadmium in the waste washing liquid recovered for comparative test, cMtThe concentrations (mg/L) of zinc, copper, chromium, nickel, lead and cadmium in the washing waste liquid recovered by the treatment test of the invention.
Determination of chlorine content: the chlorine content in the aluminum ash is measured according to the building sand (GB/T14684-2011).
Calculation of chlorine removal rate: the removal rate of the aluminum ash and the chlorine is calculated according to the formula (2), RClFor aluminum ash removal efficiency, wherein cCl0And cCltRespectively represents the chlorine content (%) in the aluminum ash before and after the treatment in the treatment test of the invention.
The test results of this example are shown in tables 1 and 2.
TABLE 1 table of chlorine content and heavy metal leaching concentration in mechanical grinding of aluminum ash
TABLE 2 influence of different mechanical grinding time on dechlorination efficiency and heavy metal leaching rate of aluminum ash
As can be seen from Table 1, the mechanical grinding time has a significant effect on both the chlorine content of the aluminum ash and the heavy metal content of the water wash. It should be noted that the 0.00 value presented in table 1 only indicates that the corresponding element concentration in the waste liquid is lower than the lower detection concentration limit, and the device cannot detect the element concentration, but does not represent the true zero concentration value. Specifically, as can be seen from table 2, subjecting the aluminum ash to mechanical grinding can further reduce the particle size of the aluminum ash by the action of shear friction, increase the specific surface area of the aluminum ash, and further increase the solubility of soluble salts in the aluminum ash by mechanical activation. Along with the change of the mechanical grinding time of the aluminum ash, the chlorine removal rate can be 97-98%, the leaching concentration of zinc, copper and chromium in the washing liquid is reduced by 97-99%, and the leaching concentration of nickel, lead and cadmium is reduced by 99-100%.
Example 2 Effect of sodium silicate aqueous solution concentration on dechlorination efficiency of aluminum Ash
And mechanically grinding the aluminum ash for 2.5 hours to obtain activated aluminum ash. And (3) placing the activated aluminum ash in a high-temperature steam generator to be treated for 2.5h to obtain denitrified aluminum ash, wherein the air temperature in the high-temperature steam generator is 200 ℃, and the relative humidity of the air is 95%. Sodium silicate was dissolved in water to prepare aqueous sodium silicate solutions having concentrations of 0.05mol/L, 0.1625mol/L, 0.275mol/L, 0.3875mol/L, and 0.5 mol/L. Respectively weighing the sodium silicate aqueous solution and the denitrified aluminum ash according to the liquid-solid ratio of 0.6:1(mL: mg), mixing, stirring for 6h, standing and aging for 15h to obtain five groups of stable aluminum ash slurry. Respectively weighing water and aluminum ash stable slurry according to the volume ratio of 2:1 of the water to the aluminum ash stable slurry, mixing, continuously stirring for 3 hours, and then centrifugally separating the mixed slurry to obtain five groups of liquid of dechlorinated aluminum mortar and water washing waste. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 2.5h to obtain five groups of dechlorinated aluminum ash.
And (3) comparison test: and respectively carrying out mechanical grinding on the aluminum ash for 2.5h to obtain activated aluminum ash. Respectively weighing water and activated aluminum ash according to the volume ratio of 2:1 of the water to the activated aluminum ash, mixing, continuously stirring for 3 hours, and then centrifugally separating the mixed slurry to obtain the dechlorinated aluminum mortar and the washing waste liquid. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 2.5 hours to obtain dechlorinated aluminum ash.
The concentration detection of zinc, copper, chromium, nickel, lead and cadmium, the percentage reduction calculation of zinc, copper, chromium, nickel, lead and cadmium leaching, the determination of chlorine content and the calculation of chlorine removal rate are the same as those in example 1, and the specific results are shown in tables 3 and 4.
Table 3 table for treating chlorine content and heavy metal leaching concentration of different sodium silicate aqueous solution concentrations
TABLE 4 influence of different sodium silicate aqueous solution concentrations on dechlorination efficiency of aluminum ash and leaching rate of heavy metals
As can be seen from Table 3, the concentration of the aqueous sodium silicate solution had a significant effect on both the chlorine content of the aluminum ash and the heavy metal content of the water wash. It should be noted that the 0.00 value presented in table 3 only indicates that the corresponding element concentration in the waste liquid is lower than the lower detection concentration limit, and the device cannot detect the element concentration, but does not represent the true concentration zero value. Specifically, as can be seen from table 4, after the aqueous solution of sodium silicate and the aluminum ash from denitrification are mixed, part of the sodium silicate reacts with heavy metal ions during stirring to generate a heavy metal silicate precipitate, and part of the sodium silicate reacts with aluminum oxide or aluminum hydroxide to generate aluminosilicate, which can further wrap the heavy metal silicate precipitate, thereby significantly reducing the leachability and the mobility of heavy metals. Along with the change of the concentration of the sodium silicate aqueous solution, the chlorine removal rate can be 98-99%, the leaching concentration of zinc, copper and chromium in the washing liquid is reduced by 98-99%, and the leaching concentration of nickel, lead and cadmium is reduced by 99-100%.
Example 3 Effect of Water to aluminum Ash Stable slurry volume ratio on aluminum Ash dechlorination efficiency
And mechanically grinding the aluminum ash for 4.5 hours to obtain activated aluminum ash. And (3) placing the activated aluminum ash in a high-temperature steam generator to be treated for 4.5h to obtain denitrified aluminum ash, wherein the air temperature in the high-temperature steam generator is 300 ℃, and the relative humidity of the air is 100%. Sodium silicate is dissolved in water to prepare a sodium silicate aqueous solution with the concentration of 0.5 mol/L. Respectively weighing the sodium silicate aqueous solution and the denitrified aluminum ash according to the liquid-solid ratio of 0.8:1(mL: mg), mixing, stirring for 10h, standing and aging for 24h to obtain the stable aluminum ash slurry. Respectively weighing water and the stable aluminum ash slurry according to the volume ratio of the water to the stable aluminum ash slurry of 1:1, 1.5:1, 2:1, 2.5:1 and 3:1, mixing, continuously stirring for 5 hours, and then centrifugally separating the mixed slurry to obtain five groups of dechlorinated aluminum mortar and washing waste liquid. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 4.5 hours to obtain five groups of dechlorinated aluminum ash.
And (3) comparison test: and respectively mechanically grinding the aluminum ash for 4.5 hours to obtain activated aluminum ash. Respectively weighing water and activated aluminum ash according to the volume ratio of 2:1 of the water to the activated aluminum ash, mixing, continuously stirring for 5 hours, and then centrifugally separating the mixed slurry to obtain the dechlorinated aluminum mortar and the washing waste liquid. And drying the dechlorinated aluminum ash slurry, and mechanically grinding for 4.5 hours to obtain dechlorinated aluminum ash.
The concentration detection of zinc, copper, chromium, nickel, lead and cadmium, the percentage reduction calculation of zinc, copper, chromium, nickel, lead and cadmium leaching, the determination of chlorine content and the calculation of chlorine removal rate are the same as those in example 1, and are specifically shown in tables 5 and 6.
TABLE 5 table of chlorine content and heavy metal leaching concentration in different water/aluminum ash stable slurry volume ratios
TABLE 6 influence of volume ratio of stable slurry of different water and aluminum ash on dechlorination efficiency and heavy metal leaching rate of aluminum ash
As can be seen from Table 5, the volume ratio of the stable slurry of water and aluminum ash has a significant influence on the chlorine content of the aluminum ash and the heavy metal content of the washing liquid. It should be noted that the 0.00 value presented in table 3 only indicates that the corresponding element concentration in the waste liquid is lower than the lower detection concentration limit, and the device cannot detect the element concentration, but does not represent the true concentration zero value. Specifically, as can be seen from table 6, water and the stable aluminum ash slurry were mixed, and chlorine and ammonium salts in the stable aluminum ash slurry were dissolved in the water during stirring, thereby dechlorinating the aluminum ash. Along with the change of the concentration of the sodium silicate aqueous solution, the chlorine removal rate can be 98-99%, the leaching concentration of zinc, copper and chromium in the washing liquid is reduced by 98-99%, and the leaching concentration of nickel, lead and cadmium is reduced by 99-100%.
Claims (7)
1. The method for dechlorinating the aluminum ash is characterized by comprising the following steps of:
(1) mechanically grinding the aluminum ash to obtain activated aluminum ash;
(2) placing the activated aluminum ash in a high-temperature steam generator for treatment to obtain denitrified aluminum ash;
(3) dissolving sodium silicate in water to obtain a sodium silicate aqueous solution;
(4) mixing the sodium silicate aqueous solution and the denitrified aluminum ash, stirring, standing and aging to obtain stable aluminum ash slurry;
(5) mixing the aluminum ash stable slurry with water, continuously stirring, and performing centrifugal separation to obtain dechlorinated aluminum mortar and washing waste liquid;
(6) and drying the dechlorinated aluminum ash slurry, and mechanically grinding to obtain dechlorinated aluminum ash.
2. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (1), the mechanical grinding time is 0.5-4.5 h.
3. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (2), the temperature of the air in the high-temperature steam generator is 100 to 300 ℃, the relative humidity of the air is 90 to 100 percent, and the treatment time is 0.5 to 4.5 hours.
4. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (3), the mass concentration of the sodium silicate aqueous solution is 0.05-0.5 mol/L.
5. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (4), the solid-to-solid ratio of the aqueous sodium silicate solution to the denitrified aluminum ash is 0.4-0.8: 1mL/mg, the stirring time is 2-10 h, and the standing and aging time is 6-24 h.
6. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (5), the volume ratio of the water to the stable aluminum ash slurry is 1-3: 1, and the continuous stirring time is 1-5 h.
7. The method for dechlorinating the aluminum ash according to claim 1, wherein in the step (6), the mechanical grinding time is 0.5-4.5 h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930716A (en) * | 1982-08-09 | 1984-02-18 | Showa Koki Kk | Method for utilizing aluminum ash |
| JP2017217606A (en) * | 2016-06-07 | 2017-12-14 | 株式会社アイザック | Manufacturing method of coagulant using aluminum-including waste as raw material |
| CN108275708A (en) * | 2018-01-23 | 2018-07-13 | 环境保护部华南环境科学研究所 | A kind of Quadratic aluminum dust resource utilization method |
| CN109277398A (en) * | 2018-10-30 | 2019-01-29 | 湖南绿脉环保科技有限公司 | A kind of method of safe and harmlessization processing aluminium ash |
| CN112093814A (en) * | 2020-09-25 | 2020-12-18 | 中铝东南材料院（福建）科技有限公司 | Method for preparing aluminum oxide by using aluminum ash without slagging |
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- 2020-12-29 CN CN202011593669.8A patent/CN112661425B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5930716A (en) * | 1982-08-09 | 1984-02-18 | Showa Koki Kk | Method for utilizing aluminum ash |
| JP2017217606A (en) * | 2016-06-07 | 2017-12-14 | 株式会社アイザック | Manufacturing method of coagulant using aluminum-including waste as raw material |
| CN108275708A (en) * | 2018-01-23 | 2018-07-13 | 环境保护部华南环境科学研究所 | A kind of Quadratic aluminum dust resource utilization method |
| CN109277398A (en) * | 2018-10-30 | 2019-01-29 | 湖南绿脉环保科技有限公司 | A kind of method of safe and harmlessization processing aluminium ash |
| CN112093814A (en) * | 2020-09-25 | 2020-12-18 | 中铝东南材料院（福建）科技有限公司 | Method for preparing aluminum oxide by using aluminum ash without slagging |
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