CN110818047A - Preparation method of polysilicate ferro-manganese graphene flocculant - Google Patents
Preparation method of polysilicate ferro-manganese graphene flocculant Download PDFInfo
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Abstract
The invention discloses a preparation method of a polysilicate ferro-manganese graphene flocculant, which comprises the following steps: (1) uniformly mixing the silica fume with concentrated sulfuric acid, and aging to obtain polysilicic acid; (2) adding graphite powder into polysilicic acid, uniformly mixing, and aging to obtain graphite polysilicic acid; (3) uniformly mixing sodium peroxodisulfate and potassium permanganate to obtain a mixed oxidant, adding the mixed oxidant into graphite polysilicic acid, uniformly mixing, performing ultrasonic treatment, and aging to obtain graphene oxide manganese polysilicate; (4) and (3) uniformly mixing humic acid, iron powder and graphene oxide manganese polysilicate, aging, adjusting the pH value to be acidic, continuously aging, drying and grinding to obtain the manganese polysilicate graphene flocculant. The polysilicate manganese graphene flocculant provided by the invention can capture various pollutants simultaneously, is high in flocculant recovery efficiency and wide in flocculant application pH range; the preparation process is simple, the requirement on preparation conditions is low, the preparation process is easy to realize, and the sources of the required raw materials are wide.
Description
Technical Field
The invention relates to a preparation method of an inorganic flocculant, in particular to a preparation method of a poly-silicon-ferrum-manganese-graphene flocculant for treating landfill leachate.
Background
Due to the natural precipitation and the anaerobic decomposition of microorganisms, the domestic garbage is easy to form a domestic garbage percolate with complex pollutant components, high pollutant concentration and toxicity in a covering soil layer in the landfill process. The domestic garbage leachate has the characteristics of complex water quality components, various heavy metals, high ammonia nitrogen content, large water quantity and water quality fluctuation and the like. The domestic garbage leachate contains a large amount of toxic and harmful substances, and if the domestic garbage leachate is not properly treated, the domestic garbage leachate can seriously damage the ecological environment and seriously affect the body health of local residents.
The method for disposing the domestic garbage percolate mainly comprises a physical and chemical treatment method, a biological treatment method and an advanced oxidation method. At present, the flocculation precipitation method is widely applied to the aspect of industrial wastewater treatment due to the characteristics of simple operation and remarkable treatment effect. However, because the variety of harmful substances in the domestic garbage leachate is complicated and the treatment difficulty is very high, the leachate treated by using the traditional polysilica flocculant is difficult to reach the discharge standard. Particularly, the problems that the effect of a flocculating agent for simultaneously capturing various pollutants is poor, the flocculating agent is easy to hydrolyze, so that the recovery efficiency of the flocculating agent is low, the applicable pH range of the flocculating agent is narrow and the like exist in the prior art of treating the domestic garbage leachate by using the polysilicone flocculating agent.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems, the invention provides a preparation method of a poly-silicon-ferrum-manganese-graphene flocculating agent for treating landfill leachate, and the prepared poly-silicon-ferrum-manganese-graphene flocculating agent can capture various pollutants simultaneously, and has high flocculating agent recovery efficiency and wide flocculating agent application pH range.
The technical scheme is as follows: the invention relates to a preparation method of a polysilicate ferro-manganese graphene flocculant, which comprises the following steps:
(1) uniformly mixing the silica fume with concentrated sulfuric acid, and aging to obtain polysilicic acid;
(2) adding graphite powder into polysilicic acid, uniformly mixing, and aging to obtain graphite polysilicic acid;
(3) uniformly mixing sodium peroxodisulfate and potassium permanganate to obtain a mixed oxidant, adding the mixed oxidant into graphite polysilicic acid, uniformly mixing, performing ultrasonic treatment, and aging to obtain graphene oxide manganese polysilicate;
(4) and (3) uniformly mixing humic acid, iron powder and graphene oxide manganese polysilicate, aging, adjusting the pH value to be acidic, continuously aging, drying and grinding to obtain the manganese polysilicate graphene flocculant.
Wherein, the mass ratio of the graphite powder to the polysilicic acid in the step (2) is 5-30: 100, and more preferably 5-25: 100.
In the step (3), the mass ratio of the sodium peroxodisulfate to the potassium permanganate is 10-25: 100, and preferably 10-20: 100.
In the step (4), the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate is 10-50: 10-25: 100, and the preferable ratio is 10-40: 10-20: 100.
The solid-liquid ratio of the silica fume to the concentrated sulfuric acid in the step (1) is 1: 1-2 (mg: mL), the aging time is 3-6 h, the mass fraction of the concentrated sulfuric acid is 70% -90%, and the aging time in the step (2) is 3-6 h.
In the step (3), the mass ratio of the mixed oxidant to the graphite polysilicic acid is 10-30: 100, the ultrasonic treatment power is 600-2400W, the treatment temperature is 60-90 ℃, the ultrasonic time is 2-4 hours, and the aging is 3-6 hours.
In the step (4), the aging is carried out for 6-12 h, the pH value is adjusted to 3-5 by using 5-10 mol/L sodium hydroxide solution, and then the aging is carried out for 6-12 h.
In a strong acid environment, silicate in the silica fume is dissolved, hydrolyzed and polymerized to generate polysilicic acid. After the graphite powder is mixed into the polysilicic acid, the graphite powder can be uniformly distributed in the polysilicic acid through the electrostatic adsorption effect on the surface of the polysilicic acid, and the graphite polysilicic acid is obtained. And mixing the mixed oxidant with graphite polysilicic acid, and directly oxidizing graphite by potassium permanganate to convert the graphite into graphene to obtain the graphene oxide manganese silicate. Under heating conditions, sodium peroxodisulfate can decompose sulfate radicals. The peroxodisulfate enhances the oxidation process of the graphite by increasing the oxidation potential, and promotes the generation of graphene. Meanwhile, sulfate radicals can convert low-valence manganese into high-valence manganese through oxidation, so that the graphite oxidation process by potassium permanganate can be maintained. The generated graphene can be uniformly dispersed in the polysilicic acid by ultrasonic wave. Meanwhile, ultrasonic waves act on water to generate a large number of cavities, and the cavities are implosion to generate strong shearing force on graphite, so that graphite stripping and layering are promoted. The effective stripping of the graphite can enable potassium permanganate to penetrate between graphite layers more effectively, and the graphite oxidation process is strengthened. Humic acid and iron powder are mixed into the graphene oxide manganese polysilicate, and part of the humic acid can directly convert the graphene oxide into graphene. Unreacted humic acid can be effectively loaded on the surface of the graphene flocculant. The iron powder can absorb hydrogen ions and convert the hydrogen ions into ferrous ions. The ferrous ions can react with graphene oxide to produce graphene and ferric ions. Meanwhile, ferrous ions can also react with high-valence manganese ions to promote the reduction of the valence of the manganese ions and generate ferro-manganese tumor-like substances. Ferric ions can interact with polysilicic acid distributed with graphene and combine with manganese with different valence states, so that the generation of a three-dimensional space structure of the flocculating agent is induced. The sodium hydroxide solution is added in the mixing process of the humic acid, the iron powder and the graphene oxide manganese polysilicate for pH adjustment, and the generation of iron-manganese layered hydroxide in the flocculating agent can be induced, so that the capturing and adsorbing effects of the flocculating agent on pollutants can be improved, and the adsorption quantity of the flocculating agent on the pollutants can be improved. The graphene is uniformly distributed in the structure of the flocculant, the replacement effect of hydrogen ions on cations in the polysilicon system structure can be effectively weakened in a hydrogen ion absorption mode, and meanwhile, the ferrimanganic nodule can effectively prevent the hydrogen ions from migrating to the inside of the flocculant, so that the hydrolysis loss rate of the flocculant is favorably reduced, and the pH application range of the flocculant is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) according to the invention, the preparation processes of the polysilicate ferro-manganese flocculant and the graphene are combined into a whole, the graphene and the polysilicate ferro-manganese are effectively compounded together to generate the flocculant with high stability and high adsorption performance, and various pollutants are captured at the same time, so that the removal of 97% of COD, 98% of ammonia nitrogen, 99% of total phosphorus, 98% of zinc, 98% of copper, 99% of lead and 99% of chromium in the landfill leachate can be realized; (2) the hydrolysis loss of the flocculant is small, and 99 percent of the flocculant can be recovered; (3) the method is not limited by the pH value of the landfill leachate, and the flocculating agent is suitable for the range of pH 1-13; (4) the preparation method has the advantages of simple preparation process, low requirement on preparation conditions, easy realization of the preparation process and wide source of required raw materials.
Drawings
FIG. 1 is a flow chart of the present invention
Detailed Description
The invention is further described below with reference to the figures and examples.
It should be noted that the landfill leachate of the present invention is obtained from a sanitary landfill of a certain domestic garbage in hong Kong, Lian. The mass concentration of COD in the landfill leachate is 1345mg/L, the concentration of ammonia nitrogen is 821mg/L, the total phosphorus is 242mg/L, and the heavy metal pollutants are 56mg/L zinc ions (Zn)2+) 21mg/L of copper ion (Cu)2+) 12mg/L of lead ion (Pb)2+) 26mg/L cadmium ion (Cd)2+)。
Example 1
Influence of mass ratio of graphite powder to polysilicic acid on treatment effect of flocculant on landfill leachate
Preparing a polysilicate ferro-manganese graphene flocculant: as shown in fig. 1, silica fume and concentrated sulfuric acid are weighed according to a solid-to-liquid ratio of 1:1(mg: mL), mixed, stirred uniformly and aged for 3 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 70%; respectively weighing graphite powder and polysilicic acid according to the mass ratio of 2.5:100, 3.5:100, 4.5:100, 5:100, 15:100, 25:100, 26:100, 28:100 and 30:100 of the graphite powder to the polysilicic acid, mixing, uniformly stirring, and aging for 3 hours to obtain graphite polysilicic acid; weighing sodium peroxodisulfate and potassium permanganate according to the mass ratio of 10:100, mixing, and uniformly stirring to obtain a mixed oxidant; weighing the mixed oxidant and the graphite polysilicic acid according to the mass ratio of the mixed oxidant to the graphite polysilicic acid of 10:100, mixing, uniformly stirring, performing ultrasonic action for 2 hours, setting the temperature to be 60 ℃ in the ultrasonic process, and then aging for 3 hours to obtain the graphene oxide manganese polysilicate, wherein the ultrasonic action power is 600W; the method comprises the steps of weighing humic acid, iron powder and graphene oxide manganese polysilicate according to the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate of 10:10:100, mixing, stirring until the iron powder is completely dissolved, aging for 6 hours, adding 5mol/L sodium hydroxide solution to adjust the pH value to 3, aging for 6 hours, drying and grinding to obtain the poly-silicon-iron-manganese-graphene flocculant.
And (3) garbage leachate treatment: adjusting the pH value of the landfill leachate to 1 by using 5mol/L sulfuric acid, weighing a flocculating agent according to a solid-liquid ratio of 20:1(g: L), adding the flocculating agent into the landfill leachate, stirring for 30 minutes, placing the landfill leachate into a centrifugal machine, centrifuging for 5 minutes at 5000rpm, carrying out solid-liquid separation, taking a supernatant for detecting pollutants in the landfill leachate, drying and weighing a solid part.
COD concentration detection and COD removal rate calculation: the concentration of Chemical Oxygen Demand (COD) in the landfill leachate is measured according to the national standard bichromate method for measuring water quality chemical oxygen demand (GB 11914-; the COD removal rate was calculated according to the formula (1), wherein RCODAs the removal rate of COD, c0And ctThe COD concentration (mg/L) of the landfill leachate before and after treatment is respectively.
Detecting the ammonia nitrogen concentration and calculating the ammonia nitrogen removal rate: the concentration of ammonia nitrogen in the landfill leachate is measured according to salicylic acid spectrophotometry for measuring ammonia nitrogen in water (HJ 536-2009); the ammonia nitrogen removal rate is calculated according to the formula (2), wherein RNFor ammonia nitrogen removal, cN0The initial concentration (mg/L) of ammonia nitrogen in the landfill leachate before treatment, cNtThe residual ammonia nitrogen concentration (mg/L) in the treated landfill leachate is adopted.
And (3) detecting the concentration of total phosphorus and calculating the removal rate of the total phosphorus: the concentration of total phosphorus in the landfill leachate is measured according to the determination of total phosphorus in water quality (GB 1893-89); the total phosphorus removal was calculated according to formula (3), where RpAs a total phosphorus removal rate, cp0Is the initial concentration (mg/L), c, of total phosphorus in the landfill leachate before treatmentptThe residual concentration (mg/L) of the total phosphorus in the landfill leachate after treatment is adopted.
Detecting the concentration of the heavy metal ions and calculating the removal rate: the concentration of four heavy metal ions, namely zinc, copper, lead and cadmium in the landfill leachate is measured according to the inductively coupled plasma emission spectrometry for measuring 32 elements in water (HJ 776-2015). The removal rate of heavy metal M ions (M: Zn, Cu, Pb, Cd) is calculated according to the formula (4), wherein RMFor heavy metal ion removal rate, cM0Is the initial concentration (mg/L), c of heavy metal M ions in the landfill leachate before treatmentMtThe concentration (mg/L) of heavy metal M ions in the treated landfill leachate is shown.
And (3) calculating the recovery rate of the flocculating agent: the flocculant recovery efficiency is calculated according to equation (5), where RSi-CFor the recovery efficiency of the flocculating agent, m is the drying mass (g) of the solid separated after the landfill leachate treatment, V is the volume (L) of the landfill leachate after the pH adjustment, cSi-C0The dosage (g/L) of the flocculant is added.
The test results of the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions and the recovery rate of the flocculating agent in the landfill leachate are shown in table 1.
TABLE 1 influence of the ratio of the quality of graphite powder and polysilicic acid on the effect of flocculant preparation for treating landfill leachate
As can be seen from table 1, when the mass ratio of the graphite powder to the polysilicic acid is less than 5:100 (for example, in table 1, when the mass ratio of the graphite powder to the polysilicic acid is 4.5:100, 3.5:100, 2.5:100 and lower values not listed in table 1), less graphite is mixed into the polysilicic acid, and the amount of graphene generated and compounded in the polysilicic flocculant is successively less, and at the same time, the amount of humic acid loaded on the surface of graphene is also reduced, which finally results in that the removal rates of COD, ammonia nitrogen and total phosphorus in the landfill leachate are all lower than 84%, the removal rates of heavy metal ions are all lower than 80%, the recovery rate of the flocculant is lower than 81%, and the removal rates of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate and the recovery rate of the flocculant are all significantly reduced as the mass ratio of the graphite powder to the. When the mass ratio of the graphite powder to the polysilicic acid is 5-25: 100 (as shown in table 1, when the mass ratio of the graphite powder to the polysilicic acid is 5:100, 15:100 and 25: 100), more graphite is dispersed in the polysilicic acid, more graphene is generated and compounded in the polysilicic flocculant, the amount of humic acid loaded on the surface of the graphene is sufficient, the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the final landfill leachate is greater than 92%, and the recovery rate of the flocculant is greater than 94%. When the mass ratio of the graphite powder to the polysilicic acid is more than 25:100 (as shown in table 1, when the mass ratio of the graphite powder to the polysilicic acid is 26:100, 28:100 and 30:100 and higher values not listed in table 1), the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions and the recovery rate of the flocculating agent in the landfill leachate are not obviously changed along with the further increase of the mass ratio of the graphite powder to the polysilicic acid. Therefore, in a comprehensive aspect, the benefit and the cost are combined, and when the mass ratio of the graphite powder to the polysilicic acid is 5-25: 100, the prepared flocculant is most beneficial to improving removal of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate and improving the recovery rate of the flocculant.
Example 2
Influence of quality ratio of sodium peroxodisulfate to potassium permanganate on treatment effect of garbage leachate by preparing flocculant
Preparing a polysilicate ferro-manganese graphene flocculant: weighing silica fume and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:1.5(mg: mL), mixing, uniformly stirring, and aging for 4.5 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 80%; weighing graphite powder and polysilicic acid according to the mass ratio of the graphite powder to the polysilicic acid of 25:100, mixing, uniformly stirring, and aging for 4.5 hours to obtain graphite polysilicic acid; respectively weighing sodium peroxodisulfate and potassium permanganate according to the mass ratio of the sodium peroxodisulfate to the potassium permanganate of 5:100, 7:100, 9:100, 10:100, 15:100, 20:100, 21:100, 23:100 and 25:100, mixing, and uniformly stirring to obtain a mixed oxidant; weighing the mixed oxidant and the graphite polysilicic acid according to the mass ratio of the mixed oxidant to the graphite polysilicic acid of 20:100, mixing, uniformly stirring, performing ultrasonic action for 3 hours, setting the temperature to be 75 ℃ in the ultrasonic process, and then aging for 4.5 hours to obtain graphene oxide manganese polysilicate, wherein the ultrasonic action power is 1500W; the method comprises the steps of weighing humic acid, iron powder and graphene oxide manganese polysilicate according to the mass ratio of 25:15:100, mixing, stirring until the iron powder is completely dissolved, aging for 9 hours, adding 7.5mol/L sodium hydroxide solution to adjust the pH value to 4, aging for 9 hours, drying, and grinding to obtain the poly-ferro-manganese-graphene flocculant.
And (3) garbage leachate treatment: adjusting the pH value of the landfill leachate to 7 by using 5mol/L sulfuric acid and 5mol/L sodium hydroxide, weighing a flocculating agent according to a solid-liquid ratio of 20:1(g: L), adding the flocculating agent into the landfill leachate, stirring for 30 minutes, placing the landfill leachate into a centrifuge, centrifuging for 5 minutes at 5000rpm, performing solid-liquid separation, taking a supernatant for detecting pollutants in the landfill leachate, and drying and weighing a solid part.
The COD concentration detection and COD removal rate calculation, ammonia nitrogen concentration detection and ammonia nitrogen removal rate calculation, total phosphorus concentration detection and total phosphorus removal rate calculation, heavy metal ion concentration detection and removal rate calculation, and flocculant recovery rate calculation were the same as in example 1, and the test results are shown in table 2.
TABLE 2 influence of the sodium peroxodisulfate and potassium permanganate mass ratio on the treatment of landfill leachate by flocculant preparation
As can be seen from table 2, when the mass ratio of sodium peroxodisulfate to potassium permanganate is less than 10:100 (as shown in table 2, when the mass ratio of sodium peroxodisulfate to potassium permanganate is 9:100, 7:100, 5:100 and lower values not listed in table 2), the amount of sodium peroxodisulfate in the mixed oxidant is less, the amount of sulfate radical generation is less, the graphite oxidation process is weakened, and more low-valence manganese is generated, so that the removal rates of COD, ammonia nitrogen and total phosphorus in the landfill leachate are all lower than 85%, the removal rates of heavy metal ions are all lower than 87%, the recovery rate of the flocculant is lower than 90%, and the removal rates of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate and the recovery rate of the flocculant are all significantly reduced as the mass ratio of sodium peroxodisulfate to potassium permanganate is reduced. When the mass ratio of the sodium peroxodisulfate to the potassium permanganate is 10-20: 100 (as shown in table 2, when the mass ratio of the sodium peroxodisulfate to the potassium permanganate is 10:100, 15:100, 20: 100), the mixed oxidant contains more sodium peroxodisulfate, sodium peroxodisulfate can decompose out a large amount of sulfate radicals under heating conditions, the sulfate radicals enhance the graphite oxidation process by increasing oxidation potential to promote graphene generation, and meanwhile, the sulfate radicals can convert low-valence manganese into high-valence manganese through oxidation, so that the graphite oxidation process by potassium permanganate can be maintained, the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the garbage leachate is higher than 94%, and the recovery rate of the flocculant is higher than 97%. When the mass ratio of the sodium peroxydisulfate to the potassium permanganate is more than 20:100 (as shown in table 3, when the mass ratio of the sodium peroxydisulfate to the potassium permanganate is 21:100, 23:100, 25:100 and higher values not listed in table 2), the removal rate of COD, ammonia nitrogen, total phosphorus, heavy metal ions and the recovery rate of the flocculating agent in the landfill leachate are not obviously changed along with the further increase of the mass ratio of the sodium peroxydisulfate to the potassium permanganate. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the sodium peroxodisulfate to the potassium permanganate is 10-20: 100, the method is most beneficial to improving the removal of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate and improving the recovery rate of the flocculant.
Example 3
Influence of mass ratio of humic acid, iron powder and graphene oxide manganese polysilicate on treatment effect of flocculant on landfill leachate
Preparing a polysilicate ferro-manganese graphene flocculant: weighing silica fume and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:2(mg: mL), mixing, uniformly stirring, and aging for 6 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 90%; weighing graphite powder and polysilicic acid according to the mass ratio of the graphite powder to the polysilicic acid of 25:100, mixing, uniformly stirring, and aging for 6 hours to obtain graphite polysilicic acid; weighing sodium peroxodisulfate and potassium permanganate according to the mass ratio of 20:100, mixing, and uniformly stirring to obtain a mixed oxidant; weighing the mixed oxidant and the graphite polysilicic acid according to the mass ratio of the mixed oxidant to the graphite polysilicic acid of 30:100, mixing, uniformly stirring, performing ultrasonic action for 4 hours, setting the temperature to be 90 ℃ in the ultrasonic process, and then aging for 6 hours to obtain graphene oxide manganese polysilicate, wherein the ultrasonic action power is 2400W; the flocculant is prepared by weighing humic acid, iron powder and graphene oxide manganese polysilicate according to the mass ratio of 5:10:100, 7:10:100, 9:10:100, 10:5:100, 10:7:100, 10:9:100, 10:10:100, 25:10:100, 40:10:100, 10:15:100, 25:15:100, 40:15:100, 10:20:100, 25:20:100, 40:20:100, 42:20:100, 45:20:100, 50:20:100, 40:21:100, 40:23:100 and 40:25:100, mixing, stirring until the iron powder is completely dissolved, aging for 12 hours, adding 10mol/L sodium hydroxide solution to adjust the pH value to 5, aging for 12 hours, drying and grinding.
And (3) garbage leachate treatment: adjusting the pH value of the landfill leachate to 13 by using 5mol/L sodium hydroxide, weighing a flocculating agent according to a solid-liquid ratio of 20:1(g: L), adding the flocculating agent into the landfill leachate, stirring for 30 minutes, placing the landfill leachate into a centrifugal machine, centrifuging for 5 minutes at 5000rpm, carrying out solid-liquid separation, taking a supernatant for detecting pollutants in the landfill leachate, drying and weighing a solid part.
The COD concentration detection and COD removal rate calculation, ammonia nitrogen concentration detection and ammonia nitrogen removal rate calculation, total phosphorus concentration detection and total phosphorus removal rate calculation, heavy metal ion concentration detection and removal rate calculation, and flocculant recovery rate calculation were the same as in example 1, and the test results are shown in table 3.
Table 3 influence of the mass ratio of humic acid, iron powder and graphene oxide manganese polysilicate on the effect of flocculant preparation on garbage leachate treatment
As can be seen from table 3, when the mass ratio of humic acid, iron powder and graphene oxide manganese polysilicate is less than 10:10:100 (as shown in table 3, when the mass ratio of humic acid, iron powder and graphene oxide manganese polysilicate is 10:9:100, 10:7:100, 10:5:100, 9:10:100, 7:10:100, 5:10:100 and lower values not listed in table 3), the humic acid and iron powder mixed into the graphene oxide manganese polysilicate is less, the graphene reduction efficiency is lower, the humic acid loaded on the surface of the graphene flocculant is less, the generation amount of ferric ions is less, so that the three-dimensional space structure of the flocculant is not fully developed, the removal rates of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate are all lower than 87%, the recovery rate of the flocculant is lower than 93%, and the removal rates and recovery rates of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate are all along with the humic acid, the ammonia nitrogen, the removal rate of the total phosphorus and the recovery, The mass ratio of the iron powder to the graphene oxide manganese polysilicate is reduced and obviously reduced. When the mass ratio of humic acid to iron powder to graphene oxide manganese polysilicate is 10-40: 10-20: 100 (as shown in table 3, when the mass ratio of humic acid to iron powder to graphene oxide manganese polysilicate is 10:10:100, 25:10:100, 40:10:100, 10:15:100, 25:15:100, 40:15:100, 10:20:100, 25:20:100, and 40:20: 100), mixing the humic acid and the iron powder into the graphene oxide manganese polysilicate, wherein part of humic acid can directly convert graphene oxide into graphene, and unreacted humic acid can be effectively loaded on the surface of the graphene flocculant. The iron powder can absorb hydrogen ions and convert the hydrogen ions into ferrous ions, the ferrous ions can react with graphene oxide to generate graphene and ferric ions, meanwhile, the ferrous ions can also react with high-valence manganese ions to promote the reduction of the valence of the manganese ions, the ferric ions can interact with polysilicic acid distributed by the graphene and combine with manganese with different valence states, so that a three-dimensional space structure of the flocculating agent is generated, finally, the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate is greater than 94%, and the recovery rate of the flocculating agent is greater than 98%. When the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate is greater than 40:20:100 (as shown in table 3, when the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate is 42:20:100, 45:20:100, 50:20:100, 40:21:100, 40:23:100 and 40:25:100, and higher values not listed in table 3), the removal rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions and the recovery rate of the flocculant in the landfill leachate are not obviously changed along with further increase of the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate. Therefore, in a comprehensive aspect, the benefits and the cost are combined, and when the mass ratio of the humic acid to the iron powder to the graphene oxide manganese polysilicate is 10-40: 10-20: 100, the prepared flocculant is most beneficial to improving the removal of COD, ammonia nitrogen, total phosphorus and heavy metal ions in the landfill leachate and improving the recovery rate of the flocculant.
Example 4
Preparing a polysilicate ferro-manganese graphene flocculant: weighing silica fume and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:2(mg: mL), mixing, uniformly stirring, and aging for 6 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 90%; weighing graphite powder and polysilicic acid according to the mass ratio of the graphite powder to the polysilicic acid of 25:100, mixing, uniformly stirring, and aging for 6 hours to obtain graphite polysilicic acid; weighing sodium peroxodisulfate and potassium permanganate according to the mass ratio of 20:100, mixing, and uniformly stirring to obtain a mixed oxidant; weighing the mixed oxidant and the graphite polysilicic acid according to the mass ratio of the mixed oxidant to the graphite polysilicic acid of 30:100, mixing, uniformly stirring, performing ultrasonic action for 4 hours, setting the temperature to be 90 ℃ in the ultrasonic process, and then aging for 6 hours to obtain graphene oxide manganese polysilicate, wherein the ultrasonic action power is 2400W; the method comprises the steps of weighing humic acid, iron powder and graphene oxide manganese polysilicate according to the mass ratio of 25:15:100, mixing, stirring until the iron powder is completely dissolved, aging for 12 hours, adding 10mol/L sodium hydroxide solution to adjust the pH value to 5, aging for 12 hours, drying, and grinding to obtain the poly-silicon-iron-manganese-graphene flocculant.
Comparative example 1
Preparing a poly-silicon-iron flocculating agent: weighing silica fume and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:2(mg: mL), mixing, uniformly stirring, and aging for 6 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 90%; weighing humic acid, iron powder and polysilicic acid according to the mass ratio of the humic acid to the iron powder to the polysilicic acid of 25:15:100, mixing, stirring until the iron powder is completely dissolved, aging for 12 hours, adding 10mol/L sodium hydroxide solution to adjust the pH value to 5, aging for 12 hours, drying and grinding to obtain the polysilicic iron flocculant.
Comparative example 2
Preparing a polysilicate ferro-manganese flocculating agent: weighing silica fume and concentrated sulfuric acid according to a solid-to-liquid ratio of 1:2(mg: mL), mixing, uniformly stirring, and aging for 6 hours to obtain polysilicic acid, wherein the mass fraction of the concentrated sulfuric acid is 90%; weighing potassium permanganate and polysilicic acid according to the mass ratio of 30:100 of the potassium permanganate to the polysilicic acid, mixing, uniformly stirring, performing ultrasonic action for 4 hours, setting the temperature to be 90 ℃ in the ultrasonic process, and then aging for 6 hours to obtain the manganese polysilicate, wherein the ultrasonic action power is 2400W; weighing humic acid, iron powder and manganese polysilicate according to the mass ratio of the humic acid to the iron powder to the manganese polysilicate of 25:15:100, mixing, stirring until the iron powder is completely dissolved, aging for 12 hours, adding 10mol/L sodium hydroxide solution to adjust the pH value to 5, aging for 12 hours, drying and grinding to obtain the manganese polysilicate flocculant.
Comparative example 3
Acrylamide flocculant (PAM): and (4) market purchase.
The flocculating agents prepared in the embodiment 4 and the comparative examples 1-3 are used for treating the landfill leachate, and the treatment process is the same as that of the embodiment 2. The COD concentration detection and COD removal rate calculation, ammonia nitrogen concentration detection and ammonia nitrogen removal rate calculation, total phosphorus concentration detection and total phosphorus removal rate calculation, heavy metal ion concentration detection and removal rate calculation, and flocculant recovery rate calculation were the same as in example 1, and the test results are shown in table 4.
Table 4 comparison of the effect of the flocculant prepared in example 4 and comparative examples 1 to 3 on treating landfill leachate
As can be seen from Table 4, compared with the acrylamide flocculant (PAM) which is generally used in the market, the poly-ferro-manganese-silicon graphene flocculant prepared by the invention has better effect on landfill leachate treatment. Due to the mutual synergistic effect of the used raw materials, the removal rate and the recovery rate of COD, ammonia nitrogen, total phosphorus and heavy metal ions of the polysilicate ferro-manganese graphene flocculant are higher than the sum of the effects of the polysilicate ferro-manganese flocculant and the polysilicate ferro-manganese flocculant.
Claims (10)
1. The preparation method of the polysilicate ferromanganese graphene flocculant is characterized by comprising the following steps:
(1) uniformly mixing the silica fume with concentrated sulfuric acid, and aging to obtain polysilicic acid;
(2) adding graphite powder into polysilicic acid, uniformly mixing, and aging to obtain graphite polysilicic acid;
(3) uniformly mixing sodium peroxodisulfate and potassium permanganate to obtain a mixed oxidant, adding the mixed oxidant into graphite polysilicic acid, uniformly mixing, performing ultrasonic treatment, and aging to obtain graphene oxide manganese polysilicate;
(4) and (3) uniformly mixing humic acid, iron powder and graphene oxide manganese polysilicate, aging, adjusting the pH value to be acidic, continuously aging, drying and grinding to obtain the manganese polysilicate graphene flocculant.
2. The preparation method of the polysilicate manganese graphene flocculant according to claim 1, wherein the mass ratio of the graphite powder to the polysilicic acid in the step (2) is 5-30: 100.
3. The preparation method of the polysilicate manganese ferrite graphene flocculant according to claim 2, wherein in the step (2), the mass ratio of the graphite powder to the polysilicic acid in the step (2) is 5-25: 100.
4. The preparation method of the polysilicate manganese graphene flocculant according to claim 1, wherein the mass ratio of sodium peroxodisulfate to potassium permanganate in the step (3) is 10-25: 100.
5. The preparation method of the polysilicate manganese graphene flocculant according to claim 4, wherein the mass ratio of the sodium peroxodisulfate to the potassium permanganate in the step (3) is 10-20: 100.
6. The preparation method of the poly-silicon-manganese-graphene flocculant according to claim 1, wherein the mass ratio of humic acid to iron powder to graphene oxide-manganese polysilicate in the step (4) is 10-50: 10-25: 100.
7. The preparation method of the polysilicate manganese graphene flocculant according to claim 6, wherein the mass ratio of humic acid to iron powder to graphene oxide manganese polysilicate in the step (4) is 10-40: 10-20: 100.
8. The preparation method of the polysilicate manganese graphene flocculant according to claim 1, wherein the solid-to-liquid ratio of silica fume to concentrated sulfuric acid in the step (1) is 1: 1-2, the aging time is 3-6 hours, the mass fraction of the concentrated sulfuric acid is 70% -90%, and the aging time in the step (2) is 3-6 hours.
9. The preparation method of the polysilicate manganese-silicon graphene flocculant according to claim 1, wherein the mass ratio of the mixed oxidant to the graphite polysilicate in the step (3) is 10-30: 100, the ultrasonic treatment power is 600-2400W, the treatment temperature is 60-90 ℃, the ultrasonic time is 2-4 hours, and the aging time is 3-6 hours.
10. The preparation method of the polysilicate manganese ferrite graphene flocculant according to claim 1, wherein in the step (4), the flocculant is aged for 6-12 hours, the pH value of the flocculant is adjusted to 3-5 by using 5-10 mol/L sodium hydroxide solution, and then the flocculant is continuously aged for 6-12 hours.
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