CN113000014B - Method for preparing efficient dephosphorizing agent by utilizing waste incineration fly ash and product thereof - Google Patents

Method for preparing efficient dephosphorizing agent by utilizing waste incineration fly ash and product thereof Download PDF

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CN113000014B
CN113000014B CN202110228503.4A CN202110228503A CN113000014B CN 113000014 B CN113000014 B CN 113000014B CN 202110228503 A CN202110228503 A CN 202110228503A CN 113000014 B CN113000014 B CN 113000014B
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黄涛
宋东平
周璐璐
张树文
徐娇娇
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Changshu Institute of Technology
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a method for preparing a high-efficiency dephosphorizing agent by utilizing waste incineration fly ash and a product thereof. The leaching concentration of heavy metal of the efficient dephosphorizing agent is not more than the highest allowable emission concentration limit value specified in GB8978, namely cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L, lead is lower than 1.0mg/L, the content of soluble chlorine is not more than 2%, the highest phosphorus adsorption capacity is 537mg/g, and the preparation process is simple.

Description

Method for preparing efficient dephosphorizing agent by utilizing waste incineration fly ash and product thereof
Technical Field
The invention relates to a method for preparing a high-efficiency dephosphorizing agent by utilizing waste incineration fly ash and a product thereof, belonging to the field of resource utilization of dangerous wastes.
Background
With the rapid development of phosphorus chemical industry, more and more phosphorus-containing sewage is generated in the process of production and use. The free discharge of the phosphorus-containing sewage is easy to cause the eutrophication of the water body (the phosphorus content exceeds 20 mg/m) 3 ) Therefore, algae in water can be quickly propagated, finally, the dissolved oxygen in the water is obviously reduced, a large amount of aquatic organisms in water die, anaerobic bacteria and bacteria are propagated, and finally, the surrounding ecological environment is influenced and the human health is threatened.
The traditional phosphorus-containing waste liquid treatment method mainly comprises a chemical precipitation method, a biological method, a crystallization method and an adsorption method. Among them, the adsorption method is widely used in the sewage advanced treatment technology. The adsorption method mainly uses materials with larger specific surface area or developed pores to realize the efficient removal of phosphorus in sewage through physical adsorption and chemical adsorption ways. The surface of the traditional adsorbent is mostly negatively charged, and the adsorption effect on phosphate ions is poor. The adsorption method for removing phosphorus has the characteristics of simple operation and small secondary pollution, but has the problems of small adsorption capacity of the adsorbent and large addition amount of the adsorbent in the treatment process.
The waste incineration fly ash belongs to dangerous waste, has extremely narrow recycling way at present, and is only successfully applied to cement kiln co-treatment in industry. Therefore, the development of diversified and high-value materials based on the waste incineration fly ash meets the current resource utilization requirement of the waste incineration fly ash. The preparation of the dephosphorizing agent by utilizing the waste incineration fly ash not only can develop a fly ash utilization way, but also can provide a new thought for solving the problem of pollution of the phosphorus-containing waste liquid.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for preparing an efficient dephosphorizing agent by utilizing waste incineration fly ash and a product thereof.
The technical scheme is as follows: the invention provides a method for preparing a high-efficiency dephosphorizing agent by utilizing waste incineration fly ash, which comprises the following steps:
(1) Mixing sodium silicate with waste incineration fly ash to obtain silicon-doped fly ash;
(2) Mixing silicon-doped fly ash with water, continuously stirring, standing, and filtering to obtain solid silicon mortar;
(3) Mixing hydrochloric acid and water to obtain a hydrochloric acid aqueous solution;
(4) Mixing the hydrochloric acid aqueous solution with the silica fume mud, continuously stirring, and filtering to obtain a solid part of silica-calcium mud;
(5) Mixing the calcium silicate mud with water, and stirring to obtain calcium silicate slurry;
(6) And (3) performing low-temperature plasma discharge treatment on the calcium silicate slurry, filtering, drying and grinding the solid part to obtain the efficient dephosphorizing agent.
Further, in the step (1), the mass ratio of the sodium silicate to the waste incineration fly ash is 1-3:10.
Further, in the step (2), the liquid-solid ratio of the water to the silicon-doped fly ash is 0.3-0.9:1 mL/mg, the continuous stirring speed is 60-360 rpm, the stirring time is 0.5-2.5 h, and the standing time is 6-24 h.
Further, in the step (3), the concentration of the aqueous hydrochloric acid solution is 0.05 to 1.5M. Further, in the step (4), the liquid-solid ratio of the hydrochloric acid aqueous solution to the silicon plaster is 0.5-1.5:1 mL/mg, the continuous stirring rotating speed is 60-360 rpm, and the continuous stirring time is 0.5-2.5 h.
Further, in the step (5), the liquid-solid ratio of the water to the calcium silicate mud is 0.5-1.5:1 mL/mg.
Further, in the step (6), the low-temperature plasma discharge treatment time is 1-4 hours, the low-temperature plasma discharge power is 5-50 kW, and the gas introduced in the low-temperature plasma discharge process is oxygen.
Further, in the step (6), the drying temperature is 50-150 ℃, and the grinding time is 0.5-4.5 h.
The invention also discloses the efficient dephosphorizing agent prepared by the method.
Reaction mechanism:
after mixing water and silicon-doped fly ash, sodium silicate reacts with calcium oxide in the waste incineration fly ash in the stirring process to generate calcium silicate, hydrated calcium silicate and ettringite. Filtering the mixed slurry, and transferring soluble sodium salt, potassium salt, sulfate radical and partial heavy metal ions in the mixed slurry into filtrate. During the mixing of the siliceous stucco with the aqueous hydrochloric acid solution, the ettringite in the siliceous stucco dissolves, the aluminum, magnesium, iron and residual heavy metal elements in the siliceous stucco are acid-dissolved into the slurry and transferred to the filtrate after filtration. And (3) carrying out low-temperature plasma discharge on the calcium silicate slurry, and ionizing and dissociating water vapor and oxygen in a discharge channel in the discharge process to generate oxygen free radicals and hydroxyl free radicals. Oxygen radicals and hydroxyl radicals react with calcium silicate in the calcium silicate slurry to produce a significant amount of tobermorite. Meanwhile, chlorine ions in the calcium silicate slurry react with oxygen free radicals and hydroxyl free radicals and then are converted into chlorine-containing active substances such as chlorine free radicals, chlorine oxygen free radicals, hypochlorite and the like, and the chlorine-containing active substances can further induce calcium silicate to generate hydrolysis polymerization reaction to generate calcium polysilicate gel, and the chlorine-containing active substances are converted into chlorine ions again after the reaction. The chloride ions in the silicon-calcium slurry comprise residual chloride ions in fly ash and chloride ions introduced by hydrochloric acid. Filtering the low-temperature plasma treated silicon-calcium slurry, and transferring residual free chloride ions in the silicon-calcium slurry into filtrate. And drying and grinding the filtered calcium silicate slurry to obtain the efficient dephosphorizing agent. If the hydrochloric acid aqueous solution is changed into the sulfuric acid aqueous solution in the preparation process, the silicon stucco is mixed with the sulfuric acid aqueous solution, more ettringite is generated in the stirring process, so that the dissolution of aluminum, magnesium, iron and residual heavy metal elements in the silicon stucco is inhibited, the tobermorite generated in the low-temperature plasma treated silicon calcium slurry finally contains the aluminum, magnesium, iron and residual heavy metal elements, and meanwhile, the generation amount of polysilicogel is obviously reduced. If the hydrochloric acid aqueous solution is changed into the nitric acid aqueous solution in the preparation process, the silicon stucco is mixed with the sulfuric acid aqueous solution, and although the aluminum, the magnesium, the iron and the residual heavy metal elements in the silicon stucco can be effectively dissolved, the generation amount of polysilico-calcium gel in the low-temperature plasma treated silicon-calcium slurry is obviously reduced.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the invention takes the waste incineration fly ash as the main raw material, and prepares the high-efficiency dephosphorization agent by adding sodium silicate and hydrochloric acid and performing low-temperature plasma discharge treatment, the preparation process is simple, the leaching concentration of heavy metal of the prepared dephosphorization agent does not exceed the maximum allowable discharge concentration limit value specified in GB8978, namely cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L, lead is lower than 1.0mg/L, the content of soluble chlorine is not more than 2%, and the highest phosphorus adsorption capacity is 537mg/g.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
The fly ash from incineration of household garbage is obtained from a well-established garbage incineration power plant and collected by a bag-type dust collector. The waste incineration fly ash sample mainly contains 30 to 45 percent of CaO, 10 to 20 percent of Cl and 6 to 12 percent of Na 2 O、6％～12％K 2 O、3％～8％SO 2 、3％～8％SiO 2 、2％～6％MgO、2％～6％Fe 2 O 3 、2％～6％Al 2 O 3 、0.5％～1.5％CrO 3 0.1 to 0.5 percent of CdO, 0.1 to 0.5 percent of NiO, 0.1 to 0.5 percent of PbO and the like.
Example 1 influence of sodium silicate and waste incineration fly ash Mass ratio on the Performance of the prepared dephosphorizing agent
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of 0.5:10, 0.7:10, 0.9:10, 1:10, 2:10, 3:10, 3.2:10, 3.5:10 and 4:10, and mixing to obtain nine groups of silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.3:1mL/mg, mixed, continuously stirred for 0.5h under the condition of rotating at 60rpm, and stood for 6h, and the solid part obtained after filtration is silicon plaster, which is nine groups. Hydrochloric acid and water were mixed to prepare a 0.05M hydrochloric acid aqueous solution. And respectively weighing the hydrochloric acid aqueous solution and the silica fume according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume of 0.5:1mL:mg, mixing, continuously stirring for 0.5h at the rotating speed of 60rpm, and filtering to obtain a solid part of the silica fume, wherein the solid part is the silica fume, and the solid part is nine groups. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 0.5:1mL:mg, and mixing to obtain nine groups of calcium silicate slurries. And carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 1h, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain nine groups of efficient dephosphorizing agents, wherein the low-temperature plasma discharge power is 5kW, the gas introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 50 ℃, and the grinding time is 0.5h, so that nine groups of efficient dephosphorizing agents are obtained.
Dephosphorization test: and adding 1g of the prepared efficient dephosphorizing agent into 500mL of aqueous solution containing 1000mg/L of sodium phosphate, mixing, stirring for 30 minutes at a stirring speed of 120rpm, and centrifuging for 5 minutes at a rotating speed of 5000rpm to obtain nine groups of treated supernatant.
Determination of phosphorus concentration in supernatant: the phosphorus concentration in the supernatant was determined according to the method of "determination of total phosphorus in Water quality" ammonium molybdate spectrophotometry (GB 11893).
Determination of chlorine content in high-efficiency dephosphorizing agent: the chlorine content of the efficient dephosphorizing agent is measured according to the construction sand (GB/T14684-2011).
Preparing a leaching solution of the efficient dephosphorizing agent: the efficient dephosphorizing agent is used for preparing leaching liquid according to the method of horizontal oscillation method (HJ 557) of solid waste leaching toxicity leaching method.
Determination of chromium, nickel, lead and cadmium concentrations in the leachate: the concentrations of three pollutants of nickel, lead and cadmium in the leaching solution are all measured according to an inductively coupled plasma emission spectrometry (HJ 776-2015) for measuring 32 elements of water quality, and the concentration of the chromium pollutant is measured according to a flow injection-diphenyl carbodihydrazide photometry (HJ 908-2017) for measuring hexavalent chromium of water quality.
Phosphorus adsorption capacity: the phosphorus removal rate is calculated according to the formula (1), R p For phosphorus removal efficiency, wherein c p0 And c pt The phosphorus concentration (mg/L) in the sodium phosphate aqueous solution and the supernatant liquid are respectively shown, m is the mass (g) of the phosphorus remover, and V is the volume (L) of the sodium phosphate aqueous solution.
R p ＝(c p0 -c pt )×V/m (1)
The test results of this example are shown in Table 1.
TABLE 1 influence of sodium silicate and waste incineration fly ash mass ratio on the Performance of the prepared dephosphorizing agent
Figure BDA0002957844670000041
Figure BDA0002957844670000051
As can be seen from the analysis in Table 1, under the condition that the mass ratio of sodium silicate to waste incineration fly ash is lower than 2%, the chlorine content in the dephosphorizing agent accords with the pollution control technical specification (HJ 1134) of the household waste incineration fly ash, and the concentration of heavy metals in the leaching liquid does not exceed the maximum allowable emission concentration limit value specified in GB8978, namely, cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L and lead is lower than 1.0mg/L. When the mass ratio of sodium silicate to waste incineration fly ash is less than 1:10, the addition amount of sodium silicate is less, calcium silicate and hydrated calcium silicate generated by the reaction of sodium silicate and calcium oxide in the waste incineration fly ash in the stirring process are less, and meanwhile, tobermorite and polysilicosane gel generated in the low-temperature plasma discharge process are reduced, so that the phosphorus adsorption capacity of the phosphorus remover is obviously reduced along with the reduction of the mass ratio of sodium silicate to waste incineration fly ash. When the mass ratio of the sodium silicate to the waste incineration fly ash is 1-3:10, the sodium silicate reacts with calcium oxide in the waste incineration fly ash in the stirring process to generate calcium silicate and hydrated calcium silicate. And (3) carrying out low-temperature plasma discharge on the calcium silicate slurry, and ionizing and dissociating water vapor and oxygen in a discharge channel in the discharge process to generate oxygen free radicals and hydroxyl free radicals. Oxygen radicals and hydroxyl radicals react with calcium silicate in the calcium silicate slurry to produce a significant amount of tobermorite. Meanwhile, chloride ions of the calcium silicate slurry react with oxygen free radicals and hydroxyl free radicals and then are converted into hypochlorite, and the hypochlorite can induce calcium silicate to generate hydrolysis polymerization reaction to generate polysilica gel and chloride ions. Finally, the phosphorus adsorption capacity of the phosphorus remover is more than 442mg/g. When the mass ratio of the sodium silicate to the waste incineration fly ash is more than 3:10, the phosphorus adsorption capacity of the phosphorus remover is not remarkably changed along with the further increase of the mass ratio of the sodium silicate to the waste incineration fly ash. Therefore, when the mass ratio of the sodium silicate to the waste incineration fly ash is 1-3:10, the combination of benefits and costs is most beneficial to improving the performance of the prepared dephosphorizing agent.
Example 2 effect of liquid-solid ratio of aqueous hydrochloric acid solution and silica fume on the Property of the prepared dephosphorizing agent
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.6:1mL:mg, mixed, continuously stirred for 1.5h under the rotating speed of 210rpm, and kept stand for 15h, and the solid part obtained after filtration is silicon plaster. Hydrochloric acid and water were mixed to prepare a hydrochloric acid aqueous solution having a concentration of 0.775M. The hydrochloric acid aqueous solution and the silica fume are respectively weighed according to the liquid-solid ratio of 0.25:1mL:mg, 0.35:1mL:mg, 0.45:1mL:mg, 0.5:1mL:mg, 1.0:1mL:mg, 1.5:1mL:mg, 1.55:1mL:mg, 1.65:1mL:mg and 1.75:1mL:mg, the hydrochloric acid aqueous solution and the silica fume are mixed, the mixture is continuously stirred for 1.5h under the rotating speed of 210rpm, and the solid part obtained after filtration is the silica fume, which is nine groups. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1:1mL to mg, and mixing to obtain nine groups of calcium silicate slurries. And respectively carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 2.5 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain nine groups of efficient dephosphorizing agents, wherein the low-temperature plasma discharge power is 27.5kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 100 ℃, and the grinding time is 2.5 hours, so that nine groups of efficient dephosphorizing agents are obtained.
The phosphorus removal test, the determination of chlorine content in the high-efficiency phosphorus removal agent, the preparation of the leaching solution of the high-efficiency phosphorus removal agent, the determination of chromium, nickel, lead and cadmium concentrations in the leaching solution, the determination of phosphorus concentration in supernatant fluid of the phosphorus removal test and the phosphorus adsorption capacity are the same as in example 1. The test results of this example are shown in Table 2.
TABLE 2 influence of aqueous hydrochloric acid solution and silica fume liquid solids ratio on the Performance of the prepared dephosphorizing agent
Figure BDA0002957844670000061
As can be seen from the analysis of Table 2, under the condition that the ratio of the hydrochloric acid aqueous solution to the siliceous dust mud liquid solid is lower than 2 percent, the chlorine content in the dephosphorizing agent is in accordance with the technical specification of the pollution control of the municipal solid waste incineration fly ash (HJ 1134), and the concentration of heavy metals in the leaching liquid does not exceed the highest allowable emission concentration limit value specified in GB8978, namely, cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L and lead is lower than 1.0mg/L. When the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica gel is less than 0.5:1mL:mg, the hydrochloric acid aqueous solution is less, and the dissolution effects of iron, magnesium, aluminum and the like in the silica gel are poor, so that the generation efficiency of tobermorite and polysilica calcium is reduced, and the phosphorus adsorption capacity of the dephosphorizing agent is obviously reduced along with the reduction of the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica gel. When the solid content of the hydrochloric acid aqueous solution and the silica fume slurry is 0.5-1.5:1 mL/mg, aluminum, magnesium, iron and residual heavy metal elements in the silica fume are dissolved in the slurry by acid in the stirring process after the silica fume is mixed with the hydrochloric acid aqueous solution, and are transferred into the filtrate after being filtered. Finally, the phosphorus adsorption capacity of the phosphorus remover is greater than 469mg/g. When the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume mud is more than 1.5:1mL:mg, the hydrochloric acid aqueous solution is excessive, and part of silicon and calcium in the silica fume mud are dissolved out, so that the phosphorus adsorption capacity of the phosphorus remover is obviously reduced along with the further increase of the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume mud. Therefore, when the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume is equal to 0.5-1.5:1 mL:mg, the performance of the prepared dephosphorizing agent is most beneficial to improvement.
Example 3 Effect of Low temperature plasma discharge time on the Performance of the prepared dephosphorizing agent
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Hydrochloric acid and water were mixed to prepare a 1.5M aqueous hydrochloric acid solution. And respectively weighing the hydrochloric acid aqueous solution and the silica fume according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume of 1.5:1mL:mg, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the silica fume. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. And respectively carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 0.5h, 0.7h, 0.9h, 1h, 2.5h, 4h, 4.5h, 5h and 5.5h, filtering, drying the solid part obtained by filtering, and grinding the solid part to obtain nine groups of efficient dephosphorizing agents, wherein the discharge power of the low-temperature plasma is 50kW, the atmosphere introduced in the discharge process of the low-temperature plasma is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5h, so as to obtain nine groups of efficient dephosphorizing agents.
The phosphorus removal test, the determination of chlorine content in the high-efficiency phosphorus removal agent, the preparation of the leaching solution of the high-efficiency phosphorus removal agent, the determination of chromium, nickel, lead and cadmium concentrations in the leaching solution, the determination of phosphorus concentration in supernatant fluid of the phosphorus removal test and the phosphorus adsorption capacity are the same as in example 1. The test results of this example are shown in Table 3.
TABLE 3 Effect of Low temperature plasma discharge time on the Performance of the prepared dephosphorizers
Figure BDA0002957844670000071
Figure BDA0002957844670000081
As shown by the analysis of the table 3, under the existing discharge time condition of low-temperature plasma discharge, the chlorine content in the dephosphorizing agent is lower than 2%, the technical specification (HJ 1134) of the pollution control of the fly ash of the household garbage incineration is met, and the concentration of heavy metals in the leaching solution does not exceed the highest allowable discharge concentration limit value specified in GB8978, namely, cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L and lead is lower than 1.0mg/L. When the low-temperature plasma discharge time is less than 1h, the low-temperature plasma discharge time is shorter, and the generation amount of oxygen free radicals and hydroxyl free radicals is smaller, so that the generation amount efficiency of tobermorite and polysilicosane gel is reduced, and the phosphorus adsorption capacity of the phosphorus remover is obviously reduced along with the reduction of the low-temperature plasma discharge time. When the discharge time of the low-temperature plasma is equal to 1-4 h, the low-temperature plasma is carried out on the calcium silicate slurry, and the water vapor and oxygen are ionized and dissociated in a discharge channel in the discharge process to generate oxygen free radicals and hydroxyl free radicals. Oxygen radicals and hydroxyl radicals react with calcium silicate in the calcium silicate slurry to produce a significant amount of tobermorite. Meanwhile, chloride ions of the calcium silicate slurry react with oxygen free radicals and hydroxyl free radicals and then are converted into hypochlorite, and the hypochlorite can induce calcium silicate to generate hydrolysis polymerization reaction to generate the calcium polysilicate gel. Finally, the phosphorus adsorption capacity of the phosphorus remover is more than 512mg/g. When the low-temperature plasma discharge time is more than 4 hours, the phosphorus adsorption capacity of the phosphorus remover is not remarkably changed along with the further increase of the low-temperature plasma discharge time. Therefore, when the discharge time of the low-temperature plasma is equal to 1-4 h, the combination of benefits and cost is most favorable for improving the performance of the prepared dephosphorizing agent.
EXAMPLE 4 Effect of hydrochloric acid solution concentration on the Performance of the prepared dephosphorizing agent
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Hydrochloric acid and water were mixed to prepare aqueous solutions of hydrochloric acid at 0.025M, 0.035M, 0.045M, 0.05M, 0.775M, 1.5M, 1.55M, 1.65M and 1.75M, respectively. And respectively weighing the hydrochloric acid aqueous solution and the silica fume according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume of 1.5:1mL:mg, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the silica fume. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. And carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 4 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain nine groups of efficient dephosphorizing agents, wherein the low-temperature plasma discharge power is 50kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5 hours, so that nine groups of efficient dephosphorizing agents are obtained.
The phosphorus removal test, the determination of chlorine content in the high-efficiency phosphorus removal agent, the preparation of the leaching solution of the high-efficiency phosphorus removal agent, the determination of chromium, nickel, lead and cadmium concentrations in the leaching solution, the determination of phosphorus concentration in supernatant fluid of the phosphorus removal test and the phosphorus adsorption capacity are the same as in example 1. The test results of this example are shown in Table 4.
TABLE 4 influence of hydrochloric acid solution concentration on the Performance of the prepared dephosphorization agent
Figure BDA0002957844670000091
As can be seen from the analysis in Table 4, under the condition of the existing concentration range of the hydrochloric acid solution, the chlorine content in the dephosphorizing agent is lower than 2%, the method accords with the technical specification (HJ 1134) of the pollution control of the fly ash of the household garbage incineration, and the concentration of heavy metals in the leaching solution does not exceed the highest allowable emission concentration limit value specified in GB8978, namely, cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L and lead is lower than 1.0mg/L. When the concentration of the aqueous hydrochloric acid solution is lower than 0.05M, ettringite in the silicon stucco is insufficiently dissolved in the stirring process after the silicon stucco and the aqueous hydrochloric acid solution are mixed, aluminum, magnesium, iron and residual heavy metal elements in the silicon stucco which are dissolved into the slurry by acid and transferred into the filtrate after filtration are reduced, so that tobermorite generated in the low-temperature plasma treated silicon calcium slurry contains aluminum, magnesium, iron and residual heavy metal elements, and the phosphorus adsorption capacity of the phosphorus remover is obviously reduced along with the reduction of the concentration of the aqueous hydrochloric acid solution. When the concentration of the aqueous hydrochloric acid solution is 0.05-1.5M, the ettringite in the silicon stucco is dissolved in the stirring process after the silicon stucco and the aqueous hydrochloric acid solution are mixed, and aluminum, magnesium, iron and residual heavy metal elements in the silicon stucco are acid-dissolved into the slurry and transferred into the filtrate after filtration. Meanwhile, chlorine ions in the calcium silicate slurry react with oxygen free radicals and hydroxyl free radicals and then are converted into chlorine-containing active substances such as chlorine free radicals, chlorine oxygen free radicals, hypochlorite and the like, and the chlorine-containing active substances can further induce calcium silicate to generate hydrolysis polymerization reaction to generate calcium polysilicate gel, and the chlorine-containing active substances are converted into chlorine ions again after the reaction. Finally, the phosphorus adsorption capacity of the phosphorus remover is larger than 517mg/g. When the concentration of the aqueous solution of hydrochloric acid is more than 1.5M, the concentration of the aqueous solution of hydrochloric acid is too high, part of silicon and calcium in the silica fume mud are dissolved out, so that the formation amount of tobermorite and polysilica calcium gel is reduced, the performance of the dephosphorizing agent is reduced, and the phosphorus adsorption capacity of the dephosphorizing agent is reduced along with the further increase of the concentration of the aqueous solution of hydrochloric acid. Therefore, the combination of benefits and cost is most beneficial to improving the performance of the prepared dephosphorizing agent when the concentration of the hydrochloric acid aqueous solution is 0.05-1.5M.
Performance comparison of dephosphorizing agents prepared by different preparation processes
Example 5
The preparation process comprises the following steps: and respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Hydrochloric acid and water were mixed to prepare a 1.5M aqueous hydrochloric acid solution. Respectively weighing the hydrochloric acid aqueous solution and the silica fume slurry according to the ratio of 1.5:1mL to mg of the hydrochloric acid aqueous solution to the silica fume slurry solid, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the silica-calcium slurry. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. And carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 4 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain the efficient phosphorus remover, wherein the low-temperature plasma discharge power is 50kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5 hours, so that the efficient phosphorus remover is obtained.
Comparative example 1
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Hydrochloric acid and water were mixed to prepare a 1.5M aqueous hydrochloric acid solution. And respectively weighing the hydrochloric acid aqueous solution and the silica fume according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume of 1.5:1mL:mg, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the silica fume. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. Stirring the calcium silicate slurry for 4 hours, filtering, drying the solid part obtained by filtering, and grinding the solid part to obtain the dephosphorizing agent, wherein the drying temperature is 150 ℃, and the grinding time is 4.5 hours to obtain the dephosphorizing agent.
Comparative example 2
The water and the waste incineration fly ash are respectively weighed according to the ratio of 0.9:1mL to mg of liquid solid, mixed, continuously stirred for 2.5h under the rotation speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is the plaster. Hydrochloric acid and water were mixed to prepare a 1.5M aqueous hydrochloric acid solution. The hydrochloric acid aqueous solution and the plaster are respectively weighed according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the plaster of 1.5:1mL:mg, mixed and continuously stirred for 2.5h under the rotating speed of 360rpm, and the solid part obtained after filtration is acid washing mud. And respectively weighing water and pickling mud according to the ratio of 1.5:1mL to mg of water to pickling mud liquid solid, and mixing to obtain pickling mud. And (3) carrying out low-temperature plasma discharge treatment on the pickling slurry for 4 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain the dephosphorizing agent, wherein the low-temperature plasma discharge power is 50kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5 hours, so as to obtain the dephosphorizing agent.
Comparative example 3
The water and the waste incineration fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is the plaster. Hydrochloric acid and water were mixed to prepare a 1.5M aqueous hydrochloric acid solution. The hydrochloric acid aqueous solution and the plaster are respectively weighed according to the liquid-solid ratio of the hydrochloric acid aqueous solution to the plaster of 1.5:1mL:mg, mixed and continuously stirred for 2.5h under the rotating speed of 360rpm, and the solid part obtained after filtration is acid washing mud. And respectively weighing water and pickling mud according to the ratio of 1.5:1mL to mg of water to pickling mud liquid solid, and mixing to obtain pickling mud. Stirring the pickling mud for 4 hours, filtering, drying the solid part obtained by filtering, and grinding the solid part to obtain the dephosphorizing agent, wherein the drying temperature is 150 ℃, and the grinding time is 4.5 hours to obtain the dephosphorizing agent.
Comparative example 4
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Sulfuric acid and water were mixed to prepare a 1.5M sulfuric acid aqueous solution. And respectively weighing the sulfuric acid aqueous solution and the silica fume slurry according to the ratio of 1.5:1mL to mg of the sulfuric acid aqueous solution to the silica fume slurry solid, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the silica-calcium slurry. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. And carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 4 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain the efficient dephosphorization agent, wherein the low-temperature plasma discharge power is 50kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5 hours, so as to obtain the dephosphorization agent.
Comparative example 5
And respectively weighing sodium silicate and waste incineration fly ash according to the mass ratio of the sodium silicate to the waste incineration fly ash of 3:10, and mixing to obtain the silicon-doped fly ash. The water and the silicon-doped fly ash are respectively weighed according to the liquid-solid ratio of 0.9:1mL:mg, mixed, continuously stirred for 2.5h under the rotating speed of 360rpm, and stood for 24h, and the solid part obtained after filtration is silicon plaster. Nitric acid and water were mixed to prepare a 1.5M aqueous nitric acid solution. Respectively weighing the nitric acid aqueous solution and the silica fume slurry according to the ratio of 1.5:1mL to mg of the nitric acid aqueous solution to the silica fume slurry solid, mixing, continuously stirring for 2.5h at the rotating speed of 360rpm, and filtering to obtain a solid part which is the calcium silicate slurry. And respectively weighing water and the calcium silicate slurry according to the liquid-solid ratio of the water to the calcium silicate slurry of 1.5:1mL:mg, and mixing to obtain the calcium silicate slurry. And carrying out low-temperature plasma discharge treatment on the calcium silicate slurry for 4 hours, filtering, drying a solid part obtained by filtering, and grinding the solid part to obtain the efficient dephosphorization agent, wherein the low-temperature plasma discharge power is 50kW, the atmosphere introduced in the low-temperature plasma discharge process is oxygen, the drying temperature is 150 ℃, and the grinding time is 4.5 hours, so as to obtain the dephosphorization agent.
The phosphorus removal test, the determination of chlorine content in the phosphorus removal agent, the preparation of leaching solution of the phosphorus removal agent, the determination of chromium, nickel, lead and cadmium concentrations in the leaching solution, the determination of phosphorus concentration in supernatant fluid of the phosphorus removal test and the phosphorus adsorption capacity are the same as in example 1. The test results of example 4 and comparative examples 1 to 5 are shown in Table 4.
Table 4 comparison of the Performance of dephosphorization agents prepared by different preparation Processes
Figure BDA0002957844670000121
As can be seen from Table 4, the chlorine content of the dephosphorization agents prepared in comparative examples 1, 2 and 3 is higher than 2%, and the heavy metal concentration in the leachate of the dephosphorization agents prepared in comparative examples 1, 2, 3, 4 and 5 exceeds the maximum allowable discharge concentration limit specified in GB8978, namely cadmium is lower than 0.1mg/L, chromium is lower than 0.5mg/L, nickel is lower than 1.0mg/L and lead is lower than 1.0mg/L. Meanwhile, the phosphorus adsorption capacity of the high-efficiency phosphorus removal agent prepared in process example 5 of the present invention is significantly higher than that of the phosphorus removal agents prepared in proportion 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, and is higher than the sum of the adsorption capacities of the phosphorus removal agents prepared in proportion 1, comparative example 2 and comparative example 3. Therefore, the high-efficiency dephosphorizing agent prepared by the method can effectively remove phosphorus in the phosphorus-containing waste liquid, and sodium silicate and low-temperature plasma discharge are added in the preparation process to have a synergistic effect. The addition of aqueous hydrochloric acid during the preparation process has the technical advantage that the addition of other acid solutions, including aqueous sulfuric acid and aqueous nitric acid, is not possible.

Claims (6)

1. The method for preparing the efficient dephosphorizing agent by utilizing the waste incineration fly ash is characterized by comprising the following steps of:
(1) Mixing sodium silicate and waste incineration fly ash to obtain silicon-doped fly ash, wherein the mass ratio of the sodium silicate to the waste incineration fly ash is 1-3:10;
(2) Mixing silicon-doped fly ash with water, continuously stirring, standing, and filtering to obtain solid silicon mortar;
(3) Mixing hydrochloric acid and water to obtain a hydrochloric acid aqueous solution, wherein the concentration of the hydrochloric acid aqueous solution is 0.05-1.5M;
(4) Mixing a hydrochloric acid aqueous solution and silica fume mud, continuously stirring, and filtering to obtain silica fume mud as a solid part, wherein the liquid-solid ratio of the hydrochloric acid aqueous solution to the silica fume mud is 0.5-1.5:1 mL/mg;
(5) Mixing the calcium silicate mud with water to obtain calcium silicate slurry;
(6) And performing low-temperature plasma discharge treatment on the calcium silicate slurry, filtering, drying and grinding the solid part to obtain the efficient dephosphorizing agent, wherein the low-temperature plasma discharge treatment time is 1-4 h, the low-temperature plasma discharge power is 5-50 kW, and the gas introduced in the low-temperature plasma discharge process is oxygen.
2. The method for preparing the efficient phosphorus removal agent by utilizing the waste incineration fly ash, which is characterized in that in the step (2), the liquid-solid ratio of water to silicon-doped fly ash is 0.3-0.9:1 mL/mg, the continuous stirring rotating speed is 60-360 rpm, the stirring time is 0.5-2.5 h, and the standing time is 6-24 h.
3. The method for preparing the efficient dephosphorizing agent by utilizing the waste incineration fly ash, which is characterized in that in the step (4), the continuous stirring rotating speed is 60-360 rpm, and the continuous stirring time is 0.5-2.5 h.
4. The method for preparing a high-efficiency dephosphorizing agent by utilizing waste incineration fly ash, which is characterized in that in the step (5), the liquid-solid ratio of water to calcium silicate mud is 0.5-1.5:1 mL/mg.
5. The method for preparing the efficient dephosphorizing agent by utilizing the waste incineration fly ash, which is disclosed in claim 1, is characterized in that in the step (6), the drying temperature is 50-150 ℃, and the grinding time is 0.5-4.5 h.
6. The efficient dephosphorizing agent prepared by the method of any one of claims 1 to 5.
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