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CN116751595B - Method for preparing soil passivating agent by utilizing waste incineration fly ash and coal tar and product thereof - Google Patents

Method for preparing soil passivating agent by utilizing waste incineration fly ash and coal tar and product thereof Download PDF

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CN116751595B
CN116751595B CN202310674218.4A CN202310674218A CN116751595B CN 116751595 B CN116751595 B CN 116751595B CN 202310674218 A CN202310674218 A CN 202310674218A CN 116751595 B CN116751595 B CN 116751595B
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fly ash
powder
soil
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CN116751595A (en
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黄涛
宋东平
冯玉轩
谢世宏
王成龙
张薇薇
刘铭阳
张树文
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Changshu Institute of Technology
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Abstract

The invention discloses a method for preparing a soil passivating agent by utilizing waste incineration fly ash and coal tar and a product thereof, which comprises the following steps: mixing coal tar, fly ash and garbage incineration fly ash, and carbonizing; adding sepiolite powder, desulfurized gypsum powder and fermentation liquid, heating, separating solid from liquid, and aging to obtain the heavy metal contaminated soil passivating agent. The preparation process is simple, the synergistic treatment and the efficient resource utilization of the waste incineration fly ash and the coal tar are realized through carbonization and fermentation processes, the heavy metal leaching toxicity of the prepared soil passivating agent is lower than 0.001mg/L, the chloride content is lower than 0.5%, the dioxin content is lower than 10ng-TEQ/kg, the passivation effect of the heavy metal polluted soil is obvious, the heavy metal thallium leaching concentration of the repaired soil is lower than 0.1 mug/L, and the heavy metal arsenic leaching concentration is lower than 0.01mg/L.

Description

Method for preparing soil passivating agent by utilizing waste incineration fly ash and coal tar and product thereof
Technical Field
The invention relates to a method for preparing a soil passivating agent by utilizing waste incineration fly ash and coal tar and a product thereof, belonging to the field of harmless disposal and resource utilization of dangerous wastes.
Background
The flue gas generated in the garbage incineration process is deacidified by a high Wen Tuoxiao, a temperature reduction (waste heat utilization) and a dry method (or a semi-dry method) and then captured by a bag-type dust remover, so that a large amount of garbage incineration fly ash can be generated. The chelation stabilization of the waste incineration fly ash and the landfill of the waste incineration fly ash into a landfill are the most mainstream disposal modes of the waste incineration fly ash adopted by the current waste incineration power plants. But the disposal mode taking landfill as a guide is not only easy to cause the diffusion of pollutants in the landfill area, but also does not fully utilize the components of the waste incineration fly ash. The water washing coupled cement kiln co-treatment is a widely accepted technology for realizing the recycling of the waste incineration fly ash at present. However, the disposal of the fly ash washing waste liquid not only requires the consumption of a large amount of sulfate, carbonate and heavy metal remover, but also severely limits the sales path of waste salt generated by evaporation, and the recycling path is not clear. Meanwhile, the fly ash washing waste liquid evaporation equipment has short service cycle and higher maintenance cost. If the raw material components are not accurately controlled, cement is burned by taking the washed plaster as cement raw material, which can easily cause the exceeding of the chlorine content of the cement.
The soil passivation technology is to add a soil passivating agent into heavy metal contaminated soil to realize efficient stabilization of heavy metal pollutants. In general, soil passivation technology has strong operability and is suitable for wide popularization, but the technical effect depends on the performance of the passivating agent.
Therefore, if the high-performance soil passivating agent can be prepared by utilizing the waste incineration fly ash, not only is a technical reference provided for harmless disposal and recycling of the waste incineration fly ash, but also a novel repairing agent material is provided for repairing heavy metal polluted soil.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for preparing a soil passivating agent by utilizing waste incineration fly ash and coal tar, which has the advantages of simple preparation process and remarkable passivation of heavy metal polluted soil, and a product thereof.
The technical scheme is as follows: in order to solve the technical problems, the invention provides a method for preparing a soil passivating agent by utilizing waste incineration fly ash and coal tar, which comprises the following steps:
(1) Respectively weighing coal tar, fly ash and waste incineration fly ash, mixing, and uniformly stirring to obtain tar coal plaster;
(2) Carbonizing the tar coal slime in the step (1), cooling, and grinding to obtain carbonized powder;
(3) Mixing sepiolite powder, desulfurized gypsum powder and carbonized powder in the step (2), uniformly stirring to obtain loaded powder, mixing with a fermentation liquid, heating, continuously stirring, carrying out solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent.
Wherein, the mass ratio of the coal tar to the fly ash to the garbage incineration fly ash in the step (1) is 7.5-32.5: 22.5 to 47.5:100.
Wherein the carbonization temperature in the step (2) is 300-900 ℃, and the carbonization time is 0.5-5.5 hours.
Wherein the grinding time in the step (2) is 0.5-2.5 hours.
Wherein, the mass ratio of sepiolite powder, desulfurized gypsum powder and carbonized powder in the step (3) is 15-45: 15-45: 100.
Wherein the liquid-solid ratio of the fermentation liquid to the loading powder in the step (3) is 1-3 mL/1 g.
Wherein the fermentation broth in the step (3) comprises 5-15 g/L tryptone, 5-15 g/L peptone, 5-15 g/L yeast extract, 0.5-2.5 g/L glucose, 5-25 g/L KH 2PO3, 20-120 g/L urea and 5-25 g/L FeSO 4.
Wherein the heating temperature in the step (3) is 25-55 ℃, and the heating time is 24-72 hours.
Wherein the stirring time in the step (3) is 24-72 hours, and the stirring speed is 20-160 rpm.
Wherein the aging time in the step (3) is 10-30 days.
The invention also provides a soil passivating agent prepared by the method.
Reaction mechanism: in the mixing and stirring process, calcium oxide, silicate, aluminosilicate and other inorganic minerals in the fly ash and the waste incineration fly ash fully absorb organic substances (complex mixture of high-aromatic hydrocarbon) in the coal tar, and simultaneously chloride salt, calcium salt and inorganic salt in the fly ash penetrate into the coal tar organic substances. In the carbonization process of the tar coal ash mud, chloride and calcium salt penetrating into the coal tar organic matters can strengthen dehydrogenation and carbonization of hydrocarbon in the coal tar through catalytic pyrolysis, and combustible gas and high-temperature water vapor released in the coal tar pyrolysis process can degrade dioxin pollutants in the fly ash and promote the reaction of calcium-based substances in the waste incineration fly ash with silicate and aluminosilicate in the fly ash to generate mineral mixtures such as calcium silicate, calcium aluminate, calcium aluminosilicate, sodium aluminosilicate and the like. Mixing the fermentation liquor and the loading powder, wherein tryptone, peptone, yeast extract, glucose, KH 2PO3, urea and FeSO 4 in the fermentation liquor are rapidly adsorbed into sepiolite powder, desulfurized gypsum powder and carbonized powder particle minerals in the stirring process, the loading powder swells by absorbing water, and the KH 2PO3, urea and FeSO 4 promote the minerals in the sepiolite powder, desulfurized gypsum powder and carbonized powder to generate complex geological polymerization reaction and hydration reaction through excitation, so that an active cementing material mixture is generated. Tryptone, peptone, yeast extract, glucose are adsorbed and filled in the active gel material mixture, and provide a micro-environment and an active site for potential microorganism landing, propagation, enrichment and fermentation in the aging process.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the preparation process is simple, the synergistic treatment and the efficient recycling of the waste incineration fly ash and the coal tar are realized through the material collocation carbonization and the fermentation process, the heavy metal leaching toxicity of the prepared soil passivating agent is lower than 0.001mg/L, the chloride content is lower than 0.5%, the dioxin content is lower than 10 ng-TEQ/kg, the passivation of the heavy metal polluted soil is remarkable, the heavy metal thallium leaching concentration of the repaired soil is lower than 0.1 mug/L, and the heavy metal arsenic leaching concentration is lower than 0.01mg/L.
Drawings
FIG. 1 is a flow chart of the processing method of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Waste incineration fly ash: is provided by a second household garbage incineration power plant which is commonly used in Jiangsu, and mainly comprises 36.2%CaO、23.9%Cl、11.0%SO3、11.6%Na2O、6.33%K2O、4.38%SiO2、1.40%Fe2O3、1.25%Al2O3 and other components (unavoidable impurities and loss on ignition);
coal tar elemental composition: from Jiangsu Pr Le Si Biotech Co., ltd., mainly composed of 89.12% C, 3.26% H, 2.75% O, 1.08% N, 0.57% S and other elements;
sepiolite: from Hongyang sepiolite Inc. of county, interior, having the general formula (Si 12Mg8O30)(OH)4(OH2)4•8H2 O;
Fly ash: the Taiku power plant from the International electric power Co., ltd mainly comprises 43.21%SiO2、27.08%Al2O3、15.62%Fe2O3、6.58%CaO、3.42%TiO2、1.43%SO3、1.04%K2O、0.63% Na2O and other components (unavoidable impurities and loss on ignition);
Desulfurization gypsum: the first thermal power plant from Hunan Heng Yang mainly comprises 91.34%CaSO4•2H2O、1.57%CaSO4、0.85%MgCO3、1.26%CaCO3、2.23%SiO2、1.09%Al2O3、0.51%Fe2O3 and other components (unavoidable impurities and loss on ignition).
Example 1 influence of the mass ratio of coal tar, fly ash and waste incineration fly ash on the Performance of the prepared soil passivator
And respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio 4.5:22.5:100、5.5:22.5:100、6.5:22.5:100、7.5:15:100、7.5:17.5:100、7.5:20:100、7.5:22.5:100、20:22.5:100、32.5:22.5:100、7.5:35:100、20:35:100、32.5:35:100、7.5:47.5:100、20:47.5:100、32.5:47.5:100、32.5:52.5:100、32.5:57.5:100、32.5:62.5:100、37.5:47.5:100、42.5:47.5:100、47.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. And (3) introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 300 ℃ and the carbonization time is 0.5 hour. Grinding the carbonized residues for 0.5 hour to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 15:15:100, mixing and stirring uniformly to obtain loading powder. Mixing the fermentation liquid and the loading powder according to the liquid-solid ratio of 1:1 mL/g, heating, continuously stirring, performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent. Wherein the fermentation broth is prepared by dissolving 5g/L tryptone, 5g/L peptone, 5g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 0.5g/L glucose, 5g/L KH 2PO3, 20g/L urea, 5g/L FeSO 4 in distilled water, stirring for 24 hours, stirring rate for 20rpm, heating for 24 hours, heating temperature for 25 ℃ and aging time for 10 days.
Preparing leaching liquid: the leaching solution of the soil passivating agent is prepared according to the horizontal oscillation method of the leaching toxicity leaching method of HJ 557-2010-solid waste.
Determination of heavy metal ion concentration in leachate of soil passivating agent: the concentrations of the two pollutants of lead and cadmium in the leaching solution of the soil passivating agent are measured according to the inductively coupled plasma emission spectrometry (HJ 776-2015) for measuring 32 elements of water quality. The total chromium in the leaching solution of the soil passivating agent is measured according to the method of flame atomic absorption spectrophotometry for measuring water quality chromium (HJ 757-2015).
Determination of dioxin-like substances of soil passivating agent: the dioxin-like substances were measured according to the method of high resolution gas chromatography-high resolution mass spectrometry (HJ 77.3-2008) for measuring isotope dilution of solid wastes dioxin-like substances.
Determination of chlorine content: the chlorine content of the soil passivating agent is measured according to the construction sand (GB/T14684-2011).
Preparing thallium and arsenic polluted soil: 1kg of an uncontaminated soil sample was weighed, 50 mg thallium and 50 mg arsenic were then added to the soil sample, water was added to the soil at a liquid-to-solid ratio of 1:1ml/mg, the mixture was stirred well, and the mixture was aged for 24 hours and then naturally air-dried.
Thallium and arsenic contaminated soil remediation test: weighing 25g of soil passivating agent, adding the soil passivating agent into the polluted soil, uniformly stirring, sprinkling water into the soil according to the liquid-solid ratio of 0.3:1ml/mg, and standing for 20 days in a natural environment to obtain the repaired soil.
Toxicity leaching test of soil after repair: toxicity leaching test was performed on the restored soil samples according to the solid waste leaching toxicity leaching method sulfuric acid nitric acid method (HJ/T299-2007).
Thallium and arsenic ion concentration detection: the thallium concentration in the leaching solution of the soil sample after the restoration is measured by a graphite furnace atomic absorption spectrophotometry (HJ 748-2015), and the arsenic concentration in the leaching solution of the soil sample after the restoration is measured by an atomic fluorescence measurement (HJ 694-2014) of mercury, arsenic, selenium, bismuth and antimony.
The test results of this example are shown in Table 1.
TABLE 1 influence of mass ratio of coal tar, fly ash and refuse incineration fly ash on performance of prepared soil passivator
As can be seen from table 1, when the mass ratio of coal tar, fly ash and waste incineration fly ash is smaller than 7.5:22.5:100 (as in table 1, the mass ratio of coal tar, fly ash and waste incineration fly ash=6.5:22.5:100, 5.5:22.5:100, 4.5:22.5:100, 7.5:20:100, 7.5:17.5:100, 7.5:15:100 and lower ratios not listed in table 1), the coal tar and fly ash are added less, the fly ash detoxification effect during carbonization is deteriorated, resulting in the leaching concentration of heavy metal, chlorine content, leaching of the prepared soil passivation agent the dioxin content and the toxicity leaching concentration of the restored soil are increased along with the decrease of the mass ratio of coal tar, fly ash and waste incineration fly ash. When the mass ratio of coal tar, coal ash and waste incineration fly ash is equal to 7.5-32.5:22.5-47.5:100 (as in table 1, when the mass ratio of coal tar, coal ash and waste incineration fly ash is =7.5:22.5:100、20:22.5:100、32.5:22.5:100、7.5:35:100、20:35:100、32.5:35:100、7.5:47.5:100、20:47.5:100、32.5:47.5:100), calcium oxide, silicate, aluminosilicate and other inorganic minerals in the coal ash and waste incineration fly ash fully absorb organic substances (complex mixture of high-aromatic hydrocarbon) in the coal tar in the mixing and stirring process, and chloride salt, calcium salt and inorganic salt in the coal ash in the waste incineration fly ash permeate into the coal tar organic substances. Finally, the leaching concentration of the heavy metal lead of the soil passivating agent is lower than 6.5X10 -4 mg/L, the leaching concentration of hexavalent chromium is lower than 9.1X10 -5 mg/L, the leaching concentration of cadmium is lower than 8.6X10 -4 mg/L, The chlorine content is lower than 0.5%, the dioxin substances are lower than 10ng-TEQ/kg, the toxic leaching concentration of the repaired soil thallium is lower than 0.1 mug/L, and the arsenic concentration is lower than 8.11 multiplied by 10 -3 mg/L. When the mass ratio of coal tar, fly ash and waste incineration fly ash is greater than 32.5:47.5:100 (as in table 1, the mass ratio of coal tar, fly ash and waste incineration fly ash=32.5:52.5:100, 32.5:57.5:100, 32.5:62.5:100, 37.5:47.5:100, 42.5:47.5:100, 47.5:47.5:100, and higher ratios not listed in table 1), the coal tar and fly ash are added in excess, the reaction between materials is unbalanced, resulting in that the prepared soil passivating agent heavy metal leaching concentration, chlorine content, dioxin content and post-remediation soil toxicity leaching concentration are all along with the coal tar, the mass ratio of the fly ash to the waste incineration fly ash is further increased to be increased. therefore, in general, the combination of benefits and costs is most beneficial to improving the performance of the prepared soil passivating agent when the mass ratio of coal tar, coal ash and waste incineration fly ash is equal to 7.5-32.5:22.5-47.5:100.
EXAMPLE 2 Effect of carbonization time on the Performance of the prepared soil passivator
And respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. And (3) introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 600 ℃, and the carbonization time is 0.25 hours, 0.3 hours, 0.4 hours, 0.5 hours, 3 hours, 5.5 hours, 5.75 hours, 6 hours and 6.25 hours. Grinding the carbonized residues for 1.5 hours to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 30:30:100, mixing and stirring uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 2:1mL, heating, continuously stirring, and performing solid-liquid separation to age the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 10g/L tryptone, 10g/L peptone, 10g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 1.5g/L glucose, 15g/L KH 2PO3, 70g/L urea, 15g/L FeSO 4 into distilled water, the stirring time is 48 hours, the stirring speed is 90rpm, the heating time is 48 hours, the heating temperature is 40 ℃, and the ageing time is 20 days.
The preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the leaching solution, the measurement of dioxin-like substances, the measurement of chlorine content, the preparation of thallium and arsenic-polluted soil, the remediation test of thallium and arsenic-polluted soil, the toxicity leaching test of the remediated soil, and the detection of the concentration of thallium and arsenic ions are all the same as in example 1.
The test results of this example are shown in Table 2.
TABLE 2 influence of carbonization time on the properties of prepared soil passivators
As can be seen from table 2, when the carbonization time is less than 0.5 hours (as in table 2, carbonization time=0.4 hours, 0.3 hours, 0.25 hours, and lower values not listed in table 2), the carbonization time is short, and carbonization is insufficient, resulting in that the heavy metal leaching concentration, chlorine content, dioxin content, and post-restoration soil toxicity leaching concentration of the prepared soil passivating agent all increase as the carbonization time decreases. When the carbonization time is equal to 0.5-5.5 hours (as shown in table 2, carbonization time=0.5 hours, 3 hours and 5.5 hours), during the carbonization process of tar coal ash mud, chlorine salt and calcium salt permeated into the coal tar organic matters can strengthen dehydrogenation and carbonization of hydrocarbon in the coal tar through catalytic cracking, and combustible gas and high-temperature water vapor released during the cracking process of the coal tar can degrade dioxin pollutants in fly ash and promote the reaction of calcium-based substances in the waste incineration fly ash with silicate and aluminosilicate in the fly ash to generate mineral mixtures such as calcium silicate, calcium aluminate, calcium aluminosilicate, sodium aluminosilicate and the like. Finally, the leaching concentration of the heavy metal lead in the soil passivating agent is lower than 3.2 multiplied by 10 -4 mg/L, the leaching concentration of hexavalent chromium is lower than 5.9 multiplied by 10 -5 mg/L, the leaching concentration of cadmium is lower than 3.0 multiplied by 10 - 4 mg/L, the chlorine content is lower than 0.2%, the dioxin substances are lower than 6ng-TEQ/kg, the toxic leaching concentration of thallium in the repaired soil is lower than 0.01 mu g/L, and the arsenic is lower than 5.2 multiplied by 10 -3 mg/L. When the carbonization time is greater than 5.5 hours (as in table 2, carbonization time=5.75 hours, 6 hours, 6.25 hours, and higher values not listed in table 2), the carbonization time is too long, and the material is over-burned, so that the surface activity of the loaded powder is reduced, and the heavy metal leaching concentration of the prepared soil passivating agent and the toxic leaching concentration of the soil after restoration are increased along with the further increase of the carbonization time. Therefore, in general, the benefit and the cost are combined, and when the carbonization time is equal to 0.5-5.5 hours, the soil passivating agent prepared is most beneficial to improving the performance.
EXAMPLE 3 Effect of carbonization temperature on the Performance of the prepared soil passivator
And respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. Introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 225 ℃, 250 ℃, 275 ℃, 300 ℃, 600 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 45:45:100, mixing and stirring uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
The preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the leaching solution, the measurement of dioxin-like substances, the measurement of chlorine content, the preparation of thallium and arsenic-polluted soil, the remediation test of thallium and arsenic-polluted soil, the toxicity leaching test of the remediated soil, and the detection of the concentration of thallium and arsenic ions are all the same as in example 1.
The test results of this example are shown in Table 3.
TABLE 3 influence of carbonization temperature on the properties of the prepared soil passivators
As can be seen from table 3, when the carbonization temperature is less than 300 ℃ (as in table 3, carbonization time=275 ℃, 250 ℃, 225 ℃ and lower values not listed in table 3), the carbonization temperature is low, and carbonization is insufficient, resulting in that the heavy metal leaching concentration, chlorine content, dioxin content and toxic leaching concentration of the soil after restoration of the prepared soil passivating agent all increase with decreasing carbonization temperature. When the carbonization temperature is 300-900 ℃ (as shown in table 3, the carbonization temperature=300 ℃, 600 ℃ and 900 ℃), in the carbonization process of the tar coal ash slurry, the chloride salt and the calcium salt which permeate into the organic matters of the coal tar can strengthen the dehydrogenation and carbonization of hydrocarbon in the coal tar through the catalytic cracking effect, and the combustible gas and the high-temperature water vapor released in the coal tar cracking process not only can degrade dioxin pollutants in the fly ash, but also can promote the calcium-based substances in the waste incineration fly ash to react with silicate and aluminosilicate in the fly ash to generate mineral mixtures such as calcium silicate, calcium aluminate, calcium aluminosilicate, sodium aluminosilicate and the like. Finally, the leaching concentration of the heavy metal lead in the soil passivating agent is lower than 1.5X10 -4 mg/L, the leaching concentration of hexavalent chromium is lower than 4.0X10 -5 mg/L, the leaching concentration of cadmium is lower than 2.4X10 -4 mg/L, the chlorine content is lower than 0.2%, the dioxin substances are lower than 2ng-TEQ/kg, the toxic leaching concentration of thallium in the restored soil is lower than 6.4X10 -3 mu g/L, and the arsenic is lower than 3.3X10 -3 mg/L. When the carbonization temperature is greater than 900 ℃ (as in table 3, carbonization temperature=950 ℃, 1000 ℃, 1050 ℃ and higher values not listed in table 3), the carbonization temperature is too high, and the material is over-burned, so that the surface activity of the loaded powder is reduced, and the heavy metal leaching concentration of the prepared soil passivating agent and the toxic leaching concentration of the soil after restoration are increased along with the further increase of the carbonization temperature. Therefore, in general, the benefits and the cost are combined, and when the carbonization temperature is 300-900 ℃, the prepared soil passivating agent is most beneficial to improving the performance.
Example 4 Effect of sepiolite powder, desulfurized Gypsum powder, carbonized powder mass ratio on the Performance of the prepared soil passivator
And respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. And (3) introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 900 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. And respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio 7.5:15:100、10:15:100、12.5:15:100、15:7.5:100、15:10:100、15:12.5:100、15:15:100、30:15:100、45:15:100、15:30:100、30:30:100、45:30:100、15:45:100、30:45:100、45:45:100、45:50:100、45:55:100、45:60:100、50:45:100、55:45:100、60:45:100, mixing and stirring uniformly to obtain the loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
The preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the leaching solution, the measurement of dioxin-like substances, the measurement of chlorine content, the preparation of thallium and arsenic-polluted soil, the remediation test of thallium and arsenic-polluted soil, the toxicity leaching test of the remediated soil, and the detection of the concentration of thallium and arsenic ions are all the same as in example 1.
The test results of this example are shown in Table 4.
TABLE 4 influence of sepiolite powder, desulfurized gypsum powder, carbonized powder mass ratio on the Performance of the prepared soil passivator
As can be seen from table 4, when the mass ratio of sepiolite powder, desulfurized gypsum powder, carbonized powder is less than 15:15:100 (sepiolite powder, desulfurized gypsum powder, carbonized powder mass ratio = 12.5:15:100, 10:15:100, 7.5:15:100, 15:12.5:15:10:100, 15:7.5:100, and lower ratios not listed in table 4), the addition amounts of sepiolite powder and desulfurized gypsum powder are small, so that the microbial landing, propagation, enrichment, and fermentation active sites are reduced, resulting in the prepared soil passivator heavy metal leaching concentration, chlorine content, The dioxin content and the toxicity leaching concentration of the restored soil are increased along with the decrease of the mass ratio of sepiolite powder, desulfurized gypsum powder and carbonized powder. When the mass ratio of sepiolite powder, desulfurized gypsum powder, carbonized powder is equal to 15-45:15-45:100 (as in table 4, sepiolite powder, desulfurized gypsum powder, carbonized powder mass ratio=15:15:100, 30:15:100, 45:15:100, 15:30:100, 30:30:100, 45:30:100, 15:45:100, 30:45:100, 45:45:100), mixing the fermentation broth and the loaded powder, and then mixing the tryptone, peptone, yeast extract, glucose, KH 2PO3 in the fermentation broth during stirring, Urea and FeSO 4 are quickly adsorbed into sepiolite powder, desulfurized gypsum powder and carbonized powder particle minerals, the loading powder absorbs water to expand, KH 2PO3, urea and FeSO 4 promote sepiolite powder, desulfurized gypsum powder, and the like by excitation, The minerals in the carbonized powder undergo complex geopolymerization reaction and hydration reaction to generate an active cementing material mixture. Tryptone, peptone, yeast extract, glucose are adsorbed and filled in the active gel material mixture, and provide a micro-environment and an active site for potential microorganism landing, propagation, enrichment and fermentation in the aging process. Finally, the leaching concentration of the heavy metal lead of the soil passivating agent is lower than 1.4 multiplied by 10 -4 mg/L, the leaching concentration of hexavalent chromium is lower than 4.1 multiplied by 10 -5 mg/L, the leaching concentration of cadmium is lower than 2.3 multiplied by 10 -4 mg/L, the chlorine content is lower than 0.01%, the dioxin substances are lower than 2ng-TEQ/kg, the toxic leaching concentration of the thallium in the restored soil is lower than 6× -3 mu g/L, and the arsenic concentration is lower than 3.3× -3 mg/L. When the mass ratio of sepiolite powder, desulfurized gypsum powder, carbonized powder is greater than 45:45:100 (as in table 4, sepiolite powder, desulfurized gypsum powder, carbonized powder mass ratio = 45:50:100, 45:55:100, 45:60:100, 50:45:100, 55:45:100, 60:45:100, and higher ratios not listed in table 4), the sepiolite powder and desulfurized gypsum powder are added in excess such that the microorganisms land, reproduce, enrich and starter active sites decrease, resulting in the prepared soil passivating agent heavy metal leaching concentration, chlorine content, dioxin content and post-remediation soil toxicity leaching concentration all following sepiolite powder, the mass ratio of the desulfurized gypsum powder to the carbonized powder is further increased to be increased. therefore, in general, the combination of benefits and costs is most beneficial to improving the performance of the prepared soil passivating agent when the mass ratio of sepiolite powder, desulfurized gypsum powder and carbonized powder is equal to 15-45:15-45:100.
Comparative examples Effect of different comparative technologies on the Performance of prepared soil passivators
The process comprises the following steps: and respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. And (3) introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 900 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 45:45:100, mixing and stirring uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
Comparison Process 1: and respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. And (3) introducing tar coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 900 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. And respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 45:45:100, mixing and stirring uniformly to obtain the heavy metal contaminated soil passivating agent.
Comparison process 2: and respectively weighing the fly ash and the waste incineration fly ash according to the mass ratio of 47.5:100, mixing and stirring uniformly to obtain the coal plaster. Introducing the coal mortar into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 900 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 45:45:100, mixing and stirring uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
Contrast process 3: and respectively weighing coal tar and coal ash according to the mass ratio of 32.5:47.5, mixing and stirring uniformly to obtain the tar ash. And (3) introducing the tar ash into a carbonization furnace for carbonization treatment, taking out and cooling to room temperature to obtain carbonized slag, wherein the carbonization temperature is 900 ℃ and the carbonization time is 5.5 hours. Grinding the carbonized residues for 2.5 hours to obtain carbonized powder. Respectively weighing sepiolite powder, desulfurized gypsum powder and carbonized powder according to the mass ratio of 45:45:100, mixing and stirring uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
Comparison process 4: and respectively weighing coal tar, fly ash and waste incineration fly ash according to the mass ratio of 32.5:47.5:100, mixing and stirring uniformly to obtain tar coal plaster. Sepiolite powder, desulfurized gypsum powder and tar coal plaster are respectively weighed according to the mass ratio of 45:45:100, and are mixed and stirred uniformly to obtain loading powder. Mixing a fermentation liquid and loading powder according to a liquid-solid ratio of 3:1mL, heating, continuously stirring, and performing solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent, wherein the fermentation liquid is prepared by dissolving 15g/L tryptone, 15g/L peptone, 15g/L yeast extract (Y1625, sigma-Aldrich, CAS number: 8013-01-2), 2.5g/L glucose, 25g/L KH 2PO3, 120g/L urea, 25g/L FeSO 4 into distilled water, the stirring time is 72 hours, the stirring speed is 160rpm, the heating time is 72 hours, the heating temperature is 55 ℃, and the aging time is 30 days.
The preparation of the leaching solution, the measurement of the concentration of heavy metal ions in the leaching solution, the measurement of dioxin-like substances, the measurement of chlorine content, the preparation of thallium and arsenic-polluted soil, the remediation test of thallium and arsenic-polluted soil, the toxicity leaching test of the remediated soil, and the detection of the concentration of thallium and arsenic ions are all the same as in example 1.
The test results of this comparative example are shown in Table 5.
TABLE 5 influence of different comparative processes on the performance of prepared soil passivators
As can be seen from Table 5, the leaching concentration of heavy metals in the soil passivating agent prepared by the process is far lower than that of the soil passivating agent prepared by the process 1, the process 2, the process 3 and the process 4, and the toxicity leaching concentration of the repaired soil achieved by the soil passivating agent prepared by the process is also far lower than that of the soil passivating agent prepared by the process 1, the process 2, the process 3 and the process 4.

Claims (5)

1. The method for preparing the soil passivating agent by utilizing the waste incineration fly ash and the coal tar is characterized by comprising the following steps of:
(1) Respectively weighing coal tar, fly ash and waste incineration fly ash, mixing, and uniformly stirring to obtain tar coal plaster; the mass ratio of the coal tar to the fly ash to the waste incineration fly ash is 7.5-32.5: 22.5 to 47.5:100;
(2) Carbonizing the tar coal slime in the step (1), cooling, and grinding to obtain carbonized powder; the carbonization temperature is 300-900 ℃, and the carbonization time is 0.5-5.5 hours; the grinding time is 0.5-2.5 hours;
(3) Mixing sepiolite powder, desulfurized gypsum powder and carbonized powder in the step (2), uniformly stirring to obtain loaded powder, mixing the loaded powder with a fermentation liquid, heating, continuously stirring, carrying out solid-liquid separation, and aging the obtained solid part to obtain the heavy metal contaminated soil passivating agent; the mass ratio of the sepiolite powder to the desulfurized gypsum powder to the carbonized powder is 15-45: 15-45: 100; the liquid-solid ratio of the fermentation liquid to the loading powder is 1-3 mL/1 g; the fermentation liquid comprises 5-15 g/L tryptone, 5-15 g/L peptone, 5-15 g/L yeast extract, 0.5-2.5 g/L glucose, 5-25 g/L KH 2PO3, 20-120 g/L urea and 5-25 g/L FeSO 4.
2. The method of claim 1, wherein the heating in step (3) is performed at a temperature of 25 to 55 ℃ for a time of 24 to 72 hours.
3. The method of claim 1, wherein the stirring in step (3) is performed for 24 to 72 hours at a rate of 20 to 160rpm.
4. The method of claim 1, wherein the aging time in step (3) is 10 to 30 days.
5. A soil passivator prepared by the method of any one of claims 1-4.
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