Preparation method of gasification furnace slag-based zeolite molecular sieve loaded with nano zero-valent iron-nickel

Abstract

The present application belongs to the technical field of comprehensive utilization of gasification furnace slag, and particularly relates to a preparation method of gasification furnace slag-based zeolite molecular sieve loaded with nano zero-valent iron-nickel. The present application uses gasification furnace slag as raw material, adopts a method of exciting with NaOH solution, and obtains zeolite / C porous material and zeolite molecular sieve in batches, and then loads zero-valent bimetallic iron-nickel to prepare zeolite molecular sieve material loaded with zero-valent bimetallic iron-nickel, which can avoid zero-valent iron agglomeration, has the advantages of smaller pore size and larger specific surface area, and improves the activity and repeated utilization rate of the zeolite molecular sieve. The method of the present application can realize high-value utilization of the gasification furnace slag on one hand, and the prepared material has good treatment effect on heavy metals in water, and can be used for removing heavy metals in domestic sewage, industrial wastewater and soil groundwater.

Description

Technical Field

[0001] This invention belongs to the field of comprehensive utilization technology of gasification slag, specifically relating to a method for preparing gasification slag-based zeolite molecular sieves loaded with nano-zero-valent iron-nickel. Background Technology

[0002] With industrial development, heavy metals are widely used in various industries, and their pollution is receiving increasing attention. Heavy metals are characterized by high solubility, strong mobility, and high toxicity, and cannot be purified by physical, chemical, or biological methods inherent in nature. Common heavy metal treatment methods include adsorption, chemical precipitation, and biomineralization. Among these, adsorption is highly valued due to its economic efficiency and high effectiveness. Common adsorption materials include biomass, lime, activated carbon, and zeolite.

[0003] my country is a country where coal is the primary energy source. While coal gasification, as a clean coal technology, is widely used, it also generates a large amount of slag. According to statistics, the amount of gasification slag produced by coal gasification technology exceeds 3.3 × 10⁷ t / a. The main methods of disposing of gasification slag are stockpiling and landfilling, which not only occupy a large amount of arable land, but also, because gasification slag contains a certain amount of heavy metals, long-term dissolution can lead to the migration of heavy metals and cause pollution to soil and groundwater.

[0004] Currently, only about 20% of gasification slag is comprehensively utilized, primarily in low-end building materials. Acosta et al. used gasification slag with low carbon content (loss on ignition = 2.64%) and added 50% clay to produce building bricks that met usage requirements. Liu Kaiping et al. used coarse gasification slag to replace natural sand as fine aggregate in concrete, producing concrete with higher strength than standard concrete. Yun Zheng et al. prepared wall materials with a density of less than 14.5 g / cm³ and a compressive strength exceeding 30 MPa when the gasification slag addition was 20%. Other researchers, such as Liu et al., used KOH as an activator to prepare activated carbon with a specific surface area of ​​1226.8 m² / g from flotation-processed gasification slag. These applications are mainly laboratory studies, with limited large-scale applications; therefore, the high-value engineering utilization of gasification slag urgently needs further research.

[0005] Zeolite is a cage-like aluminosilicate mineral, light gray or flesh-colored, whose structural framework is formed by [TO4] tetrahedra (T = Si, Al) sharing a single oxygen atom at the apex. The cage-like, porous structure of zeolite makes it widely used in water treatment, gas adsorption, and other fields. Currently, natural zeolite is gradually failing to meet market demand. Simultaneously, the adsorption performance and ion exchange capacity of natural zeolite are increasingly failing to meet the requirements of industrial applications. Therefore, the artificial synthesis of zeolite has become an important development direction. However, industrial synthesis of zeolite mainly uses chemical reagents as raw materials, resulting in high production costs. How to reduce these costs is an urgent problem to be solved. The synthesis of zeolite using power plant fly ash has been studied for some time. Gasification slag and fly ash have similar chemical compositions; therefore, using gasification slag as a raw material to synthesize zeolite can not only solve the environmental problems caused by gasification slag but also reduce the raw material costs of synthetic zeolite.

[0006] Over the past decade, nano-zero-valent iron (nZVI) has been widely used in the treatment of various pollutants in aqueous solutions due to its strong reducing activity, high activity, non-toxicity, and low cost. ZVI with nanoscale particle size exhibits outstanding activity due to its large surface area. Furthermore, nZVI has proven excellent performance in removing heavy metals from wastewater through reduction, adsorption, and co-precipitation. However, nano-zero-valent iron is prone to aggregation and oxidation, leading to decreased activity. Loading nano-zero-valent iron onto zeolite molecular sieves can prevent aggregation, facilitate recovery, and improve the activity and reusability of the zeolite molecular sieves.

[0007] Therefore, this application loads nano-zero-valent iron-nickel bimetal onto gasifier slag-based zeolite materials to obtain an economical and efficient heavy metal adsorption material. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a method for preparing gasification slag-based zeolite molecular sieve loaded with nano-zero-valent iron-nickel. The method uses an alkaline solution for treatment, and can obtain molecular sieve products of different qualities by graded treatment. It has the advantages of lower cost and higher comprehensive utilization rate of raw materials.

[0009] The technical solution adopted is as follows:

[0010] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the method comprising the following steps:

[0011] (1) Mix the gasification furnace slag with hydrochloric acid and stir thoroughly;

[0012] (2) Filter and rinse with deionized water to remove hydrochloric acid, then dry the filter residue; the hydrochloric acid filtrate can be collected and reused.

[0013] (3) Add NaOH solution to the filter residue obtained in step (2) and stir;

[0014] (4) Filter the mixture after stirring in step (3), collect the filtrate, wash the obtained filter residue thoroughly with deionized water and dry it to directly obtain zeolite / C mixture A';

[0015] (5) Add CTAB solution to the filtrate obtained in step (4) and stir, and adjust the pH to acidic with sulfuric acid;

[0016] (6) Filter the liquid from step (5) to obtain a filter cake. After washing and drying the filter cake, calcine it in a muffle furnace to obtain zeolite molecular sieve B'.

[0017] (7) Disperse the zeolite molecular sieves A' and B' obtained in steps (4) and (6) into an aqueous solution of ethanol, and slowly add an aqueous solution of ferric nitrate and nickel nitrate. After stirring thoroughly, add NaBH4 solution and stir.

[0018] (8) The suspensions obtained in step (7) are filtered, washed, and then vacuum dried to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetal.

[0019] As a further preferred option, the gasification slag is dried overnight at 105°C in a drying oven before use, and then ground to a mesh size greater than 100 using a ball mill.

[0020] The gasification slag contains 20-45% SiO2, 10-25% CaO, 8-15% Al2O3, 5-15% Fe2O3 and 3-37% residual carbon by weight.

[0021] As a further preferred option, the concentration of hydrochloric acid is 2-4 mol / L, and the ratio of gasification slag to hydrochloric acid is (1:5-20) g / mL.

[0022] As a further preferred option, the ratio of gasification slag to hydrochloric acid is (1:10-15) g / mL.

[0023] As a further preferred embodiment, in step (3), the concentration of the NaOH solution is 1.5 mol / L to 4 mol / L, and the stirring time is 0.5 h to 4 h.

[0024] Preferably, the concentration of the NaOH solution is 2-3 mol / L, and the stirring time is 1-2 h.

[0025] As a further preferred embodiment, in step (4), the filter residue is dried at 70–100°C for 4–10 hours. Preferably, the filter residue is dried at 80–90°C for 6–8 hours.

[0026] As a further preferred embodiment, in step (5), the concentration of the CTAB solution is 1-3 g CTAB / 100 mL water, and the solution is stirred at 20-50 °C for 1-4 h.

[0027] As a further preferred embodiment, in step (5), the pH of the solution adjusted with sulfuric acid is 5 to 6.5.

[0028] Preferably, the concentration of the CTAB solution is 1.5–2 g CTAB / 100 mL water, and the solution is stirred at 30–40 °C for 2–3 h, with the pH of the solution adjusted by sulfuric acid being 5–6.

[0029] As a further preferred option, in step (6), the calcination temperature in the muffle furnace is 450-550°C and the calcination time is 3-5 hours.

[0030] Preferably, the calcination temperature in the muffle furnace is 550°C and the calcination time is 5 hours.

[0031] As a further preferred option, in step (7), the ratio of zeolite molecular sieve to ethanol solution is 5-15g zeolite molecular sieve / 100mL ethanol solution.

[0032] Preferably, the ratio of zeolite molecular sieve to ethanol solution is 7-10g zeolite molecular sieve / 100mL ethanol solution.

[0033] Preferably, the concentration of the ethanol solution is 60-80%, and more preferably 70-75%.

[0034] As a further preferred option, in step (7), the mass ratio of ethanol solution, zeolite molecular sieve, iron, and nickel is 15-25:5-15:0.3-1.

[0035] Preferably, the mass ratio of the ethanol solution, zeolite molecular sieve, iron, and nickel is 18–22:8–10:0.5–0.8.

[0036] As a further preferred embodiment, in step (7), the concentration of the NaBH4 solution is 0.5–1 mol / L, and the addition rate is 2–6 mL / min.

[0037] Preferably, the concentration of the NaBH4 solution is 0.7–0.9 mol / L, and the addition rate is 3–5 mL / min.

[0038] As a further preferred option, the volume ratio of the added NaBH4 solution to the ethanol-water mixture of zeolite molecular sieve, ferric nitrate, and nickel nitrate is 1:2.

[0039] As a further preferred option, in step (8), the obtained suspension is filtered, washed three times with an aqueous ethanol solution, and then vacuum dried at 50–80°C for 10–24 hours.

[0040] Preferably, the product is dried at 60–70°C for 12–18 hours.

[0041] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0042] This invention uses gasification furnace slag as raw material to prepare zeolite molecular sieve material loaded with zero-valent bimetallic iron-nickel. On the one hand, it can realize the high-value utilization of gasification furnace slag. On the other hand, the prepared material has a good treatment effect on heavy metals in water and can be used for the removal of heavy metals in domestic sewage, industrial wastewater and soil groundwater.

[0043] This invention employs a NaOH solution-activated method, which differs from the traditional alkali fusion-hydrothermal synthesis method. This method has the advantages of lower cost and can fully utilize the high carbon content in gasification slag. Zeolite / C porous materials and zeolite molecular sieves are obtained in batches, and then zero-valent bimetallic iron-nickel is loaded onto them. This avoids the agglomeration of zero-valent iron, resulting in smaller pore size, larger specific surface area, and improved activity and reusability of zeolite molecular sieves. Attached Figure Description

[0044] Figure 1 This is a flowchart of a method for preparing gasification slag-based zeolite molecular sieves loaded with nano-zero-valent iron-nickel according to the present invention. Detailed Implementation

[0045] The accompanying drawings are for illustrative purposes only; certain well-known structures and their descriptions may be omitted from the drawings by those skilled in the art, and therefore should not be construed as limiting the invention.

[0046] To make the technical means, creative features, objectives and effects of the present invention easier to understand, the present invention will be further described in detail below with reference to embodiments and accompanying drawings.

[0047] Example 1

[0048] A method for preparing a gasification slag-based zeolite molecular sieve loaded with nano-zero-valent iron-nickel, wherein the gasification slag contains 40% by weight of SiO2, 10% by weight of CaO, 15% by weight of Al2O3, 15% by weight of Fe2O3 and 20% by weight of residual carbon.

[0049] The specific implementation steps for gasification slag-based zeolite molecular sieves loaded with nano-zero-valent iron-nickel are as follows:

[0050] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of gasification slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0051] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0052] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0053] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture, which is denoted as zeolite / C mixture A'.

[0054] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0055] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve, which is denoted as mesoporous zeolite molecular sieve B'.

[0056] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0057] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0058] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 1.

[0059] Example 2

[0060] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0061] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 2 mol / L hydrochloric acid and stir for 1 h;

[0062] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0063] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0064] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0065] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0066] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0067] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0068] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0069] Other areas not mentioned are the same as in Example 1.

[0070] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 1.

[0071] Example 3

[0072] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0073] (1) After drying the gasification slag, it is ball-milled at 300 r / min for 5 min, passed through a 100-mesh sieve, and 10 g of slag is mixed with 100 mL of 4 mol / L hydrochloric acid and stirred for 1 h.

[0074] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0075] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0076] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0077] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0078] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0079] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0080] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0081] Other areas not mentioned are the same as in Example 1.

[0082] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 1.

[0083] Examples 1-3 were prepared using hydrochloric acid of different concentrations. The performance test results of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetals were compared, and the results are shown in Table 1.

[0084] Table 1 shows the specific surface area and Cu content of the products obtained in Examples 1-3. 2+ Comparison

[0085]

[0086] Table 1 shows that the optimal hydrochloric acid concentration is 3 mol / L, at which point products A and B have higher specific surface areas and Cu adsorption capacity. 2+ The ability.

[0087] Example 4

[0088] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0089] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0090] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0091] (3) Add 1.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0092] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0093] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0094] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0095] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0096] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0097] Other areas not mentioned are the same as in Example 1.

[0098] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 2.

[0099] Example 5

[0100] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0101] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0102] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0103] (3) Add 3.0 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0104] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0105] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0106] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0107] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0108] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0109] Other areas not mentioned are the same as in Example 1.

[0110] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 2.

[0111] Example 6

[0112] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0113] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0114] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0115] (3) Add 4.0 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0116] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0117] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0118] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0119] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0120] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0121] Other areas not mentioned are the same as in Example 1.

[0122] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 2.

[0123] Examples 1, 4, 5 and 6 used different concentrations of NaOH solution in step (3) to compare the performance test results of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetals. The results are shown in Table 2.

[0124] Table 2 shows the specific surface area and Cu content of the products obtained in the examples. 2+ Comparison

[0125]

[0126] Table 2 shows that the optimal NaOH concentration is 2.5–3 mol / L, at which point products A and B have higher specific surface areas and Cu adsorption capacities. 2+ The ability.

[0127] Example 7

[0128] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0129] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0130] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0131] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0132] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0133] (5) Add 50 mL of CTAB solution with a concentration of 1.0 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0134] (6) The above liquid was filtered to obtain a filter cake. After washing and drying at 85°C for 6 hours, the filter cake was calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0135] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0136] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0137] Other areas not mentioned are the same as in Example 1.

[0138] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 3.

[0139] Example 8

[0140] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0141] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0142] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0143] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0144] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0145] (5) Add 50 mL of CTAB solution with a concentration of 2.4 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0146] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0147] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0148] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0149] Other areas not mentioned are the same as in Example 1.

[0150] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 3.

[0151] Example 9

[0152] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0153] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0154] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0155] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0156] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0157] (5) Add 50 mL of CTAB solution with a concentration of 3.0 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0158] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0159] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0160] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0161] Other areas not mentioned are the same as in Example 1.

[0162] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 3.

[0163] Example 10

[0164] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0165] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0166] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0167] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0168] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0169] (5) Add 50 mL of CTAB solution with a concentration of 1.5 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0170] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0171] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0172] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0173] Other areas not mentioned are the same as in Example 1.

[0174] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 3.

[0175] In Examples 1 and 7-10, different concentrations of CTAB solution were used in step (5) to compare the performance test results of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetals. The results are shown in Table 3.

[0176] Table 3 shows the specific surface area and Cu product obtained in Examples 1-3. 2+ Comparison

[0177]

[0178] Table 3 shows that the optimal CTAB concentration is 1.5–1.8 mol / L, at which point products A and B have higher specific surface areas and Cu adsorption capacities. 2+ The ability.

[0179] Example 11

[0180] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0181] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0182] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0183] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0184] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0185] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0186] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0187] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 4.80g and 0.03g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0188] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0189] Other areas not mentioned are the same as in Example 1.

[0190] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 4.

[0191] Example 12

[0192] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0193] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0194] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0195] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0196] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0197] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0198] (6) The above liquid was filtered, the filter cake was washed and dried at 85°C for 6 hours, and then calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0199] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 14.4g and 0.09g, respectively. Stir for 30min, and then add 300mL of 0.8mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0200] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0201] Other areas not mentioned are the same as in Example 1.

[0202] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 4.

[0203] Examples 1, 11, and 12 were prepared by adding different amounts of ferric nitrate and nickel nitrate. The performance test results of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetals were compared, and the results are shown in Table 4.

[0204] Table 4 shows the specific surface area and Cu content of the products obtained in the examples. 2+ Comparison

[0205]

[0206] Table 4 shows that the optimal concentrations of ferric nitrate and nickel nitrate are 9.6 and 0.06 g / 50 mL of ethanol aqueous solution, respectively. At these concentrations, products A and B exhibit high specific surface areas and high Cu adsorption capacity. 2+ The ability.

[0207] Example 13

[0208] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0209] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0210] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0211] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0212] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0213] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0214] (6) The above liquid was filtered to obtain a filter cake. After washing and drying at 85°C for 6 hours, the filter cake was calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0215] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.9mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0216] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0217] Other areas not mentioned are the same as in Example 1.

[0218] The performance of the obtained zeolite molecular sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 5.

[0219] Example 14

[0220] A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, the specific implementation steps of which are as follows:

[0221] (1) After drying the gasification slag, ball mill it at 300 r / min for 5 min, pass it through a 100 mesh sieve, take 10 g of slag and mix it with 100 mL of 3 mol / L hydrochloric acid and stir for 1 h;

[0222] (2) Filter and rinse with deionized water to wash away the hydrochloric acid until no Cl- is detected; then dry the filter residue at 80℃ for 12h, and collect the hydrochloric acid filtrate for reuse.

[0223] (3) Add 2.5 mol / L NaOH solution to the filter residue obtained after drying in step (2) and stir for 1 h;

[0224] (4) Filter the mixture in step (3), wash the filter cake thoroughly and dry it at 85°C for 6 hours to obtain zeolite / C mixture A';

[0225] (5) Add 50 mL of CTAB solution with a concentration of 1.8 g CTAB / 100 mL aqueous solution to the filtrate obtained in step (4), then stir at 35 °C for 2 h, and adjust the pH to 5.5 with sulfuric acid;

[0226] (6) The above liquid was filtered to obtain a filter cake. After washing and drying at 85°C for 6 hours, the filter cake was calcined at 550°C for 5 hours in a muffle furnace to obtain mesoporous zeolite molecular sieve B'.

[0227] (7) Add 4g of zeolite molecular sieve and 50mL of 70% ethanol solution obtained in steps (4) and (6) to a three-necked flask. After ultrasonic dispersion for 30min, slowly add 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate. The dosage of ferric nitrate and nickel nitrate is 9.60g and 0.06g, respectively. Stir for 30min, and then add 300mL of 0.7mol / L NaBH4 solution at a rate of 4mL / min and stir.

[0228] (8) Filter the suspensions obtained in step (7), wash them three times with ethanol solution, and then vacuum dry them at 70°C for 12 hours to obtain zeolite molecular sieve products A and B loaded with zero-valent iron-nickel bimetallic.

[0229] Other areas not mentioned are the same as in Example 1.

[0230] The performance of the obtained zeolite sieve products loaded with zero-valent iron-nickel bimetal was tested, and the results are shown in Table 5.

[0231] Comparative Example 1

[0232] 5g of gasification furnace slag and 6.5g of sodium hydroxide granules were mixed evenly in a crucible and calcined at a certain alkaline melting temperature for 90min. After cooling, a certain mass of the calcined product was weighed and added to 25mL of 2.0mol / L sodium hydroxide solution. After stirring evenly, 50mL of 1mol / L sodium aluminate solution was added, and crystallization was carried out at 100℃ for 8h. After the reaction was completed, the product was removed, filtered, and the filter cake was washed with water until neutral. It was then dried at 80℃ for 2h to obtain zeolite molecular sieve product A.

[0233] Then, 4g of zeolite molecular sieve and 50mL of 70% ethanol solution were added to a three-necked flask and ultrasonically dispersed for 30min. Then, 50mL of ethanol aqueous solution of ferric nitrate and nickel nitrate was slowly added. The dosage of ferric nitrate and nickel nitrate was 9.60g and 0.06g, respectively. The mixture was stirred for 30min. Then, 300mL of 0.8mol / L NaBH4 solution was added at a rate of 4mL / min and stirred. The resulting suspension was filtered, washed three times with ethanol solution, and then vacuum dried at 70℃ for 12h to obtain the zeolite molecular sieve product loaded with zero-valent iron-nickel bimetallic.

[0234] The products obtained in Examples 1, 13, and 14 were compared with those obtained in Comparative Example 1. Different concentrations of NaBH4 solution were selected for Examples 1, 13, and 14. The comparative example was prepared using the traditional alkali fusion-hydrothermal treatment method. The performance comparison of the obtained products is shown in Table 5.

[0235] Table 5 shows the specific surface area and Cu content of the products obtained from the examples and comparative examples. 2+ Comparison

[0236]

[0237] Table 5 shows that the optimal concentration of NaBH4 is 0.8 mol / L, at which point products A and B have higher specific surface areas and Cu adsorption capacity. 2+ Furthermore, the alkaline solution activation method enables the graded utilization of gasification slag compared to the traditional alkaline fusion-hydrothermal method, and the Jiekong zeolite molecular sieve product has a higher specific surface area.

[0238] The English abbreviations used in this invention are:

[0239] CTAB - Hexadecyltrimethylammonium bromide;

[0240] A', B', A, and B refer to products at a certain stage and do not represent actual product names.

[0241] The above embodiments do not represent all embodiments of the present invention. The present invention only lists some embodiments to illustrate the technical solutions.

[0242] Of course, the above description is not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel, characterized in that, The method includes the following steps: (1) Mix the gasification furnace slag with hydrochloric acid and stir thoroughly; (2) Filter and rinse with deionized water to remove hydrochloric acid, then dry the filter residue; (3) Add NaOH solution to the filter residue obtained in step (2) and stir; (4) Filter the mixture after stirring in step (3), collect the filtrate, wash the obtained filter residue thoroughly with deionized water and dry it to directly obtain zeolite / C mixture A'; (5) Add CTAB solution to the filtrate obtained in step (4) and stir, and adjust the pH to acidic with sulfuric acid; (6) Filter the liquid from step (5) to obtain a filter cake. After washing and drying the filter cake, calcine it in a muffle furnace to obtain zeolite molecular sieve B'. (7) Disperse the zeolite molecular sieve B' obtained in step (6) into an aqueous solution of ethanol, and slowly add an aqueous solution of ferric nitrate and nickel nitrate in ethanol. After stirring thoroughly, add NaBH4 solution and stir. (8) The suspension obtained in step (7) is filtered, washed, and then vacuum dried to obtain zeolite molecular sieve product B loaded with zero-valent iron-nickel bimetal.

2. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 1, characterized in that, Before use, the gasification slag is dried overnight at 105°C in a drying oven and then ground to a mesh size greater than 100 using a ball mill.

3. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (1), the concentration of hydrochloric acid is 2-4 mol / L, and the ratio of gasification slag to hydrochloric acid is (1:5-20) g / mL.

4. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 3, characterized in that, The ratio of gasification furnace slag to hydrochloric acid is (1:10-15) g / mL.

5. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (3), the concentration of the NaOH solution is 1.5–4 mol / L, and the mixture is stirred for 0.5–4 h.

6. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (4), the filter residue is dried at 70-100℃ for 4-10 hours.

7. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (5), the concentration of the CTAB solution is 1-3 g CTAB / 100 mL water, and the solution is stirred at 20-50 °C for 1-4 h, with a pH of 5-6.

5.

8. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (5), the pH of the solution adjusted with sulfuric acid is 5 to 6.

5.

9. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (6), the calcination temperature in the muffle furnace is 450-550℃ and the calcination time is 3-5h.

10. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (7), the ratio of zeolite molecular sieve to ethanol solution is 5-15g zeolite molecular sieve / 100mL.

11. The method for preparing a gasification slag-based zeolite molecular sieve supported on nano-zero-valent iron-nickel according to claim 2, characterized in that, In step (7), the mass ratio of ethanol solution, zeolite molecular sieve, iron and nickel is 15-25:5-15:0.3-1.

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