Method for preparing ceramite adsorption material by coupling gasification slag and biochar

Abstract

The present application relates to a kind of gasification slag coupling biochar preparation ceramsite adsorption material method, belong to solid waste resource technology field, comprising the following steps: step S1, prepare the following weight parts raw materials: 68-72 parts coal gasification slag, 9-12 parts cement, 8-10 parts sodium silicate water glass, 6-8 parts expanded perlite, 14-20 parts functionalized biochar, 130-150 parts modified liquid and 0.1-0.2 parts initiator;Step S2, preparation forming ceramsite roughcast;Step S3, modifier modification;The present application adds functionalized biochar and modifier, functionalized biochar contains hydroxyl, ester group, amide group, benzene ring and epoxy group biochar structure, not only can occur chelation with heavy metal cation, and can occur chemical crosslinking with modified liquid, form three-dimensional intercommunication network structure, through their common effect, improve the adsorption capacity of ceramsite adsorption material and chelating performance to metal ion.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of solid waste resource utilization, and particularly relates to a method for preparing ceramite adsorption material by coupling gasification slag and biochar. BACKGROUND

[0002] Coal gasification coarse slag is a mixture formed after pulverized coal is subjected to high-temperature and high-pressure gasification, and is a solid waste generated by coal gasification technology. The disposal of coal gasification coarse slag is mostly by stacking and landfill, which not only causes waste of land resources but also causes serious environmental health problems. Therefore, the comprehensive utilization of coal gasification slag has attracted widespread attention. Related researches have found that the coal gasification slag is mainly composed of SiO2, Al2O3, CaO, Fe2O3 and C, and its main mineral phase is amorphous silicate, with quartz and calcite, which meets the requirements of the raw material for ceramite production.

[0003] The existing methods for preparing ceramite material mainly include high-temperature calcination method and non-burning method. Although the ceramite material prepared by the high-temperature calcination method has high strength and large density, which can meet the demand of the building industry, the 1000 DEG C high temperature required for sintering ceramite can cause the collapse of the internal pore channel of the raw material, significantly reduce the content of active components, and reduce the adsorption capacity. Meanwhile, it has been found that the biochar of fly ash or sludge can be used as raw material to prepare ceramite with good adsorption capacity by the non-burning method. However, the biochar of sludge contains heavy metals, which will inevitably dissolve and cause secondary pollution to the environment during use. In addition, the compatibility between the pore-forming agent and the base material is poor in the process of preparing ceramite adsorption material by the non-burning method, and the adsorption capacity of the ceramite adsorption material obtained by mechanical stirring is poor, which cannot meet the actual demand. SUMMARY

[0004] In order to produce ceramite adsorption material with good chelation performance to metal ions and high adsorption capacity, and to avoid the large dissolution of heavy metals in the biochar of sludge raw material, the application provides a method for preparing ceramite adsorption material by coupling gasification slag and biochar.

[0005] The purpose of the application can be achieved by the following technical solutions.

[0006] A method for preparing ceramite adsorption material by coupling gasification slag and biochar, comprising the following steps:

[0007] Step S1, the following raw materials are prepared: 68-72 parts of coal gasification slag, 9-12 parts of cement, 8-10 parts of sodium silicate water glass, 6-8 parts of expanded perlite, 14-20 parts of functionalized biochar, 130-150 parts of modified liquid and 0.1-0.2 parts of initiator;

[0008] Step S2, preparing a shaped ceramsite roughcast: grinding and sieving the coal gasification slag to obtain coal gasification slag powder, mixing the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite and functionalized biochar uniformly according to the mass fraction to obtain a ceramsite slurry, then performing balling treatment on the prepared ceramsite slurry until the particle size reaches the standard, aging at room temperature for 1-2 h, drying, and curing at constant temperature to obtain a shaped ceramsite roughcast;

[0009] Step S3, modification by a modifier: uniformly mixing an initiator and a modification liquid to obtain a modifier, then immersing the shaped ceramsite roughcast prepared in step S2 in the modifier, heating to 74-78℃, reacting for 1-2 h, continuously heating to 175-185℃, and carbonizing for 12-14 h, then washing and drying after the reaction to obtain a ceramsite adsorption material.

[0010] Preferably, in step S2, the standard particle size of the balling roughcast is 5-8 mm.

[0011] Preferably, in step S1, the initiator is ammonium persulfate or potassium persulfate.

[0012] Preferably, the modification liquid is prepared by the following method:

[0013] Step A1: at room temperature, adding glucose and ferrous sulfate to deionized water according to the mass ratio of 12-16:6-8:75:16-20, heating to 35-45℃, stirring uniformly, continuously stirring and adding a mixed liquid a of KH-550 and anhydrous ethanol dropwise, after dropping, continuously stirring for 12-16 h, filtering, washing and drying to obtain a modified monomer, wherein in the mixed liquid a, the mass ratio of KH-550 to anhydrous ethanol is 0.3-0.5:20;

[0014] Step A2: dissolving the modified monomer in anhydrous ethanol according to the mass ratio of 3-6:35-45:0.16-0.18, then adding 1-allyl-3-methyl imidazole trifluoromethane sulfonate, and stirring uniformly to obtain a modification liquid.

[0015] Preferably, the functionalized biochar is prepared by the following method:

[0016] Step B1: uniformly mixing sludge biochar and a 30% mass fraction calcium nitrate solution according to the mass ratio of 11-13:1, drying to constant weight, then heating to 550-650℃ and maintaining the temperature for 10-16 min to obtain modified biochar; in the above reaction process, the abundant silicon dioxide in the sludge biochar carrier reacts with calcium oxide to generate Ca-O-Si in the high-temperature pyrolysis process, thereby improving the dispersion stability of the calcium-based material in the modified biochar;

[0017] Step B2, according to the mass ratio 5:10:0.32-0.54:20-24, modified biochar, deionized water and KH-560 are added into anhydrous ethanol, stirred uniformly, heated to 50-60 DEG C, continue to stir for 6-8h, centrifugal, precipitate washing and drying, get epoxy biochar;

[0018] Step B3, according to the mass ratio 5:35-45:20, epoxy biochar is added into DMF, stirred uniformly, drop four butyl ammonium bromide, alpha-acetamidocinnamic acid and DMF mixed liquid b, drop, heated to 90-110 DEG C, continue to stir for 2-3h, after the reaction, centrifugal, precipitate washing, drying, get functionalized biochar;Wherein, the mass ratio of four butyl ammonium bromide, alpha-acetamidocinnamic acid and DMF in mixed liquid b is 1:8-12:100, in the above reaction process, with epoxy biochar and alpha-acetamidocinnamic acid as raw material, four butyl ammonium bromide as catalyst, ring opening esterification reaction of epoxy biochar and alpha-acetamidocinnamic acid occurs, functionalized biochar with hydroxyl, amido and unsaturated double bond bonded on the surface is obtained.

[0019] Compared with the prior art, the present application has the following beneficial effects: in order to improve the adsorption capacity of the prepared ceramsite adsorption material and avoid the secondary pollution caused by the dissolution of heavy metal ions in the sludge biochar to the environment, the present application starts from two aspects, one is to add functionalized biochar, which contains hydroxyl, ester, amide, benzene ring and epoxy biochar structure, the presence of hydroxyl, ester, amide and benzene ring can occur physical adsorption with heavy metal cations through electrostatic interaction and van der waals force, avoiding the dissolution of heavy metal ions, the epoxy biochar is a biochar modified by KH-560 and loaded with calcium oxide, on the one hand, the presence of biochar gives the functionalized biochar and the coal gasification slag similar structure, enhances the compatibility of the calcium oxide in the functionalized biochar and the coal gasification slag, improves the adsorption capacity of the ceramsite adsorption material, on the other hand, the siloxane group on KH-560 can form chemical bonding with the hydroxyl group on the surface of the coal gasification slag after hydrolysis, further improving the compatibility of the calcium oxide in the functionalized biochar and the coal gasification slag, further improving the adsorption capacity of the ceramsite adsorption material, the second is to add a modified liquid, on the one hand, the imidazole group and trifluoromethanesulfonic acid group on the modified liquid can occur chelation with heavy metal cations through electrostatic interaction and van der waals force, on the other hand, the presence of unsaturated double bond can occur chemical crosslinking with the double bond in the functionalized biochar, forming a three-dimensional interpenetrating network structure, which can play a synergistic effect with the functionalized biochar when introduced into the ceramsite adsorption material, and improve the adsorption capacity and chelation performance of the ceramsite adsorption material to metal ions. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of the present application.

[0021] The process, conditions, reagents, experimental methods, etc. of the present application are all general knowledge and common sense in the art, and the present application does not have special limitations, except for the following specifically mentioned contents.

[0022] Cement is ordinary Portland cement No. 425 produced by Shanshui Cement; the mass concentration of sodium silicate water glass is 34%, and the modulus is 1.6; the sludge biochar is produced from a sludge pyrolysis carbonization production line of the Institute of Urban Environment, Chinese Academy of Sciences in Tongan Sewage Treatment Plant, Xiamen City; the coal gasification slag is from a coal gasification plant in Datong City, Shanxi Province; and the expanded perlite is from Hebei Yixin Energy-saving Insulation Building Material Company.

[0023] The main raw materials used in the embodiments and the content of the components thereof are as follows:

[0024] Table 1 Main chemical composition of raw materials used in the present application

[0025] %

[0026]

[0027] Preparation Examples 1-3 and Comparative Preparation Example 1 provide methods of preparing functionalized biochar.

[0028] Preparation Example 1

[0029] The functionalized biochar is prepared by the following method:

[0030] Step B1, according to the mass ratio of 11:1, the sludge biochar and the calcium nitrate solution with a mass fraction of 30% are stirred at a speed of 400 rpm for 35 min until uniform, dried at 50°C to constant weight, then heated to 550°C at a rate of 5°C / min and kept for 16 min of reaction to obtain modified biochar;

[0031] Step B2, according to the mass ratio of 5:10:0.32:20, the modified biochar, deionized water and KH-560 are added to anhydrous ethanol, stirred at a speed of 500 rpm for 30 min until uniform, heated to 50°C, the stirring speed is kept unchanged, and the stirring reaction is continued for 6 h, centrifuged, the precipitate is washed with anhydrous ethanol and deionized water in turn for 3 times, and dried at 60°C to constant weight to obtain epoxy biochar;

[0032] Step B3, according to the mass ratio 5:40:20, the epoxy group biochar is added into DMF, stirring at 550 rpm for 25 min to be uniform, maintaining the speed unchanged, continue to stir and drop the mixture of tetrabutylammonium bromide, alpha-acetamidocinnamic acid and DMF b, control in 30 min drop, drop, temperature to 100℃, stirring 2.5h, after the reaction, the precipitate is washed with anhydrous ethanol and deionized water 4 times respectively, and dried at 65℃ to constant weight, to get functionalized biochar; wherein, in the mixture b, the mass ratio of tetrabutylammonium bromide, alpha-acetamidocinnamic acid and DMF is 1:10:100.

[0033] Preparation Example 2

[0034] The functionalized biochar is prepared by the following method:

[0035] Step B1, according to the mass ratio 11-13:1, the sludge biochar and calcium nitrate solution with a mass fraction of 30% are mixed and stirred at a speed of 450 rpm for 30 min to be uniform, dried at 55℃ to constant weight, then heated to 600℃ at a rate of 5℃ / min and kept for 14 min to get modified biochar;

[0036] Step B2, according to the mass ratio 5:10:0.43:22, the modified biochar, deionized water and KH-560 are added into anhydrous ethanol, stirring at 550 rpm for 25 min to be uniform, heated to 55℃, maintaining the speed unchanged, continue to stir for 7h, centrifugal, the precipitate is washed with anhydrous ethanol and deionized water 4 times respectively, and dried at 65℃ to constant weight, to get epoxy group biochar;

[0037] Step B3, according to the mass ratio 5:40:20, the epoxy group biochar is added into DMF, stirring at 550 rpm for 25 min to be uniform, maintaining the speed unchanged, continue to stir and drop the mixture of tetrabutylammonium bromide, alpha-acetamidocinnamic acid and DMF b, control in 30 min drop, drop, temperature to 100℃, stirring 2.5h, after the reaction, the precipitate is washed with anhydrous ethanol and deionized water 4 times respectively, and dried at 65℃ to constant weight, to get functionalized biochar; wherein, in the mixture b, the mass ratio of tetrabutylammonium bromide, alpha-acetamidocinnamic acid and DMF is 1:10:100.

[0038] Preparation Example 3

[0039] The functionalized biochar is prepared by the following method:

[0040] Step B1, according to the mass ratio 13:1, the sludge biochar and calcium nitrate solution with a mass fraction of 30% are mixed and stirred at a speed of 500 rpm for 25 min to be uniform, dried at 60℃ to constant weight, then heated to 650℃ at a rate of 5℃ / min and kept for 10 min to get modified biochar;

[0041] Step B2, according to the mass ratio 5:10:0.54:24, modified biochar, deionized water and KH-560 were added into anhydrous ethanol, stirred at 650 rpm for 20 min to be uniform, heated to 60°C, maintained the same speed, continued to stir for 8 h, centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 70°C to constant weight, and the epoxy biochar was obtained;

[0042] Step B3, according to the mass ratio 5:45:20, the epoxy biochar was added into DMF, stirred at 500 rpm for 20 min to be uniform, maintained the same speed, continued to stir and added dropwise the mixture b of tetrabutylammonium bromide, α-acetylamino cinnamic acid and DMF, after dropwise addition, heated to 110°C and stirred for 2 h, after the reaction was completed, centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 70°C to constant weight, and the functionalized biochar was obtained; wherein, in the mixture b, the mass ratio of tetrabutylammonium bromide, α-acetylamino cinnamic acid and DMF was 1:12:100.

[0043] Comparative Preparation Example 1

[0044] The functionalized biochar was prepared by the following method:

[0045] Step B1, according to the mass ratio 11:1, the sludge biochar and zinc nitrate solution with a mass fraction of 30% were stirred at 400 rpm for 35 min to be uniform, dried at 50°C to constant weight, then heated to 550°C at a rate of 5°C / min and kept for 10 min, and the modified biochar was obtained;

[0046] Step B2, according to the mass ratio 5:10:0.32:20, the modified biochar, deionized water and KH-560 were added into anhydrous ethanol, stirred at 500 rpm for 30 min to be uniform, heated to 50°C, maintained the same speed, continued to stir for 6 h, centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 3 times in turn, dried at 60°C to constant weight, and the epoxy biochar was obtained;

[0047] Step B3, according to the mass ratio 5:35:20, the epoxy biochar was added into DMF, stirred at 600 rpm for 20 min to be uniform, maintained the same speed, continued to stir and added dropwise the mixture b of tetrabutylammonium bromide, α-acetylamino cinnamic acid and DMF, controlled to be dropwise added within 30 min, after dropwise addition, heated to 90°C and continued to stir for 3 h, after the reaction was completed, centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 3 times in turn, and dried, and the functionalized biochar was obtained; wherein, in the mixture b, the mass ratio of tetrabutylammonium bromide, α-acetylamino cinnamic acid and DMF was 1:8:100.

[0048] Comparative Preparation Example 2

[0049] The functionalized biochar is prepared by the following method:

[0050] Step B1, according to the mass ratio 11:1, the sludge biochar and the mass fraction of 30% calcium nitrate solution, stirring at 400 rpm for 35 min to uniform, 50 ℃ drying to constant weight, and then heating to 550 ℃ at a rate of 5 ℃ / min and keeping for 10 min, to obtain the modified biochar;

[0051] Step B2, according to the mass ratio 5:10:0.32:20, the modified biochar, deionized water and KH-560 are added into anhydrous ethanol, stirring at 500 rpm for 30 min to uniform, heating to 50 ℃, maintaining the same speed, continue to stir for 6 h, centrifugation, the precipitate is washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried at 60 ℃ to constant weight, to obtain the epoxy biochar;

[0052] Step B3, according to the mass ratio 5:35:20, the epoxy biochar is added into DMF, stirring at 600 rpm for 20 min to uniform, maintaining the same speed, continue to stir and drop the mixture b of tetrabutylammonium bromide, benzoic acid and DMF, controlling the drop within 30 min, after dropping, heating to 90 ℃, continue to stir for 3 h, after the reaction, centrifugation, the precipitate is washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried, to obtain the functionalized biochar, wherein, in the mixture b, the mass ratio of tetrabutylammonium bromide, benzoic acid and DMF is 1:8:100.

[0053] Preparation Examples 4-6 and Comparative Preparation Example 3 provide the preparation method of the modification liquid.

[0054] Preparation Example 4

[0055] The modification liquid is prepared by the following method:

[0056] Step A1, at room temperature, according to the mass ratio 12:6:75:16, the glucose and ferrous sulfate are added into deionized water, heating to 35 ℃, stirring at 400 rpm for 35 min to uniform, maintaining the same speed, continue to stir and drop the mixture a of KH-550 and anhydrous ethanol, controlling the drop within 30 min, after dropping, maintaining the same speed, continue to stir for 16 h, filtration, and then washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried at 55 ℃ to constant weight, to obtain the modified monomer, wherein, in the mixture a, the mass ratio of KH-550 and anhydrous ethanol is 0.3:20;

[0057] Step A2, the modified monomer was added into anhydrous ethanol according to the mass ratio of 4.5:40:0.17, stirred at a speed of 500 rpm for 25 min until uniform, then 1-allyl-3-methyl imidazole trifluoromethane sulfonate was added, the stirring speed was kept unchanged, and the stirring was continued for 3 h until uniform, to obtain the modified liquid.

[0058] Preparation Example 5

[0059] The modified liquid was prepared by the following method:

[0060] Step A1, glucose and ferrous sulfate were added into deionized water according to the mass ratio of 14:7:75:18 at room temperature, the temperature was increased to 40℃, and the stirring was performed at a speed of 500 rpm for 25 min until uniform, the stirring speed was kept unchanged, and the stirring was continued while the mixed solution a of KH-550 and anhydrous ethanol was added dropwise, the dropwise addition was controlled to be completed within 30 min, after the dropwise addition was completed, the stirring was continued for 14 h, then the filtration was performed, and the modified monomer was obtained after the modified monomer was washed with anhydrous ethanol and deionized water in sequence for 4 times and dried at 60℃ until the weight was constant, wherein, in the mixed solution a, the mass ratio of KH-550 and anhydrous ethanol was 0.4:20;

[0061] Step A2, the modified monomer was added into anhydrous ethanol according to the mass ratio of 4.5:40:0.17, stirred at a speed of 500 rpm for 25 min until uniform, then 1-allyl-3-methyl imidazole trifluoromethane sulfonate was added, the stirring speed was kept unchanged, and the stirring was continued for 3 h until uniform, to obtain the modified liquid.

[0062] Preparation Example 6

[0063] The modified liquid was prepared by the following method:

[0064] Step A1, glucose and ferrous sulfate were added into deionized water according to the mass ratio of 14:7:75:18 at room temperature, the temperature was increased to 40℃, and the stirring was performed at a speed of 500 rpm for 25 min until uniform, the stirring speed was kept unchanged, and the stirring was continued while the mixed solution a of KH-550 and anhydrous ethanol was added dropwise, the dropwise addition was controlled to be completed within 30 min, after the dropwise addition was completed, the stirring was continued for 14 h, then the filtration was performed, and the modified monomer was obtained after the modified monomer was washed with anhydrous ethanol and deionized water in sequence for 4 times and dried at 60℃ until the weight was constant, wherein, in the mixed solution a, the mass ratio of KH-550 and anhydrous ethanol was 0.4:20;

[0065] Step A2, the modified monomer was added into anhydrous ethanol according to the mass ratio of 4.5:40:0.17, stirred at a speed of 500 rpm for 25 min until uniform, then 1-allyl-3-methyl imidazole trifluoromethane sulfonate was added, the stirring speed was kept unchanged, and the stirring was continued for 3 h until uniform, to obtain the modified liquid.

[0066] Comparative Preparation Example 3

[0067] The modified liquid was prepared by the following method:

[0068] Step A1, glucose, ferrous sulfate were added into deionized water at a mass ratio of 12:6:75:16, and the mixture was stirred at 400 rpm for 35 min until uniform at room temperature, then the stirring was continued at the same speed, and the mixture of KH-550 and anhydrous ethanol was added dropwise within 30 min, after the dropwise addition was completed, the stirring was continued at the same speed for 16 h, then the mixture was filtered, and washed with anhydrous ethanol and deionized water for 3 times in sequence, and dried at 55℃ until constant weight to obtain the modified monomer, wherein the mass ratio of KH-550 to anhydrous ethanol in the mixture was 0.3:20;

[0069] Step A2, the modified monomer was added into anhydrous ethanol at a mass ratio of 3:35:0.16, and the mixture was stirred at 450 rpm for 20 min until uniform, then allyl cyclohexane was added, and the stirring was continued at the same speed for 2.5 h to obtain the modified liquid.

[0070] Example 1

[0071] A method for preparing a ceramsite adsorption material by coupling gasification slag and biochar, comprising the following steps:

[0072] Step S1, the following raw materials were prepared: 68 parts of coal gasification slag, 9 parts of cement, 8 parts of sodium silicate water glass, 6 parts of expanded perlite, 14 parts of functionalized biochar prepared in Preparation Example 1, 130 parts of modified liquid prepared in Preparation Example 4, and 0.1 part of ammonium persulfate;

[0073] Step S2, preparing a formed ceramsite roughcast: the coal gasification slag was ground and passed through a 100-mesh sieve to obtain a coal gasification slag powder, the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite, and functionalized biochar were stirred at a speed of 500 rpm for 25 min until uniform at a mass ratio, to obtain a ceramsite slurry, the prepared ceramsite slurry was subjected to balling treatment in a balling machine until the particle size was 5 mm, and then the ceramsite slurry was aged at room temperature for 1 h, dried at 80℃ for 2 h, and then placed in a constant-temperature incubator at 100℃ for 8 h to obtain a formed ceramsite roughcast;

[0074] Step S3, modification by a modifier: the ammonium persulfate and the modified liquid were stirred at a speed of 400 rpm for 30 min until uniform to obtain a modifier, and then the formed ceramsite roughcast prepared in step S2 was immersed in the modifier, heated to 74℃, reacted for 1 h, then heated to 175℃, and carbonized for 12 h, after the reaction was completed, the ceramsite roughcast was washed with anhydrous ethanol and deionized water for 3 times in sequence, and then dried at 75℃ for 4 h to obtain a ceramsite adsorption material.

[0075] Example 2

[0076] A method for preparing a ceramsite adsorption material by coupling gasification slag and biochar, comprising the following steps:

[0077] Step S1, prepare the following raw materials by weight: 70 parts of coal gasification slag, 10.5 parts of ordinary Portland cement No. 425, 9 parts of sodium silicate water glass, 7 parts of expanded perlite, 17 parts of functionalized biochar prepared in Preparation Example 2, 140 parts of modified liquid prepared in Preparation Example 5, and 0.15 parts of potassium persulfate;

[0078] Step S2, prepare a shaped ceramsite rough blank: grind the coal gasification slag through a 100-mesh sieve to obtain coal gasification slag powder. According to the mass fraction, the coal gasification slag powder, ordinary Portland cement No. 425, sodium silicate water glass, expanded perlite, and functionalized biochar are stirred at a speed of 550 rpm for 20 min until uniform to obtain a ceramsite slurry. The prepared ceramsite slurry is then subjected to balling treatment in a balling machine until the particle size is 6 mm, aged at room temperature for 1.5 h, dried at 110°C for 1.5 h, and then placed in a constant-temperature curing oven at 100°C for 8 h to obtain a shaped ceramsite rough blank.

[0079] Step S3, modification by a modifier: the potassium persulfate and the modified liquid are stirred at a speed of 450 rpm for 25 min until uniform to obtain a modifier. The shaped ceramsite rough blank prepared in step S2 is then immersed in the modifier, heated to 76°C, and reacted for 1.5 h. The temperature is then increased to 180°C, and carbonization reaction is carried out for 13 h. After the reaction is completed, the ceramsite is washed with anhydrous ethanol and deionized water four times in sequence, and then dried at 80°C for 3 h to obtain a ceramsite adsorption material.

[0080] Example 3

[0081] A method for preparing a ceramsite adsorption material from coal gasification slag and biochar, comprising the following steps:

[0082] Step S1, prepare the following raw materials by weight: 72 parts of coal gasification slag, 12 parts of ordinary Portland cement No. 425, 10 parts of sodium silicate water glass, 8 parts of expanded perlite, 20 parts of functionalized biochar prepared in Preparation Example 3, 150 parts of modified liquid prepared in Preparation Example 6, and 0.2 parts of ammonium persulfate;

[0083] Step S2, prepare a shaped ceramsite rough blank: grind the coal gasification slag through a 100-mesh sieve to obtain coal gasification slag powder. According to the mass fraction, the coal gasification slag powder, ordinary Portland cement No. 425, sodium silicate water glass, expanded perlite, and functionalized biochar are stirred at a speed of 600 rpm for 15 min until uniform to obtain a ceramsite slurry. The prepared ceramsite slurry is then subjected to balling treatment in a balling machine until the particle size is 8 mm, aged at room temperature for 2 h, dried at 95°C for 1.8 h, and then placed in a constant-temperature curing oven at 100°C for 8 h to obtain a shaped ceramsite rough blank.

[0084] Step S3, modifier modification: the ammonium persulfate and the modification liquid are stirred at a rotation speed of 500 rpm until uniform, a modifier is obtained, the shaped haydite rough blank prepared in step S2 is immersed in the modifier, the temperature is raised to 78 DEG C, and the reaction is carried out for 2 h, then the temperature is continuously raised to 185 DEG C, and the carbonization reaction is carried out for 14 h, after the reaction is completed, the shaped haydite rough blank is washed with anhydrous ethanol and deionized water for 5 times in sequence, and then dried at 85 DEG C for 2.5 h, and a haydite adsorption material is obtained.

[0085] In order to verify the comprehensive performance of the haydite adsorption material produced in examples 1-3 of the present application, comparative examples 1-3 are set.

[0086] Comparative example 1

[0087] A method for preparing a haydite adsorption material by coupling gasification slag and biochar, comprising the following steps:

[0088] Step S1, the following weight parts of raw materials are prepared: 68 parts of coal gasification slag, 9 parts of cement, 8 parts of sodium silicate water glass, 6 parts of expanded perlite, 14 parts of functionalized biochar prepared by comparative preparation example 1, 130 parts of modification liquid prepared by preparation example 4, and 0.1 part of ammonium persulfate;

[0089] Step S2, preparation of shaped haydite rough blank: the coal gasification slag is ground and passed through a 100 mesh sieve to obtain coal gasification slag powder, the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite and functionalized biochar are stirred at a rotation speed of 500 rpm for 25 min until uniform, a haydite slurry is obtained, the prepared haydite slurry is subjected to balling treatment in a balling machine until the particle size meets the standard, and then aged at room temperature for 1 h, dried at 80 DEG C for 2 h, and then placed in a constant temperature incubator at 100 DEG C for 8 h to obtain a shaped haydite rough blank;

[0090] Step S3, modifier modification: the initiator and the modification liquid are stirred at a rotation speed of 400 rpm for 30 min until uniform, a modifier is obtained, the shaped haydite rough blank prepared in step S2 is immersed in the modifier, the temperature is raised to 74 DEG C, and the reaction is carried out for 1 h, then the temperature is continuously raised to 175 DEG C, and the carbonization reaction is carried out for 12 h, after the reaction is completed, the shaped haydite rough blank is washed with anhydrous ethanol and deionized water for 3 times in sequence, and then dried at 75 DEG C for 4 h, and a haydite adsorption material is obtained.

[0091] Comparative example 2

[0092] A method for preparing a haydite adsorption material by coupling gasification slag and biochar, comprising the following steps:

[0093] Step S1, the following weight parts of raw materials are prepared: 68 parts of coal gasification slag, 9 parts of cement, 8 parts of sodium silicate water glass, 6 parts of expanded perlite, 14 parts of functionalized biochar prepared by comparative preparation example 1, 130 parts of modification liquid prepared by preparation example 4, and 0.1 part of ammonium persulfate;

[0094] Step S2, preparing a shaped ceramsite rough blank: grinding the coal gasification slag, passing it through a 100-mesh sieve to obtain coal gasification slag powder, mixing the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite and functionalized biochar in a mass ratio of 68:9:8:6:14:130 to obtain a ceramsite slurry, and then performing balling treatment on the ceramsite slurry in a balling machine until the particle size reaches the standard, and then aging at room temperature for 1 h, drying at 80°C for 2 h, and then curing at 100°C for 8 h to obtain the shaped ceramsite rough blank;

[0095] Step S3, modification by a modifier: mixing the initiator and the modifier liquid at a rotation speed of 400 rpm for 30 min until they are uniform to obtain a modifier, and then immersing the shaped ceramsite rough blank prepared in step S2 in the modifier, heating to 74°C, reacting for 1 h, continuously heating to 175°C, and carbonizing for 12 h, and then washing the shaped ceramsite rough blank with anhydrous ethanol and deionized water three times in sequence, and then drying at 75°C for 4 h to obtain the ceramsite adsorption material.

[0096] Comparative Example 3

[0097] A method for preparing a ceramsite adsorption material from coal gasification slag and biochar, comprising the following steps:

[0098] Step S1, preparing the following raw materials in a weight ratio: 68 parts of coal gasification slag, 9 parts of cement, 8 parts of sodium silicate water glass, 6 parts of expanded perlite, 14 parts of functionalized biochar prepared in Preparation Example 1, 130 parts of modifier liquid prepared in Comparative Preparation Example 3, and 0.1 part of ammonium persulfate;

[0099] Step S2, preparing a shaped ceramsite rough blank: grinding the coal gasification slag, passing it through a 100-mesh sieve to obtain coal gasification slag powder, mixing the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite and functionalized biochar in a mass ratio of 68:9:8:6:14:130 to obtain a ceramsite slurry, and then performing balling treatment on the ceramsite slurry in a balling machine until the particle size reaches the standard, and then aging at room temperature for 1 h, drying at 80°C for 2 h, and then curing at 100°C for 8 h to obtain the shaped ceramsite rough blank;

[0100] Step S3, modification by a modifier: mixing the initiator and the modifier liquid at a rotation speed of 400 rpm for 30 min until they are uniform to obtain a modifier, and then immersing the shaped ceramsite rough blank prepared in step S2 in the modifier, heating to 74°C, reacting for 1 h, continuously heating to 175°C, and carbonizing for 12 h, and then washing the shaped ceramsite rough blank with anhydrous ethanol and deionized water three times in sequence, and then drying at 75°C for 4 h to obtain the ceramsite adsorption material.

[0101] The ceramsite adsorption materials prepared in Examples 1-3 and Comparative Examples 1-3 were subjected to the following performance tests:

[0102] 1. Leaching toxicity test

[0103] According to HJ557-2010 "Solid waste leaching toxicity leaching method-horizontal oscillation method" and leaching standard (US-EPA), the ceramsite adsorption material leaching toxicity experiment is carried out, atomic absorption spectrophotometry is used to determine the heavy metal TCLP leaching amount (mg / L) of the ceramsite leaching solution, and the specific detection results are shown in Table 2:

[0104] Table 2

[0105]

[0106] From Table 2, although the heavy metal ion content of the ceramsite adsorption material prepared by examples 1-3 and comparative examples 1-3 meets the requirements of "Hazardous waste identification standard leaching toxicity identification" (GB5085.3-2007) standard, but the leaching rate of heavy metal ions of the ceramsite adsorption material prepared by examples 1-3 is much lower than that of comparative examples 1-3, which shows that the ceramsite adsorption material prepared by the application has better chelation performance for metal ions.

[0107] 2. CIP adsorption test

[0108] 3g of the ceramsite adsorption material prepared by examples 1-3 and comparative examples 1-3 is respectively weighed and placed in a 250mL conical flask containing 100mL of initial potassium dihydrogen phosphate solution with a mass concentration of 5mg / L, sealed with plastic film and placed in a constant temperature oscillator, and the adsorption test is carried out under the condition of 35℃ and 120r / min, and the residual phosphorus mass concentration in the solution after adsorption is determined by ammonium molybdate spectrophotometry, and the specific detection results are shown in Table 3:

[0109] Table 3

[0110]

[0111] From the data shown in Table 3, compared with comparative examples 1-3, the ceramsite adsorption material prepared in examples 1-3 has higher adsorption capacity.

[0112] The specific embodiment is only an explanation of the application, and is not a limitation of the application, and those skilled in the art can make modifications to the embodiment without creative contribution according to the needs after reading the specification, but as long as it is within the scope of the claims of the application, it is protected by the patent law.

Claims

1. A method for preparing a ceramisite adsorbing material by coupling gasification slag and biochar, characterized in that, It comprises the following steps: Step S1, prepare the following weight parts of raw materials: 68-72 parts of coal gasification slag, 9-12 parts of cement, 8-10 parts of sodium silicate water glass, 6-8 parts of expanded perlite, 14-20 parts of functionalized biochar, 130-150 parts of modified liquid and 0.1-0.2 parts of initiator; Step S2, prepare the shaped ceramsite roughcast: grind the coal gasification slag and sieve to obtain coal gasification slag powder, mix the coal gasification slag powder, cement, sodium silicate water glass, expanded perlite and functionalized biochar uniformly according to the mass fraction to obtain ceramsite slurry, then perform balling treatment on the prepared ceramsite slurry until the particle size meets the standard, age at room temperature for 1-2h, dry, and constant temperature curing to obtain the shaped ceramsite roughcast; Step S3, modification by modifier: mix the initiator and modified liquid uniformly to obtain the modifier, then immerse the shaped ceramsite roughcast prepared in step S2 in the modifier, heat to 74-78℃, react for 1-2h, continue to heat to 175-185℃, and carbonize for 12-14h, then wash and dry to obtain the ceramsite adsorption material; The functionalized biochar is modified biochar combined by sludge biochar and calcium nitrate, then modified by KH-560 to obtain epoxy biochar, and finally combined with alpha-acetylamino cinnamic acid to obtain; The modified liquid is prepared by mixing glucose and ferrous sulfate, then modified by KH-550 to obtain modified monomer, and then mixed with 1-allyl-3-methyl imidazole trifluoromethane sulfonate to obtain.

2. The method according to claim 1, wherein the method is characterized by, The modified liquid is prepared by the following method: Step A1, at room temperature, add glucose, ferrous sulfate and deionized water according to the mass ratio of 12-16:6-8:75:16-20, heat to 35-45℃, stir uniformly, continue to stir and add dropwise the mixed liquid a of KH-550 and anhydrous ethanol, after dropping, continue to stir for 12-16h, filter, wash and dry to obtain the modified monomer; Step A2, dissolve the modified monomer in anhydrous ethanol according to the mass ratio of 3-6:35-45:0.16-0.18, then add 1-allyl-3-methyl imidazole trifluoromethane sulfonate and stir uniformly to obtain the modified liquid.

3. The method according to claim 1, wherein the method is characterized by, The functionalized biochar is prepared by the following method: Step B1, mix the sludge biochar and 30% calcium nitrate solution according to the mass ratio of 11-13:1, dry to constant weight, then heat to 550-650℃ and react for 10-16min to obtain the modified biochar; Step B2, add the modified biochar, deionized water and KH-560 to anhydrous ethanol according to the mass ratio of 5:10:0.32-0.54:20-24, stir uniformly, heat to 50-60℃, continue to stir for 6-8h, centrifuge, wash and dry the precipitate to obtain the epoxy biochar; Step B3, add the epoxy biochar to DMF according to the mass ratio of 5:35-45:20, stir uniformly, add dropwise the mixed liquid b of tetrabutylammonium bromide, alpha-acetylamino cinnamic acid and DMF, after dropping, heat to 90-110℃, continue to stir for 2-3h, after the reaction is completed, centrifuge, wash and dry the precipitate to obtain the functionalized biochar.

4. The method according to claim 1, wherein the method is characterized by, The qualified particle size of the spheroidization rough blank in the step S2 is 5-8 mm.

5. The method of claim 1, wherein the method further comprises: adding a binder to the mixture of the gasification slag and the biochar; and mixing the binder with the mixture of the gasification slag and the biochar. The initiator in the step S1 is ammonium persulfate or potassium persulfate.

6. The method of claim 2, wherein the method further comprises the step of: In the mixed solution a, the mass ratio of KH-550 and anhydrous ethanol is 0.3-0.5:

20. ​ 7. The method according to claim 3, wherein the method is characterized by, In the step B1, the temperature is raised to 550-650℃ at a rate of 5℃ / min, and the temperature is kept for 10 min.

8. The method according to claim 3, wherein the method is characterized by, In the mixed solution b, the mass ratio of tetrabutylammonium bromide, alpha-acetylamino cinnamic acid and DMF is 1:8-12:100.

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