CN112090396A - Method for preparing dye wastewater adsorbing material by using biomass waste residues - Google Patents
Method for preparing dye wastewater adsorbing material by using biomass waste residues Download PDFInfo
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Abstract
The invention discloses a method for preparing a dye wastewater adsorbing material by using biomass waste residues, which comprises the following steps: (1) cleaning, drying, crushing and sieving the kelp residue to obtain kelp residue powder; (2) calcining the kelp residue powder to obtain kelp residue biochar; (3) soaking the kelp residue biochar in a maleic acid ammonium salt solution for modification to obtain maleic acid ammonium salt modified biochar; (4) calcining the maleic acid ammonium salt modified charcoal to obtain polysuccinimide modified charcoal; (5) hydrolyzing the polysuccinimide modified biochar in a hot water bath for 0.5-1 h under an alkaline condition to obtain the dye wastewater adsorbing material. According to the invention, waste kelp residues are pyrolyzed and carbonized to generate biochar, and ammonium maleate is used for modifying the biochar, so that the prepared biochar adsorbing material has a good pore structure and a large number of active sites, and has good adsorption performance on cationic dyes.
Description
Technical Field
The invention relates to the technical field of water treatment materials, in particular to a method for preparing a dye wastewater adsorbing material by using biomass waste residues.
Background
Water resource environment in China is facing to serious pollution, most of waste water is discharged without being treated, and serious influence is caused to production and life of people. The daily discharge amount of the printing and dyeing waste liquid is 300-400 ten thousand tons, and most of dye waste water is stable in property and not easy to biodegrade, so that the dye waste water is known as one of waste water with high treatment difficulty. Once the water is treated improperly or thrown into water directly, the local water environment must be damaged, resulting in serious pollution.
The adsorption method is one of the main methods for treating dye wastewater, and the current adsorbents for adsorbing dye wastewater mainly comprise: oxides, magnetic oxides of iron, activated carbon, clay, sludge, silica gel, fly ash, polymeric resins, zeolites, and the like. There are some problems like raw material, cost, transportation etc. in using these catalysts. Therefore, the finding of an inexpensive adsorbent material with better adsorption performance to replace activated carbon has been the main point of attention of many researchers.
The biochar has a better pore structure, rich functional groups and more active sites, so that the application of the biochar to dye wastewater is widely concerned. For example, a method for preparing a dye wastewater adsorbent and a method for purifying dye wastewater disclosed in chinese patent literature, whose publication No. CN110773133A, includes the following steps: (1) recovering waste corn straws in crops, drying, and removing leaves, outer-layer epidermis and stem nodes of the corn straws to obtain corn piths; (2) grinding and sieving the corn pith, mixing the corn pith with a sodium hydroxide aqueous solution, placing the mixture in an ultrasonic device for ultrasonic treatment, fully washing the corn pith to be neutral, and finally drying to obtain the alkalized corn pith; (3) uniformly mixing the alkalized corn pith and xylanase to ensure that the alkalized corn pith and the xylanase fully react, and then fully washing the reacted corn pith to be neutral and drying; (4) and (4) mixing the corn pith obtained in the step (3) with an L-malic acid aqueous solution, and uniformly stirring.
However, the properties of biochar are greatly influenced by raw materials and pyrolysis temperature, and the biochar without modification has limited number of surface active sites and adsorption capacity for cationic dyes, so that the application of the biochar in dye wastewater treatment is limited.
Disclosure of Invention
The invention aims to overcome the problems that the property of a biochar adsorbing material in the prior art is greatly influenced by raw materials and pyrolysis temperature, modified biochar is not available, the number of surface active sites is limited, the adsorption capacity for cationic dye is limited, and the application of the biochar adsorbing material in dye wastewater treatment is limited.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) cleaning, drying, crushing and sieving the kelp residue to obtain kelp residue powder;
(2) calcining the kelp residue powder in a nitrogen atmosphere to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, stirring for 5-10 h for reaction, filtering, and drying a filtered product to obtain maleic acid ammonium salt modified biochar;
(4) calcining the maleic acid ammonium salt modified biochar in nitrogen atmosphere to obtain polysuccinimide modified biochar; (5) dispersing polysuccinimide modified biochar in deionized water, adjusting the pH of a system to 8.5-9.5, hydrolyzing for 0.5-1 h in a hot water bath at 55-65 ℃, cooling to room temperature, adjusting the pH of the system to be neutral, filtering, washing and drying a product to obtain the dye wastewater adsorbing material.
According to the invention, kelp residue is used as biomass waste residue in the steps (1) and (2), and the kelp residue biochar is prepared through pyrolysis and carbonization, and has the advantages of abundant pore structure, functional groups, more active sites, more negative charges on the surface, higher charge density and good adsorption effect on cationic dyes in dye wastewater. Meanwhile, the kelp residue biochar is modified through the steps (3) to (5), so that the active sites on the surface of the kelp residue biochar are further improved, and the adsorption performance of the kelp residue biochar on cationic dye is improved.
According to the invention, through the step (3), the ammonium maleate reacts with the kelp residue biochar, and as the kelp residue biochar contains rich functional groups such as hydroxyl, carboxyl, aldehyde group and ketone group, covalent bonds and hydrogen bonds can be formed with the ammonium maleate through intermolecular electrostatic attraction, so that the ammonium maleate is grafted onto the kelp residue biochar, and the ammonium maleate modified biochar is obtained; then, through the step (4), the ammonium maleate is subjected to thermal condensation polymerization under the high-temperature condition to obtain an intermediate product, namely polysuccinimide modified biochar; and (5) at a certain temperature, using NaOH to cause the cyclization of carboxyl and-NH groups in the polysuccinimide to lose water, and generating polyaspartic acid, thereby finally obtaining the polyaspartic acid modified kelp residue biochar as the adsorption material of the dye wastewater.
The invention modifies polyaspartic acid on the surface of charcoal, because the polyaspartic acid belongs to one of polyamino acids, the main molecular chain of the polyaspartic acid contains a plurality of amido bonds formed by condensing amino groups and carboxyl groups, the side chain of a monomer contains a carboxyl group, and the carboxyl group is easy to ionize in aqueous solution to form carboxylate anions, can complex a plurality of metal cations in the aqueous solution, and has high activity. And the structure of polyaspartic acid contains a large amount of carboxyl, amido bond and other active groups, and the intra-ring C-N bond in the intermediate product polysuccinimide structure is easy to be attacked by amino to be broken and can be compounded with various substances to form a composite material, so that the active site on the surface of the biochar can be improved, and the adsorption performance on cationic dyes can be obviously improved.
The adsorbing material in the invention takes the agricultural waste kelp waste residue as a raw material, has wide source and low cost, and realizes the recycling of the waste; the preparation process of the adsorbing material is simple, the production period is short, and the industrial production is easy to realize; when the prepared adsorbing material is used for treating dye wastewater, the removal rate of cationic dye is high, the using amount of the adsorbing agent is small, and the adsorbing time is short.
Preferably, the drying temperature in the step (1) is 80-120 ℃, the drying time is 20-30 h, and the powder is sieved by a 60-100 mesh sieve.
Preferably, the calcination method in step (2) is: heating from room temperature to 390-410 ℃ at a heating rate of 5-10 ℃/min, continuously pyrolyzing for 60-90 min under the temperature condition, and then naturally cooling to room temperature.
Preferably, the mass-volume ratio of the kelp residue biochar to the ammonium maleate salt solution in the step (3) is (1-5 g): 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is (0.5-8): 1.
preferably, the stirring speed in the step (3) is 3000-5000 r/min, the drying temperature is 80-120 ℃, and the drying time is 20-30 h.
Preferably, the calcination method in step (4) is: heating from room temperature to 190-210 ℃ at a heating rate of 5-10 ℃/min, continuously pyrolyzing for 1-4 h under the temperature condition, and then naturally cooling to room temperature.
Preferably, the flow rate of nitrogen gas during the calcination in the step (2) and the step (4) is 100 to 200 mL/min.
Preferably, the mass-to-volume ratio of the polysuccinimide modified biochar to the deionized water in the step (5) is (1-5 g): 50 mL.
Preferably, in the step (5), 0.1-0.5 mol/L NaOH solution and/or 0.1-0.5 mol/L hydrochloric acid is used for adjusting the pH of the system.
Therefore, the invention has the following beneficial effects:
(1) kelp residue is used as biomass waste residue, and the kelp residue biochar is prepared through pyrolysis and carbonization, so that the agricultural waste is recycled, and the kelp residue biochar has rich pore structures, functional groups and more active sites, has more negative charges on the surface, and has a good adsorption effect on cationic dyes in dye wastewater;
(2) the polyaspartic acid is modified on the surface of the kelp residue biochar, so that the number of active sites on the surface of the biochar is effectively increased, and the adsorption performance of the biochar on cationic dyes in dye wastewater is improved.
Drawings
FIG. 1 is an SEM photograph of the dye wastewater adsorbing material prepared in example 6.
FIG. 2 is an FTIR chart of the dye waste water adsorption material prepared in example 6.
FIG. 3 is a graph showing the adsorption amount of methylene blue having an initial concentration of 20mg/L to the dye wastewater adsorbing materials prepared in examples 1 to 9.
FIG. 4 is a graph showing the adsorption amount of methylene blue having an initial concentration of 40mg/L to the dye wastewater adsorbing materials prepared in examples 1 to 9.
FIG. 5 is a graph showing the adsorption amount of methylene blue having an initial concentration of 60mg/L to the dye wastewater adsorbing materials prepared in examples 1 to 9.
FIG. 6 is a graph showing the adsorption amount of methylene blue at various pH values by the dye wastewater adsorbing material prepared in example 6.
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Example 1:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) washing the kelp residues with deionized water, drying for 24h at 100 ℃, crushing the dried kelp residues, and sieving with a 80-mesh sieve to obtain kelp residue powder;
(2) putting the kelp residue powder into a tube furnace, and calcining in nitrogen atmosphereBurning to obtain herba Zosterae Marinae residue charcoal, sealing quartz tube of tube furnace during calcination, and introducing N into the tube at flow rate of 150mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 400 ℃ at a heating rate of 8 ℃/min, continuously pyrolyzing for 1h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the kelp into the kelp at the same flow rate, cooling the kelp to room temperature, and taking the kelp out to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, wherein the mass volume ratio of the kelp residue biochar to the maleic acid ammonium salt solution is 3 g: 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is 1: 2, stirring at the speed of 5000r/min for reaction for 8 hours, filtering, and drying the filtered product at the temperature of 100 ℃ for 24 hours to obtain the maleic acid ammonium salt modified biochar;
(4) putting the biological carbon modified by maleic acid ammonium salt into a tube furnace, calcining in nitrogen atmosphere to obtain polysuccinimide modified biological carbon, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at the flow rate of 150mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 200 ℃ at a heating rate of 8 ℃/min, continuously pyrolyzing for 2h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the biomass into the reactor at the same flow rate, cooling the biomass to room temperature, and taking the biomass out to obtain polysuccinimide modified charcoal;
(5) dispersing the polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 3 g: 50mL, adjusting the pH value of the system to 9.0 by using 0.2mol/L NaOH solution, hydrolyzing for 40min in a hot water bath at 60 ℃, cooling to room temperature, adjusting the pH value of the system to be neutral by using 0.2mol/L hydrochloric acid, filtering, washing and drying the product to obtain the dye wastewater adsorbing material.
Example 2:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) washing the kelp residues with deionized water, drying for 30h at 80 ℃, crushing the dried kelp residues, and sieving with a 60-mesh sieve to obtain kelp residue powder;
(2) putting the kelp residue powder into a tube furnace, calcining in nitrogen atmosphere to obtain kelp residue biochar, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 100mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 410 ℃ at a heating rate of 10 ℃/min, continuously pyrolyzing for 70min at the temperature, then starting a natural cooling process, and maintaining N in the cooling process2Continuously introducing the kelp into the kelp at the same flow rate, cooling the kelp to room temperature, and taking the kelp out to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, wherein the mass volume ratio of the kelp residue biochar to the maleic acid ammonium salt solution is 1 g: 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is 1: 1, stirring and reacting at the speed of 3000r/min for 5 hours, filtering, and drying a filtered product at the temperature of 80 ℃ for 30 hours to obtain maleic acid ammonium salt modified biochar;
(4) putting the ammonium maleate modified biochar into a tube furnace, calcining in nitrogen atmosphere to obtain polysuccinimide modified biochar, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 100mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 210 ℃ at a heating rate of 10 ℃/min, continuously pyrolyzing for 1h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the biomass into the reactor at the same flow rate, cooling the biomass to room temperature, and taking the biomass out to obtain polysuccinimide modified charcoal;
(5) dispersing the polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 1 g: and (3) 50mL, adjusting the pH value of the system to 8.5 by using 0.1mol/L NaOH solution, hydrolyzing for 60min in a hot water bath at 55 ℃, cooling to room temperature, adjusting the pH value of the system to be neutral by using 0.1mol/L hydrochloric acid, filtering, washing and drying the product to obtain the dye wastewater adsorbing material.
Example 3:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) washing the kelp residues with deionized water, drying at 120 ℃ for 20 hours, crushing the dried kelp residues, and sieving with a 100-mesh sieve to obtain kelp residue powder;
(2) putting the kelp residue powder into a tube furnace, calcining in nitrogen atmosphere to obtain kelp residue biochar, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 200mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 390 ℃ at a heating rate of 5 ℃/min, continuously pyrolyzing for 90min at the temperature, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the kelp into the kelp at the same flow rate, cooling the kelp to room temperature, and taking the kelp out to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, wherein the mass volume ratio of the kelp residue biochar to the maleic acid ammonium salt solution is 5 g: 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is 2: 1, stirring and reacting at the speed of 5000r/min for 10 hours, filtering, and drying a filtered product at the temperature of 120 ℃ for 20 hours to obtain maleic acid ammonium salt modified biochar;
(4) putting the biological carbon modified by maleic acid ammonium salt into a tube furnace, calcining in nitrogen atmosphere to obtain polysuccinimide modified biological carbon, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 200mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 190 ℃ at a heating rate of 5 ℃/min, and continuously pyrolyzing at the temperature of 4 DEG Ch, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the biomass into the reactor at the same flow rate, cooling the biomass to room temperature, and taking the biomass out to obtain polysuccinimide modified charcoal;
(5) dispersing the polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 5 g: 50mL, adjusting the pH value of the system to 9.5 by using 0.5mol/L NaOH solution, hydrolyzing for 30min in a hot water bath at 65 ℃, cooling to room temperature, adjusting the pH value of the system to be neutral by using 0.5mol/L hydrochloric acid, filtering, washing and drying the product to obtain the dye wastewater adsorbing material.
Example 4:
in the step (3) of example 4, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 3: 1, the rest is the same as in example 1.
Example 5:
in the step (3) of example 4, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 4: 1, the rest is the same as in example 1.
Example 6:
in the step (3) of example 6, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 5: 1, the rest is the same as in example 1.
Example 7:
in the step (3) of example 7, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 6: 1, the rest is the same as in example 1.
Example 8:
in the step (3) of example 8, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 7: 1, the rest is the same as in example 1.
Example 9:
in the step (3) of example 9, the mass ratio of the kelp residue biochar to the ammonium maleate salt in the ammonium maleate salt solution is 8: 1, the rest is the same as in example 1.
Comparative example 1:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) washing the kelp residues with deionized water, drying for 24h at 100 ℃, crushing the dried kelp residues, and sieving with a 80-mesh sieve to obtain kelp residue powder;
(2) putting the kelp residue powder into a tube furnace, calcining in nitrogen atmosphere to obtain kelp residue biochar, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 150mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 400 ℃ at a heating rate of 8 ℃/min, continuously pyrolyzing for 1h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2And continuously introducing the raw materials at the same flow rate, cooling to room temperature, and taking out to obtain the dye wastewater adsorbing material.
Comparative example 2:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) washing the kelp residues with deionized water, drying for 24h at 100 ℃, crushing the dried kelp residues, and sieving with a 80-mesh sieve to obtain kelp residue powder;
(2) putting the kelp residue powder into a tube furnace, calcining in nitrogen atmosphere to obtain kelp residue biochar, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at a flow rate of 150mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 400 ℃ at a heating rate of 8 ℃/min, continuously pyrolyzing for 1h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2Continuously introducing the kelp into the kelp at the same flow rate, cooling the kelp to room temperature, and taking the kelp out to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, wherein the mass volume ratio of the kelp residue biochar to the maleic acid ammonium salt solution is 3 g: 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is 5: 1, stirring and reacting at the speed of 5000r/min for 8 hours, filtering, and drying a filtered product at the temperature of 100 ℃ for 24 hours to obtain maleic acid ammonium salt modified biochar;
(4) putting the biological carbon modified by maleic acid ammonium salt into a tube furnace, calcining in nitrogen atmosphere to obtain polysuccinimide modified biological carbon, keeping a quartz tube of the tube furnace sealed during calcination, and introducing N into the tube at the flow rate of 150mL/min2And maintaining the anaerobic condition of the whole pyrolysis process, and setting the temperature rise program of the tube furnace as follows: heating from room temperature to 200 ℃ at a heating rate of 8 ℃/min, continuously pyrolyzing for 2h at the temperature, then starting a natural cooling process, and keeping N in the cooling process2And continuously introducing the raw materials at the same flow rate, cooling to room temperature, and taking out to obtain the dye wastewater adsorbing material.
The surface structure of the adsorbing material prepared in example 6 is shown in fig. 1 when observed under a scanning electron microscope, and as can be seen from fig. 1, the surface of the adsorbing material prepared by the invention is irregular, the number of pores is obvious, and small particles of ammonium salt can be seen on the surface of the adsorbing material, which indicates that the modification of the adsorbing material by using ammonium maleate is successful. The infrared spectrum test of the adsorbing material prepared in example 6 showed that the adsorbing material prepared in the invention has the characteristic peak of polyaspartic acid, and can be seen at 1600cm, as shown in FIG. 2-1And 1400cm-1Relatively broad absorption peaks appear to the left and right, which are advantageous for changing the adsorption of methylene blue.
100mL of methylene blue solution with initial concentration of 20, 40 and 60mg/L is respectively taken, 12mg of the adsorbing material prepared in the above examples and comparative examples is added, the mixture is stirred and adsorbed on a magnetic stirrer, the adsorbing and stirring are carried out for 10h, the mixed solution is centrifuged for 5min at 4000r/min in a centrifuge, then the adsorbing material is separated from the waste water, and the concentration of the supernatant is measured at 665nm by using an ultraviolet spectrophotometer, and the results are shown in FIGS. 3 to 5 and Table 1.
Table 1: and (3) testing the adsorption amount of the adsorbing material on the methylene blue.
As can be seen from fig. 3 to 5 and table 1, the adsorbing materials prepared by the method in examples 1 to 9 have good adsorbing effect on methylene blue under the condition of low initial concentration of methylene blue, and when the mass ratio of the kelp residue biochar to the ammonium maleate is 5: 1, the adsorption performance is best. In contrast, in comparative example 1, the kelp residue biochar is not modified, in comparative example 2, polysuccinimide is not hydrolyzed to generate polyaspartic acid, and the adsorption performance of the prepared adsorbing material on methylene blue is obviously reduced compared with that in example 6.
100mL of methylene blue solution with initial concentration of 20mg/L and pH range of 2-10 is respectively taken, 12mg of the adsorbing material prepared in the embodiment 6 is added, the mixture is stirred and adsorbed on a magnetic stirrer for 10 hours, the mixed solution is centrifuged for 5 minutes at 4000r/min in a centrifuge, then the adsorbing material is separated from the wastewater, an ultraviolet spectrophotometer is used for measuring the concentration of supernatant at 665nm, and the adsorption performance of the adsorbing material on the cationic dye methylene blue solution in the wastewater in different pH value ranges is measured, and the result is shown in FIG. 6. As can be seen from FIG. 6, the adsorption material prepared by the invention has good adsorption effect on cationic dyes in a larger pH range, and has the best adsorption effect under neutral and alkaline conditions.
Claims (9)
1. A method for preparing a dye wastewater adsorbing material by using biomass waste residues is characterized by comprising the following steps:
(1) cleaning, drying, crushing and sieving the kelp residue to obtain kelp residue powder;
(2) calcining the kelp residue powder in a nitrogen atmosphere to obtain kelp residue biochar;
(3) soaking the kelp residue biochar in a maleic acid ammonium salt solution, stirring for 5-10 h for reaction, filtering, and drying a filtered product to obtain maleic acid ammonium salt modified biochar;
(4) calcining the maleic acid ammonium salt modified biochar in nitrogen atmosphere to obtain polysuccinimide modified biochar;
(5) dispersing polysuccinimide modified biochar in deionized water, adjusting the pH of a system to 8.5-9.5, hydrolyzing for 0.5-1 h in a hot water bath at 55-65 ℃, cooling to room temperature, adjusting the pH of the system to be neutral, filtering, washing and drying a product to obtain the dye wastewater adsorbing material.
2. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1, wherein the drying temperature in the step (1) is 80-120 ℃, the drying time is 20-30 h, and the material is sieved by a 60-100-mesh sieve.
3. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1, wherein the calcining method in the step (2) comprises the following steps: heating from room temperature to 390-410 ℃ at a heating rate of 5-10 ℃/min, continuously pyrolyzing for 60-90 min under the temperature condition, and then naturally cooling to room temperature.
4. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1, wherein the mass-to-volume ratio of the biomass waste residue biochar to the ammonium maleate salt solution in the step (3) is (1-5 g): 50mL, wherein the mass ratio of the kelp residue biochar to the maleic acid ammonium salt in the maleic acid ammonium salt solution is (0.5-8): 1.
5. the method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1 or 4, wherein the stirring speed in the step (3) is 3000-5000 r/min, the drying temperature is 80-120 ℃, and the drying time is 20-30 h.
6. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1, wherein the calcining method in the step (4) comprises the following steps: heating from room temperature to 190-210 ℃ at a heating rate of 5-10 ℃/min, continuously pyrolyzing for 1-4 h under the temperature condition, and then naturally cooling to room temperature.
7. The method for preparing the dye wastewater adsorbing material from the biomass waste residue as claimed in claim 1, 3 or 6, wherein the flow rate of nitrogen during the calcination in the steps (2) and (4) is 100-200 mL/min.
8. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1, wherein the mass-to-volume ratio of the polysuccinimide modified biochar to deionized water in the step (5) is (1-5 g): 50 mL.
9. The method for preparing the dye wastewater adsorbing material by using the biomass waste residue as claimed in claim 1 or 8, wherein in the step (5), 0.1-0.5 mol/L NaOH solution and/or 0.1-0.5 mol/L hydrochloric acid is used for adjusting the pH of the system.
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