CN112090396B - 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 PDF

Info

Publication number
CN112090396B
CN112090396B CN202010878776.9A CN202010878776A CN112090396B CN 112090396 B CN112090396 B CN 112090396B CN 202010878776 A CN202010878776 A CN 202010878776A CN 112090396 B CN112090396 B CN 112090396B
Authority
CN
China
Prior art keywords
biochar
adsorbing material
dye wastewater
kelp
preparing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010878776.9A
Other languages
Chinese (zh)
Other versions
CN112090396A (en
Inventor
童东绅
任来宾
董玉萧
陈星陶
俞卫华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN202010878776.9A priority Critical patent/CN112090396B/en
Publication of CN112090396A publication Critical patent/CN112090396A/en
Application granted granted Critical
Publication of CN112090396B publication Critical patent/CN112090396B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3028Granulating, agglomerating or aggregating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/305Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C10B57/10Drying
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/40Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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 for 0.5 to 1h in a hot water bath 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

Method for preparing dye wastewater adsorbing material by using biomass waste residues
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 the dye waste water has stable property and is not easy to biodegrade, so that the dye waste water is known as one of the waste water with higher 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 having better adsorption performance to replace activated carbon has been a major concern 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 an adsorbent for dye wastewater and a method for purifying dye wastewater disclosed in chinese patent document, publication No. CN110773133A, includes the following steps: (1) Recovering waste corn straws in crops, drying, and removing leaves, outer skin and stem nodes of the corn straws to obtain corn pith; (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 with xylanase, fully reacting the alkalized corn pith with the xylanase, fully washing the corn pith after reaction 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 value 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 value 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 polysuccinimide modified biochar; and finally, in the step (5), at a certain temperature, naOH is used for cyclizing carboxyl and-NH groups in the polysuccinimide to lose water, and polyaspartic acid is generated, so that polyaspartic acid modified kelp residue biochar is finally obtained and is used as an adsorption material of 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 mixture is sieved by a 60-100 mesh sieve.
Preferably, the calcination method in step (2) is: heating from room temperature to 390-410 ℃ at the 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 maleic acid ammonium 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 the 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 200mL/min.
Preferably, the mass-to-volume ratio of the polysuccinimide modified biochar to the deionized water in the step (5) is (1-5 g): 50mL.
Preferably, in the step (5), 0.1 to 0.5mol/L NaOH solution and/or 0.1 to 0.5mol/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 recycling of agricultural wastes is realized, 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 at 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 at 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 at 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 figures and embodiments.
Example 1:
a method for preparing a dye wastewater adsorbing material by using biomass waste residues comprises the following steps:
(1) Washing kelp residue with deionized water, drying at 100 ℃ for 24h, crushing the dried kelp residue, 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/min 2 And 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 under the temperature condition, then starting a natural cooling process, and keeping N in the cooling process 2 Continuously 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 3g: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, reacting for 8 hours, filtering, and drying the filtered product at the temperature of 100 ℃ for 24 hours to obtain maleic acid ammonium salt modified biochar;
(4) Mixing maleic anhydride and maleic anhydridePutting the acid ammonium salt 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 150mL/min 2 And 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 process 2 Continuously 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 polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 3g: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 kelp residue with deionized water, drying at 80 ℃ for 30h, crushing the dried kelp residue, 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/min 2 And 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 process 2 Continuously 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 1g: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 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 simultaneously introducing N into the tube at a flow rate of 100mL/min 2 And 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 process 2 Continuously 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 polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 1g: and (3) 50mL, adjusting the pH value of the system to 8.5 by using 0.1mol/L NaOH solution, hydrolyzing for 60min in 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/min 2 And 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 at a heating rate of 5 deg.C/minHeating to 390 ℃, continuously pyrolyzing for 90min under the temperature condition, then starting a natural cooling process, and keeping N in the cooling process 2 Continuously introducing the kelp residues at the same flow rate, cooling to room temperature, and taking 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 5g: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/min 2 And 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, continuously pyrolyzing for 4h at the temperature, then starting a natural cooling process, and keeping N in the cooling process 2 Continuously 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 polysuccinimide modified biochar in deionized water, wherein the mass volume ratio of the polysuccinimide modified biochar to the deionized water is 5g: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 maleic acid ammonium salt in the maleic acid ammonium 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 was 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 maleic acid ammonium salt in the maleic acid ammonium 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 was 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/min 2 And 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 process 2 And 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 kelp residue with deionized water, drying at 100 ℃ for 24h, crushing the dried kelp residue, 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/min 2 And 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 process 2 Continuously 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 3g: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/min 2 And 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 process 2 And 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 adsorbent material prepared in example 6 was placed in a scanning electronThe surface structure is shown in figure 1 when observed under the mirror, and as can be seen from figure 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 the ammonium maleate salt 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 -1 And 1400cm -1 Relatively broad absorption peaks appear to the left and right, which are advantageous for changing the adsorption of methylene blue.
100mL of methylene blue solutions each having an initial concentration of 20, 40, and 60mg/L were added with 12mg of the adsorbent prepared in the above examples and comparative examples, and the mixture was stirred and adsorbed on a magnetic stirrer for 10 hours, and the mixed solution was centrifuged at 4000r/min for 5 minutes in a centrifuge, after which the adsorbent was separated from the wastewater, and the supernatant was subjected to concentration measurement at 665nm using an ultraviolet spectrophotometer, and the results are shown in FIGS. 3 to 5 and Table 1.
Table 1: and (4) testing the adsorption amount of the adsorbing material on the methylene blue.
Figure BDA0002653456530000081
As can be seen from fig. 3 to 5 and table 1, the adsorbing materials prepared by the method of the present invention in examples 1 to 9 all 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 salt 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 adsorption 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 was taken, 12mg of the adsorbing material prepared in example 6 was added, the mixture was stirred and adsorbed on a magnetic stirrer for 10 hours, the mixture was centrifuged at 4000r/min for 5 minutes in a centrifuge, then the adsorbing material was separated from the wastewater, the concentration of the supernatant was measured at 665nm using an ultraviolet spectrophotometer, and the adsorbing performance of the adsorbing material on the cationic dye methylene blue solution in the wastewater was measured within different pH value ranges, and the results are shown in FIG. 6. As can be seen from FIG. 6, the adsorbing material prepared by the invention has good adsorption effect on cationic dye 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 to react for 5-10h, filtering, and drying a filtered product to obtain maleic acid ammonium salt modified biochar;
(4) Calcining the maleic acid ammonium salt modified biochar in a 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 0.5-1h 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 from the biomass waste residue according to claim 1, wherein the drying temperature in the step (1) is 80-120 ℃, the drying time is 20-30h, and the material is sieved by a sieve with 60-100 meshes.
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 to 410 ℃ at the heating rate of 5 to 10 ℃/min, continuously pyrolyzing for 60 to 90min under the temperature condition, and then naturally cooling to the 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 (1-5g): 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 from the biomass waste residue according to claim 1 or 4, wherein the stirring speed in the step (3) is 3000 to 5000r/min, the drying temperature is 80 to 120 ℃, and the drying time is 20 to 30h.
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 to 200mL/min.
8. The method for preparing the dye wastewater adsorbing material from the biomass waste residue according to claim 1, wherein the mass volume ratio of the polysuccinimide modified biochar to deionized water in the step (5) is (1 to 5 g): 50mL.
9. The method for preparing the dye wastewater adsorbing material from the biomass waste residue as claimed in claim 1 or 8, wherein in the step (5), 0.1 to 0.5mol/L NaOH solution and/or 0.1 to 0.5mol/L hydrochloric acid is used for adjusting the pH of the system.
CN202010878776.9A 2020-08-27 2020-08-27 Method for preparing dye wastewater adsorbing material by using biomass waste residues Active CN112090396B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010878776.9A CN112090396B (en) 2020-08-27 2020-08-27 Method for preparing dye wastewater adsorbing material by using biomass waste residues

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010878776.9A CN112090396B (en) 2020-08-27 2020-08-27 Method for preparing dye wastewater adsorbing material by using biomass waste residues

Publications (2)

Publication Number Publication Date
CN112090396A CN112090396A (en) 2020-12-18
CN112090396B true CN112090396B (en) 2022-11-22

Family

ID=73758059

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010878776.9A Active CN112090396B (en) 2020-08-27 2020-08-27 Method for preparing dye wastewater adsorbing material by using biomass waste residues

Country Status (1)

Country Link
CN (1) CN112090396B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185866B (en) * 2021-04-01 2023-04-07 浙江工业大学 Carbon ink prepared from waste kelp residues and preparation method thereof
CN114106842A (en) * 2021-11-30 2022-03-01 大连理工大学 Composite material for degrading polycyclic aromatic hydrocarbon in soil and preparation method and application thereof
CN114314794B (en) * 2021-12-10 2022-09-16 哈尔滨工业大学 Preparation method and application of graphene oxide based on high-salt spirulina residues
CN115722191A (en) * 2022-11-21 2023-03-03 天津理工大学 Biomass carbon for enhancing Cd and Pb removal capacity of water body and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106540671A (en) * 2017-01-19 2017-03-29 合肥工业大学 A kind of preparation method and applications of poly-aspartate tripolycyanamide/absorbent charcoal composite material
CN108339534A (en) * 2018-03-02 2018-07-31 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of modification biological based composite material of carbon
CN109317118A (en) * 2018-09-26 2019-02-12 宁波浙铁江宁化工有限公司 It is a kind of for the poly-aspartate hydrogel of Dye Adsorption and its application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106540671A (en) * 2017-01-19 2017-03-29 合肥工业大学 A kind of preparation method and applications of poly-aspartate tripolycyanamide/absorbent charcoal composite material
CN108339534A (en) * 2018-03-02 2018-07-31 东莞市联洲知识产权运营管理有限公司 A kind of preparation method of modification biological based composite material of carbon
CN109317118A (en) * 2018-09-26 2019-02-12 宁波浙铁江宁化工有限公司 It is a kind of for the poly-aspartate hydrogel of Dye Adsorption and its application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
聚天冬氨酸合成工艺研究;龚旌;《广东化工》;20141231;第41卷(第11期);第57-58页 *

Also Published As

Publication number Publication date
CN112090396A (en) 2020-12-18

Similar Documents

Publication Publication Date Title
CN112090396B (en) Method for preparing dye wastewater adsorbing material by using biomass waste residues
CN109534432A (en) The preparation method of the biological carbon modified material of phosphorus in a kind of removal eutrophication water
CN112121766A (en) Ramie fiber-based biochar and preparation method and application thereof
CN115475604B (en) Manufacturing method of composite multifunctional adsorbent based on cork activated carbon and amino carbon quantum dots
CN111450802A (en) Method for preparing carbon-based functional material and application thereof
CN113908811A (en) Preparation method of biomass charcoal material for removing phosphorus from sewage
CN111170297B (en) Camellia oleifera shell carbon powder material and application thereof in purification of antibiotic wastewater
CN111545163B (en) Adsorbent for heavy metal wastewater treatment and preparation method thereof
CN114632501B (en) Preparation method of attapulgite-based adsorbent and application of attapulgite-based adsorbent in dye/heavy metal ion wastewater treatment
CN111495349A (en) Modified biomass charcoal catalyst based on activated sludge and preparation method thereof
CN116459795A (en) Water treatment material for removing lead from wastewater and preparation method and application thereof
CN114700065B (en) Waste resin carbon sphere composite ozone catalyst and preparation method and application thereof
CN111939872B (en) Preparation method and application of activated hemp carbon adsorbent
CN110624496B (en) Preparation method of porous boron nitride-based composite material for purifying organic wastewater
CN106944001B (en) Preparation method of biological carbon adsorbent
CN114632515A (en) Preparation method of magnetic biochar nano photocatalyst
CN113926444A (en) Zinc oxide nano-rod ternary composite material and preparation method and application thereof
CN113750961A (en) Carbon dioxide adsorbent and preparation method thereof
CN108654584B (en) Regeneration method of activated carbon for decolorizing hydroxyketone
CN117417525B (en) Poly-N-phenylglycine@biochar composite material and preparation method and application thereof
CN116920796A (en) Surface load Bi 2 O 3 Preparation method of coal pitch-based spherical active carbon composite material
CN117486195A (en) Nitrogen-doped biochar based on alkaline lignin, low-temperature pyrolysis preparation method and application thereof
CN117797879A (en) Carbon nitride/MOF/indium sulfide heterojunction composite photocatalyst and preparation method and application thereof
CN116273128A (en) Amino grafted biochar and preparation method and application thereof
CN114308101A (en) Michelidonite-assisted synthesized carbon nitride nanosheet photocatalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant