CN115624954B - Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof - Google Patents

Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof Download PDF

Info

Publication number
CN115624954B
CN115624954B CN202211310711.XA CN202211310711A CN115624954B CN 115624954 B CN115624954 B CN 115624954B CN 202211310711 A CN202211310711 A CN 202211310711A CN 115624954 B CN115624954 B CN 115624954B
Authority
CN
China
Prior art keywords
barley
treating agent
copper
phosphorus
biomass
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
CN202211310711.XA
Other languages
Chinese (zh)
Other versions
CN115624954A (en
Inventor
陈其锦
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.)
Anhui Jinggao Water Treatment Co ltd
Original Assignee
Anhui Jinggao Water Treatment Co ltd
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 Anhui Jinggao Water Treatment Co ltd filed Critical Anhui Jinggao Water Treatment Co ltd
Priority to CN202211310711.XA priority Critical patent/CN115624954B/en
Publication of CN115624954A publication Critical patent/CN115624954A/en
Application granted granted Critical
Publication of CN115624954B publication Critical patent/CN115624954B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/283Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • B01J2220/4812Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/105Phosphorus compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • 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
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Sorption (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a biomass composite treating agent for removing nitrogen and phosphorus in sewage and a preparation method thereof. The raw materials of the biomass composite treating agent comprise the following components: 56-60 parts of barley-based treating agent and 40-44 parts of copper-based biomass charcoal. Copper salt and biomass material are utilized for cracking together, the specific surface area and adsorption sites are reserved to the maximum extent through the control of temperature and load capacity, and nitrogen and phosphorus in sewage are removed; the method comprises the steps of utilizing copper oxide on copper-based biomass charcoal to preferentially adsorb NO 3 ; taking barley as a main body, grafting methacrylate on a main chain of barley polysaccharide to obtain substances with multi-functional groups such as-OH, C= O, C-O-C and the like, and effectively cooperating with copper-based biomass charcoal to remove nitrogen and phosphorus; further tertiary amination and quaternization are carried out on the barley compound, so that the preferential adsorption capacity of PO 4 3‑ is increased; the advantages of various substances in the biomass composite treating agent are complementary, NH4 +、NO3 、PO4 3‑ in sewage is removed together, and the aim of removing nitrogen and phosphorus is fulfilled.

Description

Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a biomass composite treating agent for removing nitrogen and phosphorus in sewage and a preparation method thereof.
Background
In recent years, the excessive use of crop fertilizers and the discharge of a large amount of domestic sewage containing phosphorus and nitrogen cause water bodies to present eutrophication. However, eutrophication of water body can cause degradation of water ecosystem, so that algae overgrows, a large amount of fishes die, biodiversity is reduced and the like.
The nitrogen and the phosphorus in the water body generally exist in the forms of ammonia nitrogen, nitric acid nitrogen and phosphate, and can be metabolized by physical methods, chemical adsorption and organisms. Wherein, the bacteria culture and carbon source selection of the biological metabolism are complex and the cost is high; the physical method can be realized by electrodialysis and the like, and the removal rate is low. The chemical adsorption treating agent has higher nitrogen and phosphorus removal rate in the water body and is convenient to use. Most of the chemical adsorbents are only treated for one of ammonia nitrogen, nitric acid nitrogen and phosphate, and few adsorbents are removed simultaneously. And when the common treating agents such as zeolite, activated carbon, fly ash and the like are used for removing the real sewage, the removal rate of nitric acid nitrogen and phosphate can be reduced due to competitive adsorption in the sewage, and the effect is poor.
Meanwhile, the biomass raw material is low in price and easy to obtain, and the utilization of biomass waste can reduce environmental pollution, so that the biomass waste has great potential in chemical adsorption treatment agents. Therefore, how to use biomass materials to prepare the biomass composite treating agent for removing ammonia nitrogen, nitric acid nitrogen and phosphate simultaneously has important significance.
Disclosure of Invention
The invention aims to provide a biomass composite treating agent for removing nitrogen and phosphorus in sewage and a preparation method thereof, so as to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
A biomass composite treating agent for removing nitrogen and phosphorus in sewage, the raw materials of the biomass composite treating agent comprise the following components: 56-60 parts of barley-based treating agent and 40-44 parts of copper-based biomass charcoal.
More preferably, the raw materials of the barley based treatment agent comprise the following components: 50-55 parts of barley compound, 2-4 parts of N, N-dimethyl-1, 3-propanediamine and 2-4 parts of 2-bromoethanol.
More preferably, the raw materials of the barley composite comprise the following components: 5-8 parts of barley, 48-82 parts of methyl methacrylate and 2-4 parts of cerium nitrate.
More optimally, the raw materials of the copper-based biomass charcoal comprise the following components: 58-63 parts of corn straw and 2-7 parts of copper nitrate by weight.
More optimally, the preparation method of the biomass composite treating agent for removing nitrogen and phosphorus in sewage comprises the following steps:
step 1: preparation of barley complex: under the nitrogen atmosphere, adding the weighed barley into a reaction kettle containing deionized water, adding methyl methacrylate, and reacting; adding acetone, washing, filtering and drying to obtain barley compound for later use;
step 2: preparation of barley-based treatment agent: adding N, N-dimethyl-1, 3-propylene diamine into a reaction kettle containing deionized water; adding barley complex, reacting, washing and drying to obtain tertiary aminated barley complex; sequentially adding the mixture, ethanol and 2-bromoethanol into a reaction kettle for reaction; washing, filtering and drying to obtain a barley-based treating agent;
Step 3: preparation of copper-based biomass charcoal: grinding, washing, drying and sieving the corn straw waste to obtain corn straw; placing the mixture in a copper nitrate solution, stirring and dipping; drying; setting the temperature to be 350-400 ℃ in a nitrogen atmosphere to obtain copper-based biomass charcoal;
Step 4: and stirring the barley-based treating agent and the copper-based biomass charcoal in a high-speed mixer for 40-60 minutes to obtain the biomass composite treating agent.
More preferably, the specific steps of step 1 are as follows: under the nitrogen atmosphere, adding the weighed barley into a reaction kettle containing deionized water, setting the temperature to be 40-45 ℃, and stirring and mixing for 30-40 minutes; cooling to 23-28 ℃, adding methyl methacrylate, and stirring for 15-30 minutes; slowly adding 0.1mol/L cerium nitrate in sequence, and continuously stirring for 20-24 hours; adding excessive acetone, washing, filtering, and drying to obtain barley compound.
More preferably, in the step 1, the mass ratio of the barley to the deionized water is (1.2-1.5): 1.
More preferably, the specific steps of step 2 are as follows: adding N, N-dimethyl-1, 3-propanediamine into a reaction kettle containing deionized water, and stirring and mixing for 10-15 minutes; adding the barley compound, refluxing for 4-5 hours at the temperature of 110-120 ℃, and washing and drying to obtain the tertiary aminated barley compound; sequentially adding the ethanol, ethanol and 2-bromoethanol into a reaction kettle, and refluxing for 1-2 hours at the temperature of 55-65 ℃; washing with ethanol, filtering, and drying to obtain barley-based treating agent.
More preferably, in the step 2, the mass ratio of the N, N-dimethyl-1, 3-propanediamine to the deionized water is 1 (0.05-0.1).
More preferably, the specific steps of step 3 are as follows: grinding, washing and drying corn straw waste, and sieving with a 0.45mm screen to obtain corn straw; placing the mixture in a copper nitrate solution with the weight percent of 5-10%, setting the rotating speed to be 180-240 rmp, stirring the mixture at the constant temperature of 25-30 ℃ for 20-23 hours, and stirring the mixture at the constant temperature of 75-80 ℃ for 30-40 minutes; transferring and spreading in a glass plate, and vacuum drying at 100-105 ℃; transferring the mixture into a horse fluorine furnace, and reacting for 2-3 hours at the temperature of 350-400 ℃ in a nitrogen atmosphere to obtain the copper-based biomass charcoal.
According to the technical scheme, the barley-based treatment agent and the copper-based biomass charcoal are respectively prepared, the barley-based treatment agent and the copper-based biomass charcoal are mixed, the biomass composite treatment agent capable of removing nitrogen and phosphorus in sewage is obtained through complementary advantages, and NH 4 +、NO3 -、PO4 3- nitrogen and phosphorus substances in sewage can be effectively removed at the same time. Meanwhile, the water-based biological agent has antibacterial property and can remove harmful bacteria in biomass water.
(1) Copper-based biomass charcoal: the surface of the biomass charcoal usually contains a plurality of oxygen-containing groups with negative charges, which is favorable for adsorbing NH 4 + and weak for anion adsorption, but NO 3 - plasma exists in the water body, so that the load of the cupric oxide is increased, thereby effectively adsorbing NO 3 -, but the pore structure and the specific surface area of the biomass charcoal are reduced along with the increase of the cupric oxide, the load of the cupric oxide needs to be controlled, and the maximum specific surface area of the biomass charcoal is reserved. Thereby the copper-based biomass charcoal achieves the optimal NH 4 +、NO3 - removal capacity. The preparation process comprises the following steps: (1) The pyrolysis temperature is set at 350-400 ℃, the largest specific surface area of the biomass charcoal can be reserved to be porous, more oxygen-containing groups are reserved, and acid groups can be ionized in the solution to carry negative charges, and are electrostatically attracted to NH 4 + and ion-exchanged; and hydroxide ions can be subjected to anion exchange with NO 3 -, so that more adsorption sites are reserved, and the nitrogen removal capacity is improved. (2) The presence of copper oxide increases the roughness of the biomass char, while reducing the void area, but increases the surface area, which may enhance the adsorption of anions such as NO 3 -、PO4 3-, where copper oxide is reactive with NO 3 - and therefore preferentially adsorbs NO 3 -. (3) Copper is pre-impregnated in the co-pyrolysis, and as copper oxide and biomass materials (corn stalks) have different thermal properties, carbonization of biomass is affected, and nitrogen and carbon contents are increased along with the increase of the contents, so that the porosity is increased.
However, in the actual wastewater, anions such as Cl -、SO4 2-、CO3 2- are present which compete for adsorption, and certainly have little effect on NH 4 + removal, but have an effect on NO 3 -、PO4 3- adsorption, particularly on PO 4 3-. Therefore, barley-based treatment agents are introduced to cooperatively remove NH 4 + while enhancing competitive adsorption of PO 4 3- in wastewater.
(2) Barley-based treatment agent: barley is a substance containing 90-95% of polysaccharides, which contain linear compounds linked by glycosidic bonds. Taking the cerium nitrate as an initiator, taking the methyl methacrylate monomer as a branched chain, and grafting the methyl methacrylate monomer on the main chain to form the barley compound. Wherein: cerium nitrate forms Ce 4+ and nitric acid in the reaction, and Ce 4+ is dissociated in nitric acid medium, so that free radical sites are generated on barley polysaccharide, and methacrylate is guided to graft; since the radical site is generated by single electron conversion of Ce 4+ with barley polysaccharide to Ce 3+, the reaction must be in a nitrogen reaction to prevent oxidation of Ce 4+. The barley complex prepared contains a large number of oxygen-containing groups: -OH, c= O, C-O-C, can react with NH4 +、NO3 -、PO4 3- and is therefore removed. But there is a need for further improvements in the ability to increase competitive adsorption of PO 4 3-; therefore, the branched chain methyl methacrylate on the barley compound is tertiary aminated by utilizing the reaction amino alkylation reaction between the amino and the ester group, and the tertiary amine group is quaternized by utilizing the 2-bromoethanol to obtain the barley base treating agent; (1) Hydroxyl and PO 4 3- can generate intermolecular hydrogen bonding force, so that the hydroxyl and PO can be removed; (2) Sites generated by positively charged quaternary carbon in the barley-based treatment agent can be electrostatically reacted with PO 4 3- to be adsorbed and removed, and have preferential adsorption capacity due to the exchange capacity between free bromide ions and phosphate ions on the quaternary carbon.
(3) The prepared biomass composite treating agent can be settled and filtered for removal.
Compared with the prior art, the invention has the following beneficial effects: the invention (1) utilizes copper salt and biomass material to crack together, through the control of temperature and load capacity, the specific surface area and adsorption site are reserved to the maximum extent, and simultaneously nitrogen and phosphorus in the sewage are removed; (2) The method comprises the steps of utilizing copper oxide on copper-based biomass charcoal to preferentially adsorb NO 3 -; (3) Taking barley as a main body, grafting methacrylate on a main chain of barley polysaccharide to obtain substances with multi-functional groups such as-OH, C= O, C-O-C and the like, and effectively cooperating with copper-based biomass charcoal to remove nitrogen and phosphorus; (4) To increase the preferential adsorption capacity of PO 4 3-, the barley complex is further tertiary aminated, quaternized, thereby allowing preferential adsorption of PO 4 3-; (5) The advantages of various substances in the biomass composite treating agent are complementary, NH4 +、NO3 -、PO4 3- in sewage is removed together, and the aim of removing nitrogen and phosphorus is fulfilled.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
Step 1: preparation of barley complex: under the nitrogen atmosphere, adding 8 parts of weighed barley into a reaction kettle containing deionized water, wherein the mass ratio of the barley to the deionized water is 1.2:1; setting the temperature to 45 ℃, and stirring and mixing for 35 minutes; cooling to 25 ℃, adding 65 parts of methyl methacrylate, and stirring for 20 minutes; slowly adding 1.5 parts of 0.1mol/L solution prepared from cerium nitrate in sequence, and continuously stirring for 22 hours; adding excessive acetone, washing, filtering, and drying to obtain barley compound.
Step 2: preparation of barley-based treatment agent: adding 3 parts of N, N-dimethyl-1, 3-propylene diamine into a reaction kettle containing deionized water, wherein the mass ratio of the N, N-dimethyl-1, 3-propylene diamine to the deionized water is 1:0.08; stirring and mixing for 12 minutes; adding 52 parts of barley compound, refluxing at 115 ℃ for 4.5 hours, washing and drying to obtain tertiary aminated barley compound; sequentially adding the ethanol, 3 parts of 2-bromoethanol and the mixture into a reaction kettle, and refluxing at 60 ℃ for 1.5 hours; washing with ethanol, filtering, and drying to obtain barley-based treating agent.
Step 3: preparation of copper-based biomass charcoal: grinding, washing and drying corn straw waste, and sieving with a 0.45mm screen to obtain corn straw; 5 parts of copper nitrate is prepared into a copper nitrate solution with the concentration of 8wt percent for standby; weighing 60.5 parts of corn stalks, placing the corn stalks in a copper nitrate solution, setting the rotating speed to be 210rmp, stirring the corn stalks at the constant temperature of 28 ℃ for 22 hours, and stirring the corn stalks at the constant temperature of 78 ℃ for 35 minutes; transferring and spreading in a glass plate, and vacuum drying at 102 ℃; transferring the mixture into a horse fluorine furnace, and reacting for 2 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the copper-based biomass charcoal.
Step 4: 58 parts of the barley based treatment agent and 42 parts of copper based biomass charcoal are stirred in a high-speed mixer for 50 minutes to obtain the biomass composite treatment agent.
Example 2:
Step 1: preparation of barley complex: under the nitrogen atmosphere, adding 5 parts of weighed barley into a reaction kettle containing deionized water, wherein the mass ratio of the barley to the deionized water is 1.25:1; setting the temperature at 42 ℃, stirring and mixing for 30 minutes; cooling to 23 ℃, adding 48 parts of methyl methacrylate, and stirring for 15 minutes; slowly adding 1 part of 0.1mol/L solution prepared from cerium nitrate in sequence, and continuously stirring for 20 hours; adding excessive acetone, washing, filtering, and drying to obtain barley compound.
Step 2: preparation of barley-based treatment agent: adding 2 parts of N, N-dimethyl-1, 3-propylene diamine into a reaction kettle containing deionized water, wherein the mass ratio of the N, N-dimethyl-1, 3-propylene diamine to the deionized water is 1:0.05; stirring and mixing for 10 minutes; 50 parts of barley compound is added, reflux is carried out for 4 hours at the temperature of 110 ℃, and the tertiary amination barley compound is obtained after washing and drying; sequentially adding the ethanol, 2 parts of 2-bromoethanol and the mixture into a reaction kettle, and refluxing for 1 hour at the temperature of 55 ℃; washing with ethanol, filtering, and drying to obtain barley-based treating agent.
Step 3: preparation of copper-based biomass charcoal: grinding, washing and drying corn straw waste, and sieving with a 0.45mm screen to obtain corn straw; 2 parts of copper nitrate is prepared into a copper nitrate solution with the weight percent of 10 percent for standby; weighing 58 parts of corn stalks, placing the corn stalks in a copper nitrate solution, setting the rotating speed to be 180rmp, stirring the corn stalks for 20 hours at the constant temperature of 25 ℃, and stirring the corn stalks for 30 minutes at the constant temperature of 75 ℃; transferring and spreading in a glass plate, and vacuum drying at 100deg.C; transferring the mixture into a horse fluorine furnace, and reacting for 3 hours at the temperature of 350 ℃ in a nitrogen atmosphere to obtain the copper-based biomass charcoal.
Step 4: 56 parts of the barley based treatment agent and 44 parts of copper based biomass charcoal are stirred in a high-speed mixer for 40 minutes to obtain the biomass composite treatment agent.
Example 3:
Step 1: preparation of barley complex: under the nitrogen atmosphere, adding 6 parts of weighed barley into a reaction kettle containing deionized water, wherein the mass ratio of the barley to the deionized water is 1.5:1; setting the temperature to 45 ℃, and stirring and mixing for 40 minutes; cooling to 28 ℃, adding 82 parts of methyl methacrylate, and stirring for 30 minutes; slowly adding 2 parts of 0.1mol/L solution prepared from cerium nitrate in sequence, and continuously stirring for 24 hours; adding excessive acetone, washing, filtering, and drying to obtain barley compound.
Step 2: preparation of barley-based treatment agent: adding 4 parts of N, N-dimethyl-1, 3-propylene diamine into a reaction kettle containing deionized water, wherein the mass ratio of the N, N-dimethyl-1, 3-propylene diamine to the deionized water is 1:0.1; stirring and mixing for 15 minutes; adding 55 parts of barley compound, refluxing at 120 ℃ for 5 hours, washing and drying to obtain tertiary aminated barley compound; sequentially adding the ethanol, 4 parts of 2-bromoethanol and the mixture into a reaction kettle, and refluxing for 2 hours at the temperature of 65 ℃; washing with ethanol, filtering, and drying to obtain barley-based treating agent.
Step 3: preparation of copper-based biomass charcoal: grinding, washing and drying corn straw waste, and sieving with a 0.45mm screen to obtain corn straw; 7 parts of copper nitrate is prepared into a copper nitrate solution with the weight percent of 5 percent for standby; weighing 63 parts of corn stalks, placing the corn stalks in a copper nitrate solution, setting the rotating speed to 240rmp, stirring the corn stalks at the constant temperature of 30 ℃ for 23 hours, and stirring the corn stalks at the constant temperature of 80 ℃ for 40 minutes; transferring and spreading in a glass plate, and vacuum drying at 105 ℃; transferring the mixture into a horse fluorine furnace, and reacting for 2.5 hours at the temperature of 400 ℃ in a nitrogen atmosphere to obtain the copper-based biomass charcoal.
Step 4: 60 parts of the barley based treating agent and 40 parts of the copper based biomass charcoal are stirred in a high-speed mixer for 60 minutes to obtain the biomass composite treating agent.
Example 4: the biomass charcoal is not loaded with copper oxide; the remainder was the same as in example 1;
Example 5: setting the pyrolysis temperature of biomass charcoal to be 500 ℃; the remainder was the same as in example 1;
example 6: no barley-based treatment agent is added, and 100% copper-based biomass charcoal is used as a treatment agent; the remainder was the same as in example 1;
Example 7: the barley compound is used for replacing a barley-based treating agent, and tertiary amination and quaternization are not carried out; the remainder was the same as in example 1;
Example 8: replacing the barley-based treatment agent with a tertiary aminated barley complex without quaternization; the remainder was the same as in example 1;
Experiment: the biomass composite treating agent prepared in the examples 1-8 is used for sewage treatment. The treated sewage is displayed according to the detection report: the concentration of ammonium ions is 33.4mg/L, and the concentration of nitrate ions is 26.1mg/L; the concentration of phosphate radical ion is 10mg/L; taking 0.4mg of sewage for treating 100 mL; and obtaining the removal rate according to the concentration difference before and after treatment. The results obtained are shown in Table 1:
Table 1:
Conclusion: from the experimental data of examples 1 to 3, it is known that: the prepared biomass composite treating agent has the property of simultaneously adsorbing ammonia nitrogen, nitrate nitrogen and phosphorus, and can remove more than 92% of nitrogen and phosphorus in sewage, so that the sewage reaches the common emission standard.
Comparing the data of example 4 with the data of example 1, it can be seen that: the NH 4 + removal rate is increased, and the NO 3 - removal rate is reduced more than the PO 4 3- removal rate; the reason is that: the loading of copper oxide reduces the pore area, thereby reducing the active sites of acidic substances, the presence of copper oxide increases the roughness of the biomass char, and can enhance the adsorption of anions such as NO 3 -、PO4 3-, where copper oxide is reactive with NO 3 - and therefore preferentially adsorbs NO 3 -.
Comparing the data of example 5 with the data of example 1, it can be seen that: NH 4 + removal rate, NO 3 - removal rate and PO 4 3- removal rate are reduced slightly, because: the pyrolysis temperature is set to be lower than 400 ℃, the largest specific surface area of the biomass charcoal can be reserved to be porous, more oxygen-containing groups are reserved, and acid groups can be ionized in the solution to carry negative charges, and the acid groups are electrostatically attracted to NH 4 + and are subjected to ion exchange; and hydroxide ions can be subjected to anion exchange with NO 3 -, so that more adsorption sites are reserved, and the nitrogen removal capacity is improved.
Comparing the data of example 6 with the data of example 1, it can be seen that: the NH 4 + removal rate is reduced to a certain extent, which shows that the removal rate of ammonia nitrogen by biomass is not high as that of a barley treatment agent, and the method takes barley as a main body, grafts methacrylate on the main chain of barley polysaccharide, and obtains substances with multi-functional groups such as-OH, C= O, C-O-C and the like, thereby effectively cooperating with the removal of nitrogen and phosphorus by copper-based biomass charcoal; it can be seen that the removal rate for NO 3 - increases because copper oxide is reactive with NO 3 - and therefore preferentially adsorbs NO 3 -; the decrease in PO 4 3- removal rate was significant because of competitive adsorption in the wastewater, which had a severe effect on phosphate, as demonstrated by the data of comparative examples 7 and 8: further tertiary amination and quaternization of the barley complex enable sites generated by the quaternary carbon with positive charges to generate electrostatic reaction with PO 4 3-, so that adsorption removal is realized, and the barley complex has preferential adsorption capacity.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A biomass composite treating agent for removing nitrogen and phosphorus in sewage is characterized in that: the raw materials of the biomass composite treating agent comprise the following components: 56-60 parts of barley-based treating agent and 40-44 parts of copper-based biomass charcoal by weight;
the preparation method of the biomass composite treating agent comprises the following steps:
step 1: preparation of barley complex: under the nitrogen atmosphere, adding the weighed barley into a reaction kettle containing deionized water, adding methyl methacrylate, and reacting; adding acetone, washing, filtering and drying to obtain barley compound for later use;
step 2: preparation of barley-based treatment agent: adding N, N-dimethyl-1, 3-propylene diamine into a reaction kettle containing deionized water; adding barley complex, reacting, washing and drying to obtain tertiary aminated barley complex; sequentially adding the mixture, ethanol and 2-bromoethanol into a reaction kettle for reaction; washing, filtering and drying to obtain a barley-based treating agent;
Step 3: preparation of copper-based biomass charcoal: grinding, washing, drying and sieving the corn straw waste to obtain corn straw; placing the mixture in a copper nitrate solution, stirring and dipping; drying; setting the temperature to be 350-400 ℃ in a nitrogen atmosphere to obtain copper-based biomass charcoal;
Step 4: and stirring the barley-based treating agent and the copper-based biomass charcoal in a high-speed mixer for 40-60 minutes to obtain the biomass composite treating agent.
2. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: the raw materials of the barley-based treatment agent comprise the following components: 50-55 parts of barley compound, 2-4 parts of N, N-dimethyl-1, 3-propanediamine and 2-4 parts of 2-bromoethanol.
3. A biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 2, wherein: the raw materials of the barley composite comprise the following components: 5-8 parts of barley, 48-82 parts of methyl methacrylate and 2-4 parts of cerium nitrate.
4. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: the raw materials of the copper-based biomass charcoal comprise the following components: 58-63 parts of corn straw and 2-7 parts of copper nitrate by weight.
5. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: the specific steps of the step 1 are as follows: under the nitrogen atmosphere, adding the weighed barley into a reaction kettle containing deionized water, setting the temperature to be 40-45 ℃, and stirring and mixing for 30-40 minutes; cooling to 23-28 ℃, adding methyl methacrylate, and stirring for 15-30 minutes; slowly adding 0.1mol/L cerium nitrate in sequence, and continuously stirring for 20-24 hours; adding excessive acetone, washing, filtering, and drying to obtain barley compound.
6. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: in the step 1, the mass ratio of the barley to the deionized water is (1.2-1.5): 1.
7. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: the specific steps of the step 2 are as follows: adding N, N-dimethyl-1, 3-propanediamine into a reaction kettle containing deionized water, and stirring and mixing for 10-15 minutes; adding the barley compound, refluxing for 4-5 hours at the temperature of 110-120 ℃, and washing and drying to obtain the tertiary aminated barley compound; sequentially adding the ethanol, ethanol and 2-bromoethanol into a reaction kettle, and refluxing for 1-2 hours at the temperature of 55-65 ℃; washing with ethanol, filtering, and drying to obtain barley-based treating agent.
8. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: in the step 2, the mass ratio of the N, N-dimethyl-1, 3-propylene diamine to the deionized water is 1 (0.05-0.1).
9. The biomass composite treating agent for removing nitrogen and phosphorus in sewage according to claim 1, wherein: the specific steps of the step 3 are as follows: grinding, washing and drying corn straw waste, and sieving with a 0.45mm screen to obtain corn straw; placing the mixture in a copper nitrate solution with the weight percent of 5-10%, setting the rotating speed to be 180-240 rmp, stirring the mixture at the constant temperature of 25-30 ℃ for 20-23 hours, and stirring the mixture at the constant temperature of 75-80 ℃ for 30-40 minutes; transferring and spreading in a glass plate, and vacuum drying at 100-105 ℃; transferring the mixture into a horse fluorine furnace, and reacting for 2-3 hours at the temperature of 350-400 ℃ in a nitrogen atmosphere to obtain the copper-based biomass charcoal.
CN202211310711.XA 2022-10-25 2022-10-25 Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof Active CN115624954B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211310711.XA CN115624954B (en) 2022-10-25 2022-10-25 Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211310711.XA CN115624954B (en) 2022-10-25 2022-10-25 Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof

Publications (2)

Publication Number Publication Date
CN115624954A CN115624954A (en) 2023-01-20
CN115624954B true CN115624954B (en) 2024-05-03

Family

ID=84907187

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211310711.XA Active CN115624954B (en) 2022-10-25 2022-10-25 Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115624954B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101628762A (en) * 2009-07-28 2010-01-20 上海理工大学 Method for processing negative ion surface active agent in wastewater
CN102802781A (en) * 2009-06-13 2012-11-28 赛多利斯司特蒂姆生物工艺公司 Polysaccharide matrix having a grafted polymer, method for producing the same and use thereof
CN106010601A (en) * 2016-06-01 2016-10-12 湖南农业大学 Biochar prepared from banana peel, preparation method and application thereof
CN108585101A (en) * 2017-10-27 2018-09-28 卢伟 A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization
CN112978905A (en) * 2021-04-25 2021-06-18 广州市点滴生物科技有限公司 Microbial filtering membrane for treating high ammonia nitrogen sewage and preparation method thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6998367B2 (en) * 2001-12-06 2006-02-14 Kimberly-Clark Worldwide, Inc. Absorbent composition containing transitional crosslinking points
EP2792688B1 (en) * 2013-04-15 2015-06-10 King Saud University Amine grafted chitosan nanofiber, method for preparation thereof and its use in heavy metal adsorption

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102802781A (en) * 2009-06-13 2012-11-28 赛多利斯司特蒂姆生物工艺公司 Polysaccharide matrix having a grafted polymer, method for producing the same and use thereof
CN101628762A (en) * 2009-07-28 2010-01-20 上海理工大学 Method for processing negative ion surface active agent in wastewater
CN106010601A (en) * 2016-06-01 2016-10-12 湖南农业大学 Biochar prepared from banana peel, preparation method and application thereof
CN108585101A (en) * 2017-10-27 2018-09-28 卢伟 A kind of recovery method of the multiporous biological matter microballoon of heavy metal-polluted water process inorganic material hydridization
CN112978905A (en) * 2021-04-25 2021-06-18 广州市点滴生物科技有限公司 Microbial filtering membrane for treating high ammonia nitrogen sewage and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ethylenediamine and Pentaethylene Hexamine Modified Bamboo Sawdust by Radiation Grafting and Their Adsorption Behavior for Phosphate;Du, JF等;《APPLIED SCIENCES-BASEL》;7854 *
阳离子化稻草纤维对诱惑红吸附性能的研究;朱琦浩等;《森林工程》;68-74 *

Also Published As

Publication number Publication date
CN115624954A (en) 2023-01-20

Similar Documents

Publication Publication Date Title
CN111068632A (en) Lead ion composite adsorbent and preparation method thereof
CN109126697B (en) Natural material composite adsorbent and preparation method and application thereof
CN112573642B (en) Water treatment denitrification filler and preparation method thereof
Duan et al. Characterization and adsorption properties of cross-linked yeast/β-cyclodextrin polymers for Pb (II) and Cd (II) adsorption
CN112897627A (en) Method for removing heavy metal wastewater
CN110801815A (en) Modified cyclodextrin/mesoporous silicon for adsorbing Pb and Cd and application thereof
CN111676020B (en) Composite soil remediation agent and preparation method and application thereof
CN110066512B (en) Preparation method of polyaniline compound for antibiosis and heavy metal removal and polyaniline compound prepared by method
CN111729652B (en) Preparation method of high-adsorption-selectivity phosphate adsorbent
CN101985101B (en) Hydrophobic chitosan absorbent, and preparation method and application thereof
CN1302687A (en) X-zeolite for lithium exchange, its preparation method and its application as nitrogen adsorber
CN114735795A (en) Sodium alginate-diatomite composite magnetic flocculant and preparation method thereof
CN115624954B (en) Biomass composite treating agent for removing nitrogen and phosphorus in sewage and preparation method thereof
CN111450805A (en) Chitosan-based lead ion imprinted adsorbent and preparation method thereof
CN116809034B (en) Preparation method of dephosphorizing agent based on rare earth modified gangue
CN111514861B (en) Preparation method and application of tridentate ligand heavy metal ion imprinting material
CN112675810A (en) Amorphous high-efficiency phosphorus removal adsorption material, preparation method and water treatment application thereof
CN112774584B (en) Floatable FeS-lignin hydrogel nanocomposite and preparation method and application thereof
CN108160047B (en) Preparation method of modified zeolite loaded with nano zero-valent iron for removing lead from coal-fired flue gas
CN113145118B (en) Synchronous denitrification dephosphorization defluorination catalytic particle carrier and preparation method thereof
CN114259952A (en) Stable regulation and control method and application of functional group of strong acid-resistant pyridyl hydrogel
CN101053824A (en) Method for embedding lead ion poly (m-phenylene diamine) adsorbent
Klimiuk et al. The effect of poly (vinyl alcohol) on cadmium adsorption and desorption from alginate adsorbents
JPS6248725A (en) Novel chelate resin and production thereof
CN113368833A (en) Inorganic-organic flocculant and preparation method 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
TA01 Transfer of patent application right

Effective date of registration: 20240408

Address after: No. 7 Huaxing Road, Chemical Industry Park, Hexian Economic Development Zone, Ma'anshan City, Anhui Province, 238299

Applicant after: Anhui Jinggao water treatment Co.,Ltd.

Country or region after: China

Address before: Room 912, no.346-1, South Tangde Road, Tianhe District, Guangzhou, Guangdong 510000

Applicant before: Guangzhou Diandi Biotechnology Co.,Ltd.

Country or region before: China

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant