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 PDFInfo
- 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
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010865 sewage Substances 0.000 title claims abstract description 31
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 30
- 239000011574 phosphorus Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 241000209219 Hordeum Species 0.000 claims abstract description 94
- 235000007340 Hordeum vulgare Nutrition 0.000 claims abstract description 94
- 239000003610 charcoal Substances 0.000 claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 30
- 240000008042 Zea mays Species 0.000 claims description 29
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 29
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 235000005822 corn Nutrition 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 17
- 239000010902 straw Substances 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 22
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 12
- 239000005751 Copper oxide Substances 0.000 abstract description 10
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- 150000004676 glycans Chemical class 0.000 abstract description 6
- 229920001282 polysaccharide Polymers 0.000 abstract description 6
- 239000005017 polysaccharide Substances 0.000 abstract description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 4
- 238000005576 amination reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005956 quaternization reaction Methods 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 150000001879 copper Chemical class 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 12
- 229960004643 cupric oxide Drugs 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- -1 hydroxide ions Chemical class 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- VGPSUIRIPDYGFV-UHFFFAOYSA-N [N].O[N+]([O-])=O Chemical compound [N].O[N+]([O-])=O VGPSUIRIPDYGFV-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000002860 competitive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007281 aminoalkylation reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003124 biologic agent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological 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
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.
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)
| 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)
| 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 |
-
2022
- 2022-10-25 CN CN202211310711.XA patent/CN115624954B/en active Active
Patent Citations (5)
| 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)
| 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 |