CN116239224B - Constructed wetland composite material and preparation method and application thereof - Google Patents
Constructed wetland composite material and preparation method and application thereof Download PDFInfo
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- CN116239224B CN116239224B CN202310103663.5A CN202310103663A CN116239224B CN 116239224 B CN116239224 B CN 116239224B CN 202310103663 A CN202310103663 A CN 202310103663A CN 116239224 B CN116239224 B CN 116239224B
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- polycaprolactone
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- 239000002131 composite material Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 101
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 36
- 230000008569 process Effects 0.000 abstract description 32
- 244000005700 microbiome Species 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 18
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000001272 nitrous oxide Substances 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 4
- 230000000813 microbial effect Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- RRZKHZBOZDIQJG-UHFFFAOYSA-N azane;manganese Chemical compound N.[Mn] RRZKHZBOZDIQJG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 35
- 229910002651 NO3 Inorganic materials 0.000 description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000004626 polylactic acid Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- 239000010865 sewage Substances 0.000 description 8
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 241001453382 Nitrosomonadales Species 0.000 description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006396 nitration reaction Methods 0.000 description 3
- 210000002966 serum Anatomy 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 241000108664 Nitrobacteria Species 0.000 description 2
- 241000605122 Nitrosomonas Species 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000001651 autotrophic effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 241000203069 Archaea Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000304459 Tacitus Species 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
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QYTBWVFCSVDTEC-UHFFFAOYSA-N azane;iron Chemical compound N.[Fe] QYTBWVFCSVDTEC-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229960002713 calcium chloride Drugs 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- -1 cotton Chemical compound 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
-
- 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
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
Abstract
The application discloses an artificial wetland composite material, a preparation method and application thereofComprising degradable solid carbon and MnO supported on the degradable solid carbon 2 . In the application, mnO is added into the reaction kettle 2 The composite material formed by compounding the modified polycaprolactone and the polycaprolactone obviously improves the nitrification-denitrification effect of the vertical flow constructed wetland, and the total nitrogen content in the tail water after the composite material is adopted for treatment is close to 0. The reason for this is: mnO in composite material 2 Can participate in electron transfer in the microbial denitrification process, and promote the nitrification of the microorganisms through the catalysis of manganese ammonia oxidation and manganese ions; PCL is used as an electron donor in the denitrification process, so that the intensity of the denitrification process is improved; therefore, the composite material can effectively reduce the discharge of nitrous oxide in the denitrification process.
Description
Technical Field
The application relates to the technical field of denitrification of domestic sewage, in particular to an artificial wetland composite material and a preparation method and application thereof.
Background
Constructed wetland refers to a constructed wetland system which is artificially constructed according to the principle of natural wetland and is used for strengthening and optimizing certain physical or biological processes to remove pollutants in sewage. According to national first-grade B standard, ammonia Nitrogen (NH) in tail water discharged by sewage treatment plants 4 + The content of-N is not more than 8mg/L (more than 12 ℃), and the nitrogen element in the sewage is more Nitrate (NO) 3 - N) exists in a form, the total nitrogen is not more than 20mg/L, but the denitrification rate is low due to the poor bioavailability of carbon in sewage, and meanwhile, ammonia nitrogen with low concentration still needs to be further nitrified and removed, so that the improvement of the treatment effect of secondary effluent treated by the artificial wetland and the reinforcement of the nitrification-denitrification capability have important significance for the development of the environmental field.
Disclosure of Invention
In order to solve the problem of weak nitrification-denitrification capacity of the existing constructed wetland, one of the purposes of the application is to provide a constructed wetland composite material.
The technical scheme for solving the technical problems is as follows:
an artificial wetland composite material comprises degradable solid carbon and MnO loaded on the degradable solid carbon 2 。
Based on the technical scheme, the application can also be improved as follows:
further, degradable solid carbon and MnO 2 The mass ratio of (10-20): 1.
further, degradable solid carbon and MnO 2 The mass ratio of (2) is 20:1.
further, the degradable solid carbon comprises polycaprolactone.
The second purpose of the application is to provide a preparation method of the constructed wetland composite material, which comprises the following steps: mnO is added to 2 Adding into melted polycaprolactone, dispersing, heating and melting, and cooling to room temperature.
Further, the molecular weight of polycaprolactone is 60000-70000.
Further, the temperature of the heating and melting is 75-86 ℃.
The application further aims to apply the composite material to denitrification of the constructed wetland.
The application has the following beneficial effects:
1. in the application, mnO is added into the reaction kettle 2 The composite material formed by compounding the modified polycaprolactone and the polycaprolactone obviously improves the nitrification-denitrification effect of the vertical flow constructed wetland, and when the modified polycaprolactone is used in the constructed wetland, the total nitrogen of the tail water treated by the composite material is reduced to be close to 0. The reason for this is: mnO in composite material 2 Can participate in electron transfer in the microbial denitrification process, improves the ammonia nitrogen removal effect and efficiency through the actions of manganese ammonia oxidation (Mnamox) and manganese ion catalytic nitration process, and can effectively reduce nitrous oxide (N) in the denitrification process 2 O) emissions; while PCL is anti-nitratedThe polymer is used as an electron donor in the process of chemical conversion, has good biocompatibility and improves the intensity of the denitrification process; and PCL also effectively reduces the discharge of nitrous oxide when promoting the denitrification process.
2. The composite material provided by the application does not pollute water in the use process, and is an efficient and environment-friendly environment material.
Drawings
FIG. 1 is a graph showing ammonia nitrogen removal effect of a composite material in the application;
FIG. 2 is a graph showing the effect of nitrate removal of the composite material of the present application;
FIG. 3 is a graph showing the effect of removing total nitrogen from the composite material of the present application;
FIG. 4 is a graph showing the variation of chemical oxygen demand of the composite material according to the present application;
FIG. 5 is a composite N of the present application 2 An O test chart;
FIG. 6 is a graph showing ammonia nitrogen removal effect of PCL, manganese dioxide and composite materials of the present application;
FIG. 7 is a graph showing the effect of PCL, manganese dioxide, and composite materials of the present application for nitrate removal;
FIG. 8 is a graph of total nitrogen removal for PCL, manganese dioxide, and composites of the present application;
FIG. 9 shows the composition of PLA and MnO 2 Formed composite material (PLA+MnO) 2 ) Composite material (PCL+MnO) of the present application 2 ) An ammonia nitrogen removal effect graph of (2);
FIG. 10 shows the composition of PLA and MnO 2 Formed composite material (PLA+MnO) 2 ) Composite material (PCL+MnO) of the present application 2 ) Is a graph of nitrate removal effect;
FIG. 11 shows the composition of PLA and MnO 2 Formed composite material (PLA+MnO) 2 ) Composite material (PCL+MnO) of the present application 2 ) Is a graph of total nitrogen removal effect;
FIG. 12 is a graph composed of PCL and Fe 2 O 3 The resulting composite (PCL+Fe) 2 O 3 ) Composite material (PCL+MnO) of the present application 2 ) An ammonia nitrogen removal effect graph of (2);
FIG. 13 is a graph composed of PCL and Fe 2 O 3 The resulting composite (PCL+Fe) 2 O 3 ) Composite material (PCL+MnO) of the present application 2 ) Is a graph of nitrate removal effect;
FIG. 14 shows the PCL and Fe 2 O 3 The resulting composite (PCL+Fe) 2 O 3 ) Composite material (PCL+MnO) of the present application 2 ) Is a graph of total nitrogen removal effect.
Detailed Description
An artificial wetland composite material, a preparation method and application thereof according to the present application will be described below with reference to examples.
This application may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein, but rather should be construed in order that the application will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
The inventor deeply cultivates in the technical field of artificial wetland, and intensively researches the removal of nitrogen in sewage, and finds that the removal of nitrogen in sewage mainly comprises three ways: the nitrification process, the denitrification process and the anaerobic ammoxidation (Anammox) process are specifically:
the nitrification process is that microorganisms carry out NH treatment in the water body 4 + The process of oxidation of N, different microorganisms having different metabolic characteristics, thus oxidizing NH 4 + The products after-N are also different and the appropriate conditions are also met. Traditional nitration processes, i.e. NH by Ammonia Oxidizing Bacteria (AOB) and archaea ammoxidation (AOA) 4 + Oxidation of N to Nitrite (NO) 2 - -N), whereas Nitrite Oxidizing Bacteria (NOB) will produce NO in the last step 2 - Further oxidation of N to nitrate (NO 3 - -N); wherein the ammoxidation stage is mainly of the genus Nitrosomonas (Nitrosomonas), and the nitrite oxidation stage is mainly of the genus Nitrobacteria (Nitrobacteria); the whole nitration involves the following formulas (1) to (3):
the general reaction formula is:
the anaerobic ammoxidation process (Anamox) is carried out by reacting NO 2 - -N as electron acceptor, NH 4 + N as electron donor, NH 4 + Direct oxidation of N to N 2 The method comprises the steps of carrying out a first treatment on the surface of the The discovery of the process in the constructed wetland challenges the traditional concept that the denitrification of the wetland mainly depends on the nitrification-denitrification process, and the bacteria in the process are called anaerobic ammonia oxidizing bacteria (AnAOB), which were discovered in 1995 at the earliest, are autotrophic bacteria with wide distribution and are N in the atmosphere 2 The main production source of (2) is as follows (formula 4) in the stoichiometric formula of the reaction relation
Based on this, an embodiment of the first aspect of the present application provides an artificial wetland composite material comprising degradable solid carbon, and MnO supported on the degradable solid carbon 2 。
In this embodiment, mnO 2 MnO in composite material formed by compounding Polycaprolactone (PCL) 2 The prepared composite material remarkably improves the nitrification-denitrification effect of the vertical flow constructed wetland by mutual synergy with polycaprolactone, and the Total Nitrogen (TN) of the tail water treated by adopting the composite material is reduced to be close to 0 after the test; the principle is as follows:
MnO in composite material 2 Can be involved in electron transfer during microbial denitrification by manganese ammoxidation (Mnamox) and manganeseThe effect of ion catalytic nitrification promotes the removal of ammonia nitrogen by microorganisms, and can effectively reduce nitrous oxide (N) in the denitrification process 2 O), wherein Mnamox is related to the process of the following formulas (5-7):
3MnO 2 +2NH 4 + +4H + →3Mn 2+ +N 2 +6H 2 O (5)
3MnO 2 +NH 4 + +4H + →3Mn 2+ +NO 2 - +4H 2 O (6)
4MnO 2 +NH 4 + +6H + →4Mn 2+ +NO 3 - +5H 2 O (7)
and, mnO in the composite material 2 Divalent manganese ion (Mn) generated after Mnamox process 2+ ) The method can also participate in autotrophic denitrification process to further promote denitrification;
in addition, the degradable solid carbon in the composite material of the embodiment is used as an electron donor in the denitrification process, has good biocompatibility, and improves the intensity of the denitrification process; wherein the denitrification involves the processes of formulas (8) to (11):
2NO+2H + →N 2 O+H 2 O (10)
N 2 O+2H + →N 2 +H 2 O (11)
the general reaction formula is:
preferably, the degradable solid carbon in this embodiment is a synthetic polymerSolid carbon, wherein, the synthetic polymer solid carbon has the problem of short carbon release period compared with natural degradable solid carbon (such as cotton, bark, crab shell, etc.), and meanwhile, COD exceeds standard in the initial stage of system operation, the long-term carbon release is insufficient, and even the problems of water chromaticity, ammonia nitrogen rise and wetland blockage are caused; the synthetic polymer solid carbon has the characteristics of long carbon release period, stable carbon release and the like; further preferably, the degradable solid carbon is Polycaprolactone (PCL), and the PCL has good biocompatibility, good organic polymer compatibility and biodegradability, so that the aggregation of microorganisms to the composite material in the embodiment is facilitated to a certain extent, the content of microorganisms around the composite material is improved, and MnO is facilitated 2 The participation also makes the electron transfer more efficient, so that the better denitrification effect is shown, and finally the nitrification-denitrification effect is improved to a certain extent; wherein, the expression of the PCL participating in the denitrification process is shown as the formula (13):
additionally, in some embodiments, the solid carbon is degradable with MnO 2 The mass ratio of (10-20): 1, a step of; in this embodiment, the mass ratio of degradable solid carbon to MnO is in the range 2 MnO while ensuring that the degradable solid carbon is completely decomposed by microorganisms 2 And just consume, avoid degradable solid carbon and MnO 2 And simultaneously ensures the best effect of the formed composite material on the nitrification-denitrification of the vertical flow constructed wetland. In addition, when the mass ratio of the range is less than 10:1, mnO 2 Too much to be fully loaded by PCL; at the same time, when the mass ratio exceeds 20:1, mnO is avoided 2 The effect of the composite material formed by the composite material and PCL on the nitrification-denitrification of the vertical flow constructed wetland is along with MnO 2 The problem of unobvious change caused by the increase of the dosage is solved to a certain extent 2 And waste of PCL. Preferably, the degradable solid carbon in this embodiment is in combination with MnO 2 The mass ratio of (2) is 20:1.
embodiments of the second aspect of the present application provide a method for preparing a composite material according to embodiments of the first aspect, comprising the steps of:
MnO is added to 2 Adding into molten polycaprolactone, dispersing, heating and melting, and cooling to room temperature; the specific operation is as follows:
step 1, heating and melting polycaprolactone;
step 2, mnO is added 2 Adding into molten polycaprolactone and dispersing;
step 3, dispersing MnO 2 And (3) heating and melting the polycaprolactone, and finally cooling to normal temperature.
In the embodiment, PCL has a lower melting point, and can be melted by simple heating, so that the preparation process of the composite material is simplified; in addition, mnO is added to 2 Added into the melted PCL, which is beneficial to MnO 2 Is uniformly dispersed in PCL to improve MnO 2 Stability with PCL, avoiding MnO in the composite material 2 Precipitation phenomenon causes MnO 2 Loss, the service life of the composite material is prolonged to a certain extent; in addition, mnO is added to 2 Mixing with molten PCL also avoids powdery MnO 2 The water is lost with the external environment in the using process.
In addition, in this embodiment, mnO is added to 2 The polycaprolactone of (a) is then heated and melted (i.e., step 3 above) due to the presence of MnO 2 The polycaprolactone has very irregular shape, and the polycaprolactone can be filled in the grinding tool by heating and melting the polycaprolactone, so that the polycaprolactone can be better attached to the grinding tool and is convenient to form; next, for the mixture of MnO 2 The polycaprolactone of (C) is heated and melted again to further improve MnO 2 Dispersibility in PCL, avoiding MnO in composite material 2 Is lost.
In addition, in some embodiments, the polycaprolactone has a molecular weight of 60000 to 70000. In this example, the polycaprolactone particles having an average particle diameter of about 4mm were used. In the embodiment, the polycaprolactone with the molecular weight in the range is very easy to obtain, so that the preparation cost of the composite material is reduced to a certain extent; of course, in the actual process, polycaprolactone with other molecular weight can be selected according to the PCL price in the market.
In addition, in some embodiments, the temperature of the heat fusion of polycaprolactone is 75-86 ℃ (i.e., the heat fusion temperature in step 1 and step 3 above); preferably, the polycaprolactone is heated to a temperature of 80 ℃; further, the time of the heat fusion in step 3 in this embodiment is 5 to 10 minutes, and preferably the time of the heat fusion in step 3 is 5 minutes.
An embodiment of the third aspect of the present application provides an application of the composite material in the embodiment of the first aspect in denitrification of constructed wetland.
Examples
Example 1
The preparation of the constructed wetland composite material comprises the following steps:
step 1, melting 3g of polycaprolactone with an average particle size of 4mm and a molecular weight of 65000 at 80 ℃;
step 2, then 0.3g of MnO 2 Added to the molten PCL and mixed;
and step 3, continuously heating the mixed substances in the step 2 at 80 ℃ for 5min, and naturally cooling the heated mixed substances to room temperature to obtain the composite material.
Example 2
The preparation of the constructed wetland composite material comprises the following steps:
step 1, melting 4.5g of polycaprolactone with an average particle size of 4mm and a molecular weight of 65000 at 80 ℃;
step 2, mixing 0.3g of MnO 2 Added to the molten PCL and mixed;
and step 3, continuously heating the mixed substances in the step 2 at 80 ℃ for 5min, and naturally cooling the heated mixed substances to room temperature to obtain the composite material.
Example 3
The preparation of the constructed wetland composite material comprises the following steps:
step 1, melting 6g of polycaprolactone with an average particle size of 4mm and a molecular weight of 65000 at 80 ℃;
step 2, mixing 0.3g of MnO 2 Added to the molten PCL and mixed;
and step 3, continuously heating the mixed substances in the step 2 at 80 ℃ for 5min, and naturally cooling the heated mixed substances to room temperature to obtain the composite material.
Comparative example 1
The preparation method of the composite material in this example was the same as in example 3, except that polycaprolactone having a molecular weight of 65000 was replaced with polylactic acid (PLA) having a molecular weight of 65000, PLA and MnO 2 The melting temperature was 180 ℃.
Comparative example 2
The preparation method of the composite material in this example was the same as in example 3, except that MnO was used 2 Substitution for Fe of the same mass 2 O 3 。
Test analysis:
1. the composite material prepared in example 3 above was tested for denitrification properties, which were specifically: the test is carried out by adopting a cylindrical artificial wetland reactor with the height of 60cm and the inner diameter of 20cm, the height of the filling material is 50cm during the test, the water inlet mode adopts a lower inlet and upper outlet mode, and the planted plants are Graptopetalum album; specifically, the filler comprises composite materials and gravels with different volume ratios and the gravels positioned at a section 10-20 cm away from the bottom of the reactor, and the gravels are positioned at the rest position of the reactor, wherein the particle size of the gravels is 0.5-1.5 cm.
During testing, three groups of artificial wetlands are arranged according to different volume ratios of the composite material and the gravel arranged in a section 10-20 cm away from the bottom of the reactor, and specifically:
a high concentration group (H group), wherein the volume ratio of the composite material to the gravel is 1 in a section of 10-20 cm: 1, filling gravel in other positions;
a low concentration group (group L), in a 10-20 cm section, the volume ratio of the composite material to the gravel is 1:3, filling gravel in other positions;
blank (group C), with all gravel in the reactor.
And, testThe inlet water (i.e. simulated tail water) refers to the first grade B standard (COD concentration is 60mg/L, NH) 4 + -N concentration of 8mg/L, TN concentration of 20 mg/L), specifically: dissolving cellulose, ammonium chloride, sodium nitrate, potassium dihydrogen phosphate, calcium chloride, magnesium chloride hexahydrate, ferrous chloride tetrahydrate, EDTA-Na, and microelements (zinc sulfate, manganese chloride, cobalt chloride, copper chloride, boric acid, nickel chloride, sodium molybdate) in tap water to obtain water, wherein COD concentration in the water is 60mg/L, NH 4 + -N concentration of 8mg/L and NO 3 - The N concentration was 12mg/L. In addition, in the test, after the system is stable, the water retention time is 4 days, the sampling time is once every two days, and after each sampling, the water COD, ammonia nitrogen, nitrate nitrogen and total nitrogen concentration are measured after filtering by a 0.45 mu m filter head.
The test results are shown in FIGS. 1-5, wherein FIG. 1 is a graph of ammonia nitrogen removal effect of the composite material, FIG. 2 is a graph of nitrate removal effect of the composite material, FIG. 3 is a graph of total nitrogen removal effect of the composite material, FIG. 4 is a graph of Chemical Oxygen Demand (COD) change of the composite material, and FIG. 5 is a graph of N of the composite material 2 O test chart.
As can be seen from the graph 1, the ammonia nitrogen concentration of the inlet water is about 8mg/L, the ammonia nitrogen concentration of the high concentration group is lower than that of the low concentration group, the low concentration group is lower than that of the blank group, the ammonia nitrogen removal rate of the high concentration group can reach 91.3% at the highest, compared with the ammonia nitrogen removal rate of the blank group which is only maintained at about 67%, the ammonia nitrogen removal effect is increased along with the increase of the composite material, and the promotion effect of the composite material on the ammonia nitrogen removal of the constructed wetland is shown.
As can be seen from FIG. 2, the nitrate concentration of the inlet water is about 12mg/L, the nitrate concentration of the outlet water of the high concentration group is almost 0, the nitrate concentration of the outlet water of the high concentration group is next to the nitrate concentration of the outlet water of the low concentration group, and the nitrate concentration of the blank group is 2-3 mg/L, which shows that the addition of the composite material promotes the removal of the nitrate.
As can be seen from FIG. 3, the Total Nitrogen (TN) of the inlet water is 20mg/L, the TN of the high-concentration group outlet water fluctuates approximately in the range of 2 to 4mg/L, the TN of the low-concentration group outlet water fluctuates approximately in the range of 3 to 5mg/L, and the TN of the blank group fluctuates in the range of 4 to 7 mg/L; it can be seen that the blank group fluctuates relatively more and the removal effect is also poor.
As can be seen from fig. 4, the Chemical Oxygen Demand (COD) fluctuation of the intake water is large because the solubility of the cellulose used as the carbon source of the intake water is low; in terms of effluent, the three groups of COD are not obviously different, which indicates that the composite material cannot pollute the effluent, and is an efficient and environment-friendly environment material.
As can be seen from FIG. 5, N of H groups 2 The emission of O is the lowest, i.e. the composite material in the application effectively reduces nitrous oxide (N) 2 O) emissions.
2. The composite material prepared in example 3 above, PCL and manganese dioxide, was tested for ammonia nitrogen and nitrate removal in tail water, specifically:
seven groups were set, each group was set in two parallels (the average of the two parallels), 200ml serum bottles were used, 250ml of tail water (i.e., feed water) was added (cod=60 mg/L, ammonia nitrogen=8 mg/L, NO) 3 - -N concentration is 12 mg/L), nitrogen aeration is carried out until Dissolved Oxygen (DO) is less than or equal to 0.02mg/L before the experiment; wherein, seven groups are respectively:
group 1: only microorganisms, group 2 were added: PCL alone, group 3: microorganism+pcl, group 4: adding only MnO 2 Group 5: microorganism +MnO 2 Group 6: only composite material, group 7: microorganism + composite material; when tested, the amount of PCL in groups 2 and 3 was 6g, mnO in groups 4 and 5 2 In an amount of 0.3g, the composites in both group 6 and group 7 were 6 gcl and 0.3gMnO 2 Composition;
in addition, the microorganisms in the test are microorganisms after tail water domestication simulation, and specifically: taking 2mL of sludge (the sludge is taken from a chicken crown sewage treatment plant in Chongqing city, in order to ensure the diversity of microorganism population), pouring the taken sludge comprising aeration Chi Wuni (aerobic sludge), reflux Chi Wuni (anaerobic sludge) and egg-shaped nitrification Chi Wuni into a serum bottle, adding a culture solution (namely tail water simulated by us), and aerating N 2 Until the dissolved oxygen is lower than 0.5mg/L (for simulating anaerobic and anoxic environment in the artificial wetland), placing in a shaking table for constant-temperature shake culture, changing water once in two days, and the same appliesAnd when the water quality is measured, but when the water quality of the effluent is stable, namely the microbial population is stable, the obtained microbes are used in the test.
The results of each set of tests are shown in fig. 6 to 8, wherein fig. 6 is a graph of ammonia nitrogen removal effect of PCL, manganese dioxide and the composite material of the present application, fig. 7 is a graph of nitrate removal effect of PCL, manganese dioxide and the composite material of the present application, and fig. 8 is a graph of total nitrogen removal of PCL, manganese dioxide and the composite material of the present application.
As can be seen from FIG. 6, the composite material of the present application has a good ammonia nitrogen removal effect, but it can also be seen that microorganisms +MnO are added 2 The ammonia nitrogen removal of (group 5) is not ideal because of MnO 2 Is a solid mineral, and is directly added with powdery MnO if the Mnammox is to be participated in, the adhesion and the utilization of microorganisms are needed 2 Is not beneficial to the fixation and utilization of microorganisms, but adopts PCL and MnO 2 Compounding can effectively reduce MnO 2 Is lost, and MnO is prolonged 2 At the same time, the excellent biocompatibility of PCL induces the aggregation of microorganisms, and at the same time, the PCL provides favorable loading opportunities for the microorganisms, so that the microorganisms can better utilize MnO 2 ；
In addition, as can be seen from fig. 6, the effect of removing ammonia nitrogen is better than that of other groups except the group 7 even though only PCL and microorganism are added in the group 3, because the larger specific surface area of PCL has strong adsorption capacity to ammonia nitrogen, macroscopic reduction of ammonia nitrogen is shown, and the use of ammonia nitrogen by microorganism loaded on the surface of the filler is more favorable after adsorption.
As can be seen from FIG. 7, since the same amount of PCL was added to both group 3 and group 7, heterotrophic denitrification was effectively performed, and as can be seen from the experimental results, the nitrate of both groups was effectively removed, but the removal rate of group 7 was faster than that of group 3, because of MnO 2 The addition of the metal element (Mn) makes the original smooth surface of the PCL rough, is more beneficial to the loading and the utilization of microorganisms, and simultaneously makes the transfer of electrons more efficient, so that the PCL has better denitrification effect.
As can be seen from fig. 8, the composite material of the present application significantly improves the nitrification-denitrification effect, the TN of the inlet water treated by the composite material is reduced to approximately 0, and the TN of group 3 is significantly higher than that of group 7 due to the inability to perform the effective ammonia nitrogen removal process.
3. The composite materials prepared in the above example 3 and comparative examples 1 and 2 were tested for ammonia nitrogen and nitrate removal in the feed water, specifically:
in the test, two parallel (the average value of the two parallel results) were set, and 250ml of water was added to each serum bottle (COD=60 mg/L, ammonia nitrogen=8 mg/L, NO) 3 - -N concentration is 12 mg/L)), nitrogen aeration is carried out until Dissolved Oxygen (DO) is less than or equal to 0.02mg/L before the experiment; in addition, the same microorganisms as in 2 above were added after acclimation with water during the test.
The test results of example 3 and comparative example 1 are shown in FIGS. 9 to 11, in which FIG. 9 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PLA+MnO) prepared in comparative example 1 2 ) An ammonia nitrogen removal effect graph of (2); FIG. 10 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PLA+MnO) prepared in comparative example 1 2 ) Is a removal effect graph of (1); FIG. 11 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PLA+MnO) prepared in comparative example 1 2 ) Is a graph of total nitrogen removal effect;
as can be seen from fig. 9, the composite material pla+mno 2 Is lower than the PCL+MnO of the composite material 2 The reason for this is that PLA has too high a melting point, and its production requires high temperature (180 ℃ C.), and the difficulty of production is greater, resulting in MnO 2 The dispersion condition of the (2) is relatively poor, and the loading capacity is relatively weaker than that of PCL, so that the utilization of the manganese by microorganisms is obviously weakened, and the reorganization change curve is more similar to the adsorption effect of PLA on ammonia nitrogen and weaker microorganism effect;
as can be seen from fig. 10, the trends of nitrate removal are substantially consistent for both composites, but the composite pla+mno 2 The denitrification rate of (2) is smaller than that of the composite material PCL+MnO 2 Is a denitrification rate of (2);
as can be seen from FIG. 11, PLA+MnO 2 Is less efficient than PCL+MnO 2 The total nitrogen removal rate is lower than PCL+MnO 2 。
The test results of example 3 and comparative example 2 are shown in FIGS. 12 to 14, wherein FIG. 12 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PCL+Fe) prepared in comparative example 2 2 O 3 ) An ammonia nitrogen removal effect graph of (2); FIG. 13 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PCL+Fe) prepared in comparative example 2 2 O 3 ) Is a graph of nitrate removal effect; FIG. 14 shows the composite material (PCL+MnO) prepared in example 3 2 ) And the composite material (PCL+Fe) prepared in comparative example 2 2 O 3 ) Is a graph of total nitrogen removal effect.
As can be seen from FIG. 12, the ammonia nitrogen trend is approximately the same for both composites, but PCL+Fe 2 O 3 The ammonia nitrogen removal effect of the iron ammonia oxidation in the later stage is smaller than that of PCL+MnO 2 The manganese ammonia oxidation has the effect of removing ammonia nitrogen in the later stage;
as can be seen from fig. 13, the removal effect of the two composites on nitrate is close;
as can be seen from FIG. 14, PCL+Fe 2 O 3 Has lower denitrification efficiency than PCL+MnO 2 。
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (6)
1. The constructed wetland composite material is characterized by comprising degradable solid carbon and MnO loaded on the degradable solid carbon 2 The method comprises the steps of carrying out a first treatment on the surface of the The degradable solid carbon is polycaprolactone;
the degradable solid carbon and the MnO 2 The mass ratio of (10-20): 1, a step of;
the preparation of the constructed wetland composite material comprises the following steps: mnO is added to 2 Added to molten polycaprolactoneDispersing, heating and melting, and cooling to room temperature.
2. The composite of claim 1, wherein the degradable solid carbon is in combination with the MnO 2 The mass ratio of (2) is 20:1.
3. a method of preparing a composite material according to claim 1 or 2, comprising the steps of: mnO is added to 2 Adding into melted polycaprolactone, dispersing, heating and melting, and cooling to room temperature.
4. The method for preparing a composite material according to claim 3, wherein the polycaprolactone has a molecular weight of 60000-70000.
5. The method for producing a composite material according to claim 3, wherein the temperature of the heating and melting is 75 to 86 ℃.
6. Use of the composite material according to claim 1 or 2 in denitrification of constructed wetlands.
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