CN113019431B - Preparation method of ceramic-based zeolite-nano zero-valent iron composite material - Google Patents
Preparation method of ceramic-based zeolite-nano zero-valent iron composite material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000007787 solid Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 14
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- 238000007605 air drying Methods 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 5
- 239000012265 solid product Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 48
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 24
- 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 abstract description 17
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000008187 granular material Substances 0.000 abstract 2
- 239000010883 coal ash Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000233948 Typha Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
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Abstract
The invention relates to a process for preparing ceramic-based zeolite-nano zero-valent iron composite material, which comprises mixing zeolite, coal ash, kaolin, sodium silicate and magnesium oxide in the mass ratio of 10 (5-7): (6-10): (3-6): 2-3), adding water, stirring uniformly, extrusion forming and granulating, naturally air drying the granules, then high-temperature heat treating, naturally cooling, placing the granules in Fe 2+ Soaking the solid particles in the solution for 1-3 h, drying the solid particles to constant weight after solid-liquid separation, then heating and thermally treating to obtain solid particles loaded with ferric iron, carrying out contact reaction on the solid particles loaded with ferric iron and a potassium borohydride solution under the nitrogen atmosphere, and drying a solid product to constant weight after solid-liquid separation to obtain the product. The composite material can avoid the agglomeration of the nano zero-valent iron, reduces nitrate nitrogen into ammonia nitrogen through the nano zero-valent iron, further removes nitrogen in wastewater through the adsorption of the ammonia nitrogen by zeolite, and has the advantages of high conversion and removal rate and high selectivity removal rate.
Description
Technical Field
The invention belongs to the field of development and application of water treatment functional materials, and particularly relates to a preparation method of a ceramic-based zeolite-nano zero-valent iron composite material for enhancing wastewater denitrification.
Background
At present, the problem of nitrogen pollution in water is more serious, and the nitrogen pollution has attracted extensive attention of people. In the prior art, nitrogen removal in sewage treatment is mainly achieved through a biological denitrification process, but with the improvement of the tail water discharge standard of sewage plants, some regions propose the discharge standard of IV water or quasi-IV water in reference to the surface water environmental quality standard (GB 3838-2002), wherein the problem that the total nitrogen is difficult to reach the standard is generally faced. The biochemical poor of lower COD and surplus COD in the tail water leads to the biological denitrification carbon source not enough, restricts the further promotion of denitrogenation effect, continues to reduce the total nitrogen of effluent and faces great difficulty. In addition, one of the major tasks faced by the current polluted water body remediation is also to solve the problems of eutrophication and the like caused by nitrogen and phosphorus pollution. The nitrogen in the water mainly exists in the form of nitrate nitrogen, the nitrate nitrogen in the water has strong stability and is not easy to convert, but the nitrate nitrogen can be converted into toxic nitrite in a human body and easily forms 'three-cause' substances, thereby seriously harming the health of the human body.
At present, the common treatment technologies for nitrogen in water mainly include biological denitrification, ion exchange, chemical reduction, reverse osmosis and the like. The biological denitrification method has slow reaction, generally needs organic matters as electron donors, has low COD of tail water of a sewage plant and poor biodegradability of the residual organic matters, and has certain difficulty in further denitrification by utilizing the biological denitrification method; reverse osmosis and ion exchange processes are costly and cannot be completely removed; the chemical reduction method can convert nitrate nitrogen into nitrogen which is easy to be absorbed, has simple principle, does not depend on organic matters and the like, and has better application prospect.
The nanometer zero-valent iron is an environmental functional nanometer material, and has the advantages of large specific surface area, strong reducibility, high reaction activity, strong pollutant removal capability and the like, so the nanometer zero-valent iron can be widely applied to the field of environmental remediation such as underground water and the like. The agglomeration of the nano zero-valent iron seriously affects the treatment efficiency, and in recent years, the aspects of inhibiting the agglomeration of nano particles, enhancing the removal efficiency of the nano zero-valent iron on environmental pollutants and the like become important points of research. The loading of the nano zero-valent iron particles on the solid carrier can increase the specific surface area of the nano particles and inhibit the occurrence of agglomeration, which is the research direction in recent years.
The application of the nanometer zero-valent iron is increasingly wide due to strong reducibility and reactivity, the patent application documents with the Chinese patent application numbers of 201310292598.1, 201210205021.8 and 201380027599.1 utilize the generated functional material with the nanometer zero-valent iron to remove heavy metals, and the Chinese patent application number of 201610524313.6 discloses a preparation method of the nanometer zero-valent iron/carbon nanotube/zeolite hybrid mesoporous molecular sieve composite material and a method for removing organic matters. The prior art uses the nano zero-valent iron for removing heavy metals or organic matters in wastewater, and the preparation method is formed by mixing and granulating the nano zero-valent iron powder and other materials and then sintering the mixture at high temperature, so that the method is difficult to control the agglomeration and existence of nano particles of the nano zero-valent iron powder to influence the performance of the nano zero-valent iron powder, and the zero-valent iron is oxidized into high-valent iron if the oxygen-free environment cannot be well controlled in the high-temperature sintering process.
Disclosure of Invention
The invention aims to overcome the defects of the existing wastewater denitrification technology and provides a preparation method of a ceramic-based zeolite-nano zero-valent iron composite material, and the prepared composite material can avoid the agglomeration of nano zero-valent iron and has excellent efficiency of removing total nitrogen and ammonia nitrogen in water.
Technical scheme
A preparation method of a ceramic-based zeolite-nano zero-valent iron composite material comprises the following steps:
(1) Mixing zeolite, fly ash, kaolin, sodium silicate and magnesium oxide according to the mass ratio of 10 (5-7) to 6-10 to 3-6 to 2-3 to obtain a raw material mixture, adding water, uniformly stirring, carrying out extrusion forming granulation, naturally air-drying the obtained particles, carrying out high-temperature heat treatment, and naturally cooling to obtain material particles;
(2) Placing the material particles in 0.01-0.1mol/L Fe 2+ Soaking the solid particles in the solution for 1-3 h, after solid-liquid separation, drying the solid particle materials to constant weight, then heating for heat treatment to obtain solid particles loaded with ferric iron, and naturally cooling and taking out the solid particles;
(3) And (3) under the protection of nitrogen atmosphere, fully contacting and reacting the ferric iron-loaded solid particles prepared in the step (2) with a potassium borohydride solution, carrying out solid-liquid separation, and drying a solid product in a vacuum drying oven to constant weight to obtain the ceramic-based zeolite-nano zero-valent iron composite material.
Preferably, in the step (1), the amount of water added is 10-15% of the mass of the raw material mixture.
Preferably, in step (1), the diameter of the particles is 3 to 12mm.
Preferably, in the step (1), the temperature of the high-temperature heat treatment is 700-900 ℃, the treatment time is 40-60 min, and the heating rate is 5-10 ℃/min.
Preferably, in the step (2), the drying temperature is 100 ℃,
preferably, in the step (2), the heat treatment temperature is 350-550 ℃, the heating rate is 5-10 ℃/min, and the heat treatment time is 2-3 h.
Preferably, in step (3), the drying temperature is 70 ℃.
Preferably, in the step (3), the concentration of the potassium borohydride solution is 0.5-5 mol/L, and the reaction time is 1-3 h.
The ceramic-based zeolite-nano zero-valent iron composite material prepared by the method is spherical particles with the particle size of 3-12 mm and the density of 1.20-1.42 g/cm 3 The strength is 3.8-6.2 MPa, the specific surface area is 22-35 m 2 (g), the acid resistance is more than 95%.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) The current situation that lower COD and the biodegradability of surplus COD are poor to lead to the carbon source not enough in tail water and the partial natural water body of current urban sewage factory, restriction denitrogenation effect further promotes. The composite material chemically reduces nitrate nitrogen into ammonia nitrogen through the nano zero-valent iron and further removes nitrogen in wastewater through adsorbing the ammonia nitrogen through zeolite, and has the advantages of high conversion and removal rate and high selective removal rate.
(2) The invention prepares the loaded nano zero-valent iron by preparing the ceramic-based zeolite porous load material, can effectively avoid the agglomeration of the nano zero-valent iron, and simultaneously slows down the rapid oxidation of the zero-valent iron and prolongs the service life due to the structure of the porous material. Through characterization and analysis, the prepared material has developed pores, the internal pores are communicated, and the zero-valent iron particles are uniformly loaded on the material.
(3) The ceramic-based zeolite-nano zero-valent iron composite material has excellent effect of removing total nitrogen and ammonia nitrogen in water, plays an important role in removing nitrogen in wastewater and water body, and is beneficial to promoting water environment protection.
Drawings
FIG. 1 is an SEM image of a ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1;
FIG. 2 is an XPS spectrum of the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1;
FIG. 3 shows the conversion result of nitrate nitrogen in the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1;
fig. 4 is a result of nitrogen removal effect test of the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 2.
Detailed Description
The technical scheme of the invention is clearly and specifically described in the following by combining the attached drawings and specific embodiments.
Example 1
A preparation method of a ceramic-based zeolite-nano zero-valent iron composite material comprises the following steps:
(1) Uniformly mixing 100g of zeolite, 50g of fly ash, 70g of kaolin, 50g of sodium silicate and 20g of magnesium oxide to obtain a raw material mixture, adding 40g of water, uniformly stirring, carrying out extrusion forming granulation, wherein the particle diameter is 3.5-5.0mm, naturally air-drying the obtained particles, transferring the obtained particles into a muffle furnace, controlling the heating rate to be 10 ℃/min, heating to 800 ℃, keeping the temperature for 60min, and naturally cooling to obtain material particles;
(2) The material particles were placed in 0.033mol/L Fe 2+ Soaking the solid particles in the solution for 2 hours, after solid-liquid separation, drying the solid particle materials at 100 ℃ to constant weight, then transferring the solid particle materials into a muffle furnace, controlling the heating rate to 5 ℃/min, heating the solid particle materials to 500 ℃ for heat treatment for 3 hours to obtain solid particles loaded with ferric iron, and naturally cooling the solid particles and then taking the solid particles out;
(3) And (3) under the protection of nitrogen atmosphere, fully contacting and reacting the solid particles loaded with ferric iron prepared in the step (2) with 1mol/L potassium borohydride solution for 2 hours, carrying out solid-liquid separation, and drying the solid product in a vacuum drying oven at 70 ℃ to constant weight to obtain the ceramic-based zeolite-nano zero-valent iron composite material.
The particle size, density, mechanical strength, specific surface area and acid resistance of the ceramic-based zeolite-nanoscale zero-valent iron composite material were measured respectively, and the results show that the ceramic-based zeolite-nanoscale zero-valent iron composite material prepared in this example is spherical particles with an average particle size of 4.76mm, and has an average bulk density of 1.26g/cm 3 Average strength of 4.9MPa and specific surface area of 32m 2 G, acid resistance of 96.1 percent on average.
Fig. 1 is an SEM image of the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1, wherein fig. 1a is the material particles prepared in step (1) before loading, and fig. 1b is the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1, and it can be seen that the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1 has developed pores, the internal pores are connected, and the zero-valent iron particles are uniformly loaded on the material.
FIG. 2 is an XPS spectrum of the ceramic-based zeolite-nano zero-valent iron composite material prepared in example 1, and it can be seen that the composite material prepared in example 1 has stronger Fe 0 Characteristic peaks, and successfully realizes the preparation of the porous ceramic-based zeolite-nano zero-valent iron composite material.
Static adsorption test:
50mL of simulated wastewater with nitrate nitrogen concentration of 5mg/L is configured in a 100mL beaker, 1.0g of the prepared ceramic-based zeolite-nano zero-valent iron composite material is added into a beaker solution to carry out a static adsorption test, the adsorption reaction time is controlled to be 1h, 2h, 4h and 7h respectively, and the concentrations of the nitrate nitrogen, nitrite nitrogen and ammonia nitrogen in water after the reaction are measured.
The conversion result of nitrate nitrogen by the ceramic-based zeolite-nanoscale zero-valent iron composite material prepared in example 1 under different adsorption reaction time conditions is shown in fig. 3. It can be seen that, with the increase of time, the amount of nitrate nitrogen in water is firstly and rapidly reduced and then increased, the amount of nitrite nitrogen is gradually reduced, the amount of ammonia nitrogen is gradually increased, and the nitrogen adsorbed by zeolite after reduction is firstly increased and then slightly reduced. When the reaction time is 7 hours, the removal rate of nitrate nitrogen is highest, and at the moment, the conversion rate of nitrate nitrogen is as high as 75.10%, wherein nitrite nitrogen accounts for 24.13%, ammonia nitrogen accounts for 15.96%, and the nitrogen adsorbed and removed after reduction accounts for 59.91%. The static test result of a laboratory shows that the prepared material has good conversion and adsorption removal efficiency on total nitrogen and nitrate nitrogen in water.
Example 2
A preparation method of a ceramic-based zeolite-nano zero-valent iron composite material comprises the following steps:
(1) Uniformly mixing 100g of zeolite, 50g of fly ash, 80g of kaolin, 60g of sodium silicate and 25g of magnesium oxide to obtain a raw material mixture, adding 40g of water, uniformly stirring, carrying out extrusion forming granulation, wherein the particle diameter is 3.0-6.5mm, naturally air-drying the obtained particles, transferring the obtained particles into a muffle furnace, controlling the heating rate to be 8 ℃/min, heating to 900 ℃, keeping the temperature for 50min, and naturally cooling to obtain material particles;
(2) The material particles were exposed to 0.05mol/L Fe 2+ Soaking the solid particles in the solution for 3 hours, after solid-liquid separation, drying the solid particle materials at 100 ℃ to constant weight, then transferring the solid particle materials into a muffle furnace, controlling the heating rate to be 8 ℃/min, heating the solid particle materials to 550 ℃ for heat treatment for 3 hours to obtain solid particles loaded with ferric iron, and naturally cooling the solid particles and then taking the solid particles out;
(3) And (3) under the protection of nitrogen atmosphere, fully contacting and reacting the solid particles loaded with ferric iron prepared in the step (2) with 0.5mol/L potassium borohydride solution for 3 hours, carrying out solid-liquid separation, and drying the solid product in a vacuum drying oven at 70 ℃ to constant weight to obtain the ceramic-based zeolite-nano zero-valent iron composite material.
The particle size, density, mechanical strength, specific surface area and acid resistance of the ceramic-based zeolite-nano zero-valent iron composite material were measured respectively, and the results show that the ceramic-based zeolite-nano zero-valent iron composite material prepared in this example is spherical particles with an average particle size of 6.15mm, and the average bulk density is 1.27g/cm 3 Average strength of 5.2MPa and specific surface area of 30m 2 The acid resistance is 92.4 percent on average per gram.
And (3) testing the nitrogen removal effect:
a vertical flow constructed wetland test column is constructed, the height of the device is 80cm, the diameter of the device is 160mm, the constructed wetland filler matrix is respectively a 5cm gravel supporting layer, 40cm ceramic-based zeolite-nano zero-valent iron composite material prepared in the embodiment 2 and 20cm quartz fine sand (the particle size is 1-4 mm) from bottom to top, and typha is planted on the surface of the wetland. After the reactor is started and stably operated, simulated wastewater with COD, nitrate nitrogen, ammonia nitrogen and TP respectively being 60mg/L, 30mg/L, 20mg/L and 1mg/L is prepared, the operation is carried out for 3 months, and the nitrogen removal effect of the constructed wetland operated by using the composite material is inspected.
Fig. 4 is a result of a nitrogen removal effect test of the ceramic-based zeolite-nanoscale zero-valent iron composite material prepared in example 2, and it can be seen that the removal rates of nitrate nitrogen and total nitrogen of the constructed wetland device respectively reach 72.6% -92.4% and 60.2% -80.9%, which indicates that the prepared material has good removal efficiency for total nitrogen and nitrate nitrogen in water, and can be used as a constructed wetland substrate for removing nitrogen in tail water, natural water bodies and the like of urban sewage plants, thereby achieving the purposes of protecting and controlling water pollution and protecting water environment.
The embodiments described above are intended to enable those skilled in the art to make and use the invention. It will be readily apparent to those skilled in the art that modifications may be made to these embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention according to the principle of the present invention without departing from the scope of the present invention.
Claims (6)
1. A preparation method of a ceramic-based zeolite-nano zero-valent iron composite material is characterized by comprising the following steps:
(1) Mixing zeolite, fly ash, kaolin, sodium silicate and magnesium oxide according to the mass ratio of 10 (5-7) to 6-10 to 3-6 to 2-3 to obtain a raw material mixture, adding water, uniformly stirring, carrying out extrusion forming granulation, naturally air-drying the obtained particles, carrying out high-temperature heat treatment, and naturally cooling to obtain material particles;
(2) Placing the material particles in 0.01-0.1mol/L Fe 2+ Soaking the solid particles in the solution for 1-3 h, after solid-liquid separation, drying the solid particle materials to constant weight, then heating for heat treatment to obtain solid particles loaded with ferric iron, and naturally cooling and taking out the solid particles;
(3) Under the protection of nitrogen atmosphere, fully contacting and reacting the ferric iron-loaded solid particles prepared in the step (2) with a potassium borohydride solution, carrying out solid-liquid separation, and drying a solid product in a vacuum drying oven to constant weight to obtain the ceramic-based zeolite-nano zero-valent iron composite material;
in the step (1), the temperature of the high-temperature heat treatment is 700-900 ℃, the treatment time is 40-60 min, and the heating rate is 5-10 ℃/min;
in the step (2), the heat treatment temperature is 350-550 ℃, the heating rate is 5-10 ℃/min, and the heat treatment time is 2-3 h.
2. The method for preparing the ceramic-based zeolite-nanoscale zero-valent iron composite material according to claim 1, wherein in the step (1), the amount of water added is 10-15% of the mass of the raw material mixture.
3. The method for preparing the ceramic-based zeolite-nano zero-valent iron composite material according to claim 1, wherein in the step (1), the diameter of the particles is 3 to 12mm.
4. The method for preparing the ceramic-based zeolite-nanoscale zero-valent iron composite material according to claim 1, wherein in the step (2), the drying temperature is 100 ℃.
5. The method for preparing the ceramic-based zeolite-nano zero-valent iron composite material according to claim 1, wherein the drying temperature in the step (3) is 70 ℃.
6. The method for preparing the ceramic-based zeolite-nano zero-valent iron composite material according to any one of claims 1 to 5, wherein in the step (3), the concentration of the potassium borohydride solution is 0.5 to 5mol/L, and the reaction time is 1 to 3 hours.
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