CN113877518B - Adsorbent and preparation method and application thereof - Google Patents
Adsorbent and preparation method and application thereof Download PDFInfo
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- CN113877518B CN113877518B CN202111226455.1A CN202111226455A CN113877518B CN 113877518 B CN113877518 B CN 113877518B CN 202111226455 A CN202111226455 A CN 202111226455A CN 113877518 B CN113877518 B CN 113877518B
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- ammonia nitrogen
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 30
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 13
- 239000000347 magnesium hydroxide Substances 0.000 claims description 13
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 13
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 10
- 229910019440 Mg(OH) Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 2
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 2
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 2
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 2
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 abstract description 18
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 22
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 16
- 229910052567 struvite Inorganic materials 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 229940091250 magnesium supplement Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 159000000003 magnesium salts Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 ammonium ions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910017958 MgNH Inorganic materials 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229960002337 magnesium chloride Drugs 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
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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
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses an adsorbent, a preparation method and application thereof, and belongs to the field of environment. Firstly, mixing and granulating a magnesium source, then atomizing by using a phosphorus source solution, spraying the atomized magnesium source solution onto the surfaces of magnesium source particles, stirring the mixture in the reaction process, and controlling the reaction temperature; cooling to normal temperature after the reaction is finished, cleaning, filtering, drying and grading to obtain a target product. The ammonia adsorbent disclosed by the invention not only can be slowly dissolved in the wastewater, has no residue and no regeneration pollution, but also is simple to operate, and can be used for efficiently removing ammonia nitrogen in the wastewater without adjusting the pH value in the solution. And can be used as ammonia adsorbent, and has stronger adsorption performance.
Description
Technical Field
The invention relates to the field of environment, in particular to an adsorbent, a preparation method and application thereof.
Background
With the development of industry and agriculture and the improvement of the living standard of people, a large amount of wastewater containing ammonia nitrogen and ammonia gas are discharged into the environment. The excessive ammonia nitrogen content in the wastewater can cause eutrophication of water body, thereby frequently generating lake bloom and offshore red tide; ammonia gasIs easily oxidized to form NO after being discharged into the air 3 - Or NO x Thus, acidic rainfall can be caused, and ammonia gas has high water solubility and weak alkalinity, thus causing environmental hazard and endangering human health. Ammonia nitrogen is an indispensable element for growth and development of animals and plants, and plays an important role in nature. Therefore, the treatment of ammonia nitrogen wastewater and ammonia becomes important. For the treatment of ammonia nitrogen in ammonia nitrogen wastewater and ammonia in air at present, not only is the denitrification effect pursued, but also energy conservation, consumption reduction and full recovery of valuable ammonia nitrogen resources are pursued, so that the aim of combining higher-level environment and economy is fulfilled, and the comprehensive utilization of ammonia nitrogen in different fields is realized.
In recent years, many studies have been made on the treatment of ammonia nitrogen wastewater and the recovery of ammonia gas. For ammonia nitrogen recovery, the research scope relates to a plurality of ammonia nitrogen wastewater treatment methods: ion exchange, electrochemical oxidation, break point chlorination, magnesium ammonium phosphate crystallization. The ion exchange method has high removal rate for ammonia nitrogen wastewater, but is not suitable for large-scale industrial application due to the defects of limited exchange capacity, easy secondary pollution and the like. The electrochemical oxidation method has high degradation efficiency for treating ammonia nitrogen wastewater, but has high treatment cost due to difficult recycling of the catalyst, and is difficult to widely popularize. The break point chlorination method has high treatment efficiency and stable effect, but has the defects of difficult wide application due to excessive medicament cost, easy secondary pollution and the like. For ammonia recovery, the scope of research involves a variety of methods for treating ammonia: catalytic conversion, absorption, adsorption, and the like. The catalytic conversion method is to convert ammonia gas into nitrogen gas and water by using a catalyst and then discharge the nitrogen gas and water, and has the advantages that the catalyst has longer service life and simple equipment installation, but has higher energy consumption and difficult circulation. The absorption method is to recycle ammonia into liquid by using absorbent, and has simple operation, but consumes a large amount of solvent and is easy to cause secondary pollution. Adsorption is the most commonly used method, and commonly used adsorbents such as zeolite, activated carbon, MOFs and the like are used for recycling ammonia through physical adsorption, so that the adsorption method has high selectivity and high adsorption efficiency, but the existing method has the defects of small adsorption amount of the adsorbent, high post-treatment cost and the like.
The crystallization method of magnesium ammonium phosphate uses Mg 2+ 、NH 4+ 、PO 4 3- The three ions are subjected to chemical reaction to generate a magnesium ammonium phosphate crystal product, so that ammonium ions in water can be effectively removed, and the generated magnesium ammonium phosphate is a compound slow-release fertilizer which can be recycled in agriculture and has high added value and market prospect. And the adsorbent made by the patent can utilize the mechanism to adsorb ammonia.
The patent (CN 100384754C) discloses a method for treating ammonia nitrogen wastewater by utilizing a chemical precipitation method, wherein mixed solution of magnesium chloride hexahydrate, magnesium oxide, phosphoric acid and the like is added into the ammonia nitrogen wastewater as a precipitator, a certain amount of flocculant is added, meanwhile, sodium hydroxide is added to adjust the pH value for removing ammonia nitrogen in the water, and the result shows that the product is a slow-release fertilizer with high added value: magnesium ammonium phosphate hexahydrate has higher removal rate for ammonia nitrogen in high-concentration ammonia nitrogen wastewater, but the removal effect for wastewater with lower ammonia nitrogen concentration is not mentioned, alkali liquor is continuously added to adjust the pH value of the wastewater in the experimental process, and time and labor are wasted. The patent (CN 102674523B) discloses a method for recycling ammonia nitrogen in wastewater by utilizing a chemical crystallization method, which utilizes pyrolysis products of magnesium ammonium phosphate and magnesium hydroxide added into ammonia nitrogen wastewater to remove ammonia nitrogen in the wastewater, so as to obtain magnesium ammonium phosphate crystals, the obtained precipitate is recovered, dried, heated and added with magnesium hydroxide again for recycling, acidolysis is carried out after 2-5 times of circulation, the acidolysis-finished product is put into the ammonia nitrogen wastewater for recycling, the material can be recycled, the problem of excessive cost of the magnesium ammonium phosphate crystallization method medicament is effectively solved, ammonia nitrogen in high-concentration ammonia nitrogen wastewater can be effectively removed, but the removal of wastewater with lower ammonia nitrogen concentration is not mentioned, magnesium hydroxide is continuously added in the circulation process, acidolysis treatment is carried out, time and labor are wasted, the cost is increased, and the method has a certain danger. The patent (CN 103466841B) discloses a treatment method of ammonia nitrogen wastewater, which is to remove ammonia nitrogen in the wastewater by utilizing a magnesium ammonium phosphate crystallization method and a three-stage precipitation method, and obtain magnesium ammonium phosphate and magnesium phosphate precipitation, wherein ammonia nitrogen in the wastewater containing high-concentration ammonia nitrogen can be effectively removed by the method, but the removal of wastewater with lower ammonia nitrogen concentration is not mentioned, and the process is complicated.
In summary, the existing methods for removing ammonia nitrogen in wastewater by using magnesium ammonium phosphate crystallization method have good effect, but the patent mentioned above can be known to be mostly limited to treating high-concentration ammonia nitrogen wastewater (more than 500 ppm), and nothing is mentioned about middle-low concentration (100-500 ppm) ammonia nitrogen wastewater. Meanwhile, the operation process of the existing technology is complex, and the safety is not high, so that the existing technology has a great problem.
Disclosure of Invention
The invention provides an adsorbent, a preparation method and application aiming at the technical problems.
The aim of the invention can be achieved by the following technical scheme:
an adsorbent is MgHPO 4 ·3H 2 O is coated on Mg (OH) 2 And other magnesium source surfaces, expressed as MgHPO 4 ·3H 2 O@(Mg(OH) 2 +a), wherein the magnesium salt a is one or more of magnesium carbonate, magnesium chloride or magnesium bicarbonate.
The technical scheme of the invention is as follows: the particle size of the adsorbent is 0.1-0.2mm.
The technical scheme of the invention is as follows: mgHPO 4 ·3H 2 The molar ratio of O to magnesium salt is 1: (0.1-0.9).
The preparation method of the adsorbent comprises the steps of firstly mixing and granulating a magnesium source, then atomizing and spraying a phosphorus source solution onto the surfaces of magnesium source particles, stirring simultaneously in the reaction process, cooling to normal temperature after the reaction is finished, then cleaning, filtering, drying and grading to obtain a target product, wherein the magnesium source is magnesium hydroxide and magnesium source a.
The technical scheme of the invention is as follows: the phosphorus source solution is one or more of phosphoric acid, sodium dihydrogen phosphate or aluminum dihydrogen phosphate.
The technical scheme of the invention is as follows: the mole ratio between phosphate ions in the dropwise added phosphorus source solution and magnesium ions in the magnesium source is 1: (1.1-1.9).
The technical scheme of the invention is as follows: the molar ratio of magnesium hydroxide in the magnesium source to magnesium ions in the magnesium source a is 1: (0.5-1).
The technical scheme of the invention is as follows: the reaction temperature is 50-90 ℃; preferably: the reaction temperature is 60-90 ℃.
The technical scheme of the invention is as follows: the temperature of the drying is 60-90 ℃ and the time is 2-5h. Too low a drying temperature can result in too long drying time, causing unnecessary energy consumption; the drying temperature is too high, so that the material decomposition or the material crystal form is changed, and the reactivity is reduced, and therefore, the drying temperature is 80 ℃ and the drying time is 4 hours as the best through multiple experiments.
The technical scheme of the invention is as follows: the adsorbent is applied to the aspect of adsorbing ammonia nitrogen or ammonia gas.
The ammonia nitrogen adsorbent is prepared by mixing a phosphorus source solution and a magnesium source, and ammonia is adsorbed by using a magnesium ammonium phosphate crystallization method. According to research, a certain alkaline environment is needed for ammonia adsorption by a magnesium ammonium phosphate crystallization method, the best adsorption condition is between 9 and 10pH, so that the prepared adsorbent not only provides enough magnesium ions and phosphate ions through the slow release effect of the adsorbent, but also gradually exposes the magnesium hydroxide in the interior to the solution in the reaction process, magnesium hydroxide is dissolved and simultaneously generates magnesium ions and hydroxyl, so that an alkaline and ion balanced micro-area can be provided for crystal nucleation growth, and magnesium ions are provided, magnesium ammonium phosphate crystallization is promoted to be positively carried out, other soluble alkali lyes such as sodium hydroxide are effectively replaced, the medicament cost and waste are reduced, and secondary pollution caused by alkali lye addition is also reduced; the effect is far better than that of simply adding magnesium hydroxide. The molar ratio of phosphate ions to magnesium ions is 1: (1.1-1.9) ensures that MgHPO is prepared 4 ·3H 2 O@(Mg(OH) 2 +a) surface, and ammonium ions or ammonia gas in the treated water, a suitable ratio can be selected according to different ammonia nitrogen concentrations or ammonia gas concentrations. When the ammonia nitrogen concentration is high, the pH value is high, so the selectionWith relatively small molar adsorbents, since Mg (OH) is not required 2 Providing greater alkalinity; when the ammonia nitrogen concentration is low, the pH value is low, so that the adsorbent with larger molar ratio and Mg (OH) are selected 2 Providing greater alkalinity. This allows the adsorbent to react under optimally alkaline conditions without the need for further pH adjustment with soluble bases.
The invention has the beneficial effects that:
1. the MgHPO can be obtained simply by dripping the phosphorus source solution into the magnesium salt solution 4 ·3H 2 O@(Mg(OH) 2 +a) the mixed crystal structure of the surface.
2. The MgHPO is obtained 4 ·3H 2 The mixed crystal structure of O coated on the surface of the magnesium salt has the characteristics of stable active components and excellent ammonia adsorption performance, and has higher ammonia nitrogen removal rate for 100ppm-1000ppm ammonia nitrogen wastewater; in magnesium ammonium phosphate crystallization, the presence of magnesium hydroxide increases the adsorption capacity of the adsorbent and provides the alkaline environment required for magnesium ammonium phosphate crystallization, facilitating crystallization.
3. The ammonia adsorbent disclosed by the invention not only can be slowly dissolved in the wastewater, has no residue and no regeneration pollution, but also is simple to operate, and can be used for efficiently removing ammonia nitrogen in the wastewater without adjusting the pH value in the solution. And can be used as ammonia adsorbent, and has stronger adsorption performance.
4. The produced magnesium ammonium phosphate product has a certain added value, can be used as a slow release fertilizer, and can be pyrolyzed to be in small particle size and put into experiments again.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings described below are only embodiments of the present invention, and that other drawings may be obtained according to the provided drawings without inventive effort for a person skilled in the art.
Fig. 1 is an XRD pattern of the mixed crystal material obtained by the application of example 3.
Fig. 2 is a raman spectrum of the mixed crystal material obtained by the application of example 3.
FIG. 3 is an XRD pattern of a mixed crystal material surface product obtained by the application of example 3.
Detailed Description
The invention is further illustrated below with reference to examples, but the scope of the invention is not limited thereto:
example 1:
dissolving magnesium hydroxide and magnesium carbonate (the molar ratio of magnesium ions in the magnesium hydroxide and the magnesium carbonate is 1:0.5) in part of deionized water for granulation treatment, obtaining 13mol/L phosphoric acid to be sprayed according to the molar ratio of magnesium ions to phosphate ions of 1.1:1, spraying the phosphoric acid to the surface of magnesium source particles in an atomizing mode, stirring and spraying, and controlling the reaction temperature to be 60 ℃. After spraying, stirring continuously until the reaction temperature is cooled to normal temperature, cleaning, filtering, and drying in a blast drying oven at 70 ℃ for 4 hours. XRD and Raman analyses were performed on the product, and as shown in FIGS. 1 to 2, XRD results showed that the product was MgHPO 4 ·3H 2 O and Mg (OH) 2 In the presence of magnesium carbonate, but by carrying out a Raman analysis with the same sample, the result shows that only MgHPO is present 4 ·3H 2 The Raman peak of O exists and does not contain Mg (OH) 2 The raman peak of (c) exists, so that the composition can be proved to be MgHPO 4 ·3H 2 O@(Mg(OH) 2 +a) the mixed crystal structure of the surface.
When in use, the prepared MgHPO 4 ·3H 2 O@(Mg(OH) 2 +MgCO 3 ) Two parts of 0.1g are weighed, one part is placed in a solution with the concentration of 100ppm and the volume of 100ml to carry out an ammonia nitrogen adsorption experiment in water, and the experiment is used for measuring the ammonia nitrogen removal rate. The other part is placed above an ammonia solution with the concentration of 0.5mol/L and the volume of 30ml for ammonia adsorption experiments.
In this example, the determination of ammonia nitrogen removal rate and adsorption rate by salicylic acid method shows that the ammonia nitrogen/ammonia adsorbent MgHPO is used 4 ·3H 2 O@(Mg(OH) 2 +MgCO 3 ) The ammonia nitrogen removal rate of the material is 91.5%, and the ammonia adsorption capacity is 698.2mg/g. Completion of the experimentXRD analysis of the resulting product was carried out as shown in FIG. 3, which shows that the product was MgNH 3 PO 4 ·6H 2 O。
Examples 2 to 12, comparative examples 1 to 6, specifically shown in Table 1, were conducted under the same conditions as in example 1.
Claims (10)
1. An adsorbent, characterized in that: the adsorbent is MgHPO 4 ·3H 2 O is coated on Mg (OH) 2 And other magnesium source a surface, expressed as MgHPO 4 ·3H 2 O@ (Mg(OH) 2 +a), wherein the magnesium source a is one or more of magnesium carbonate, magnesium chloride or magnesium bicarbonate;
the preparation method of the adsorbent comprises the steps of firstly mixing and granulating a magnesium source, then atomizing and spraying a phosphorus source solution onto the surfaces of magnesium source particles, stirring in the reaction process, and controlling the reaction temperature; and cooling to normal temperature after the reaction is finished, cleaning, filtering, drying and grading to obtain a target product, wherein the magnesium source is magnesium hydroxide and a magnesium source a.
2. The adsorbent according to claim 1, characterized in that: the particle size of the adsorbent is 0.1-0.2mm.
3. According to claim 1The adsorbent is characterized in that MgHPO 4 ·3H 2 The molar ratio of O to magnesium source is 1: (0.1-0.9).
4. The adsorbent according to claim 1, characterized in that: the phosphorus source solution is one or more of phosphoric acid, sodium dihydrogen phosphate or aluminum dihydrogen phosphate.
5. The adsorbent according to claim 1, characterized in that: the mole ratio between phosphate ions in the dropwise added phosphorus source solution and magnesium ions in the magnesium source is 1: (1.1-1.9).
6. The adsorbent according to claim 1, characterized in that: the molar ratio of magnesium hydroxide in the magnesium source to magnesium ions in the magnesium source a is 1: (0.5-1).
7. The adsorbent according to claim 1, characterized in that: the reaction temperature is 50-90 ℃.
8. The adsorbent of claim 7, wherein: the reaction temperature is 60-90 ℃.
9. The adsorbent of claim 4, wherein: the temperature of the drying is 60-90 ℃ and the time is 2-5h.
10. Use of the adsorbent of claim 1 for adsorbing ammonia nitrogen or ammonia gas.
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