CN117504812A - Synchronous Mn removal in mine water 2+ Preparation and treatment method of ammonia nitrogen modified zeolite - Google Patents
Synchronous Mn removal in mine water 2+ Preparation and treatment method of ammonia nitrogen modified zeolite Download PDFInfo
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- CN117504812A CN117504812A CN202311476983.1A CN202311476983A CN117504812A CN 117504812 A CN117504812 A CN 117504812A CN 202311476983 A CN202311476983 A CN 202311476983A CN 117504812 A CN117504812 A CN 117504812A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 62
- -1 ammonia nitrogen modified zeolite Chemical class 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000001360 synchronised effect Effects 0.000 title claims description 22
- 239000011572 manganese Substances 0.000 claims abstract description 95
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 88
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 34
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims abstract description 30
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims abstract description 30
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 26
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001603 clinoptilolite Inorganic materials 0.000 claims abstract description 25
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 30
- 239000010457 zeolite Substances 0.000 claims description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- 229940099596 manganese sulfate Drugs 0.000 claims description 16
- 239000011702 manganese sulphate Substances 0.000 claims description 16
- 235000007079 manganese sulphate Nutrition 0.000 claims description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 10
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
-
- 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
-
- 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
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for synchronously removing Mn in mine water 2+ And a preparation method and a treatment method of ammonia nitrogen modified zeolite. Firstly, soaking natural clinoptilolite in sodium hexametaphosphate solution, then carrying out solid-liquid separation, washing and drying to obtain a first material, then placing the first material in divalent manganese salt solution, adjusting the pH value, adding potassium permanganate solution, heating in water bath for a period of time, and then carrying out solid-liquid separation, washing and drying to obtain Mn in mine water synchronously removed 2+ And modified zeolite for ammonia nitrogen.
Description
Technical Field
The invention relates to the technical field of mine water treatment, in particular to a preparation method and a treatment method of modified zeolite for synchronously removing manganese and ammonia nitrogen in mine water.
Background
According to statistics, mn in partial coal mine water in regions of inner Mongolia, shaanxi, shanxi and the like in China 2+ And the mass concentration of ammonia nitrogen ions is respectively 0.2-2.8 and 1.2-3.3mg/L. The main coal production area in the above area is required to improve the mine water discharge standard to the III class standard of GB3838-2002 ground water environment quality standard according to the division rule of the environmental function of the receiving water body, wherein the water outlet limit values of manganese and ammonia nitrogen ions are 0.1mg/L and 1mg/L respectively. Excessive manganese and ammonia nitrogen have great harm to human health and industrial production. The mining area adopts a two-stage process of 'contact oxidation demanganization+ion exchange resin ammonia nitrogen removal', and reports on synchronous demanganization and ammonia nitrogen removal of mine water.
The two-stage treatment process of removing the ammonia nitrogen by the manganese oxide and the ion exchange resin is high in management and operation difficulty, impurities in mine water are easy to abrade the resin, the special ammonia nitrogen removal selectivity is low, secondary pollution exists in the regenerated waste liquid, and the waste resin after use is used as HW13 dangerous waste management, so that the engineering investment and maintenance cost are increased. In order to meet the increasingly strict environmental management requirements, materials and processes for synchronously removing manganese and ammonia nitrogen in mine water are researched and developed, so that the contradiction between sustainable development of production and water resource shortage of coal mine enterprises can be alleviated, and the method has important practical significance for greatly improving the comprehensive utilization efficiency of the mine water and is also an urgent requirement for implementation of ecological protection strategies in mining areas.
The method for removing low concentration manganese ions in water generally adopts a natural oxidation method, an adsorption method, a biological method, a contact oxidation method and the like. The natural oxidation method is difficult to make Mn by aeration alone 2+ Oxidation to MnO 2 To remove manganese, alkali is often added to raise the pH to achieve the removal of manganese. However, the pH value of the water treated by the natural oxidation method is higher, the water can be normally used after the pH value is reduced, and the process system is complex, equipment is huge, investment is large, and the manganese removal effect is not ideal.
Adsorption refers to adsorption of Mn in wastewater by electrostatic attraction, chemical adsorption, surface ion exchange, etc 2+ . The adsorption method has the problems of difficult control of flow rate, small water treatment amount, reduced regenerated adsorption capacity and the like. The current application potential is large, and the mature method is a biological method and a contact oxidation method. The biological method has low biological activity under the low-temperature condition, biological inoculation is needed, and the starting period of the filter tank is long. The contact oxidation method for removing Mn in water has relatively quick start-up period, but also needs 1-3 months start-up period, and its principle is that potassium permanganate is added into the water to oxidize Mn in water 2+ To form a quartz sand filter material loaded by manganese oxide, mn 2+ Can be oxidized by manganese oxide on the surface of the filter material to generate a new active filter membrane substance. However, the contact oxidation method has longer time and higher difficulty in generating the filter membrane with catalytic oxidation activity, potassium permanganate needs to be added into water frequently, the adding amount of the potassium permanganate is high in chromaticity of water, and the adding amount is small, so that the water outlet requirement is difficult to meet.
The treatment method of low-concentration ammonia nitrogen in water generally adopts an adsorption method, an ion exchange method and the like. The ion exchange method is a process in which a material having ion exchange ability performs ion exchange of target ions having high selectivity in water. The ion exchange method for removing ammonia usually refers to treating ammonia nitrogen sewage or wastewater by using ion exchange resin. The specific surface area of the resin is large, the adsorption capacity is large, the regeneration is simple, the regeneration rate is high, but the engineering investment cost is high, the abrasion rate of impurities in mine water to the resin is high, the recycling of the resin is affected, the secondary pollution exists in waste liquid generated by the resin regeneration, and the used waste resin is used as HW13 dangerous waste for management. The adsorption method is to adsorb ammonia nitrogen by using an adsorption material, the adsorption effect of the adsorption material occurs at the junction of two phases and is an interface reaction, and the pollution components in the mixture are adsorbed from a liquid phase to the surface of a solid-phase adsorption material by using unsaturated molecular force or chemical bond force on the surface of the adsorption material, so that the purpose of separating and removing ammonia nitrogen is achieved.
Zeolite is a natural mineral of porous aluminosilicate with good environment, and is prepared from [ SiO 2 ]And [ AlO ] 4 ]The tetrahedral units are staggered to form a three-dimensional framework structure, so that the tetrahedral unit has good adsorption and ion exchange capacity on ammonia nitrogen and heavy metals, and cationic pollutants can be subjected to ion exchange with alkali metals or alkaline earth metals on sites of the tetrahedral units, so that zeolite becomes a natural adsorbent. And the natural zeolite has rich storage capacity, good stable structure and wide application in the field of water treatment. The zeolite has the advantages of simple operation, high efficiency, high speed, no need of adding a large amount of chemical reagents, low energy consumption, regenerable adsorbent, no secondary pollution, relative environmental protection and the like, but often has limited adsorption capacity, low selectivity to ammonia nitrogen, no catalytic oxidation capability, unsatisfactory advanced treatment of manganese and no expected effect.
Aiming at the problems that the two-stage process of 'contact oxidation manganese removal and resin ammonia nitrogen removal' adopted on a mining area is high in management and operation difficulty and complex in process and manganese and ammonia nitrogen cannot be removed synchronously, the development of a novel material capable of removing manganese and ammonia nitrogen in mine water synchronously through multiple mechanisms is urgently needed, synchronous manganese and ammonia nitrogen ion removal is realized to meet the increasingly strict environmental management requirements, engineering investment and operation management difficulty are reduced, and the recycling comprehensive utilization rate of the mine water is improved.
Disclosure of Invention
In order to solve the problems of high management and operation difficulty, complex process and incapability of synchronously removing manganese and ammonia nitrogen in the two-stage treatment process of 'manganese removal by contact oxidation and ammonia nitrogen removal by resin' adopted by coal mine enterprises,
according to one aspect of the present invention, there is provided a method for simultaneous removal of Mn from mine water 2+ And ammonia nitrogenThe preparation method of the modified zeolite is characterized in that the modified zeolite is prepared by a method of loading birnessite type manganese dioxide by a sodium hexametaphosphate impregnated zeolite combined hydrothermal method, and the preparation method comprises the following steps:
(1) Soaking natural clinoptilolite in a sodium hexametaphosphate solution, and then carrying out solid-liquid separation, washing and drying to obtain a first material;
(2) Placing the first material in a divalent manganese salt solution, adjusting the pH value, adding a potassium permanganate solution, heating in a water bath for a period of time, and performing solid-liquid separation, washing and drying to obtain Mn in the mine water synchronously 2+ And modified zeolite for ammonia nitrogen.
In some embodiments, the modified zeolite is used to simultaneously remove Mn from mine water 2+ And ammonia nitrogen, and the ammonia nitrogen is mixed,
the modified zeolite takes natural clinoptilolite as a substrate material.
In some embodiments, the natural clinoptilolite has a particle size of 100 to 300 mesh,
the divalent manganese salt includes manganese sulfate and manganese chloride.
In some embodiments, in step (1), the concentration of sodium hexametaphosphate solution is 0.02 to 0.3mol/L; the pH value of the sodium hexametaphosphate solution is 4.0-8.0; the soaking time is 2-24h.
In some embodiments, the solid to liquid ratio (g/mL) of the natural clinoptilolite to sodium hexametaphosphate solution is 1:10 to 1:100.
In some embodiments, in step (2), the solid to liquid ratio (g/mL) of the natural clinoptilolite to the mixed solution of divalent manganese salt and potassium permanganate is 1:40; the concentration of the divalent manganese ion in the divalent manganese salt solution is 1.5-2.2mmol/L.
In some embodiments, the divalent manganese salt is manganese sulfate.
The molar ratio of the divalent manganese ions to the permanganate ions in the manganese sulfate and potassium permanganate mixed solution is 1:2.5-2.5:1; the pH value of the mixed solution is 6.0-12.0; heating in 40-90deg.C water bath.
According to another aspect of the present invention, there is provided a method for simultaneous Mn removal from mine water using a modified zeolite 2+ And ammonia nitrogenThe modified zeolite is used for synchronously removing Mn in mine water 2+ And ammonia nitrogen modified zeolite,
the processing method comprises the following steps:
will contain Mn 2+ And the pH value of the mine water of ammonia nitrogen is regulated to 6.0-8.0;
to the Mn-containing to be treated 2+ And adding modified zeolite into the mine water containing ammonia nitrogen, and oscillating at a certain temperature, an oscillating rate and an oscillating time by using a constant-temperature water bath oscillator.
In some embodiments, the Mn-containing is adjusted using an acid or alkali solution having a mass concentration of 5-15% 2+ And the pH value of mine water of ammonia nitrogen;
to contain Mn 2+ Adding 1-5g/L modified zeolite into mine water containing ammonia nitrogen;
the temperature of the constant-temperature water bath oscillator is 20-35 ℃, the oscillation rate is 150-300r/min, and the oscillation time is 2-12h.
In some embodiments, the acid solution comprises hydrochloric acid, sulfuric acid, or nitric acid, and the base solution comprises sodium hydroxide, potassium hydroxide, or calcium hydroxide;
mn-containing to be treated 2+ And the pH value of the ammonia nitrogen mine water is in the range of 6.0-8.0;
mn-containing to be treated 2+ And Mn in ammonia nitrogen mine water 2+ And the initial mass concentration of ammonia nitrogen is respectively smaller than 0.5-20 and 1-20mg/L, and after oscillating for 2 hours, the mass concentration of manganese and ammonia nitrogen in water is respectively smaller than 0.1mg/L and 1mg/L.
The preparation method and the treatment method of the modified zeolite for synchronously removing manganese and ammonia nitrogen in mine water have at least one of the following advantages:
synchronous treatment of Mn in mine waters with materials according to the invention 2+ And ammonia nitrogen has the advantages of simple preparation process, low price of natural clinoptilolite and the modified zeolite of the invention, and low cost for treating wastewater. For Mn in mine water 2+ And the ammonia nitrogen removal effect is high, the effluent quality is stable, and the treatment process is simple.
Drawings
These and/or other aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings, in which:
FIGS. 1A, 1B and 1C are, respectively, a natural clinoptilolite, a first material and simultaneous removal of Mn from mine water in accordance with one embodiment of the present invention 2+ And a scanning electron microscope image of modified zeolite of ammonia nitrogen;
FIG. 2 is a synchronous removal of Mn from mine water according to one embodiment of the invention 2+ And a flow chart of a process for preparing the modified zeolite of ammonia nitrogen;
FIG. 3 is a synchronous removal of Mn from mine water using a modified zeolite according to another embodiment of the present invention 2+ And a flow chart of a treatment method of ammonia nitrogen.
Detailed Description
The features of the invention are further illustrated by the following specific examples. The following description of embodiments of the present invention with reference to the accompanying drawings is intended to illustrate the general inventive concept and should not be taken as limiting the invention.
The invention provides a modified zeolite for synchronously removing manganese and ammonia nitrogen ions in mine water, and a method for synchronously removing Mn in mine water 2+ Preparation method of modified zeolite with ammonia nitrogen (ions) and method for synchronously removing Mn in mine water by using modified zeolite 2+ And a method for treating ammonia nitrogen (ions).
In one aspect of the invention, a modified zeolite for simultaneous removal of manganese and ammonia nitrogen ions from mine water is provided. The modified zeolite uses natural clinoptilolite as a base material.
Preferably, the modified zeolite is used for synchronously removing manganese and ammonia nitrogen ions in mine water, and the particle size of the zeolite particles is 100-300 meshes.
In another aspect of the invention, a method of preparing a modified zeolite for simultaneous removal of manganese and ammonia nitrogen ions from water is provided. The preparation method comprises the following steps: firstly, natural clinoptilolite is immersed in a sodium hexametaphosphate solution, and then solid-liquid separation, washing and drying are carried out to obtain a first material; and (3) placing the first material in a manganese sulfate solution, adjusting the pH value, adding a potassium permanganate solution, heating in a water bath for a period of time, and then performing solid-liquid separation, washing and drying to obtain the modified zeolite for synchronously removing manganese and ammonia nitrogen in mine water.
After the natural clinoptilolite is modified by sodium hexametaphosphate, a large amount of metal cations such as calcium, magnesium and the like in the zeolite can be chelated, so that the sodium ions occupy active sites of the zeolite in a large amount and high efficiency, the cation adsorption capacity of the zeolite is obviously increased, the pore structure is improved, and the zeolite has a good effect on Mn in water 2+ And the adsorption capacity of ammonia nitrogen is enhanced; then the first material is further loaded with manganese dioxide of birnessite type by a hydrothermal method to Mn in water 2+ Has high catalytic oxidation capability and specific adsorption capability with ammonia nitrogen, and improves the specific surface area of zeolite, thereby achieving synchronous removal of Mn in mine water 2+ And the action of ammonia nitrogen.
Typically inorganic sodium salt modifiers such as sodium chloride, sodium nitrate, etc., which rely on Na during the modification process + The ammonia nitrogen removing effect of the modified zeolite prepared by the modification mode of the concentration gradient between the priority and the exchangeable ions of the zeolite is general, the root cause is that the inhibition effect of metal cations such as calcium, magnesium and the like can not be removed in the modification process, and Na + The first material modification mechanism is very different from the inorganic sodium salt modification mechanism, the sodium hexametaphosphate is inorganic metal chelated sodium salt, and metaphosphate can chelate calcium, magnesium and other metal cations in zeolite in the process of impregnating and modifying natural clinoptilolite, so that the concentration of free metal ions in the modification process is effectively reduced, sodium ions occupy the active sites of the zeolite in a large quantity and high efficiency, the cation adsorption capacity of the zeolite is obviously increased, the pore canal of the zeolite is dredged, the micropore volume of the zeolite is reduced, mesopores, macropores and average pore diameters are increased, and Mn is facilitated 2+ And migration and diffusion of ammonia nitrogen ions.
Then, the first material is further loaded with birnessite type manganese dioxide by a hydrothermal method, the process ensures that the surface of the first material is rich in hydroxyl groups, the surface adsorbs oxygen and lattice oxygen, the content of trivalent manganese and tetravalent manganese with catalytic oxidation capability is increased, and the specific surface area of the material is further increasedIncrease in Mn can be improved 2+ And the catalytic oxidation capability and the specific adsorption capability of ammonia nitrogen ions, thereby achieving the synchronous removal of Mn in mine water 2+ And ammonia nitrogen effects.
The key points of the preparation of the zeolite material of the invention are as follows:
(1) Firstly, sodium hexametaphosphate dipping modification is carried out on the natural clinoptilolite, and the first material is obtained after solid-liquid separation and drying.
Preferably, the concentration of the sodium hexametaphosphate solution is 0.02-0.3mol/L
Preferably, the pH value of the sodium hexametaphosphate solution is 4.0-8.0;
preferably, the impregnation time is 2 to 24 hours.
Preferably, the solid-to-liquid ratio (g/mL) of the natural clinoptilolite to sodium hexametaphosphate solution is 1:10-1:100.
(2) Manganese dioxide of birnessite type is loaded on the first material by a hydrothermal method, so that the effect of synchronously removing manganese (II) and ammonia nitrogen in water is achieved. The solid-to-liquid ratio (g/mL) of the first material to the mixed solution of manganese sulfate and potassium permanganate is 1:40.
Preferably, the concentration of the manganese sulfate solution is 1.5-2.2mmol/L;
preferably, the molar ratio of the divalent manganese ions to the permanganate ions is 1:2.5-2.5:1;
preferably, the pH value of the mixed solution is 6.0-12.0;
preferably, the water bath temperature is 40-90 ℃.
According to yet another aspect of the present invention, there is provided a method for simultaneous removal of Mn from water using a modified zeolite 2+ And a treatment method of ammonia nitrogen, the treatment method comprising the steps of: will contain Mn 2+ And adjusting the pH value of the mine water containing ammonia nitrogen to 6.0-8.0, then adding modified zeolite into the water to be treated, and oscillating at a certain temperature, oscillation rate and oscillation time by using a constant-temperature water bath oscillator.
Preferably, the oscillation temperature is 20-35 ℃.
Preferably, the oscillation rate is 150-300r/min.
Preferably, the oscillation time is 2 to 12 hours.
In some embodiments, the Mn-containing is adjusted using 10% by mass hydrochloric acid or sodium hydroxide solution 2+ And the pH value of ammonia nitrogen mine water.
In some embodiments, the Mn-containing to be treated 2+ And the pH value of the ammonia nitrogen mine water is in the range of 6.0-8.0; mn-containing to be treated 2+ And ammonia nitrogen in mine water, mn 2+ And the initial mass concentration of ammonia nitrogen is 0.5-20 and 2-20mg/L respectively, mn in water is synchronously removed 2+ And ammonia nitrogen, wherein the adding amount of the modified zeolite is 1-10g/L, and after oscillating for 2 hours, the mass concentration of manganese and ammonia nitrogen in water is respectively smaller than 0.1mg/L and 1mg/L.
Example 1:
referring to fig. 1A, 1B, 1C and 2, the embodiment of the invention is used for synchronously removing Mn in mine water 2+ The preparation method of the modified zeolite with ammonia nitrogen comprises the following steps:
step (1): immersing 100-300 mesh natural clinoptilolite in sodium hexametaphosphate solution with the concentration of 0.02-0.3mol/L at the solid-liquid ratio (g/mL) of 1:10-1:100, wherein the pH value of the sodium hexametaphosphate solution is 4.0-8.0, and carrying out solid-liquid separation, washing and drying after immersing for 2-24 hours to obtain the first material.
Preferably, the natural clinoptilolite is 200 meshes, the concentration of the sodium hexametaphosphate solution is 0.1mol/L, the pH value of the sodium hexametaphosphate solution is 5.6, the solid-to-liquid ratio (g/mL) of the zeolite to the sodium hexametaphosphate solution is 1:20, and the impregnation is carried out for 3 hours.
Step (2): adding the first material prepared in the step (1) into 1.5-2.2mmol/L manganese sulfate solution, regulating the pH value to be 6-12, heating to 40-90 ℃ in a water bath, adding potassium permanganate solution to ensure that the solid-liquid ratio (g/mL) of the first material to the mixed solution is 1:40 and the molar ratio of divalent manganese ions to permanganate ions is 1:2.5-2.5:1, and finally carrying out solid-liquid separation, washing and drying after 2 hours of reaction to obtain Mn in the synchronous mine water removal product 2+ And modified zeolite for ammonia nitrogen.
Preferably, the concentration of the manganese sulfate solution is 2mmol/L, the pH value is 10.0, the water bath temperature is 70 ℃, and the molar ratio of the divalent manganese ions to the permanganate ions is 1.5:1.
Thereby making synchronous removalMn in mine water 2+ And ammonia nitrogen modified zeolite material.
Referring to FIG. 3, a modified zeolite material is shown for Mn-containing materials using the above 2+ And ammonia nitrogen mine water treatment, the treatment method comprises the following steps:
(a) Mn-containing to be treated 2+ And the pH value of the ammonia nitrogen mine water is adjusted to 6.0-8.0, preferably, the pH value is adjusted to 7.0 by using hydrochloric acid or sodium hydroxide solution with the mass concentration of 10 percent.
(b) To the Mn-containing to be treated 2+ And ammonia nitrogen, preferably using a thermostatic water bath shaker at 25 c and a shaking rate of 200r/min for 2 hours.
The modified zeolite for synchronously removing manganese and ammonia nitrogen in mine water is used for treating Mn-containing water 2+ And mine water for ammonia nitrogen. Wherein Mn is 2+ And the initial concentration of ammonia nitrogen, the addition amount of modified zeolite, and the concentrations of manganese and ammonia nitrogen in the effluent are shown in Table 1.
It can be seen that effluent Mn and NH 4 + The concentration of the N is respectively lower than 0.1 and 1mg/L, and meets the III class limit requirement in the standard of surface water environment quality standard.
The pH value of the mine water containing manganese (II) and ammonia nitrogen in the table 1 is 6-8, the oscillation temperature of the water bath constant temperature oscillator is 25 ℃, the oscillation speed is 200r/min, and the oscillation time is 2h.
Table 1 effect of modified zeolite on simultaneous removal of manganese and ammonia nitrogen from mine water
Comparative example 1:
treatment of sample 2 of Table 1 with unmodified Natural clinoptilolite containing Mn 2+ And ammonia nitrogen mine water. The mass concentration of the manganese and ammonia nitrogen in the effluent is 0.67-1.69mg/L and 1.5-2.1mg/L.
Example 2:
the only difference from example 1 is that the solid to liquid ratio of the natural clinoptilolite to sodium hexametaphosphate solution was 1:10.
Example 3:
the only difference from example 1 is that the solid to liquid ratio of the natural clinoptilolite to sodium hexametaphosphate solution was 1:100.
Example 4:
the difference from example 1 was only that the concentration of the sodium hexametaphosphate solution was 0.3mol/L.
Example 5:
the only difference from example 1 is that the pH of the sodium hexametaphosphate solution was 4.
Example 6:
the only difference from example 1 is that the pH of the sodium hexametaphosphate solution was 8.
Example 7:
the only difference from example 1 is that the impregnation time is 24 hours.
Example 8:
the only difference from example 1 is that the concentration of the manganese sulfate solution is 1.5mmol/L.
Example 9:
the only difference from example 1 is that the concentration of the manganese sulfate solution is 2.2mmol/L.
Example 10:
the only difference from example 1 is that the molar ratio of manganese sulfate to permanganate is 1:2.5.
Example 11:
the only difference from example 1 is that the molar ratio of manganese sulfate to permanganate is 2.5:1.
Example 12:
the only difference from example 1 is that the pH of the mixed solution was 7.
Example 13:
the only difference from example 1 is that the pH of the mixed solution was 12.
Example 15:
the only difference from example 1 is that the hydrothermal temperature is 40 ℃.
Example 16:
the only difference from example 1 is that the hydrothermal temperature is 90 ℃.
Comparative example 2:
the only difference from example 1 is that the solid to liquid ratio of the sodium hexametaphosphate solution of the natural clinoptilolite was 1:5. Comparative example 3:
the difference from example 1 was only that the concentration of the sodium hexametaphosphate solution was 0.01mol/L.
Comparative example 4:
the only difference from example 1 is that the impregnation time was 1h.
Comparative example 5:
the only difference from example 1 is that the concentration of the manganese sulfate solution is 1mmol/L.
Comparative example 6:
the only difference from example 1 is that the hydrothermal temperature is 30 ℃.
Treatment of Mn-containing Using the modified zeolite materials obtained in examples 2 to 16 and comparative examples 1 to 6 2+ And ammonia nitrogen mine water, differing from example 1 only in that the solid-to-liquid ratio of the modified zeolite to mine water to be treated was (2 g:1000 mL). The quality of the effluent containing manganese (II) and ammonia nitrogen in the mine water is shown in Table 2.
In Table 2, the initial mass concentration percentages of manganese and ammonia nitrogen in the mine water containing manganese (II) and ammonia nitrogen are 3 and 5mg/L.
TABLE 2 synchronous treatment of modified wastewater containing Mn 2+ And ammonia nitrogen mine water implementation effect
As can be seen from the results of the treated effluent water qualities shown in examples 1 to 16, the Mn removal is performed simultaneously by the present invention 2+ And ammonia nitrogen modified zeolite capable of stably and synchronously removing Mn in water 2+ And ammonia nitrogen, so that the concentration of manganese and ammonia nitrogen in the treated water is less than the limit value of 0.1 and 1.0mg/L required by the water body.
The foregoing is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above-described embodiment, it will be appreciated by those skilled in the art that changes may be made to the embodiment without departing from the principles and spirit of the general inventive concept, and such changes should also be construed as falling within the scope of the present invention. The scope of the invention is defined by the claims and their equivalents.
Claims (10)
1. Synchronous Mn in mine water removal 2+ And a preparation method of ammonia nitrogen modified zeolite, wherein the modified zeolite is prepared by a method of loading birnessite type manganese dioxide by a sodium hexametaphosphate impregnated zeolite combined hydrothermal method, and the preparation method comprises the following steps:
(1) Soaking natural clinoptilolite in a sodium hexametaphosphate solution, and then carrying out solid-liquid separation, washing and drying to obtain a first material;
(2) Placing the first material in a divalent manganese salt solution, adjusting the pH value, adding a potassium permanganate solution, heating in a water bath for a period of time, and performing solid-liquid separation, washing and drying to obtain Mn in the mine water synchronously 2+ And modified zeolite for ammonia nitrogen.
2. Synchronous Mn removal in mine water according to claim 1 2+ And a method for preparing ammonia nitrogen modified zeolite, which is characterized in that,
the modified zeolite is used for synchronously removing Mn in mine water 2+ And ammonia nitrogen, and the ammonia nitrogen is mixed,
the modified zeolite takes natural clinoptilolite as a substrate material.
3. Synchronous Mn removal in mine water according to claim 2 2+ And a method for preparing ammonia nitrogen modified zeolite, which is characterized in that,
the grain diameter of the natural clinoptilolite is 100-300 meshes,
the divalent manganese salt solution includes manganese sulfate and manganese chloride.
4. Synchronous Mn removal in mine water according to claim 1 2+ And a method for preparing the modified zeolite of ammonia nitrogen,it is characterized in that the method comprises the steps of,
in the step (1), the concentration of the sodium hexametaphosphate solution is 0.02-0.3mol/L; the pH value of the sodium hexametaphosphate solution is 4.0-8.0; the soaking time is 2-24h.
5. Synchronous Mn removal in mine water according to claim 4 2+ And a method for preparing ammonia nitrogen modified zeolite, which is characterized in that,
the solid-to-liquid ratio (g/mL) of the natural clinoptilolite to the sodium hexametaphosphate solution is 1:10-1:100.
6. The synchronous Mn removal in mine water of claim 3 2+ And a method for preparing ammonia nitrogen modified zeolite, which is characterized in that,
in the step (2), the solid-to-liquid ratio (g/mL) of the mixed solution of the natural clinoptilolite, the divalent manganese salt and the potassium permanganate is 1:40; the concentration of the divalent manganese ion in the divalent manganese salt solution is 1.5-2.2mmol/L.
7. Synchronous Mn removal in mine water according to claim 6 2+ And a method for preparing ammonia nitrogen modified zeolite, which is characterized in that,
the divalent manganese salt solution is a manganese sulfate solution,
the molar ratio of the divalent manganese ions to the permanganate ions in the manganese sulfate and potassium permanganate mixed solution is 1:2.5-2.5:1; the pH value of the mixed solution is 6.0-12.0; heating in 40-90deg.C water bath.
8. Synchronous Mn removal in mine water by using modified zeolite 2+ And a method for treating ammonia nitrogen, wherein the modified zeolite is used for synchronously removing Mn in mine water according to any one of claims 1 to 7 2+ And ammonia nitrogen modified zeolite, which is characterized in that,
the processing method comprises the following steps:
will contain Mn 2+ And the pH value of the mine water of ammonia nitrogen is regulated to 6.0-8.0;
to the Mn-containing to be treated 2+ And ammonia nitrogen are added into mine waterThe zeolite was modified and oscillated using a thermostatic water bath oscillator at a temperature, oscillation rate and oscillation time.
9. Synchronous removal of Mn in mine water using modified zeolite according to claim 8 2+ And a method for treating ammonia nitrogen, which is characterized in that,
adjusting Mn content with 5-15% acid or alkali solution 2+ And the pH value of mine water of ammonia nitrogen;
to contain Mn 2+ Adding 1-5g/L modified zeolite into mine water containing ammonia nitrogen;
the temperature of the constant-temperature water bath oscillator is 20-35 ℃, the oscillation rate is 150-300r/min, and the oscillation time is 2-12h.
10. Synchronous removal of Mn in mine water using modified zeolite as claimed in claim 9 2+ And a method for treating ammonia nitrogen, which is characterized in that,
the acid solution comprises hydrochloric acid, sulfuric acid or nitric acid, and the alkali solution comprises sodium hydroxide, potassium hydroxide or calcium hydroxide;
mn-containing to be treated 2+ And the pH value of the ammonia nitrogen mine water is in the range of 6.0-8.0;
mn-containing to be treated 2+ And Mn in ammonia nitrogen mine water 2+ And the initial mass concentration of ammonia nitrogen is respectively smaller than 0.5-20 and 1-20mg/L, and after oscillating for 2 hours, the mass concentration of manganese and ammonia nitrogen in water is respectively smaller than 0.1mg/L and 1mg/L.
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