CN111804304A - Core-shell structure composite filter material, preparation method and application thereof, ammonia nitrogen wastewater treatment method and device - Google Patents
Core-shell structure composite filter material, preparation method and application thereof, ammonia nitrogen wastewater treatment method and device Download PDFInfo
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- CN111804304A CN111804304A CN202010631558.5A CN202010631558A CN111804304A CN 111804304 A CN111804304 A CN 111804304A CN 202010631558 A CN202010631558 A CN 202010631558A CN 111804304 A CN111804304 A CN 111804304A
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- 239000000463 material Substances 0.000 title claims abstract description 222
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000002131 composite material Substances 0.000 title claims abstract description 94
- 239000011258 core-shell material Substances 0.000 title claims abstract description 57
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 140
- 239000011572 manganese Substances 0.000 claims abstract description 121
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 105
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000004576 sand Substances 0.000 claims abstract description 101
- 239000002351 wastewater Substances 0.000 claims abstract description 69
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 53
- 238000011069 regeneration method Methods 0.000 claims abstract description 49
- 230000008929 regeneration Effects 0.000 claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000001301 oxygen Substances 0.000 claims abstract description 44
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000011001 backwashing Methods 0.000 claims abstract description 29
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 11
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims description 31
- 238000001514 detection method Methods 0.000 claims description 21
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 2
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- 229910021645 metal ion Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 85
- 239000000243 solution Substances 0.000 description 42
- 230000000694 effects Effects 0.000 description 26
- 239000010410 layer Substances 0.000 description 25
- 230000008569 process Effects 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000010865 sewage Substances 0.000 description 12
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 7
- 230000002238 attenuated effect Effects 0.000 description 7
- 238000011010 flushing procedure Methods 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- 230000001172 regenerating effect Effects 0.000 description 7
- 229960005191 ferric oxide Drugs 0.000 description 6
- 235000013980 iron oxide Nutrition 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000010170 biological method Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical class N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- -1 and simultaneously Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 238000012216 screening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/397—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention provides a core-shell structure composite filter material, a preparation method and application thereof, and an ammonia nitrogen wastewater treatment method and device. The core-shell structure composite filter material comprises a manganese sand filter material and a transition metal oxide shell coated on the surface of the manganese sand filter material; the transition metal oxide is one or a combination of iron oxide, manganese oxide and iron-manganese composite oxide. The method for preparing the core-shell structure composite filter material comprises the following steps: enabling the solution containing the transition metal ions to flow through the manganese sand filter material, and simultaneously aerating oxygen-containing gas into the manganese sand filter material to obtain a core-shell structure composite filter material; the transition metal ion is a low valence ion of the transition metal element. The core-shell structure composite filter material, the preparation method and the application thereof, and the ammonia nitrogen wastewater treatment method and the ammonia nitrogen wastewater treatment device have the advantages that the ammonia nitrogen wastewater is treated without adding an oxidizing agent, the secondary pollution of a water body is avoided, the regeneration of the filter material can be realized through simple back washing and the online secondary preparation of an active shell layer, the operation is simple, the regeneration cost is low, and the stability of produced water is high.
Description
Technical Field
The invention belongs to the technical field of ammonia nitrogen wastewater treatment, and particularly relates to a core-shell structure composite filter material, a preparation method and application thereof, and an ammonia nitrogen wastewater treatment method and device.
Background
Ammonia nitrogen is one of the most main existing forms of nitrogen pollutants in wastewater, mainly comes from decomposition of nitrogenous organic matters in domestic sewage, drainage of farmland irrigation, coking, synthetic ammonia and other industrial wastewater, and has a plurality of pollution sources and large discharge amount. As a main oxygen-consuming pollutant in a water body, the over-standard content of ammonia nitrogen can cause water eutrophication, blackening and smelling of the water body, and water quality reduction, which cause serious harm to human beings and aquatic organisms, so that the removal of ammonia nitrogen becomes one of the hot problems of the research of environmental workers.
Aiming at the treatment of ammonia nitrogen in municipal sewage, the current main methods comprise a biological method, a breakpoint chlorination method and an ion exchange method. The biological method has good denitrification capability, mature process and wide application, but is greatly influenced by factors such as water body temperature, pH and the like, the stability of produced water is poor, and an organic carbon source needs to be added in the operation process, so that the cost is increased, and the application of the biological method in water treatment is hindered. The breakpoint chlorination method is to oxidize ammonia nitrogen into N by adding chlorine or sodium hypochlorite into the wastewater2The chemical denitrification method has simple operation and stable treatment, but because excessive chlorine needs to be added in practical application, the excessive chlorine in the water body can exceed the standard, and the waste water can be increasedSalinity, secondary pollution is caused. The ion exchange method can selectively remove ammonia nitrogen, but when the adsorbent is saturated in adsorption, the adsorbent needs to be regenerated, the regeneration cost is high, the difficulty is high, the adsorption capacity of the regenerated adsorbent is reduced, the ammonia nitrogen removal performance is attenuated, and the engineering application of the adsorbent is limited. Therefore, the treatment method for ammonia nitrogen wastewater, which can treat ammonia nitrogen wastewater without adding an oxidizing agent, has the advantages of simple regeneration, low regeneration cost and strong water production stability, needs to be provided.
Disclosure of Invention
The invention solves the technical problem of providing a core-shell structure composite filter material, a preparation method and application thereof, an ammonia nitrogen wastewater treatment method and a device, ammonia nitrogen wastewater can be treated without adding an oxidizing agent, secondary pollution of a water body can not be caused, the regeneration of the filter material can be realized through simple back washing and online secondary preparation of an active shell layer, the operation is simple, the regeneration cost is low, and the stability of produced water is strong.
In order to solve the above problems, an aspect of the present invention provides a core-shell structure composite filter material, including:
the manganese sand filter material comprises a manganese sand filter material and a transition metal oxide shell coated on the surface of the manganese sand filter material; the transition metal oxide is one or a combination of iron oxide, manganese oxide and iron-manganese composite oxide.
The manganese sand filter material is prepared from natural manganese ores serving as raw materials through the processes of crushing, washing, polishing, impurity removal, drying, magnetic separation, screening, dust removal and the like, and mainly comprises manganese dioxide, iron and silicon dioxide. The transition metal in the transition metal oxide can be one or a mixture of iron and manganese; the iron oxide can be one of 2-valent iron oxide and 3-valent iron oxide or the mixture or composite of two of the two, such as FeO and Fe2O3、Fe4O3(ii) a The manganese oxide can be one or more of 2-valent oxide, 3-valent oxide and 4-valent oxide, such as MnO2、Mn2O3、Mn3O4(ii) a The iron-manganese composite oxide is a composite of the iron oxide and the manganese oxide. Wherein the manganese sand filter material is a core, the transition metal oxide is a shell, and the transition metal refers to transition goldBelongs to a film layer formed by coating oxides on the surface of a manganese sand filter material.
The transition metal oxide shell layer on the surface of the core-shell structure composite filter material, namely the manganese sand filter material has high catalytic activity and can react with NH4 +Has good adsorption capacity and can make NH4 +Is enriched on the surface of the filter material and is catalytically oxidized into NO3 -、NO2 -、N2And (3) an oxidation product; when the catalytic activity of the transition metal oxide shell on the surface is reduced, the filter material can be backwashed to enable the inactivated shell to fall off, the manganese sand filter material in the filter material is retained, then a solution containing transition metal element low-valence ions is introduced into the manganese sand filter material, and oxygen-containing gas is simultaneously introduced to oxidize the transition metal ions under the catalytic action of the manganese sand, so that the transition metal oxide shell is formed on the surface of the manganese sand again to enable the filter material to be regenerated.
Preferably, the transition metal oxide is a ferrimanganic composite oxide. Iron manganese composite oxide to NH in ammonia nitrogen wastewater4 +The catalytic oxidation effect of (3) is the best.
Another aspect of the present invention provides a method for preparing a core-shell structure composite filter material, comprising the following steps:
treating the manganese sand filter material by using a solution containing transition metal ions, enabling the solution containing the transition metal ions to be in contact with the manganese sand filter material, and simultaneously aerating oxygen-containing gas into the manganese sand filter material to obtain the core-shell structure composite filter material; the transition metal ion is Fe2+、Mn2+One or a mixture of both.
The principle of the preparation method is as follows: so as to contain transition metal ions Fe2+、Mn2+The solution flows through a manganese sand filter material, the manganese sand filter material has adsorption effect on transition metal ions in the solution, so that the transition metal ions are adsorbed to the surface of the manganese sand filter material and are oxidized by oxygen in the aerated oxygen-containing gas under the catalysis of the manganese sand filter material to generate transition metal oxides, and the newly generated transition metal oxides have high catalytic activity and NH (NH) resistance4 +Has good adsorption capacity and can adsorb NH4 +Is enriched and utilized on the surface of the filter materialThe catalytic performance of the catalyst activates dissolved oxygen to generate an intermediate product O with strong oxidizing property, and NH in an adsorption state can be adsorbed under the action of the O in an activated state4 +Oxidation to NO3 -、NO2 -、N2And the like.
Wherein the transition metal ions exist in the forms of inorganic salt, organic salt and the like, and can be hydrochloride, sulfate, nitrate, formate, acetate and the like; preferably, the transition metal ion exists in the form of inorganic salt, and the transition metal ion exists in the form of hydrochloride, sulfate or nitrate; preferably, the transition metal ion is present in the form of a hydrochloride salt; further preferably, the solution containing transition metal ions is FeCl2With MnCl2The mixed solution of (1).
The oxygen-containing gas may be air, oxygen or other oxygen-containing gas.
Preferably, the total mass ratio of the manganese sand filter material to the transition metal ions is 80:1-450: 1.
Preferably, the transition metal ion is Fe2+With Mn2+And (3) mixing.
Preferably, the manganese sand filter material and the total Fe in the solution containing the transition metal ions2+The mass ratio of (50-250): 1; further preferably, the manganese sand filter material and the total Fe in the solution containing the transition metal ions2+The mass ratio of (A) to (B) is 181: 1;
preferably, the manganese sand filter material and the total Mn in the solution containing the transition metal ions2+The mass ratio of (30-200): 1; further preferably, the manganese sand filter material and the total Mn in the solution2+The mass ratio of (A) to (B) is 91.6: 1;
preferably, the solution is Fe2+The concentration of (A) is 80-300 mg/L; further preferably, the solution is Fe2+The concentration of (A) is 110 mg/L;
preferably, Mn in the solution2+The concentration of (b) is 200-600 mg/L; further preferably, Mn in the solution2+The concentration of (B) was 218.4 mg/L.
Preferably, the flow rate of the solution containing the transition metal ions flowing through the manganese sand filter material is 2-20mL/min when the solution is used for treating the manganese sand filter material; further preferably, the flow rate of the solution stream containing transition metal ions is 4 mL/min;
preferably, the hydraulic retention time of the solution containing the transition metal ions flowing through the manganese sand filter material is 30-60 min; further preferably, the hydraulic retention time of the solution containing the transition metal ions flowing through the manganese sand filter material is 40 min;
preferably, the flow rate of the oxygen-containing gas is 20-100 mL/min; further preferably, the flow rate of the oxygen-containing gas is 20 mL/min;
preferably, the concentration of oxygen in the oxygen-containing gas is 21% -100%; further preferably, the oxygen-containing gas is air.
The invention also provides a core-shell structure composite filter material prepared by the method for preparing the core-shell structure composite filter material.
The invention also provides application of the core-shell structure composite filter material in ammonia nitrogen wastewater treatment.
The invention also provides application of the core-shell structure composite filter material as a catalyst for catalytic oxidation of ammonia nitrogen wastewater.
The invention also provides a method for treating ammonia nitrogen wastewater, which comprises the following steps:
the preparation step comprises the steps of preparing the core-shell structure composite filter material on line by adopting the method for preparing the core-shell structure composite filter material or directly using the core-shell structure composite filter material;
the ammonia nitrogen wastewater treatment step comprises the steps of enabling ammonia nitrogen wastewater to flow through the core-shell structure composite filter material, and simultaneously, aerating oxygen-containing gas into the core-shell structure composite filter material to enable the ammonia nitrogen wastewater to be catalytically oxidized;
the regeneration step comprises the steps of carrying out back washing on the core-shell structure composite filter material to remove a transition metal oxide shell, so as to obtain a manganese sand filter material; treating the manganese sand filter material obtained by backwashing by using a solution containing transition metal ions, and simultaneously aerating the manganese sand filter materialOxygen-containing gas is contained to obtain a regenerated core-shell structure composite filter material; the transition metal ion is Fe2+、Mn2+One or a mixture of both; the ammonia nitrogen wastewater treatment step and the regeneration step are carried out in a circulating way.
The principle of the ammonia nitrogen wastewater treatment method is as follows: firstly, natural manganese sand is utilized to react with transition metal ions (such as Mn)2+With Fe2 +) The transition metal ions are adsorbed on the surface of the manganese sand and oxidized by dissolved oxygen in water under the catalytic action of the manganese sand to generate metal oxides (such as iron-manganese composite oxides), and the nascent metal oxides have high catalytic activity and are resistant to NH4 +Has good adsorption capacity, and can adsorb NH by using adsorption performance4 +Enriching on the surface of the filter material, activating the dissolved oxygen by utilizing the catalytic performance to generate an intermediate product O with strong oxidizing property, and adsorbing NH under the action of the activated O4 +Oxidation to NO3 -、NO2 -、N2Oxidizing the product to obtain NH in the ammonia nitrogen wastewater4 +Catalytic oxidation treatment of (3).
The principle of regenerating the core-shell structure composite filter material is as follows: in the process of treating ammonia nitrogen wastewater, when the catalytic activity of the active layer is reduced, the filter material is backwashed to enable the inactivated shell layer to fall off, the manganese sand filter material nuclear layer is retained, and transition metal ions (such as Mn) are introduced into the adsorption column2+And Fe2+) And the solution is simultaneously aerated with oxygen-containing gas, and under the catalytic action of the manganese sand filter material, a new metal oxide shell layer with ammonia nitrogen oxidation capability can be generated on the surface of the manganese sand again to complete the regeneration of the filter material, so that the continuous and stable use of the filter material is realized.
Preferably, in the step of treating the ammonia nitrogen wastewater, the flow rate of the ammonia nitrogen wastewater is 2-20 mL/min; the hydraulic retention time of the ammonia nitrogen wastewater flowing through the core-shell structure composite filter material is 40-80 min; the flow rate of the oxygen-containing gas is 20-100 mL/min; the oxygen concentration in the oxygen-containing gas is 21% -100%. Further preferably, in the step of treating the ammonia nitrogen wastewater, the flow rate of the ammonia nitrogen wastewater is 5 mL/min; the hydraulic retention time of the ammonia nitrogen wastewater flowing through the core-shell structure composite filter material is 50 min; the flow rate of the oxygen-containing gas is 40 mL/min; the oxygen-containing gas is air.
Preferably, in the regeneration step, the total mass ratio of the manganese sand filter material to the transition metal ions is 80:1-450: 1.
Further preferably, in the regeneration step, the transition metal ion is Fe2+With Mn2+And (3) mixing. The total mass ratio of the manganese sand filter material to the transition metal ions is (80-450): 1; further preferably, the transition metal ion is Fe2+With Mn2+The manganese sand filter material and the total Fe in the solution2+The mass ratio of (50-250): 1, manganese sand Filter and Total Mn in solution2+The mass ratio of (30-200): 1; further preferably, the manganese sand filter material and the total Fe in the solution2+The mass ratio of the manganese sand filter material to the total Mn in the solution is 181:12+The mass ratio of (A) to (B) is 91.6: 1.
preferably, in the regeneration step, the total concentration of the transition metal ions in the solution is 280-900 mg/L; further, the transition metal ion in the solution is Fe2+And Mn2+，Fe2+The concentration of (B) is 80-300mg/L, Mn2+The concentration of (b) is 200-600 mg/L; more preferably, the solution is Fe2+Has a concentration of 110mg/L, Mn2+The concentration of (B) was 218.4 mg/L.
Preferably, in the regeneration step, the flow rate of the solution flow filter material is 2-20 mL/min; the hydraulic retention time of the solution flowing through the manganese sand filter material is 30-60 min; the flow rate of the oxygen-containing gas is 20-100 mL/min; the concentration of oxygen in the oxygen-containing gas is 21% -100%. Preferably, the flow rate of the solution flow filter is 4 mL/min; the hydraulic retention time of the solution flowing through the manganese sand filter material is 40 min; the flow rate of the oxygen-containing gas is 20 mL/min; the oxygen-containing gas is air.
Another aspect of the present invention provides an ammonia nitrogen wastewater treatment apparatus, comprising:
the filter column is filled with a manganese sand filter material and is provided with an ammonia nitrogen wastewater inlet, a treated water outlet, a regenerated liquid inlet, a wastewater outlet and a gas inlet;
a regenerated liquid supply device suitable for supplying a solution containing transition metal ions into the filter column, wherein the transition metal ions are Fe2+、Mn2+One or a mixture of both; a liquid outlet of the regeneration liquid supply device is connected with the regeneration liquid inlet through a first pipeline;
and the gas supply device is suitable for exposing oxygen-containing gas into the filter column, and a gas supply port of the gas supply device is connected with the gas inlet.
Corresponding to the ammonia nitrogen wastewater treatment method, the ammonia nitrogen wastewater treatment device comprises the following working processes: the regenerating liquid supplying means supplies ions containing transition metal (e.g. Mn) to the filter column2+And Fe2+) The gas supply device simultaneously aerates oxygen-containing gas into the filter column, the transition metal ions are oxidized by the oxygen under the catalytic action of the manganese sand filter material, a metal oxide shell with catalytic oxidation action is formed on the surface of the manganese sand filter material, and the metal oxide shell can catalyze and oxidize NH in the ammonia nitrogen wastewater4 +And finishing the treatment of the ammonia nitrogen wastewater.
Preferably, the device further comprises a produced water collecting device, wherein the produced water collecting device is provided with a produced water inlet and a backwashing water supply port, and the produced water inlet is connected with the treated water outlet of the filter column through a second pipeline;
the filter column is also provided with a backwashing water inlet which is connected with a backwashing water supply port of the produced water collecting device through a third pipeline;
the device is characterized by further comprising an ammonia nitrogen wastewater supply device, wherein the ammonia nitrogen wastewater supply device is suitable for introducing ammonia nitrogen wastewater into the filter column, and a water outlet of the ammonia nitrogen wastewater supply device is connected with the ammonia nitrogen wastewater inlet through a fourth pipeline.
When the catalytic activity of the metal oxide shell on the surface of the manganese sand filter material is reduced, the treated water collected by the produced water collecting device can enter the filter column through a backwashing water inlet to perform backwashing on the filter material, so that an inactivated shell layer falls off, and a manganese sand filter material core layer is reserved; then supplying a regeneration liquid supply device containing transition metal ions (such as Mn) to the filter column2+And Fe2+) Is/are as followsAnd aerating the solution, and forming a metal oxide shell with catalytic oxidation on the surface of the manganese sand filter material under the catalytic action of the manganese sand filter material so as to regenerate the filter material.
Preferably, the method further comprises the following steps:
the ammonia nitrogen concentration detection device is used for detecting the ammonia nitrogen concentration in the treated water at the treated water outlet;
the first control valve is arranged on the first pipeline;
the second control valve is arranged on the second pipeline;
the third control valve is arranged on the third pipeline;
the fourth control valve is arranged on the fourth pipeline;
the controller is electrically connected with the ammonia nitrogen concentration detection device, the first control valve, the second control valve, the third control valve and the fourth control valve respectively;
the controller is used for receiving the ammonia nitrogen concentration signal sent by the ammonia nitrogen concentration detection device and controlling the first control valve, the second control valve, the third control valve and the fourth control valve to be opened and closed according to the ammonia nitrogen concentration signal detected by the ammonia nitrogen concentration detection device.
The ammonia nitrogen concentration detection device is used for detecting the ammonia nitrogen concentration in the treated water and feeding the ammonia nitrogen concentration back to the controller, and the controller automatically controls the opening and closing of each control valve according to the ammonia nitrogen concentration value, so that the automatic control of each pipeline of the ammonia nitrogen wastewater treatment device is realized.
Further preferably, after receiving that the ammonia nitrogen concentration signal is higher than a threshold value, the controller controls the second control valve and the fourth control valve to be closed, controls the third control valve to be opened, performs backwashing on the filter column, and starts to calculate backwashing time;
after the preset back flushing time is reached, the controller controls the third control valve to close, the first control valve to open for regeneration, and meanwhile, the regeneration time is calculated;
and after the preset regeneration time is reached, the controller controls the first control valve to be closed, and controls the second control valve and the fourth control valve to be opened.
The controller receives an ammonia nitrogen concentration signal in the treated water transmitted by the ammonia nitrogen concentration detection device in real time, compares the detection value with a set threshold value, and controls to close the second control valve and the fourth control valve after the ammonia nitrogen concentration in the treated water is higher than the threshold value, so that the water inlet of the ammonia nitrogen wastewater and the water outlet of the treated water are stopped; and then controlling the third control valve to be opened, performing backwashing on the filter material in the filter column, controlling the third control valve to be closed after the preset backwashing time is reached, controlling the first control valve to be opened, regenerating the filter material, controlling the first control valve to be closed, controlling the second control valve and the fourth control valve to be opened after the regeneration time is reached, and starting to treat the ammonia nitrogen wastewater again and produce water.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention relates to a core-shell structure composite filter material, a preparation method thereof, a treatment method of ammonia nitrogen wastewater and a device, wherein a manganese sand filter material is used as a core structure of the composite filter material, and transition metal ions (such as Mn) are contained in the core structure2+With Fe2+) The manganese sand filter material is treated by the solution, and transition metal ions (such as Mn) are treated by the manganese sand filter material2+With Fe2+) The adsorption of the ion to the surface of the manganese sand filter material, and the oxidation of the manganese sand filter material by the dissolved oxygen in water under the catalytic action of the manganese sand filter material to generate a transition metal oxide (such as an iron-manganese composite oxide), wherein the nascent state transition metal oxide has high catalytic activity and NH (hydrogen) resistance4 +Has good adsorption capacity, and can adsorb NH by using adsorption performance4 +Enriching on the surface of the composite filter material, activating dissolved oxygen by utilizing the catalytic performance of the composite filter material to generate an intermediate product O with strong oxidizing property, and adsorbing NH under the action of the activated O4 +Oxidation to NO3 -、NO2 -、N2And (3) an oxidation product; in the process of treating ammonia nitrogen wastewater, when the catalytic activity of the transition metal oxide active layer on the surface of the composite filter material is reduced, the composite filter material is backwashed to enable the inactivated shell layer to fall off, the manganese sand filter material nuclear layer is reserved, and then transition metal oxide-containing active layer is introduced into the adsorption columnMetal ions (e.g. Mn)2+With Fe2+) The solution is aerated at the same time, namely a new oxide shell layer with ammonia nitrogen catalytic oxidation capability is generated on the surface of the manganese sand filter material again to complete the regeneration of the composite filter material, thereby realizing the continuous and stable use of the filter material;
2. according to the core-shell structure composite filter material, the preparation method thereof, the ammonia nitrogen wastewater treatment method and the ammonia nitrogen wastewater treatment device, when the ammonia nitrogen wastewater is treated, no oxidizing agent is required to be added, an active shell layer with a catalytic oxidation effect can be formed on the surface of manganese sand only by utilizing the catalytic action of the manganese sand and the dissolved oxygen in the treated water, so that secondary pollution of a water body is avoided, the catalytic efficiency of the active shell layer is high, and the ammonia nitrogen wastewater treatment process can be continuously and stably operated for a long time; after the active shell is inactivated, the inactivated shell is removed through simple backwashing, and a solution containing transition metal ions is introduced for on-line secondary preparation of the active shell, so that the composite filter material can be regenerated, the regeneration process is simple to operate, the efficiency is high, the cost is low, and the activity of the regenerated composite filter material has no obvious performance attenuation;
3. the ammonia nitrogen concentration detection device is used for detecting the ammonia nitrogen concentration in the treated water at the treated water outlet in real time, and the controller is used for controlling the control valves, so that the water production is automatically stopped and the regeneration of the composite filter material is carried out after the ammonia nitrogen concentration is detected to be higher than a preset value, the ammonia nitrogen treatment and the composite filter material regeneration are automatically controlled and circulated, and the treatment operation of the ammonia nitrogen wastewater is simpler.
Drawings
FIG. 1 is a scanning electron microscope image of a core-shell structure composite filter material obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the core-shell structure composite filter material obtained in example 1 of the present invention;
FIG. 3 is a graph showing the variation of the ammonia nitrogen concentration of the influent water and the produced water with the operation time in the ammonia nitrogen wastewater treatment method of example 2 of the present invention;
FIG. 4 is a graph showing the variation of the ammonia nitrogen concentration of the influent water and the produced water with the operation time in the ammonia nitrogen wastewater treatment method of example 3 of the present invention;
FIG. 5 is a schematic structural view of an ammonia nitrogen wastewater treatment apparatus according to embodiment 6 of the present invention;
FIG. 6 is a circuit diagram of the ammonia nitrogen wastewater treatment apparatus according to embodiment 6 of the present invention.
Wherein: 1-a filter column; 2-manganese sand filter material; 3-a regenerating liquid supply device; 4-a first pipeline; 5-an air supply device; 6-produced water collecting device; 7-a second pipeline; 8-ammonia nitrogen wastewater supply device; 9-a third pipeline; 10-a fourth pipeline; 11-ammonia nitrogen concentration detection device; 12-a first control valve; 13-a second control valve; 14-a third control valve; 15-fourth control valve.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the core-shell structure composite filter material comprises the following steps:
1. filling a natural manganese sand filter material into an organic glass filter column with the volume of 1L, and filling 200g of natural manganese sand into the filter column;
2. 10L of 500mg/LMnCl is prepared2And 250mg/L FeCl2Mixed solution (manganese sand filtering material and Fe can be obtained by conversion)2+The mass ratio of the manganese sand filter material to Mn is 181:12+The mass ratio of the manganese particles to the core-shell structure composite filter material is 91.6:1), the manganese particles enter a filter column at a water inlet speed of 4mL/min, flow through a natural manganese sand filter material, and simultaneously, air is aerated into the manganese sand filter material at the bottom end of the filter column, in the process, the hydraulic retention time of the mixed solution in the manganese sand filter material layer is controlled to be 40min, the air flow is controlled to be 20mL/min, and the operation is continuously carried out for 42h until the prepared mixed solution is completely operated, so that the core-shell structure composite filter material is prepared.
As shown in FIG. 1 and FIG. 2, which are scanning electron micrographs of the core-shell structure composite filter material obtained in this example, it can be seen from the electron micrographs that the core-shell structure composite filter material is MnCl2With FeCl2After the mixed solution is treated, the product is obtainedThe obtained filter material takes the manganese sand filter material as a core, and a layer of manganese-iron composite oxide shell is formed on the surface of the manganese sand filter material, namely the core-shell structure composite filter material.
Example 2
The ammonia nitrogen wastewater treatment method of the embodiment is used for treating an actual water sample taken back by a certain municipal sewage treatment plant in Beijing and comprises the following steps:
1. the preparation steps comprise that the core-shell structure composite filter material obtained in the embodiment 1 is directly adopted;
2. the ammonia nitrogen wastewater treatment step comprises: introducing an ammonia nitrogen wastewater water sample into a filter column filled with the core-shell structure composite filter material, introducing 200L of municipal sewage into a composite filter material filter column with the volume of 1L through a peristaltic pump according to the water inlet speed of 5mL/min, keeping the hydraulic retention time of the water sample in the composite filter material layer to be 50min, simultaneously opening an air inlet valve for aeration, wherein the air flow is 40mL/min, so that NH in the ammonia nitrogen wastewater is subjected to NH treatment4 +Is catalyzed and oxidized, and the content of ammonia nitrogen in produced water is less than 1 mg/L;
3. a regeneration step comprising: when the ammonia nitrogen content of produced water rises to 1mg/L, stopping water inflow, performing back flushing on the composite filter material in the filter column, flushing for 6 hours, completely stripping the old shell layer, retaining the natural manganese sand nuclear layer, and then introducing 500mg/LMnCl into the manganese sand filter material in the filter column2And 250mg/L FeCl2Mixing the solution, keeping the hydraulic retention time of the filter material layer at 30min, continuously operating for 48h, and simultaneously aerating air to the manganese sand filter material at the bottom end of the filter column, wherein the air flow is 40mL/min, so as to prepare a new composite filter material;
4. and circularly performing the ammonia nitrogen wastewater treatment step and the regeneration step.
In the embodiment, sampling is carried out at intervals to test the ammonia nitrogen concentration of inlet water and produced water, the test result is shown in fig. 3, the ammonia nitrogen of the inlet water is 40mg/L, the filter material for water treatment for the first time can continuously run for 19 days to treat 144L water, the ammonia nitrogen of the produced water is always less than 1mg/L in the whole running process to meet the requirement of III-class water on the ground surface, when the filter material runs for 20 days, the ammonia nitrogen of the produced water is increased to 1mg/L, the activity of the filter material is reduced, the inlet water is stopped, the filter material in the filter column is backwashed and regenerated to obtain a new composite filter material, municipal sewage is continuously introduced into the regenerated filter column at the flow rate of 5mL/min, the filter material continuously runs for 20 days, the ammonia nitrogen of the produced water is still less than 1mg/L and runs stably, no obvious performance attenuation occurs in the activity; after the regeneration is carried out again, the operation is carried out for 20 days according to the same treatment condition again, the ammonia nitrogen produced in the water is still less than 1mg/L, the operation is stable, the activity of the filter material is not obviously attenuated compared with the activity of the filter material in the previous period, and the activity recovery rate of the filter material can reach 100 percent. The method for treating the ammonia nitrogen wastewater is proved to be capable of continuously and stably treating the ammonia nitrogen in the wastewater by repeating the steps of ammonia nitrogen wastewater treatment, back washing and composite filter material regeneration in a column passing mode, and has practical application prospect.
Example 3
The ammonia nitrogen wastewater treatment method of the embodiment is used for treating an actual water sample taken back by a certain municipal sewage treatment plant in Beijing and comprises the following steps:
1. the preparation steps comprise that the core-shell structure composite filter material obtained in the embodiment 1 is directly adopted;
2. the ammonia nitrogen wastewater treatment step comprises: introducing an ammonia nitrogen wastewater water sample into a filter column filled with the core-shell structure composite filter material, introducing 200L of municipal sewage into a composite filter material filter column with the volume of 1L through a peristaltic pump according to the water inlet speed of 5mL/min, keeping the hydraulic retention time of the water sample in the composite filter material layer to be 50min, simultaneously opening an air inlet valve for aeration, wherein the air flow is 40mL/min, so that NH in the ammonia nitrogen wastewater is subjected to NH treatment4 +Is catalyzed and oxidized, and the content of ammonia nitrogen in produced water is less than 1 mg/L;
3. a regeneration step comprising: when the ammonia nitrogen content of produced water rises to 1mg/L, stopping water inflow, performing back flushing on the composite filter material in the filter column, flushing for 8 hours, completely stripping the old shell layer, retaining the natural manganese sand nuclear layer, and then introducing 500mg/LMnCl into the manganese sand filter material in the filter column2And 250mg/L FeCl2Mixing the solution, keeping the hydraulic retention time of a filter material layer at 50min, continuously operating for 40h, and simultaneously aerating air to the manganese sand filter material at the bottom end of a filter column, wherein the air flow is 40mL/min, so as to prepare a new composite filter material;
4. and circularly performing the ammonia nitrogen wastewater treatment step and the regeneration step.
In the embodiment, sampling is carried out at intervals to test the ammonia nitrogen concentration of inlet water and produced water, the test result is shown in fig. 4, the ammonia nitrogen concentration of the inlet water is 68mg/L, the filter material for first water treatment can continuously run for 17 days, the ammonia nitrogen concentration of the produced water is always less than 1mg/L in the whole running process, the requirement of surface III type water is met, the activity of the filter material is reduced after 17 days, the ammonia nitrogen concentration of the produced water is increased to 1mg/L, the inlet water is stopped, the filter material in the filter column is back flushed and regenerated to obtain a new composite filter material, municipal sewage is continuously introduced into the regenerated filter column at the flow rate of 5mL/min, the operation is continuously carried out for 17 days, the ammonia nitrogen concentration of the produced water is still less than 1mg/L and the running is stable, no obvious performance attenuation occurs in the filter material activity; after the regeneration is carried out again, the operation is carried out for 17 days according to the same treatment condition again, the ammonia nitrogen produced in the water is still less than 1mg/L, the operation is stable, the activity of the filter material is not obviously attenuated compared with the activity of the filter material in the previous period, and the activity recovery rate of the filter material can reach 100 percent. The method for treating the ammonia nitrogen wastewater is proved to be capable of continuously and stably treating the ammonia nitrogen in the wastewater by repeating the steps of ammonia nitrogen wastewater treatment, back washing and composite filter material regeneration in a column passing mode, and has practical application prospect.
Example 4
The ammonia nitrogen wastewater treatment method of the embodiment is used for treating an actual water sample taken back by a certain municipal sewage treatment plant in Beijing and comprises the following steps:
1. the preparation steps are the same as the other basic steps in the example 1, except that:
10L of 700mg/LMnCl is prepared2And 500mg/L FeCl2And (3) feeding the mixed solution into a filter column at a water inlet speed of 20mL/min, and treating 200g of manganese sand filter material.
2. The ammonia nitrogen wastewater treatment step is the same as that in the embodiment 2;
3. regeneration procedure, identical to that of example 2, except that a solution containing 700mg/LMnCl was used2And 500mg/LFeCl2And (5) regenerating the mixed solution.
In the embodiment, the first water treatment filter material can continuously run for 17 days to treat 128L water, the ammonia nitrogen of produced water is always less than 1mg/L in the whole running process to meet the requirement of III-class water on the earth surface, when the running time reaches 18 days, the ammonia nitrogen of the produced water is increased to 1mg/L, the activity of the filter material is reduced, water inlet is stopped, the filter material in a filter column is backwashed and regenerated to obtain a new composite filter material, municipal sewage is continuously introduced into the regenerated filter column at the flow rate of 5mL/min, the continuous running time lasts for 18 days, the ammonia nitrogen of the produced water is still less than 1mg/L and the running is stable, the activity of the filter material is not obviously attenuated in the last period, and the activity recovery rate of the filter material can reach 100; after the regeneration is carried out again, the operation is carried out for 18 days according to the same treatment condition again, the ammonia nitrogen produced in the water is still less than 1mg/L, the operation is stable, the activity of the filter material is not obviously attenuated compared with the activity of the filter material in the previous period, and the activity recovery rate of the filter material can reach 100 percent.
Example 5
The ammonia nitrogen wastewater treatment method of the embodiment is used for treating an actual water sample taken back by a certain municipal sewage treatment plant in Beijing and comprises the following steps:
1. the preparation steps are the same as the other basic steps in the example 1, except that:
10L of 1000mg/LMnCl is prepared2And 200mg/L FeCl2And (3) feeding the mixed solution into a filter column at a water inlet speed of 2mL/min, and treating 200g of manganese sand filter material.
2. The ammonia nitrogen wastewater treatment step is the same as that in the embodiment 2;
3. regeneration procedure, identical to that of example 2, except that a solution containing 1000mg/LMnCl was used2And 200mg/LFeCl2And (5) regenerating the mixed solution.
In the embodiment, the first water treatment filter material can continuously run for 18 days to treat 136L of water, the ammonia nitrogen of produced water is always less than 1mg/L in the whole running process to meet the requirement of III-class water on the earth surface, when the running time reaches 19 days, the ammonia nitrogen of the produced water is increased to 1mg/L, the activity of the filter material is reduced, water inlet is stopped, the filter material in a filter column is backwashed and regenerated to obtain a new composite filter material, municipal sewage is continuously introduced into the regenerated filter column at the flow rate of 5mL/min, the continuous running time lasts for 19 days, the ammonia nitrogen of the produced water is still less than 1mg/L and the running is stable, the activity of the filter material is not obviously attenuated in the last period, and the activity recovery rate of the filter material can reach; after the regeneration is carried out again, the operation is carried out for 19 days according to the same treatment condition again, the ammonia nitrogen produced in the water is still less than 1mg/L, the operation is stable, the activity of the filter material is not obviously attenuated compared with the activity of the filter material in the previous period, and the activity recovery rate of the filter material can reach 100 percent.
Example 6
The ammonia nitrogen wastewater treatment device of this embodiment, as shown in fig. 5, fig. 6, includes: the device comprises a filter column 1, an ammonia nitrogen wastewater supply device 8, a produced water collecting device 6, a regenerated liquid supply device 3, a gas supply device 5, an ammonia nitrogen concentration detection device 11 and a controller.
Wherein, the filter column 1 is filled with manganese sand filter material 2, and the filter column 1 is provided with an ammonia nitrogen wastewater inlet, a treated water outlet, a regenerated liquid inlet, a wastewater outlet, a gas inlet and a backwashing water inlet; the outlet of the regeneration liquid supply means 3 is connected to the regeneration liquid inlet of the filtration column 1 via a first line 4 and is adapted to supply MnCl to the filtration column 12With FeCl2The mixed aqueous solution of (1); the air supply port of the air supply device 5 is connected with the air inlet of the filter column 1 and is suitable for aerating air into the filter column 1; the produced water collecting device 6 is provided with a produced water inlet and a backwashing water supply port, the produced water inlet is connected with a treated water outlet of the filter column 1 through a second pipeline 7, and the backwashing water supply port is connected with a backwashing water inlet of the filter column 1 through a third pipeline 9; the water outlet of the ammonia nitrogen wastewater supply device 8 is connected with the ammonia nitrogen wastewater inlet of the filter column 1 through a fourth pipeline 10, and is suitable for introducing ammonia nitrogen wastewater into the filter column 1.
An ammonia nitrogen concentration detection device 11 for detecting the ammonia nitrogen concentration in the treated water at the treated water outlet of the filter column 1; the first control valve 12 is arranged on the first pipeline 4; the second control valve 13 is arranged on the second pipeline 7; the third control valve 14 is arranged on the third pipeline 9; the fourth control valve 15 is arranged on the fourth pipeline 10; the controller is electrically connected with the ammonia nitrogen concentration detection device 11, the first control valve 12, the second control valve 13, the third control valve 14 and the fourth control valve 15 respectively; the controller is used for receiving the ammonia nitrogen concentration signal sent by the ammonia nitrogen concentration detection device 11 and controlling the opening and closing of the first control valve 12, the second control valve 13, the third control valve 14 and the fourth control valve 15 according to the ammonia nitrogen concentration signal detected by the ammonia nitrogen concentration detection device. After the controller receives that the ammonia nitrogen concentration signal 11 is higher than the threshold value, the controller controls 13 the second control valve and the fourth control valve 15 to close, controls 14 the third control valve to open, performs back flushing on the filter column 1, and simultaneously starts to calculate the back flushing time; after the preset back washing time is reached, the controller controls the third control valve 14 to be closed, the first control valve 12 to be opened for regeneration, and meanwhile, the regeneration time is calculated; after the preset regeneration time is reached, the controller controls the first control valve 12 to close, and controls the second control valve 13 and the fourth control valve 14 to open.
The ammonia nitrogen wastewater treatment device of the embodiment has the working process that: starting a regeneration liquid supply device and a gas supply device, wherein the regeneration liquid supply device supplies MnCl into the filter column2With FeCl2The gas supply device is aerated with oxygen, and the manganese sand filter material is used for filtering Mn2+Ions, Fe2+The ions are adsorbed on the surface of the manganese sand filter material, and Mn is caused to be adsorbed under the catalytic action of the manganese sand filter material2+Ions, Fe2+Ions are oxidized by dissolved oxygen in water into iron-manganese composite oxides with high catalytic activity; then closing the regenerated liquid supply device, opening the ammonia nitrogen wastewater supply device to supply water, opening the produced water collecting device to collect the treated water, and after the ammonia nitrogen wastewater enters the filter column, NH in the wastewater4 +Under the catalytic action of the ferro-manganese composite oxide, the aerated air is oxidized into NO3 -、NO2 -、N2Completing wastewater treatment; the ammonia nitrogen concentration detection device detects the ammonia nitrogen concentration in the treated water of the filter column in real time, when the catalytic activity of the filter material is reduced and the ammonia nitrogen concentration of the treated water is increased, the ammonia nitrogen concentration detection device transmits an ammonia nitrogen concentration signal to the controller, the controller compares the detection value with a set threshold value, and after the ammonia nitrogen concentration of the treated water is higher than the threshold value, the controller controls to close the second control valve and the fourth control valve, and the water inlet of the ammonia nitrogen wastewater and the water outlet of the treated water are stopped; then controlling the third control valve to be opened, backwashing the filter material in the filter column, starting to calculate the backwashing time, when the preset backwashing time is reached, controlling the third control valve to be closed by the controller, opening the first control valve, regenerating the filter material, after the regeneration time is reached, controlling the first control valve to be closed by the controller, opening the second control valve and the fourth control valve, and starting to treat ammonia againAnd (4) producing water by the nitrogen wastewater, and treating the ammonia nitrogen wastewater in the next period.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A core-shell structure composite filter material is characterized by comprising:
the manganese sand filter material comprises a manganese sand filter material and a transition metal oxide shell coated on the surface of the manganese sand filter material; the transition metal oxide is one or a combination of iron oxide, manganese oxide and iron-manganese composite oxide.
2. A method for preparing a core-shell structure composite filter material is characterized by comprising the following steps:
treating the manganese sand filter material by using a solution containing transition metal ions, enabling the solution containing the transition metal ions to be in contact with the manganese sand filter material, and simultaneously aerating oxygen-containing gas into the manganese sand filter material to obtain the core-shell structure composite filter material; the transition metal ion is Fe2+、Mn2+One or a mixture of both.
3. The method for preparing the core-shell structure composite filter material according to claim 2, wherein:
the transition metal ion is Fe2+With Mn2+The manganese sand filter material and the total Fe in the solution containing the transition metal ions2+The mass ratio of (50-250): 1; the total Mn in the manganese sand filter material and the solution containing transition metal ions2+The mass ratio of (30-200): 1;
the flow rate of the solution containing the transition metal ions when the manganese sand filter material is treated is 2-20 mL/min; said alloy containing transition goldThe hydraulic retention time of the solution of the metal ions in the manganese sand filter material is 30-60 min; fe in the solution containing transition metal ions2+The concentration of (B) is 80-300mg/L, Mn2+The concentration of (b) is 200-600 mg/L;
the flow rate of the oxygen-containing gas is 20-100 mL/min; the concentration of oxygen in the oxygen-containing gas is 21% -100%.
4. The core-shell structure composite filter material prepared by the method for preparing the core-shell structure composite filter material according to claim 2 or 3.
5. The application of the core-shell structure composite filter material as claimed in claim 1 or 4 as a catalyst for catalytic oxidation of ammonia nitrogen wastewater.
6. The ammonia nitrogen wastewater treatment method is characterized by comprising the following steps:
the preparation step comprises the steps of preparing the core-shell structure composite filter material on line by adopting the method for preparing the core-shell structure composite filter material according to the claim 2 or 3 or directly using the core-shell structure composite filter material according to the claim 1;
the ammonia nitrogen wastewater treatment step comprises the steps of contacting ammonia nitrogen wastewater with the core-shell structure composite filter material, and simultaneously aerating oxygen-containing gas to the core-shell structure composite filter material to enable the ammonia nitrogen wastewater to be catalytically oxidized;
the regeneration step comprises the steps of carrying out back washing on the core-shell structure composite filter material to remove a transition metal oxide shell, so as to obtain a manganese sand filter material; treating the manganese sand filter material obtained by backwashing by using a solution containing transition metal ions, and simultaneously aerating oxygen-containing gas into the manganese sand filter material to obtain a regenerated core-shell structure composite filter material; the transition metal ion is Fe2+、Mn2+One or a mixture of both; the ammonia nitrogen wastewater treatment step and the regeneration step are carried out in a circulating way.
7. The ammonia nitrogen wastewater treatment method of claim 6,
in the step of treating the ammonia nitrogen wastewater, the flow of the ammonia nitrogen wastewater flowing through the core-shell structure composite filter material is 2-20 mL/min; the hydraulic retention time of the ammonia nitrogen wastewater flowing through the core-shell structure composite filter material is 40-80 min; the flow rate of the oxygen-containing gas is 20-100 mL/min.
8. The utility model provides an ammonia nitrogen effluent treatment plant which characterized in that includes:
the filter column is filled with a manganese sand filter material and is provided with an ammonia nitrogen wastewater inlet, a treated water outlet, a regenerated liquid inlet, a wastewater outlet and a gas inlet;
a regenerated liquid supply device suitable for supplying a solution containing transition metal ions into the filter column, wherein the transition metal ions are Fe2+、Mn2+One or a mixture of both; a liquid outlet of the regeneration liquid supply device is connected with the regeneration liquid inlet through a first pipeline;
and the gas supply device is suitable for exposing oxygen-containing gas into the filter column, and a gas supply port of the gas supply device is connected with the gas inlet.
9. The ammonia nitrogen wastewater treatment device of claim 8, characterized in that:
the device is characterized by also comprising a produced water collecting device, wherein the produced water collecting device is provided with a produced water inlet and a backwashing water supply port, and the produced water inlet is connected with the treated water outlet of the filter column through a second pipeline;
the filter column is also provided with a backwashing water inlet which is connected with a backwashing water supply port of the produced water collecting device through a third pipeline;
the device is characterized by further comprising an ammonia nitrogen wastewater supply device, wherein the ammonia nitrogen wastewater supply device is suitable for introducing ammonia nitrogen wastewater into the filter column, and a water outlet of the ammonia nitrogen wastewater supply device is connected with the ammonia nitrogen wastewater inlet through a fourth pipeline.
10. The ammonia-nitrogen wastewater treatment device according to claim 8, further comprising:
the ammonia nitrogen concentration detection device is used for detecting the ammonia nitrogen concentration in the treated water at the treated water outlet;
the first control valve is arranged on the first pipeline;
the second control valve is arranged on the second pipeline;
the third control valve is arranged on the third pipeline;
the fourth control valve is arranged on the fourth pipeline;
the controller is electrically connected with the ammonia nitrogen concentration detection device, the first control valve, the second control valve, the third control valve and the fourth control valve respectively;
the controller is used for receiving the ammonia nitrogen concentration signal sent by the ammonia nitrogen concentration detection device and controlling the first control valve, the second control valve, the third control valve and the fourth control valve to be opened and closed according to the ammonia nitrogen concentration signal detected by the ammonia nitrogen concentration detection device.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371184A (en) * | 2020-12-03 | 2021-02-19 | 北京碧水源膜科技有限公司 | Resin-based ammonium catalyst and preparation method and application thereof |
| CN113648991A (en) * | 2021-09-03 | 2021-11-16 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof |
| CN114620823A (en) * | 2022-03-22 | 2022-06-14 | 北京碧水源膜科技有限公司 | Water treatment system using ammonium catalyst |
| CN115367904A (en) * | 2022-05-17 | 2022-11-22 | 北京碧水源膜科技有限公司 | Water treatment facilities of ammonium catalyst can regenerate in circulation |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035489A1 (en) * | 2002-10-21 | 2004-04-29 | Andrzej Panuszewski | Method and apparatus for water treatment |
| CN103553237A (en) * | 2013-11-06 | 2014-02-05 | 西安建筑科技大学 | Process system for efficiently removing ammonia nitrogen in surface water |
| CN103553236A (en) * | 2013-11-06 | 2014-02-05 | 西安建筑科技大学 | Process system for removing ammonia nitrogen/alga in surface water by enhancing conventional treatment |
| CN105000653A (en) * | 2015-06-25 | 2015-10-28 | 西安建筑科技大学 | In-situ stripping method for filter material surface active oxide film |
| CN105000722A (en) * | 2015-06-17 | 2015-10-28 | 西安建筑科技大学 | System for preparing active filtering materials used for removing ammonia and nitrogen in water in catalysis and oxidation mode |
| CN105036288A (en) * | 2015-06-17 | 2015-11-11 | 西安唯源环保科技有限公司 | Method for synchronously removing high-concentration ammonia nitrogen, iron and manganese in water through reverse flow oxygenation multi-stage catalytic oxidation |
| CN108164102A (en) * | 2018-03-22 | 2018-06-15 | 北京科泰兴达高新技术有限公司 | A kind of water purification installation |
| CN109967026A (en) * | 2019-03-04 | 2019-07-05 | 浙江大学 | A kind of modified ammonia nitrogen absorption material and preparation method thereof |
| CN110818059A (en) * | 2019-11-29 | 2020-02-21 | 北京碧水源科技股份有限公司 | Non-photoelectric response composite deammoniation material, preparation method and application thereof in sewage deammoniation |
-
2020
- 2020-07-03 CN CN202010631558.5A patent/CN111804304A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004035489A1 (en) * | 2002-10-21 | 2004-04-29 | Andrzej Panuszewski | Method and apparatus for water treatment |
| CN103553237A (en) * | 2013-11-06 | 2014-02-05 | 西安建筑科技大学 | Process system for efficiently removing ammonia nitrogen in surface water |
| CN103553236A (en) * | 2013-11-06 | 2014-02-05 | 西安建筑科技大学 | Process system for removing ammonia nitrogen/alga in surface water by enhancing conventional treatment |
| CN105000722A (en) * | 2015-06-17 | 2015-10-28 | 西安建筑科技大学 | System for preparing active filtering materials used for removing ammonia and nitrogen in water in catalysis and oxidation mode |
| CN105036288A (en) * | 2015-06-17 | 2015-11-11 | 西安唯源环保科技有限公司 | Method for synchronously removing high-concentration ammonia nitrogen, iron and manganese in water through reverse flow oxygenation multi-stage catalytic oxidation |
| CN105000653A (en) * | 2015-06-25 | 2015-10-28 | 西安建筑科技大学 | In-situ stripping method for filter material surface active oxide film |
| CN108164102A (en) * | 2018-03-22 | 2018-06-15 | 北京科泰兴达高新技术有限公司 | A kind of water purification installation |
| CN109967026A (en) * | 2019-03-04 | 2019-07-05 | 浙江大学 | A kind of modified ammonia nitrogen absorption material and preparation method thereof |
| CN110818059A (en) * | 2019-11-29 | 2020-02-21 | 北京碧水源科技股份有限公司 | Non-photoelectric response composite deammoniation material, preparation method and application thereof in sewage deammoniation |
Non-Patent Citations (6)
| Title |
|---|
| 布浩等: "石英砂表面活性滤膜去除地下水中氨氮的试验研究", 《中国环境科学》 * |
| 张蓓蓓等: "不同挂膜时间铁锰复合氧化物活性滤料对地表水中氨氮去除效果的研究", 《成组技术与生产现代化》 * |
| 张蓓蓓等: "铁锰复合活性滤料去除冬季地表水中氨氮的效能", 《中国给水排水》 * |
| 朱月海, 同济大学出版社 * |
| 杨彦锋等: "逆向流充氧强化除地下水中高浓度氨氮的研究", 《中国环境科学》 * |
| 赵玉华等: "滤料组合方式对接触氧化法处理复合微污染地下水的影响", 《沈阳建筑大学学报(自然科学版)》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112371184A (en) * | 2020-12-03 | 2021-02-19 | 北京碧水源膜科技有限公司 | Resin-based ammonium catalyst and preparation method and application thereof |
| CN113648991A (en) * | 2021-09-03 | 2021-11-16 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrite nitrogen, preparation method and application thereof |
| CN113648991B (en) * | 2021-09-03 | 2023-11-03 | 北京碧水源膜科技有限公司 | Deamination catalyst capable of stably producing nitrous nitrogen, preparation method and application thereof |
| CN114620823A (en) * | 2022-03-22 | 2022-06-14 | 北京碧水源膜科技有限公司 | Water treatment system using ammonium catalyst |
| CN114620823B (en) * | 2022-03-22 | 2023-10-17 | 北京碧水源膜科技有限公司 | Water treatment system using ammonium catalyst |
| CN115367904A (en) * | 2022-05-17 | 2022-11-22 | 北京碧水源膜科技有限公司 | Water treatment facilities of ammonium catalyst can regenerate in circulation |
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Application publication date: 20201023 |