CN114105244A - Sewage purification system, sewage treatment system and sewage treatment method - Google Patents
Sewage purification system, sewage treatment system and sewage treatment method Download PDFInfo
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- CN114105244A CN114105244A CN202010906253.0A CN202010906253A CN114105244A CN 114105244 A CN114105244 A CN 114105244A CN 202010906253 A CN202010906253 A CN 202010906253A CN 114105244 A CN114105244 A CN 114105244A
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- 239000010865 sewage Substances 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 26
- 238000001179 sorption measurement Methods 0.000 claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000000463 material Substances 0.000 claims abstract description 69
- 239000003245 coal Substances 0.000 claims abstract description 48
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 26
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 9
- 239000011707 mineral Substances 0.000 claims abstract description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 8
- 239000002910 solid waste Substances 0.000 claims abstract description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 7
- 239000010457 zeolite Substances 0.000 claims abstract description 7
- 239000002734 clay mineral Substances 0.000 claims abstract description 5
- 239000010881 fly ash Substances 0.000 claims description 33
- 239000002699 waste material Substances 0.000 claims description 22
- 239000003463 adsorbent Substances 0.000 claims description 18
- 238000005065 mining Methods 0.000 claims description 10
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- 238000012856 packing Methods 0.000 claims description 4
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- 238000010521 absorption reaction Methods 0.000 claims description 3
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- 239000005995 Aluminium silicate Substances 0.000 claims description 2
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- 239000004113 Sepiolite Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052908 analcime Inorganic materials 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
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- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 2
- 229910052676 chabazite Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052621 halloysite Inorganic materials 0.000 claims description 2
- 229910052677 heulandite Inorganic materials 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229910052674 natrolite Inorganic materials 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910052679 scolecite Inorganic materials 0.000 claims description 2
- 229910052624 sepiolite Inorganic materials 0.000 claims description 2
- 235000019355 sepiolite Nutrition 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 16
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 15
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- 239000003513 alkali Substances 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000010883 coal ash Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000010802 sludge Substances 0.000 description 2
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
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- 235000020681 well water Nutrition 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—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
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/583—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
Abstract
The invention provides a sewage purification system which comprises a coal mine underground water reservoir filled with an adsorption material, wherein the adsorption material is selected from one or more of zeolite minerals, clay minerals and solid wastes. This sewage purification system uses through the cooperation of adsorbing material and colliery underground reservoir including filling the colliery underground reservoir that has the adsorbing material, can get rid of the pollutant in the sewage, especially can get rid of fluoride and heavy metal in the sewage.
Description
Technical Field
The invention relates to the field of water treatment, in particular to a sewage purification system, a sewage treatment system and a sewage treatment method.
Background
In recent years, mine water is more and more regarded as unconventional water resource, and particularly in western coal main producing areas of jin, shan an, Mongolia, Ning, Gansu and the like, the development of upstream and downstream industries of coal is severely restricted due to water resource shortage, and the mine water utilization work is vigorously carried out. With the deep development of the action plan for preventing and treating water pollution (ten water items), the supervision of mine water is gradually strengthened, and the mine water is required to be treated to reach the standard no matter the mine water is discharged or utilized under the current situation.
One important type of mine water is mine water containing special components, common mine water containing special components mainly comprises high-fluorine mine water and mine water containing heavy metals, and the flocculation-precipitation-filtration treatment process adopted by most of coal mines at present cannot effectively remove the special components. Fluoride and heavy metal in mine water are removed by adding an adsorption process to part of coal mines and utilizing the adsorption effect of an adsorption material.
However, the adsorption treatment method has a great defect, firstly, the price of the commonly used product-grade efficient adsorption material is generally high, and the treatment cost is always high. Secondly, the adsorption material gradually tends to be saturated in adsorption and finally loses working capacity after being used for a period of time, the ineffective adsorbent needs to be regenerated, the adsorption material is regenerated by using strong alkali or strong acid in the conventional method, waste liquid and sludge containing high-concentration pollutants are generated, a lot of waste materials belong to dangerous waste, and the waste materials also belong to dangerous waste after being regenerated and eliminated for many times, so that the treatment is difficult.
Disclosure of Invention
In order to solve the problems in the prior art, an object of the present invention is to provide a sewage purification system, which includes a coal mine underground reservoir filled with an adsorption material, and can remove pollutants in sewage, especially fluoride and heavy metals in sewage, by using the adsorption material and the coal mine underground reservoir in a matching manner.
The second purpose of the invention is to provide a sewage treatment system corresponding to the first purpose.
It is a further object of the present invention to provide an application corresponding to the above object.
The fourth object of the present invention is to provide a method for treating sewage corresponding to the above object.
In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:
a sewage purification system comprises a coal mine underground reservoir filled with adsorption materials,
wherein the adsorption material is selected from one or more of zeolite minerals, clay minerals and solid wastes.
Through research, the inventor of the application finds that the adsorbing material filled in the coal mine underground reservoir can generate a synergistic effect with a broken rock mass in the coal mine underground reservoir, and can purify sewage more effectively. In addition, when the adsorption material is filled into the coal mine underground reservoir, a front coal mining mode and a rear filling mode are generally adopted, and after the adsorption material is filled into a goaf, the adsorption material not only can play a role in purifying sewage, but also can achieve the effects of reducing mining damage and ground surface subsidence.
In some preferred embodiments of the present invention, the zeolite-based mineral is selected from one or more of analcime, scolecite, heulandite, natrolite, chabazite, and mordenite, the clay-based mineral is selected from one or more of kaolin, bentonite, montmorillonite, vermiculite and halloysite, sepiolite, palygorskite, and illite, and the solid waste is selected from one or more of fly ash, slag, alumina red mud, mining waste rock, concrete waste slag, and construction waste.
According to the invention, the zeolite minerals and the clay minerals are widely distributed in nature, have large reserves and low prices, and the solid wastes are cheap and easily obtained, so that the cost can be reduced by using the substances as the adsorption materials, and the substances can be directly discharged into underground goafs or abandoned roadways or used as underground yellow mud grouting materials after the adsorption materials are adsorbed and saturated without regeneration, thereby avoiding the defect of regeneration of the adsorption materials. Especially, the utilization of the fly ash and the slag also plays a role of treating wastes with wastes, and simultaneously solves the problem of treatment of the fly ash.
According to the invention, after the solid waste is subjected to physical and chemical modification treatment, the solid waste can have better ion exchange property and adsorbability, and the purification efficiency can be further improved. The physical and chemical modification treatment mode comprises one or more of acid modification, alkali modification, pyrogenic modification, oxide mixed modification and mineral modification.
In some preferred embodiments of the present invention, the adsorbent material has a particle size of 0.01mm to 1 mm.
According to the invention, in order to increase the contact area of the adsorption material and sewage such as mine water so as to improve the adsorption effect, the adsorption material is generally selected from granular or powdery, and meanwhile, as the main purpose is not to avoid subsidence damage and no requirement is required on the filling compactness, when the inclination angle of the goaf is large, the goaf can be filled by adopting self-sliding, and when the inclination angle of the goaf is small, the adsorption material can be blown into the goaf through a pipeline by adopting a wind filling process. Compared with the traditional gangue filling, the filling process of the adsorption material is simpler and is easy to realize.
In some preferred embodiments of the present invention, the packing ratio of the adsorbent material is 10% to 50%.
In some embodiments of the invention, the packing fraction of the adsorbent material is 20% to 40%.
In some embodiments of the invention, the packing fraction of the adsorbent material is 25% to 35%.
According to the present invention, the filling rate of the adsorbent may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any value therebetween.
According to the invention, the filling rate refers to the weight percentage of the filled adsorption material relative to the mined coal.
In some preferred embodiments of the invention, the length of the coal mine underground water reservoir is 500m to 3000 m; and/or the inclination angle of the coal mine underground reservoir is 0-15 degrees.
In some specific embodiments of the present invention, the length of the coal mine underground water reservoir is 1500m to 2500m, and preferably, the length of the coal mine underground water reservoir is 1800m to 2200 m.
In some embodiments of the invention, the angle of inclination of the coal mine underground reservoir is 0 ° to 5 °, preferably 0 ° to 2 °.
According to the invention, the coal mine underground reservoir is reconstructed from an underground goaf, and the coal pillar and the artificial dam body are utilized to form the underground reservoir. The coal mine underground reservoir has the characteristics of large area, large water storage capacity and capability of manually controlling the residence time of the mine water in the reservoir, and the broken rock mass in the reservoir has good purification effect on the mine water through the filtering, adsorbing and exchanging effects.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a sewage treatment system comprises the sewage purification system and an adsorption device which are sequentially connected, wherein the adsorption device is filled with the adsorption material.
According to the invention, the adsorption device can be used for treating the water which flows out of the sewage purification system and is treated by the sewage purification system again, and further removing residual pollution components, thereby achieving the synergistic effect with the sewage purification system.
In some preferred embodiments of the present invention, the adsorption device is selected from one or more of an adsorption tank, an adsorption bed, and an adsorption column.
According to the present invention, when the adsorption tanks are used as the adsorption device, the number and connection manner of the adsorption tanks are not limited, for example, the number of the adsorption tanks may be one or more, and the connection manner may be in series or in parallel, and may be selected by those skilled in the art as needed.
According to the invention, the adsorption material filled in the adsorption device can be the same as or different from the adsorption material filled in the coal mine underground water reservoir.
In some preferred embodiments of the present invention, the filling amount of the adsorbent material in the adsorption device is 100m3～5000m3。
According to the invention, the adsorption device may be arranged in a downhole tunnel.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
an application of the sewage purification system or the sewage treatment system in the field of water treatment, in particular the field of mine water treatment.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
a method for treating sewage comprises the following steps:
and introducing the sewage to be treated into the coal mine underground reservoir filled with the adsorption material or the coal mine underground reservoir filled with the adsorption material in the sewage treatment system, so as to obtain purified water at the outlet of the coal mine underground reservoir filled with the adsorption material or the outlet of the adsorption device.
According to the invention, the purified water can be used in the well for comprehensive utilization of production, life, ecological water, underground dust suppression, fire protection and the like.
According to the invention, the adsorption material can be transferred to an underground goaf or an exhaust gas roadway for storage after being adsorbed and saturated, and can also be used as an underground yellow mud grouting material.
In some preferred embodiments of the invention, the retention time of the sewage to be treated in the coal mine underground water reservoir filled with the adsorption material is 1-48 h, preferably 2-24 h; and/or the retention time of the sewage to be treated in the absorption device is 0.1-5 h, preferably 0.1-2 h.
In some preferred embodiments of the present invention, the wastewater to be treated is mine water.
In some preferred embodiments of the invention, the fluoride content in the mine water is 1mg/L to 10 mg/L; and/or the content of heavy metal is 0.1 mg/L-5 mg/L.
In some preferred embodiments of the invention, the heavy metal is selected from one or more of mercury, lead, cadmium, chromium and zinc.
The invention has the advantages that at least the following aspects are achieved:
(1) traditional adsorption method need use strong base or strong acid to carry out regeneration treatment to inefficacy adsorbent after adsorbent adsorption saturation, can produce waste liquid and the mud that contains the high concentration pollutant, and a lot of belong to dangerous discarded object, need to eliminate after adsorbing material regeneration is many times simultaneously, and the adsorbing material of eliminating also belongs to dangerous discarded object a lot, deals with comparatively difficultly. The invention adopts a method of one-time adsorption without regeneration to fix the waste adsorbent in the goaf or the waste roadway, thereby completely avoiding the defect of adsorbent regeneration.
(2) The method which adopts one-time adsorption and is not regenerated supports the selection of cheap natural minerals or fly ash and the like as the adsorption materials, and can reduce the mine water treatment cost. The method is particularly suitable for selecting the fly ash, can play a role of treating wastes with wastes, and solves the problem of treatment of the fly ash.
(3) The treatment method provided by the invention is completely underground, and compared with the traditional mine water ground treatment method, the treatment method saves the occupation of ground space.
(4) The coal mine underground reservoir has the characteristics of large water storage capacity, adjustable hydraulic retention time, self-purification effect and the like, and can realize large-scale and low-cost treatment of mine water.
(5) The adsorption material is filled into the goaf, so that the effect of reducing surface subsidence is achieved.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
FIG. 2 is a schematic view showing the filling of the adsorbent in example 1 of the present invention.
FIG. 3 is a schematic diagram of the mine water purification by the cooperation of the crushed rock mass and the adsorbing material in the underground coal mine reservoir in embodiment 1 of the invention.
Fig. 4 is a schematic view of mine water purification by the adsorption apparatus of embodiment 1 of the present invention.
FIG. 5 is a schematic view showing the steps of treating the waste adsorbent in example 1 of the present invention.
FIG. 6 is a bar graph of the effluent quality of example 1 of the present invention.
FIG. 7 is a bar graph of the effluent quality of example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available from commercial sources.
Example 1
As shown in fig. 1, the facility apparatus used in the present embodiment includes: the coal mine underground reservoir filled with the fly ash, wind power filling equipment used for filling the fly ash, an adsorption device consisting of 3 adsorption tanks, an underground clear water bin and a mixing pool used for mixing a waste adsorbent with mine water.
The embodiment is applied to a modernized ten-million-ton-level mine of a certain large coal-electricity base in the west. The mine generates about 5000m of well water every day3The mine water has the problem of excessive fluoride, the fluoride concentration is about 3.2mg/L, and the fluoride concentration standard of the permitted discharge and ecological recycling of the mine is 1.0 mg/L. The existing 'coagulation-precipitation-filtration' treatment of the mine cannot effectively reduce the fluoride concentration, so the mine water is treated by using the method.
The first step is to fill and store the adsorbing material, and fig. 2 is a schematic view of the filling of the adsorbing material. In the selection of the adsorbing material, because regeneration is not needed in one-time adsorption, requirements on material durability and the like are not high, and the power plant fly ash (with the particle size of 0.01-0.1 mm and without modification treatment) is selected as the adsorbing material in the embodiment. A large number of research and practice results show that the fly ash has good ion exchange property and adsorbability, and has good adsorption effect on fluoride in mine water. Because the coal ash storage yard is positioned in a large coal-electricity base and is nearby, a large amount of coal ash can be obtained only with low transportation cost. The fly ash is fine and light in particle, so that the method is suitable for a wind filling process, and the fly ash is blown into a goaf for filling through a pipeline by using air flow with certain pressure and certain initial speed as a power source. The existing mature equipment and process for wind power filling are simple and convenient to realize, and the filling cost is low. The mining surface of the mine has the length of about 2000m, the width of 100m and the mining height of 7m, and the mining height is about 140 ten thousand m3The coal of (2) can fill about 42 ten thousand m in terms of 30% filling rate3Fly ash.
The second step is coal mine underground water reservoir purification. Mine water produced underground is simply collected and then is pumped into a coal mine underground reservoir through a water pump. The crushed rock mass and the fly ash in the reservoir firstly play a role in filtering mine water, and effectively reduce suspended matters in the mine water, and fig. 3 is a schematic diagram of the mine water purification by the cooperation of the crushed rock mass and an adsorption material in the mine underground reservoir. As the mine water, the crushed rock mass and the fly ash are fully contacted, adsorption and exchange actions occur among the mine water, the crushed rock mass and the fly ash, and the fluoride concentration in the mine water can be effectively reduced. The adsorption mechanism of the fly ash to the fluoride ions is shown as the formula (1):
(Al2O3)n·H2SO4+2F-→(Al2O3)n·2HF+SO4 2-formula (1)
Adsorption capacity: the theoretical maximum saturated adsorption capacity qmax of the fly ash at 20 ℃ is 0.62mg/g calculated according to a langmuir model (shown as a formula (2)).
Wherein q iseIs the equilibrium adsorption capacity of fluorinion, mg/g; q. q.smMaximum saturated adsorption capacity, mg/g; ceIs the equilibrium concentration of fluorine ions, mg/L; b is a constant of Langmuir.
5000m per day3And (3) injecting all the mine water into the coal mine underground reservoir, wherein the average stay time of the mine water in the reservoir is about 8 hours, and the average fluoride concentration of the outlet water can be reduced to about 1.2mg/L (as shown in figure 6) by continuously monitoring the operation of the outlet water. The fly ash in the reservoir reaches adsorption saturation after about 4 months, and at the moment, a new working face finishes mining and is filled with the fly ash, so that the fly ash can be used as a new coal mine underground reservoir for treating mine water.
The third step is a post-library enhancement process, which is schematically illustrated in FIG. 4. After mine water is purified by a coal mine underground reservoir, the fluoride concentration is effectively reduced to 1.2mg/L, but still exceeds the standard requirement of 1.0 mg/L. The mine water that flows out colliery underground reservoir pours into through the water pump and strengthens adsorption equipment in the pit (promptly strengthen the absorption processing apparatus in the pit), and this embodiment uses 3 columniform adsorption tanks to establish ties and constitutes and strengthen adsorption equipment in the pit, and every cylinder adsorption tank height is 5m, and bottom surface area 48m2Can hold 240m3Adsorbing the material. The adsorption material is modified by small granular Polymeric Ferric Sulfate (PFS) with the grain diameter of 0.5-1mmThe adsorption capacity of the zeolite is calculated according to a Langmuir model shown in the formula (2) that the maximum saturated adsorption capacity is 9.72mg/g, the adsorption rate of mine water staying in a tank body for about 0.5 hour is about 56%, and the fluoride concentration in the mine water can be reduced to 0.6mg/L (shown in figure 6). The requirements of underground production, ecological irrigation in mining areas or discharged water quality are met.
The fourth step is the waste adsorbent treatment, which is schematically shown in fig. 5. The underground reinforced adsorption device can process 5000m of the oil per day3The modified zeolite adsorbing material used for mine water reaches adsorption saturation in about 10 days, and the adsorbing material is not subjected to treatment and is directly replaced by a new adsorbing material. The changed waste adsorbing materials are discharged into a special mixing tank and mixed with mine water flowing out of an underground reservoir in the tank, and the adsorbing materials are mixed with the water in small granular forms and then discharged into a goaf or a waste roadway by using a sludge pump or used as an underground yellow mud grouting material.
Example 2
Example 2 the same purification system and purification method as in example 1 was used except that the fluoride concentration in the mine water was increased from 3.2mg/L to 6.1 mg/L. Due to the improvement of the fluoride concentration, the adsorption rate of the fly ash to the fluoride is correspondingly improved, after the mine water stays in the reservoir for about 8 hours, the fluoride concentration of the water discharged from the reservoir can be reduced to about 3.3mg/L, the mine water stays in the tank body for about 1.5 hours, the fluoride concentration of the mine water can be reduced to 0.9mg/L, and the effluent quality characteristics are shown in figure 7.
Comparative example 1
Comparative example 1 the treatment capacity of the coal mine underground water reservoir in example 1 for mine water before filling with the adsorbing material was examined.
The adsorption system used in comparative example 1, i.e., the coal mine underground reservoir in example 1, having the dimensions "about 2000m long, 100m wide and 7m high in mining face". Mine water with fluoride concentration of about 3.2mg/L and the same fluoride concentration as in example 1 is added for about 5000m3And (3) introducing the coal mine underground reservoir in the comparative example 1, and after the mine water stays in the reservoir for about 8 hours on average, reducing the fluoride concentration of the water discharged from the reservoir to 2.9 mg/L.
Comparative example 2
Comparative example 2 the ability of fly ash to adsorb fluoride ions was investigated.
80g of the fly ash used in example 1 was placed in a 100mL beaker, and 50g of the mine water used in example 1 was added to the beaker, with the surface of the mine water being below the fly ash and in sufficient contact with the fly ash (in a state similar to that in example 1). After standing for 8 hours, the fluoride concentration of the mine water is reduced from 3.2mg/L to about 1.9 mg/L.
Comparative example 3
Comparative example 3 was set to be substantially the same as comparative example 1 except that the mine water used in comparative example 3 was the same as that used in example 2. Specifically, the same mine water with fluoride concentration of about 6.1mg/L as that of example 2 is mixed for about 5000m3And (3) introducing the coal mine underground reservoir in the comparative example 1, and after the mine water stays in the reservoir for about 8 hours on average, reducing the fluoride concentration of the water discharged from the reservoir to 5.6 mg/L.
Comparative example 4
Comparative example 4 the ability of fly ash to adsorb fluoride ions was examined.
80g of the fly ash used in example 2 was placed in a 100mL beaker, and 50g of the mine water used in example 2 was added to the beaker, with the surface of the mine water being below the fly ash and in sufficient contact with the fly ash (in a state similar to that in example 2). After standing for 8 hours, the fluoride concentration of the mine water is reduced from 6.1mg/L to about 4.2 mg/L.
Comparing the data of example 1 and comparative examples 1 to 2 and the data of example 2 and comparative examples 3 to 4, it can be seen that the defluorination effect can be improved by utilizing the synergistic effect between the coal mine underground reservoir and the fly ash after the fly ash is filled in the coal mine underground reservoir.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A sewage purification system comprises a coal mine underground reservoir filled with adsorption materials,
wherein the adsorption material is selected from one or more of zeolite minerals, clay minerals and solid wastes, preferably, the zeolite minerals are selected from one or more of analcime, scolecite, heulandite, natrolite, chabazite and mordenite, the clay minerals are selected from one or more of kaolin, bentonite, montmorillonite, vermiculite and halloysite, sepiolite, palygorskite and illite, and the solid wastes are selected from one or more of fly ash, slag, alumina red mud, mining waste stones, concrete waste residues and construction waste materials.
2. The sewage purification system according to claim 1, wherein the particle size of the adsorption material is 0.01mm to 1 mm; and/or the packing ratio of the adsorbent is 10% to 50%, preferably 20% to 40%, more preferably 25% to 35%.
3. The sewage purification system according to claim 1 or 2, wherein the length of the coal mine underground water reservoir is 500m to 3000 m; and/or the inclination angle of the coal mine underground reservoir is 0-15 degrees.
4. A sewage treatment system comprising the sewage purification system according to any one of claims 1 to 3 and an adsorption device connected in series, wherein the adsorption device is filled with the adsorption material.
5. The wastewater treatment system of claim 4, wherein the adsorption device is selected from one or more of an adsorption tank, an adsorption bed, and an adsorption tower.
6. Sewage treatment system according to claim 4 or 5, characterised in that the adsorbent material is filled in the adsorbent device in an amount of 100m3～5000m3。
7. Use of a sewage purification system according to any of claims 1 to 3 or of a sewage treatment system according to any of claims 4 to 6 in the field of water treatment, in particular in the field of mine water treatment.
8. A method for treating sewage comprises the following steps:
passing the sewage to be treated into the coal mine underground reservoir filled with the adsorption material according to any one of claims 1 to 3 or the coal mine underground reservoir filled with the adsorption material in the sewage treatment system according to any one of claims 4 to 6, thereby obtaining purified water at an outlet of the coal mine underground reservoir filled with the adsorption material or an outlet of the adsorption device.
9. The treatment method according to claim 8, wherein the retention time of the sewage to be treated in the coal mine underground water reservoir filled with the adsorption material is 1-48 h, preferably 2-24 h; and/or the retention time of the sewage to be treated in the absorption device is 0.1-5 h, preferably 0.1-2 h.
10. The treatment method according to claim 8 or 9, wherein the sewage to be treated is mine water, preferably the mine water has a fluoride content of 1mg/L to 10 mg/L; and/or the content of heavy metal is 0.1 mg/L-5 mg/L, and more preferably, the heavy metal is selected from one or more of mercury, lead, cadmium, chromium and zinc.
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