CN114751563B - A step purifying filter for getting rid of acid mine in water sulphate - Google Patents

A step purifying filter for getting rid of acid mine in water sulphate Download PDF

Info

Publication number
CN114751563B
CN114751563B CN202210663873.5A CN202210663873A CN114751563B CN 114751563 B CN114751563 B CN 114751563B CN 202210663873 A CN202210663873 A CN 202210663873A CN 114751563 B CN114751563 B CN 114751563B
Authority
CN
China
Prior art keywords
filter
filter material
purification filter
material unit
primary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210663873.5A
Other languages
Chinese (zh)
Other versions
CN114751563A (en
Inventor
尹兆龙
尹希杰
赵春红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing North Hongtuo Environmental Technology Co ltd
Original Assignee
Beijing North Hongtuo Environmental Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing North Hongtuo Environmental Technology Co ltd filed Critical Beijing North Hongtuo Environmental Technology Co ltd
Priority to CN202210663873.5A priority Critical patent/CN114751563B/en
Publication of CN114751563A publication Critical patent/CN114751563A/en
Application granted granted Critical
Publication of CN114751563B publication Critical patent/CN114751563B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211—Compounds of Ti, Zr, Hf
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/165—Natural alumino-silicates, e.g. zeolites
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • 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
    • C02F2101/101—Sulfur 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/203—Iron or iron compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/206—Manganese or manganese compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a step purifying filter for removing sulfate in acid mine water, which comprises a primary purifying filter, a secondary purifying filter and a tertiary purifying filter, wherein three different filter material units are arranged in the primary purifying filter, so that suspended matters and macromolecular pollutants in a water body can be primarily removed, and four unit modules are staggered in the secondary purifying filter, so that pollutants such as sulfate and the like can be pertinently adsorbed; two stirring devices and an inclined tube sedimentation tank are arranged in the three-stage purification filter tank, so that impurities can be further precipitated, and a water body can be purified. The invention carries out gradient purification by three purification filters with different structures, adopts the S-shaped step purification filter, can effectively reduce the operation load of equipment while prolonging the hydraulic retention time by the height difference of the filter and the design of the turn-back type water flow, and has simple structure, small occupied area and convenient operation and transportation.

Description

A step purifying filter for getting rid of acid mine in water sulphate
Technical Field
The invention belongs to the technical field of advanced wastewater treatment, and particularly relates to a stepped purification filter for removing sulfate in acid mine water.
Background
In the process of mine production and exploitation, due to the fact that a large amount of sulfur-containing waste rocks and tailings are exposed for a long time and rain wash causes spontaneous oxidation of sulfide minerals, pH of mine water is gradually reduced, dissolution and migration of metal ions in various mine wastes are further aggravated, water bodies contain a large amount of Fe ions and sulfate ions, and potential harm is caused to surface water and underground water ecological environments.
At present, the treatment method aiming at the acid mine wastewater mainly comprises a physical and chemical method (such as ion exchange, adsorption and magnetic separation), an artificial wetland method and a microbiological method. Wherein, chemical precipitationThe precipitation method is the most widely applied method, but the disadvantages of large sludge amount and easy secondary pollution exist by singly adding chemical agents to adjust the pH and precipitating metal ions. Aiming at the characteristics of uneven dispersion, poor water quality, small scale and the like of the acid mine water, the adsorption method has obvious advantages in the treatment of the acid mine wastewater due to the characteristics of high efficiency, simplicity and convenience. The natural zeolite is a class of adsorption materials which are applied more at present due to the fact that the natural zeolite has silicon and aluminum groups, however, the silicon-aluminum structure has negative charges, the adsorption efficiency of the natural zeolite on anionic pollutants in a water body is low, and the practical application value of the natural zeolite is reduced due to the defect. Therefore, it is necessary to modify natural zeolite to improve the adsorption performance of zeolite to anions by changing the active groups and cation types of zeolite and increasing the number of positive surface charges. The first prior art discloses a novel sulfate adsorbing material which is prepared by modifying quartz and is used for adsorbing SO in water 4 2- The adsorption effect is obvious. In the second prior art, the fly ash and the sodium carbonate are used for modifying the zeolite, so that the positive charges on the surface of the zeolite are increased, and the removal effect on phosphate is further increased. In the prior art, cationic surfactant and hydroxyapatite are utilized to modify zeolite, so that a high-efficiency zeolite adsorption material capable of adsorbing heavy metals and organic matters is prepared. Other relevant studies include modification studies of zeolites using multiple parameters such as metals (e.g., zirconium, aluminum, lanthanum, copper, etc.), surfactants (e.g., cetylpyridinium bromide), and pH.
However, most of the current researches on modification of zeolite are mainly to enhance the removal capability of zeolite to metal cations, organic matters, ammonia nitrogen and other substances, while a small part of the researches are to achieve the purpose of removing F ions and phosphate ions in water by increasing positive charges on the surface of zeolite, and the modified zeolite is rarely used for removing sulfate ions, and has the problems of complex preparation process, high cost, strict requirements on application conditions and the like.
Disclosure of Invention
The invention aims to provide a stepped purification filter for removing sulfate in acid mine water, aiming at the characteristics of poor acid mine water quality and large water quality and water quantity fluctuation generated after pit closure in mining, and combining a special S-shaped structure and a filter material, the problems of high treatment cost, low efficiency and easy generation of secondary pollution of the closed-pit acid mine water can be solved.
In order to achieve the aim, the invention provides a step purifying filter for removing sulfate in acid mine water, which comprises a primary purifying filter, a secondary purifying filter and a tertiary purifying filter, wherein the primary purifying filter, the secondary purifying filter and the tertiary purifying filter are sequentially connected through a wall plate, the primary purifying filter is connected with a water inlet system, and the primary purifying filter is sequentially provided with a primary filter material unit, a secondary filter material unit and a tertiary filter material unit from top to bottom;
the side wall of the secondary purification filter tank is provided with four unit modules in a staggered manner, a modified acid-resistant sulfate adsorption filter material is arranged in each unit module, the modified acid-resistant sulfate adsorption filter material is a mixture of hydrated lime and modified zeolite, and the proportion of the modified zeolite is increased from top to bottom; the three-stage purification filter is provided with an inclined tube sedimentation tank and a stirring device.
Preferably, the mixing volume ratio of the hydrated lime and the modified zeolite of the modified acid-resistant sulfate adsorption filter material is 1:2, 1:3, 1:4 and 1:5 from top to bottom in sequence.
Further, the volume ratio of the first-stage filter material unit to the second-stage filter material unit to the third-stage filter material unit is 1-2: 1-2, and the total volume of the first-stage filter material unit to the second-stage filter material unit to the third-stage filter material unit accounts for 30-40% of that of the first-stage purification filter; the primary filter material unit, the secondary filter material unit and the tertiary filter material unit are all fixed on the side wall of the primary purification filter tank through a hoop;
the primary filter material unit, the secondary filter material unit and the tertiary filter material unit are all fixed on the side wall of the primary purification filter tank through clamps and all comprise external stainless steel nets and filter materials wrapped by the stainless steel nets, the filter materials of the primary filter material unit are mixtures formed by mixing coal gangue fragments and limestone fragments according to the volume ratio of 3: 2-4: 2, and the particle sizes of the coal gangue fragments and the limestone fragments are 5-10 cm.
Preferably, the volume ratio of the first-stage filtering material unit, the second-stage filtering material unit and the third-stage filtering material unit is 1:1: 1.
Furthermore, the filter material of the secondary filter material unit is a mixture formed by mixing coal gangue fragments, gravel fragments and limestone fragments according to a volume ratio of 3-5: 2:2, and the particle sizes of the coal gangue fragments, the gravel fragments and the limestone fragments are 3-5 cm.
Furthermore, the filter material of the third-stage filter material unit is a mixture of natural clinoptilolite, limestone and montmorillonite mixed according to the volume ratio of 1-2: 2:2, the particle size of the natural clinoptilolite is 0.8-2 cm, preferably 0.8-1.5 cm, and the particle size of the limestone and the montmorillonite is 2-4 cm.
Furthermore, the water inlet system comprises a water inlet pump, a water inlet pipeline, a flow meter and a flow regulating valve, wherein the water inlet pipeline penetrates through the water inlet pump to be connected with the primary purification filter, and the flow meter and the flow regulating valve are arranged at the water inlet of the primary purification filter.
Further, the modified zeolite is prepared by the following method:
(1) grinding and sieving natural clinoptilolite and quartz, soaking in an alkali solution, cleaning and drying for later use;
(2) soaking the mixture prepared in the step (1) in acid mine water, adjusting the pH value to 4-5, adding zirconium oxychloride, and stirring and soaking for 12-18 h;
(3) adding an iron-containing solution and an alkali solution into the solution obtained in the step (2), adjusting the pH value to be more than 8.0, and continuously stirring for 8-12 h; the iron-containing solution is preferably an iron chloride hexahydrate solution;
(4) and (4) separating the solution obtained in the step (3), cleaning the filter material, and draining to obtain the filter material.
Preferably, the separation method is a magnetic separation method, and filling is needed after draining, wherein the filling method comprises the following steps: the filter material can be filled into a nylon porous filter screen without drying after being drained, and is filled and applied, and the filled material structure is spherical.
Further, the alkali solution is a sodium hydroxide solution with the concentration of 0.05-0.15 mol/L, and the mass ratio of the zirconium oxychloride to the mixture in the step (2) is 8-10: 1.
Furthermore, the particle size of the natural clinoptilolite is 0.5-1.2 cm, preferably 0.7-1.0 cm, the particle size of the quartz is 0.2-0.6 cm, the volume ratio of the natural clinoptilolite to the quartz is 3-4: 1, and the volume ratio of the mixture to the acid mine water is 1: 10-15.
Further, the bottom of the second-stage purification filter is provided with a water inlet pipe communicated with the first-stage purification filter, a high-pressure pump is arranged on the water inlet pipe, and the bottoms of the first-stage purification filter, the second-stage purification filter and the third-stage purification filter are respectively provided with a drain A, a drain B and a drain C.
Further, the second grade purification filtering pond left and right sides and tertiary purification filtering pond right side do not are provided with overflow weir A, overflow weir B and overflow weir C in high difference punishment, and agitating unit is including agitating unit A who is located the pipe chute sedimentation tank top and agitating unit B who is located the pipe chute sedimentation tank below, and overflow weir C sets up in the pipe chute sedimentation tank lateral wall, and overflow weir A is higher than overflow weir B, and overflow weir B is higher than overflow weir C.
Preferably, the inclined tube sedimentation tank is made of materials used in the conventional water treatment process, such as PP, PVC or FRP materials; the volume ratio of the inclined tube sedimentation tank to the three-stage purification filter tank is preferably 1: 1.
In conclusion, the invention has the following advantages:
1. the invention aims at the problems of low pH, high acidity and Fe of acidic mine water 2+ /Fe 3+ The problem of high content of ions and sulfate is that a step purifying filter for removing sulfate in acid mine water is provided, which comprises a primary purifying filter, a secondary purifying filter and a tertiary purifying filter, wherein the primary purifying filter adopts the advantage combination of natural mineral adsorbing materials, mineral filtering materials with different particle sizes are respectively arranged along the water flow direction from top to bottom, and the functions of primarily adjusting pH and adsorbing and removing suspended matters and macromolecular pollutants are achieved;
the secondary purification filter tank is provided with 4 acid-resistant sulfate adsorption filter material units in a staggered manner, and the mixed carrier of the ferric hydroxide/zirconium modified zeolite filter material and hydrated lime particles is adopted, so that the stepped pH adjustment, sulfate purification and regeneration of iron hydroxide on the surface of modified zeolite of the secondary filter tank from bottom to top can be realized, and the secondary purification filter tank has a good adsorption effect, a long application period and a certain regeneration capacity.
2. The ball-type filled acid-resistant sulfate adsorption filter material prepared by the invention is a multifunctional adsorption material integrating micropores into mesopores, and can simultaneously purify and adsorb pollutants and anions with different molecular weights, such as fluoride ions, sulfate ions, iron, manganese and other heavy metals.
3. The S-shaped step purification filter tank adopted by the invention can effectively reduce the operation load of equipment while prolonging the hydraulic retention time through the height difference of the filter tank and the design of the turn-back water flow, and has the advantages of simple structure, small occupied area and convenient operation and transportation.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a surface SEM image of a modified zeolite prepared in example 1;
FIG. 3 is an EDS spectrum of the modified zeolite obtained in example 1;
FIG. 4 is a graph of adsorption capacity before and after zeolite modification at different pH;
FIG. 5 shows the effect of the amount of addition on the adsorption effect of sulfate;
wherein, 1-a water inlet pipeline; 2-a water inlet pump; 3-water quantity regulating valve; 4-first-stage filtering material unit; 5-a secondary filtering material unit; 6-three-stage filtering material units; 7-water inlet pipe; 8-a high pressure pump; 9-a unit module; 10-overflow weir a; 11-overflow weir B; 12-an inclined tube sedimentation tank; 13-stirring device a; 14-stirring means B; 15-sewage draining exit A; 16-a sewage draining exit B; 17-weir C; 18-sewage draining exit C; 19-clamping hoop.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. 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 commercially.
Example 1
The embodiment provides a step purification filter for removing sulfate in acid mine water, which comprises a first-stage purification filter, a second-stage purification filter and a third-stage purification filter which are connected in sequence, wherein the three filters are connected by a wall plate.
The specific structure is shown in figure 1:
the one-level purification filter is connected with water inlet system, and water inlet system includes intake pump 2, inlet channel 1, flowmeter and flow control valve 3, and wherein inlet channel 1 passes intake pump 2 and is connected with the one-level purification filter, and the flowmeter sets up in the water inlet of one-level purification filter with flow control valve 3.
Wherein, the one-level purifying filter includes three group's filter material units, includes one-level filter material unit 4, second grade filter material unit 5 and tertiary filter material unit 6 from last to down in proper order, and three group's filter material units comprise by the double-deck stainless steel net cage that the aperture is 1.0cm, are fixed in one-level purifying filter both sides wall by clamp 19. Coal gangue and limestone fragments with the particle size of 6-8 cm are filled in the primary filtering material unit, and the filling volume ratio is 3: 2. Coal gangue, gravel and limestone with the particle size of 3-5 cm are filled in the secondary filter material unit, and the filling volume ratio is 2:1: 1. The natural clinoptilolite, limestone and montmorillonite are filled in the third-stage filter material unit, the average grain sizes are 1.5cm, 2.0cm and 3.0cm respectively, and the filling volume ratio is 1:2: 2.
Preferably, the total volume of the first-stage filtering material unit 4, the second-stage filtering material unit 5 and the third-stage filtering material unit 6 is 1/3 of the first-stage purification filter.
Wherein, be provided with 4 unit modules 9 in the second grade purification filtering pond, stagger setting respectively on the left and right sides pond wall of second grade purification filtering pond. The device comprises a first-level unit module, a second-level unit module, a third-level unit module and a fourth-level unit module from top to bottom in sequence. All filled with modified acid-proof sulfate adsorption filter material in 4 unit modules 9, fill modified acid-proof sulfate adsorption filter material by 2 layers of stainless steel nets that the aperture is 1cm and constitute, waste water can fully contact with adsorption filter material after bottom injection.
The modified acid-resistant sulfate adsorption filter material is a mixture of hydrated lime and modified zeolite, and the volume ratio of the hydrated lime to the modified zeolite in the first-stage unit module, the second-stage unit module, the third-stage unit module and the fourth-stage unit module is 1:2, 1:3, 1:4 and 1:5 respectively.
Wherein the modified zeolite is prepared by the following method:
(1) crushing, grinding and sieving natural clinoptilolite and quartz, soaking in 0.1mol/L NaOH solution, washing with deionized water, and drying for later use; wherein the particle size of the sieved zeolite particles is 0.8cm, the particle size of the sieved quartz particles is 0.5cm, and the volume ratio of the zeolite to the quartz is 3.5: 1;
(2) putting the zeolite and quartz mixture obtained in the step (1) into acidic mine water, and adding a dilute hydrochloric acid solution to adjust the pH value to 4.5; the volume ratio of the zeolite and quartz mixture to the acid mine water is 1: 12;
(3) adding proper amount of ZrOCl into the product obtained in the step (2) 2 Continuously soaking and stirring at constant speed for 15 h; ZrOCl 2 The addition amount of the agent is that the mass ratio of the zeolite to the quartz mixture is 10: 1;
(4) adding a proper amount of FeCl into the mixture liquid obtained in the step (3) 3 ·6H 2 O medicament and 0.1mol/L sodium hydroxide solution, wherein the mass ratio of Fe to Zr in the mixed solution is 1:1, adjusting the pH value of the mixed solution to be more than 8, and continuously stirring for 10 hours;
(5) separating the mixed material liquid obtained in the step (4) by a magnetic separation method, and cleaning the separated filter material by deionized water for 2-3 times;
(6) and (4) draining the filter material obtained in the step (5), then filling the filter material into a nylon porous filter screen without drying, and filling and applying the filter material.
Wherein, the bottom of the second-stage purification filter is provided with a water inlet pipe 7 which is communicated with the bottom of the first-stage purification filter, and the water inlet pipe is provided with a high-pressure pump 8. The high-pressure pump 8 can pump the wastewater treated by the primary purification filter into the secondary purification filter for further treatment.
Preferably, a sewage draining exit A15, a sewage draining exit B16 and a sewage draining exit C18 are respectively arranged at the bottoms of the primary purifying filter, the secondary purifying filter and the tertiary purifying filter, and can be used for cleaning, slag discharging and the like.
Wherein, be provided with two agitating unit and pipe chute sedimentation tank 12 in the tertiary purification filtering pond, wherein agitating unit A13 sets up in pipe chute sedimentation tank 12 top, and agitating unit B14 sets up in pipe chute sedimentation tank 12 below. As can be seen from fig. 1, in the preferred embodiment of the present invention, the right walls of the primary, secondary and tertiary clarifying filters are sequentially provided with an overflow weir a 10, an overflow weir B11 and an overflow weir C17, and in order to ensure the overflow effect, the height of the overflow weir a 10 is sequentially higher than that of the overflow weir B11 and the overflow weir C17. The wastewater overflowed from the overflow weir C17 can be discharged out of the step purification filter for removing the sulfate in the acid mine water.
The use method of the cascade purification filter for removing sulfate in acid mine water provided by the embodiment comprises the following steps:
acid mine water enters a primary purifying filter through a water inlet pump 2 and a water inlet flow regulating valve 3 in a water inlet pipeline 1 and respectively flows through a primary filtering material unit 4, a secondary filtering material unit 5 and a tertiary filtering material unit 6 from top to bottom;
the wastewater primarily purified by the primary purification filter is injected into the secondary purification filter through a bottom water inlet pipe 7 and a high-pressure pump 8. Wherein 4 groups of acid-resistant sulfate adsorption filter material unit modules 9 are arranged in the secondary purification filter tank in a staggered manner, and the wastewater can be fully contacted with the adsorption filter material after being injected from the bottom. The top parts of the two sides of the secondary purification filter tank are provided with an overflow weir A10 and an overflow weir B11 with certain height difference so as to ensure water circulation;
the wastewater flows into the third-level purification filter tank through the overflow weir B11 after being adsorbed and purified by the second-level purification filter tank, and is precipitated by the PVC inclined tube sedimentation tank 12, and the purified water is discharged from the overflow weir C17.
Particularly, the three-stage purification filter is provided with a stirring device A13 and a stirring device B14, and the water body in the three-stage purification filter can be uniformly stirred. The bottoms of the first-stage purifying filter, the second-stage purifying filter and the third-stage purifying filter are provided with drain outlets for cleaning, deslagging and the like.
Test example 1
The surface SEM and XRD pattern results of the modified zeolite prepared in example 1 of the present invention are shown in fig. 2 and 3.
As can be seen from FIGS. 2 and 3, the surface of the filter material is porous, and the pore size distribution varies from tens of nanometers to hundreds of nanometers, so that a porous adsorption material is formed, and the specific surface area of the adsorption material is greatly increased. EDS results further prove that the surface of the modified zeolite prepared by the invention is covered with elements such as Fe, Zr and the like. In addition, because the surface of the zeolite is attached with iron hydroxide and zirconium metal, the surface of the modified zeolite has a large number of positive charges and cationic metal sites, and the adsorption performance of the modified zeolite on sulfate and other anions can be further improved.
It is worth mentioning that the preparation of the ferric hydroxide/Zr modified zeolite by the invention utilizes Fe in acid mine water 3+ 、Fe 2 + And added FeCl 3 ·6H 2 And (4) an O agent. Firstly, acidizing pretreatment is carried out by utilizing acid mine water, and if the pH value does not reach the standard, the acid mine water can be adjusted by using dilute hydrochloric acid; secondly, ZrOCl is adopted 2 Activating zeolite, and loading Zr ions on the surface of the zeolite; finally by adding Fe 3+ Realization of Fe (OH) 3 Is loaded excessively. It is noted that the modified zeolite of the invention does not need drying treatment, and can be directly filled in acid mine water after being loaded, and a layer of stable Fe exists around the surface of the zeolite 3+ The positive charge micelle system can be further used for adsorbing sulfate radical anions. In addition, the second-stage purifying filter chamber is filled with modified zeolite and hydrated lime in different proportion, and the filter material can fully ensure Fe in mine water in the operation process 2+ And Fe 3+ In OH - The zeolite surface carrier is continuously accumulated and deposited on the surface of the zeolite under the condition, so that the storage life of the modified zeolite surface carrier is greatly prolonged.
Test example 2
The adsorption performance test of the modified zeolite prepared in example 1 of the present invention includes: the modified zeolite of the invention and the natural zeolite before modification are used for verifying the sulfate ion adsorption capacity in different pH environments under the same conditions, and the adsorption curve is shown in figure 4.
As can be seen from FIG. 4, the zeolite prepared by the invention has an obvious adsorption effect on sulfate under the acidic condition of pH, and when the pH is 3-7, the adsorption capacity is 25.5-16.4 mg/g, which is much higher than that of the zeolite before modification (12.4-8.1 mg/g), so that the zeolite has a larger adsorption performance. This is mainly the active Fe under acidic conditions (OH) 3 The surface exists in a colloidal ion form, a positively charged colloidal particle group is formed, and sulfate ions can be effectively adsorbed.
Test example 3
In a specific application verification case, in an experiment comparing the adding amount of the natural zeolite and the modified zeolite, when the initial sulfate concentration is 100mg/L, 5-35 g of zeolite filter material is respectively added, and the removal rate after 5 hours of reaction time is shown in fig. 5.
When the adding amount of the filter material is 25g/L, the removal rate of the modified zeolite to sulfate is 78.8 percent, which is 34.6 percent higher than that of the natural zeolite. The modified zeolite of the invention has greatly improved adsorption efficiency and adsorption capacity to sulfate under the modification of ferric hydroxide and zirconium.
Test example 4
In another specific application case, acid mine water in a certain closed pit mining area is used as raw water, and the water quality characteristics are as follows: the pH =4.1, the fluoride ion concentration is 3.6mg/L, the sulfate concentration is 852mg/L, and the ferric ion concentration is 28.6 mg/L; after the wastewater respectively flows out of the overflow weir C17 from the water inlet pipeline 1 to the inclined tube sedimentation tank 12, the effluent quality effects under the influence of different hydraulic retention time are shown in Table 1.
TABLE 1 effluent quality Effect under influence of different Hydraulic Retention times
Hydraulic retention time (h) Sulfate concentration (mg/L) Removal rate (. times.100%)
1 668 0.22
2 522 0.39
3 437 0.49
4 355 0.58
5 278 0.67
6 272 0.68
7 283 0.67
8 265 0.69
It can be found that the optimal hydraulic retention time parameter of the filter chamber is determined by controlling the inflow and the flow rate by adjusting the inflow pump 2 and the inflow adjusting valve 3. When the hydraulic retention time is 5 hours, the sulfate removal effect is optimal, the pH value of the effluent is 6.8, the fluorine ion concentration is 0.7mg/L, the sulfate concentration is 319mg/L, the ferric ion concentration is 0.8mg/L, and the effluent quality is stable after continuous operation.
While the present invention has been described in detail with reference to the specific embodiments thereof, it should not be construed as limited by the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.

Claims (8)

1. A step purification filter for removing sulfate in acid mine water is characterized by comprising a primary purification filter, a secondary purification filter and a tertiary purification filter, wherein the primary purification filter, the secondary purification filter and the tertiary purification filter are sequentially connected through a wall plate, the primary purification filter is connected with a water inlet system, and the primary purification filter is sequentially provided with a primary filter material unit, a secondary filter material unit and a tertiary filter material unit from top to bottom;
the side wall of the secondary purification filter tank is provided with four unit modules in a staggered manner, a modified acid-resistant sulfate adsorption filter material is arranged in each unit module, the modified acid-resistant sulfate adsorption filter material is a mixture formed by mixing hydrated lime and modified zeolite, and the volume ratio of the modified zeolite in the mixture is increased from top to bottom; an inclined tube sedimentation tank and a stirring device are arranged in the third-stage purification filter;
the volume ratio of the first-stage filter material unit to the second-stage filter material unit to the third-stage filter material unit is 1-2: 1-2, and the total volume of the first-stage filter material unit to the second-stage filter material unit to the third-stage filter material unit accounts for 30-40% of that of the first-stage purification filter; the primary filter material unit, the secondary filter material unit and the tertiary filter material unit are all fixed on the side wall of the primary purification filter tank through a hoop;
the primary filter material unit, the secondary filter material unit and the tertiary filter material unit respectively comprise an external stainless steel mesh and a filter material wrapped by the stainless steel mesh, the filter material of the primary filter material unit is a mixture formed by mixing coal gangue fragments and limestone fragments according to a volume ratio of 3-4: 2, and the particle sizes of the coal gangue fragments and the limestone fragments are 5-10 cm;
the modified zeolite is prepared by the following method:
(1) grinding and sieving natural clinoptilolite and quartz, soaking in an alkali solution, cleaning and drying for later use;
(2) soaking the mixture prepared in the step (1) in acid mine water, adjusting the pH value to 4-5, adding zirconium oxychloride, and stirring and soaking for 12-18 h;
(3) adding an iron-containing solution and an alkali solution into the solution obtained in the step (2), adjusting the pH value to be more than 8.0, and continuously stirring for 8-12 h;
(4) and (4) separating the solution obtained in the step (3), cleaning the filter material, and draining to obtain the filter material.
2. The cascade purification filter tank for removing sulfate in acid mine water as claimed in claim 1, wherein the filter material of the secondary filter material unit is a mixture of coal gangue fragments, gravel fragments and limestone fragments mixed according to a volume ratio of 3-5: 2:2, and the particle sizes of the coal gangue fragments, the gravel fragments and the limestone fragments are all 3-5 cm.
3. The cascade purification filter tank for removing sulfate in acid mine water as claimed in claim 1, wherein the filter material of the third stage filter material unit is a mixture of natural clinoptilolite, limestone and montmorillonite mixed according to a volume ratio of 1-2: 2:2, the particle size of the natural clinoptilolite is 0.8-2 cm, and the particle size of the limestone and the montmorillonite is 2-4 cm.
4. The stepped clarifier according to claim 1, wherein the water inlet system comprises a water inlet pump, a water inlet pipe, a flow meter and a flow regulating valve, the water inlet pipe passes through the water inlet pump and is connected with the primary clarifier, and the flow meter and the flow regulating valve are arranged at the water inlet of the primary clarifier.
5. The cascade purification filter for removing sulfate in acid mine water as claimed in claim 1, wherein the alkali solution is a sodium hydroxide solution with a concentration of 0.05-0.15 mol/L, and the mass ratio of the zirconium oxychloride to the mixed material in step (2) is 8-10: 1.
6. The cascade purification filter tank for removing sulfate in acid mine water as claimed in claim 1, wherein after crushing, the particle size of the natural clinoptilolite is 0.5-1.2 cm, the particle size of the quartz is 0.2-0.6 cm, the volume ratio of the mixture of the natural clinoptilolite and the quartz is 3-4: 1, and the volume ratio of the mixture to the acid mine water is 1: 10-15.
7. The cascade purification filter for removing sulfate in acidic mine water as claimed in claim 1, wherein the bottom of the secondary purification filter is provided with a water inlet pipe communicated with the primary purification filter, the water inlet pipe is provided with a high pressure pump, and the bottoms of the primary purification filter, the secondary purification filter and the tertiary purification filter are respectively provided with a drain A, a drain B and a drain C.
8. The cascade clarifier according to claim 1, wherein the left and right sides of the secondary clarifier and the right side of the tertiary clarifier are respectively provided with an overflow weir a, an overflow weir B and an overflow weir C at different heights, the stirring device comprises a stirring device a above the inclined tube clarifier and a stirring device B below the inclined tube clarifier, the overflow weir C is arranged on the side wall of the inclined tube clarifier, the overflow weir a is higher than the overflow weir B, and the overflow weir B is higher than the overflow weir C.
CN202210663873.5A 2022-06-14 2022-06-14 A step purifying filter for getting rid of acid mine in water sulphate Active CN114751563B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210663873.5A CN114751563B (en) 2022-06-14 2022-06-14 A step purifying filter for getting rid of acid mine in water sulphate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210663873.5A CN114751563B (en) 2022-06-14 2022-06-14 A step purifying filter for getting rid of acid mine in water sulphate

Publications (2)

Publication Number Publication Date
CN114751563A CN114751563A (en) 2022-07-15
CN114751563B true CN114751563B (en) 2022-08-16

Family

ID=82336481

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210663873.5A Active CN114751563B (en) 2022-06-14 2022-06-14 A step purifying filter for getting rid of acid mine in water sulphate

Country Status (1)

Country Link
CN (1) CN114751563B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996020139A1 (en) * 1994-12-28 1996-07-04 Roman Andreevich Penzin Drinking water purification and conditioning system and a filter charge for purifying drinking water
CN102285665A (en) * 2011-06-07 2011-12-21 天津大学 Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water
WO2012158288A1 (en) * 2011-05-16 2012-11-22 3M Innovative Properties Company Porous composite block, filter assembly, and method of making the same
CN102872790A (en) * 2012-09-24 2013-01-16 中国地质大学（武汉） Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof
CN110170338A (en) * 2019-05-30 2019-08-27 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of the modified difunctional zeolite ion exchanger of Zr-Cu/ zeolite and products thereof and application
CN113387446A (en) * 2021-07-13 2021-09-14 中国科学院、水利部成都山地灾害与环境研究所 Landscape type multi-medium tail water treatment vertical subsurface flow constructed wetland

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996020139A1 (en) * 1994-12-28 1996-07-04 Roman Andreevich Penzin Drinking water purification and conditioning system and a filter charge for purifying drinking water
WO2012158288A1 (en) * 2011-05-16 2012-11-22 3M Innovative Properties Company Porous composite block, filter assembly, and method of making the same
CN102285665A (en) * 2011-06-07 2011-12-21 天津大学 Liquid phase chemical deposition modified natural zeolite and method for removing fluorine from water
CN102872790A (en) * 2012-09-24 2013-01-16 中国地质大学（武汉） Sulfate radical sorbent magnetic nanometer zirconium hydroxide and preparation method thereof
CN110170338A (en) * 2019-05-30 2019-08-27 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of the modified difunctional zeolite ion exchanger of Zr-Cu/ zeolite and products thereof and application
CN113387446A (en) * 2021-07-13 2021-09-14 中国科学院、水利部成都山地灾害与环境研究所 Landscape type multi-medium tail water treatment vertical subsurface flow constructed wetland

Also Published As

Publication number Publication date
CN114751563A (en) 2022-07-15

Similar Documents

Publication Publication Date Title
CN105000713B (en) A kind of desulfurization wastewater treatment system and method
CN102503030B (en) System for treating heavy metal wastewater
CN105771881A (en) Material and method for removing phosphorus in water
CN102085473A (en) Application of iron sulphide ores and method for adsorbing trace phosphor in water by using iron sulphide ores
CN110510773A (en) A kind of acid mine water treatment system and method
CN102649608B (en) Process method for treating mine acidic waste water
CN100447094C (en) Multistage gradient adsorption channel adsorption technology
CN114751563B (en) A step purifying filter for getting rid of acid mine in water sulphate
CN113511777A (en) Chemical industry park comprehensive sewage treatment system and process
CN110627265B (en) Sulfur-containing waste ore leaching wastewater pretreatment system and method
CN105906096B (en) The desulfurization wastewater treatment system of power-plant flue gas boiler
CN106830251A (en) Recombination chitosan flocculant and preparation method and application for processing desulfurization wastewater
CN105152267B (en) A kind of method for removing phosphorus in water removal with calcining limonite depth
CN107867770A (en) A kind of desulfurization wastewater treatment system and its processing method
CN207210146U (en) Garbage percolation liquid treating system
CN213570041U (en) Domestic sewage phosphorus removal device
CN206645859U (en) A kind of sewage-treatment plant for stirring Joint adsorption
CN103641259B (en) Desulfurization wastewater treatment device
CN209522624U (en) ECSF type integration electric flocculation high suspended matter wastewater treatment equipment
CN113493274A (en) Deep and efficient purification method for water body
CN105289067A (en) Modified rice hull ash pre-coated film device used for treating rural high ammonia-nitrogen water source water, and method used for treating rural high ammonia-nitrogen water source water using modified rice hull ash pre-coated film device
CN111484173A (en) High-efficient clean system of degree of depth of water
CN111875048A (en) Reaction device for nitrogen and phosphorus removal by synergism of autotrophic denitrification and heterotrophic denitrification, process and application
CN212425583U (en) Reaction device for removing nitrogen and phosphorus by using autotrophic denitrification and heterotrophic denitrification in cooperation
CN214528447U (en) Treatment system for fluorine-containing wastewater

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information

Inventor after: Yin Zhaolong

Inventor before: Yin Zhaolong

Inventor before: Yin Xijie

Inventor before: Zhao Chunhong

CB03 Change of inventor or designer information