CN115318245A - Preparation and rapid starting method of modified zeolite demanganization filter material - Google Patents

Preparation and rapid starting method of modified zeolite demanganization filter material Download PDF

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CN115318245A
CN115318245A CN202211022655.XA CN202211022655A CN115318245A CN 115318245 A CN115318245 A CN 115318245A CN 202211022655 A CN202211022655 A CN 202211022655A CN 115318245 A CN115318245 A CN 115318245A
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manganese
filter
potassium permanganate
oxidation
removal
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CN115318245B (en
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李星
朱文博
杨艳玲
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Beijing University of Technology
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Beijing University of Technology
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    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • 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
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Abstract

A preparation and rapid start method of a modified zeolite demanganization filter material belongs to the field of drinking water purification, and the modified zeolite demanganization filter material takes natural zeolite as a raw material, and sequentially comprises NaOH solution and MnCl solution with a certain concentration 2 ·4H 2 O solution and KMnO 4 The rapid starting method is realized by alternately performing adsorption coupling catalytic oxidation manganese removal of the modified zeolite manganese removal filter material, intensified oxidation manganese removal of potassium permanganate and contact oxidation manganese removal of a manganese active filter membrane and intensified oxidation manganese removal of potassium permanganate in sequence at the initial stage of operation of the contact oxidation manganese removal filter. The invention can solve the problems of insufficient yield and high cost of natural manganese sand, long start-up period of the existing contact oxidation manganese removal filter, excessive manganese risk in the start-up period and the like, is not influenced by areas, the quality of raw water and the filter speed of the filter, can flexibly deal with various water source water with excessive manganese, and ensures that the manganese of the effluent of the contact oxidation manganese removal filter reaches the standard stably in the whole operation period.

Description

Preparation and rapid starting method of modified zeolite demanganization filter material
Technical Field
The invention belongs to the field of drinking water purification, and particularly relates to a preparation and rapid starting method of a modified zeolite manganese removal filter material.
Background
The exceeding standard of manganese is a ubiquitous water quality problem of rural underground water, the manganese content in the underground water in many regions reaches 0.5-2.0 mg/L, and even exceeds 2.0mg/L in some regions. The excessive manganese in the water seriously threatens the life of residents and the water supply safety, and on one hand, the excessive manganese can increase the chromaticity of the water, so that the yellow water phenomenon occurs, peculiar smell is generated, and inconvenience is brought to the life of the residents; on the other hand, after manganese-containing water enters a water supply pipe network, manganese can react with residual chlorine in the water to generate manganese oxide and deposit the manganese oxide on the inner wall of the pipeline, so that the water delivery capacity of the pipe network is reduced, bacteria can be bred, the pipeline is corroded, the service life of the pipeline is shortened, and the water supply safety is influenced; in addition, drinking water with excessive manganese can damage the inner wall of an artery and cardiac muscle, and coronary artery stenosis and coronary heart disease are caused. Therefore, raw water with excessive manganese is treated to ensure that the water quality meets the standard that the manganese content does not exceed 0.1mg/L specified in the national sanitary Standard for Drinking Water (GB 5749-2022).
Aiming at underground water with excessive manganese, the traditional manganese removal technology comprises a natural oxidation method, a chemical oxidation method, a biological oxidation method, a contact oxidation method and the like, wherein the natural oxidation method generally needs to increase the pH value of water to be more than 9.5, so that the treatment process is complex and the water production cost is increased; the chemical oxidation method increases the cost of the oxidant, and in order to avoid secondary pollution of water quality in application, the dosage of the oxidant needs to be strictly controlled; the biological oxidation method has the defects of longer start-up period, larger influence of temperature and lower manganese removal efficiency; the contact oxidation method is a currently applied manganese removal technology, quartz sand, natural manganese sand and the like are used as filter materials in a contact oxidation manganese removal filter, and bivalent manganese in water is removed through the catalytic oxidation action of a manganese active filter membrane formed on the surface of the filter materials. Because the formation of the manganese active filter membrane is a slow process, manganese is removed mainly by depending on the adsorption effect of a fresh filter material on divalent manganese in the start-up period of the contact oxidation manganese removal filter tank, and quartz sand does not have the capacity of adsorbing divalent manganese, the manganese removal filter tank using the quartz sand as the filter material has the problems of long start-up period and unstable manganese removal effect. The natural manganese sand is influenced by the production place, the difference of manganese removal effects is large, some high-quality natural manganese sand, such as Mashan manganese sand, leping manganese sand and the like, have strong capacity of adsorbing divalent manganese in water, and drinking water with manganese reaching the standard can be obtained at the early stage of filtration. In addition, the high-quality natural manganese sand has a certain contact oxidation demanganization function, and can oxidize bivalent manganese in water to generate a manganese active filter membrane with continuous demanganization capacity, thereby shortening the start-up period of the filter. However, the quality of the natural manganese sand sold in the market is greatly different, the natural manganese sand is influenced by the production reduction or production stoppage of manganese ore exploitation, the high-quality natural manganese sand is difficult to obtain, the price also tends to rise year by year, and in addition, the risk that the manganese in the effluent exceeds the standard also exists in the start-up period of the filter tank due to the limitation of the adsorption capacity of the manganese sand. Therefore, the demanganization filter material capable of replacing natural manganese sand is urgently needed to be developed so as to reduce the water treatment cost, shorten the start-up period of the contact oxidation demanganization filter tank and ensure that the manganese in the effluent reaches the standard stably.
The invention content is as follows:
aiming at the problems of insufficient yield, high price, long start-up period of the contact oxidation manganese removal filter tank, excessive manganese risk of effluent and the like of natural manganese sand, the invention provides a preparation method and a quick start-up method of a modified zeolite manganese removal filter material which is easy to obtain materials, simple to prepare, convenient for industrial application and capable of replacing the natural manganese sand, so that the water treatment cost can be reduced, the start-up period of the contact oxidation manganese removal filter tank is shortened, and the stable standard reaching of the manganese of the effluent in the whole operation period is ensured.
The technical scheme adopted by the invention for realizing the aim is as follows:
the invention provides a preparation method of a modified zeolite demanganization filter material, which comprises the following steps:
A. washing zeolite with pure water, draining, and oven drying;
B. weighing the zeolite, adding 0.5-2% (preferably 1%) NaOH solution by mass, shaking and contacting at room temperature for 24h, cleaning with pure water until pH is neutral, draining, and oven drying;
C. adding 2-6% (preferably 4%) of MnCl into the zeolite 2 ·4H 2 The solution O is vibrated and contacted for 24 hours at room temperature, and then is drained and dried;
D. adding KMnO with mass fraction of 1-5% (preferably 2%) to the obtained zeolite 4 And (3) vibrating and contacting the solution at room temperature for 12 hours, and then draining and drying to obtain the modified zeolite manganese removal filter material.
In the step A, the particle size range of the zeolite is 0.8-1.5 mm, and the nonuniform coefficient is 1.4-1.6;
in the step B, the mass/volume of the zeolite and the NaOH solution is 1kg/L;
in step C, zeolite and MnCl 2 ·4H 2 The mass/volume of the O solution is 2kg/L;
in step D, zeolite is reacted with KMnO 4 The mass/volume of the solution is 2kg/L;
in the steps, the drying temperature is 100-110 ℃ (preferably 105 ℃), and the drying time is not less than 4h.
The invention also provides a quick starting method for the contact oxidation manganese removal filter tank by using the modified zeolite manganese removal filter material, which is characterized by comprising the following steps:
the rapid starting method is realized by sequentially and alternately performing adsorption coupling catalytic oxidation manganese removal, potassium permanganate enhanced oxidation manganese removal, contact oxidation manganese removal or contact oxidation manganese removal and potassium permanganate enhanced oxidation manganese removal, and specifically comprises the following steps:
(1) Firstly, carrying out adsorption coupling catalytic oxidation manganese removal in a filter tank, feeding fully aerated raw water into the filter tank, adopting periodic operation of filtration and backwashing until the manganese concentration of the outlet water of the filter tank is increased to 0.1mg/L, finishing the adsorption coupling catalytic oxidation manganese removal, and feeding the outlet water into potassium permanganate to enhance oxidation manganese removal;
the structure of the filter is the same as that of a conventional contact oxidation manganese removal filter, the thickness of a filter material layer is 700-1000 mm, a supporting layer and a water distribution system are arranged below the filter material layer, and the difference is that the modified zeolite manganese removal filter material provided by the invention is adopted as a filter material, the particle size range is 0.8-1.5 mm, the non-uniform coefficient is 1.4-1.6, the filtering speed is 5-8 m/h, and the filtering time is 24h; the back washing strength is 10 to 12L/(s.m) 2 ) The back washing time is 3-5 min.
The operation method for removing manganese by adsorption coupling catalytic oxidation comprises the following steps: raw water is fully aerated in a raw water tank, then the fully aerated raw water is filtered by a filter material layer at a certain filtering speed, divalent manganese in the raw water is continuously intercepted by the filter material layer under the adsorption action of the modified zeolite manganese removal filter material, in addition, the modified zeolite manganese removal filter material has a certain catalytic manganese removal action, partial adsorbed divalent manganese can be further oxidized into high-valence manganese oxide, a manganese active filter membrane with the catalytic manganese removal capacity is gradually formed on the surface of the filter material, and under the adsorption coupling catalytic oxidation action of the modified zeolite manganese removal filter material, effluent with manganese reaching the standard can be obtained at the initial stage of the operation of the filter. The formation of the manganese active filter membrane is a slow process, the concentration of manganese in the effluent water is gradually increased along with the gradual exhaustion of the adsorption capacity of the filter material layer, when the concentration of the manganese in the effluent water is increased to 0.1mg/L, the filtering process is stopped, the adsorption coupling catalytic oxidation manganese removal is finished, and the manganese removal is performed by potassium permanganate enhanced oxidation.
(2) After the step (1), performing potassium permanganate enhanced oxidation and manganese removal, wherein the potassium permanganate enhanced oxidation and manganese removal is realized by performing downward circulating filtration on a potassium permanganate solution from a filter material layer in the step (1) for a period of time in a circulating system consisting of the filter tank in the step (1), a circulating water tank and a circulating pump after the filter tank stops filtering, and the specific operation method comprises the following steps:
a. the required potassium permanganate dosage was calculated according to the following formula:
W 1 ＝1.149nSVt,
wherein, the first and the second end of the pipe are connected with each other,
W 1 for the first time, for the manganese removal by potassium permanganate with enhanced oxidationG, the dosage of potassium permanganate; the first time refers to the overall first time of potassium permanganate enhanced oxidation;
n-average concentration of bivalent manganese in raw water, mg/L;
filtration area, m, of S-filter 2 ；
V-filtration speed, m/h;
t-before the first potassium permanganate enhanced oxidation demanganization, the accumulated filtering time of the filter is h;
b. quantitatively weighing the potassium permanganate W required for the first time of manganese removal by potassium permanganate enhanced oxidation according to the calculation result of the step a 1 And preparing 1 percent KMnO by pure water 4 A solution;
c. mixing KMnO 4 Adding the solution into a circulating water tank, starting a circulating pump to enable a potassium permanganate solution to be added from the upper part of the filter tank in the step (1), filtering the solution from top to bottom through a filter material layer at a filtering speed of 3m/h, returning filtered effluent to the circulating water tank, sending the filtered effluent into the filter tank by the circulating pump again for circulating filtration, performing intensified oxidation on divalent manganese adsorbed in the filter material layer by the potassium permanganate in the circulating filtration process, retaining the generated high-valence manganese oxide in the filter material layer until the circulating filtration time reaches 4-6 h, completing the intensified oxidation and manganese removal by the potassium permanganate, and entering a contact oxidation and manganese removal stage;
in the stage of removing manganese by potassium permanganate enhanced oxidation, only the potassium permanganate is circularly flushed, and the filtration treatment of raw water is not carried out.
(3) And (3) performing contact oxidation manganese removal in the filter tank treated in the step (2), introducing fully aerated raw water into the filter tank treated in the step (2), oxidizing bivalent manganese in the raw water by dissolved oxygen in water under the catalytic action of a manganese active filter membrane formed on the surface of a filter material to ensure that the manganese concentration of the filter tank outlet water is lower than 0.1mg/L, further forming a new manganese active filter membrane on the surface of the filter material, accelerating the starting process of the manganese removal filter tank, and if the manganese concentration of the filter tank outlet water is kept lower than 0.1mg/L for a long time (more than 60 days), indicating that the start of the contact oxidation manganese removal filter tank is finished.
(4) And (4) if the manganese concentration of the effluent rises to 0.1mg/L again after the operation of the step (3) for a period of time, repeating the operations of the step (2) of removing manganese by potassium permanganate enhanced oxidation and the step (3) of removing manganese by contact oxidation until the manganese concentration of the effluent of the filter tank for removing manganese by contact oxidation is continuously lower than 0.1mg/L (more than 60 days), and finishing the quick start of the filter tank for removing manganese by contact oxidation.
The operation method for removing manganese by potassium permanganate enhanced oxidation of the repeated step (2) is completely the same as the operation method for removing manganese by potassium permanganate enhanced oxidation of the step (2) except that the required calculation method of the potassium permanganate dosage is different.
The potassium permanganate input required for the second and later manganese removal by potassium permanganate enhanced oxidation is calculated according to the following formula:
W m ＝0.8 m-1 W m-1 (m is more than or equal to 2), wherein m refers to the mth potassium permanganate intensified oxidation of the whole;
W m the potassium permanganate dosage, g, required for the m-th (m is more than or equal to 2) potassium permanganate enhanced oxidation manganese removal
Compared with the existing contact oxidation manganese removal filter tank, the invention has the advantages that:
1. the invention takes the natural zeolite with easily available materials and low price as the material to prepare the modified zeolite demanganization filter material which can replace the natural manganese sand, and can effectively solve the dilemma that the natural manganese sand has insufficient yield and high price in the treatment of the manganese over-standard water;
2. the prepared modified zeolite manganese removal filter material is simple in preparation process and convenient for industrial application, has excellent performance of high-quality natural manganese sand, and has the packing density of only half of that of the natural manganese sand, so that the dosage of the manganese removal filter material can be greatly reduced, the defects of large dosage and high cost of the natural manganese sand filter material are overcome, and the water preparation cost is reduced;
3. the rapid starting method for the contact oxidation manganese removal filter tank by using the modified zeolite manganese removal filter material provided by the invention fully exerts the advantages of adsorption coupling catalytic oxidation manganese removal, potassium permanganate enhanced oxidation manganese removal and contact oxidation manganese removal in each operation stage, shortens the starting time of the contact oxidation manganese removal filter tank, is not influenced by regions, water quality, manganese content and filter tank filtration speed, can flexibly deal with various water source water with over-standard manganese, can realize the standard reaching of the manganese of the filter tank effluent from the beginning of operation, avoids the problems of long starting period, over-standard manganese risk of the filter tank effluent during the starting period and the like of the existing contact oxidation manganese removal filter tank, and ensures the sanitation and safety of drinking water.
Description of the drawings:
FIG. 1 is a flow chart of a rapid start test of a contact oxidation manganese removal filter tank for a modified zeolite manganese removal filter material.
Reference numerals are as follows:
1. a raw water tank; 2. a raw water pump; 3. an aeration pump; 4. a water inlet pipe of the filter tank; 5. a filter chamber; 6. a filter material layer; 7. a support layer; 8. A water distribution system; 9. a water outlet pipe of the filter tank; 10. a filter outlet valve; 11. a clear water tank; 12. a backwash valve; 13. a backwash pump; 14. A circulating drain valve; 15. a circulating pump water suction pipe; 16. a circulation pump; 17. a circulating water tank; 18. a backwash water drain pipe.
FIG. 2 shows the effect of demanganization in the operation of the filter column of example 1;
FIG. 3 shows the manganese removal effect of the filter column in example 2;
FIG. 4 shows the manganese removal effect of the filter column operation of example 3.
The specific implementation mode is as follows:
the present invention will be further illustrated by the following specific examples, but the present invention is not limited to the following examples.
Example 1
The preparation method of the modified zeolite demanganization filter material comprises the following specific steps:
A. weighing 3kg of zeolite with the particle size range of 0.8-1.5 mm and the non-uniformity coefficient of 1.4, cleaning with pure water, draining, and drying at 105 ℃ for 4h;
B. adding 3L of NaOH solution with the mass fraction of 1% into the obtained zeolite, shaking and contacting the obtained zeolite at the constant temperature of 25 ℃ for 24 hours at the speed of 150r/min, then washing the zeolite with pure water until the pH value is neutral, draining water and drying the zeolite for 4 hours at the temperature of 105 ℃;
C. to the zeolite obtained above was added 1.5L of MnCl with a mass fraction of 4% 2 ·4H 2 O solution, shaking and contacting the O solution for 24 hours at the constant temperature of 25 ℃ at the speed of 150r/min, draining water and drying the O solution for 4 hours at the temperature of 105 ℃;
D. to the zeolite obtained above was added 1.5L of 2% by mass KMnO 4 And (3) vibrating and contacting the solution at the constant temperature of 25 ℃ for 12h at the speed of 150r/min, draining water, and drying at 105 ℃ for 4h to obtain the modified zeolite manganese removal filter material.
A quick start method for a contact oxidation manganese removal filter tank with a modified zeolite manganese removal filter material is disclosed, and the quality of experimental raw water is as follows: the water temperature is 17-18 ℃, the total number of bacteria is 1.1 multiplied by 10 2 ～1.7×10 2 One per mL, 3-5 total coliform groups per 100mL, turbidity of 6.5NTU, COD mn 2.0mg/L, mn 2+ The concentration is 1.9-2.1 mg/L, and the ammonia nitrogen concentration is 0.5mg/L.
The rapid starting method is realized by sequentially carrying out adsorption coupling catalytic oxidation manganese removal, potassium permanganate enhanced oxidation manganese removal and contact oxidation manganese removal and potassium permanganate enhanced oxidation manganese removal alternately:
(1) The manganese removal by adsorption coupling catalytic oxidation is carried out in a filter 5;
the filter 5 is a filter column with the diameter of 6cm, a modified zeolite manganese removal filter material is used as a filter material, the thickness of the filter material layer 6 is 1000mm, a supporting layer 7 and a water distribution system 8 are arranged below the filter material layer 6, the filtering speed is 5m/h, the filtering time is 24h, and the backwashing strength is 10L/(s.m.m) 2 ) And the backwashing time is 5min.
The operation method for removing manganese by adsorption coupling catalytic oxidation comprises the following steps: closing a backwashing valve 12 and a circulating drain valve 14, opening a filter outlet valve 10, feeding raw water with the manganese concentration of 1.9-2.1 mg/L into a raw water tank 1, aerating the raw water by using an aeration pump 3, sending the fully aerated raw water into a filter 5 by using a raw water pump 2 through a filter inlet pipe 4, filtering by using a filter material layer 6, continuously intercepting bivalent manganese in the raw water in the filter material layer 6 under the adsorption coupling catalytic oxidation action of the modified zeolite manganese removal filter material, feeding the filtered water into a water distribution system 8 through a supporting layer 7, and feeding the filtered water into a clear water tank 11 through a filter outlet pipe 9; after the filtration is finished, closing the filter outlet valve 10, opening the backwashing valve 12 and the backwashing pump 13, allowing filtered water in the clean water tank 11 to enter from the bottom of the filter 5, and backwashing the filter material layer 6 from bottom to top; along with the periodic proceeding of filtration-backwashing, the adsorption capacity of the filter material layer 6 to the divalent manganese is gradually exhausted, the concentration of the manganese in the effluent water is gradually increased, when the operation lasts for 96 hours and the concentration of the manganese in the effluent water is increased to 0.1mg/L, the adsorption coupling catalytic oxidation manganese removal is finished, and the manganese removal is performed by potassium permanganate enhanced oxidation.
(2) The potassium permanganate enhanced oxidation demanganization is carried out in a circulating system consisting of the filter 5, a circulating water tank 17 and a circulating pump 16, and the operation method of the potassium permanganate enhanced oxidation demanganization comprises the following steps:
firstly, a raw water pump 2, a backwashing valve 12 and a filter outlet valve 10 are closed, raw water filtration is stopped, and the potassium permanganate adding amount is calculated according to the following formula:
W 1 ＝1.149nSVt＝1.149×2×2.86×10 -3 ×5×96＝3.154g
3.154g of potassium permanganate is dissolved by pure water and prepared into 1 percent of KMnO 4 And adding the solution into a circulating water tank 17, then opening a circulating water discharge valve 14 and a circulating pump 16, adding the potassium permanganate solution into a filter 5 from the upper part of a filter material layer 6, performing circulating filtration for 6 hours through the filter material layer 6 at a filtering speed of 3m/h, and completing the manganese removal by potassium permanganate enhanced oxidation, and closing the circulating water discharge valve 14 and the circulating pump 16 and entering a contact oxidation manganese removal stage.
(3) The contact oxidation manganese removal is carried out in the filter 5, in the process of the contact oxidation manganese removal, bivalent manganese in the fully aerated raw water is oxidized and removed by dissolved oxygen in the water under the catalytic action of a manganese active filter membrane formed on the surface of a filter material, filtered water with the manganese concentration lower than 0.1mg/L is obtained, and a new manganese active filter membrane is formed, so that the starting process of the manganese removal filter is accelerated, and when the filter is operated for 144 hours, the manganese concentration of the water discharged from the filter is increased to 0.1mg/L again, so that the second operation of the potassium permanganate enhanced oxidation manganese removal is carried out.
(4) The second operation of removing manganese by potassium permanganate enhanced oxidation specifically comprises the following steps:
firstly, the raw water pump 2, the backwashing valve 12 and the filter outlet valve 10 are closed, the raw water filtration is stopped, and the potassium permanganate input amount, W, required by the second potassium permanganate enhanced oxidation manganese removal is calculated 2 ＝0.8W 1 ＝0.8×3.154＝2.523g
2.523g of potassium permanganate were dissolved in pure water andprepared into 1 percent KMnO 4 Adding the solution into a circulating water tank 17, then opening a circulating drain valve 14 and a circulating pump 16, adding the potassium permanganate solution from the upper part of the filter material layer 6, circularly filtering the potassium permanganate solution through the filter material layer 6 at the filtering speed of 3m/h for 6h to finish the manganese removal by potassium permanganate enhanced oxidation, then closing the circulating drain valve 14 and the circulating pump 16, and entering again to remove the manganese by contact oxidation, wherein the manganese concentration of the effluent water is always lower than 0.1mg/L after continuous operation for 60 days, which indicates that the start-up of the contact oxidation manganese removal filter tank is finished.
Example 2
The preparation method of the modified zeolite manganese removal filter material comprises the following specific steps:
A. weighing 5kg of zeolite with the particle size range of 0.8-1.5 mm and the nonuniform coefficient of 1.5, washing with pure water, draining, and drying at 105 ℃ for 4h;
B. adding 5L of NaOH solution with the mass fraction of 1% into the obtained zeolite, shaking and contacting the obtained zeolite at the constant temperature of 25 ℃ for 24 hours at the speed of 150r/min, then washing the zeolite with pure water until the pH value is neutral, draining water and drying the zeolite for 4 hours at the temperature of 105 ℃;
C. 2.5L of 4% by mass MnCl was added to the zeolite obtained above 2 ·4H 2 O solution, shaking and contacting the O solution for 24 hours at the constant temperature of 25 ℃ at the speed of 150r/min, draining water and drying the O solution for 4 hours at the temperature of 105 ℃;
D. 2.5L of KMnO with the mass fraction of 2% was added to the zeolite obtained above 4 And (3) vibrating and contacting the solution at the constant temperature of 25 ℃ for 12h at the speed of 150r/min, draining water, and drying at 105 ℃ for 4h to obtain the modified zeolite manganese removal filter material.
A quick start method for a contact oxidation manganese removal filter tank with a modified zeolite manganese removal filter material is disclosed, and the quality of experimental raw water is as follows: the water temperature is 12-14 ℃, the total number of bacteria is not detected, the total coliform group is not detected, the turbidity is 2.0NTU mn 0.8mg/L, mn 2+ The concentration is 1.4-1.6 mg/L, and ammonia nitrogen is not detected.
The quick starting method is realized by sequentially removing manganese through adsorption coupling catalytic oxidation, removing manganese through potassium permanganate enhanced oxidation and removing manganese through contact oxidation:
(1) The manganese removal by adsorption coupling catalytic oxidation is carried out in a filter 5;
the filter 5 is a filter column with the diameter of 6cm, a modified zeolite manganese removal filter material is used as a filter material, the thickness of the filter material layer 6 is 800mm, a supporting layer 7 and a water distribution system 8 are arranged below the filter material layer 6, the filtering speed is 8m/h, the filtering time is 24h, and the backwashing strength is 12L/(s.m.m) 2 ) And the backwashing time is 3min.
The operation method for removing manganese by adsorption coupling catalytic oxidation comprises the following steps: closing a backwashing valve 12 and a circulating drain valve 14, opening a filter outlet valve 10, feeding raw water with the manganese concentration of 1.4-1.6 mg/L into a raw water tank 1, aerating the raw water by an aeration pump 3, feeding the fully aerated raw water into a filter 5 by a raw water pump 2 through a filter inlet pipe 4, filtering by a filter material layer 6, continuously intercepting divalent manganese in the raw water in the filter material layer 6 under the adsorption coupling catalytic oxidation action of the modified zeolite manganese removal filter material, feeding the filtered water into a water distribution system 8 through a supporting layer 7, and feeding the filtered water into a clear water tank 11 through a filter outlet pipe 9; after the filtration is finished, closing the filter outlet valve 10, opening the backwashing valve 12 and the backwashing pump 13, allowing filtered water in the clean water tank 11 to enter from the bottom of the filter 5, and backwashing the filter material layer 6 from bottom to top; along with the periodic progress of filtration-backwashing, the adsorption capacity of the filter material layer 6 on the divalent manganese is gradually exhausted, the concentration of the manganese in the effluent water is gradually increased, when the operation lasts for 120h and the concentration of the manganese in the effluent water is increased to 0.1mg/L, the adsorption coupling catalytic oxidation manganese removal is finished, and the manganese removal is performed by potassium permanganate enhanced oxidation.
(2) The potassium permanganate enhanced oxidation demanganization is carried out in a circulating system consisting of the filter 5, a circulating water tank 17 and a circulating pump 16, and the potassium permanganate enhanced oxidation demanganization operation method comprises the following steps:
firstly, a raw water pump 2, a backwashing valve 12 and a filter outlet valve 10 are closed, raw water filtration is stopped, and the potassium permanganate adding amount is calculated according to the following formula:
W 1 ＝1.149nSVt＝1.149×1.5×2.86×10 -3 ×8×120＝4.732g
4.732g of potassium permanganate were dissolved in pure water and prepared to 1% KMnO 4 Adding the solution into a circulating water tank 17, then opening a circulating drain valve 14 and a circulating pump 16, adding the potassium permanganate solution into the filter 5 from the upper part of the filter material layer 6, and circulating through the filter material layer 6 at the filtering speed of 3m/hPerforming ring filtration for 5h to complete the manganese removal by potassium permanganate enhanced oxidation, closing the circulating drain valve 14 and the circulating pump 16, and entering a contact oxidation manganese removal stage.
(3) The contact oxidation demanganization is carried out in the filter 5, in the process of the contact oxidation demanganization, bivalent manganese in the fully aerated raw water is oxidized and removed by dissolved oxygen in the water under the catalytic action of a manganese active filter membrane formed on the surface of a filter material to obtain filtered water with the manganese concentration lower than 0.1mg/L, and a new manganese active filter membrane is formed, so that the starting process of the demanganization filter is accelerated, the manganese concentration of the effluent water is always lower than 0.1mg/L within 60 days of continuous operation, and the starting of the contact oxidation demanganization filter is finished.
Example 3
The preparation method of the modified zeolite demanganization filter material comprises the following specific steps:
A. weighing 6kg of zeolite with the particle size range of 0.8-1.5 mm and the nonuniform coefficient of 1.6, washing with pure water, draining, and drying at 105 ℃ for 4h;
B. adding 6L of NaOH solution with the mass fraction of 1% into the obtained zeolite, shaking and contacting the obtained zeolite at the constant temperature of 25 ℃ for 24 hours at the speed of 150r/min, then washing the zeolite with pure water until the pH value is neutral, draining water and drying the zeolite for 4 hours at the temperature of 105 ℃;
C. adding 3L of MnCl with the mass fraction of 4% into the obtained zeolite 2 ·4H 2 O solution, shaking and contacting the O solution for 24 hours at the constant temperature of 25 ℃ at the speed of 150r/min, draining water and drying the O solution for 4 hours at the temperature of 105 ℃;
D. to the zeolite obtained above was added 3L of KMnO with a mass fraction of 2% 4 And (3) shaking and contacting the solution at a constant temperature of 25 ℃ at a speed of 150r/min for 12 hours, then draining and drying at 105 ℃ for 4 hours to obtain the modified zeolite manganese removal filter material.
A quick start method for a contact oxidation manganese removal filter tank with a modified zeolite manganese removal filter material is disclosed, and the quality of experimental raw water is as follows: the water temperature is 15-16 ℃, the total number of bacteria is 1.7 multiplied by 10 2 ～1.0×10 3 one/mL, 10 total coliform bacteria/100 mL, turbidity of 3.0NTU, COD mn 1.8mg/L, mn 2+ The concentration is 0.9-1.1 mg/L.
The quick starting method is realized by sequentially removing manganese through adsorption coupling catalytic oxidation, removing manganese through potassium permanganate enhanced oxidation and removing manganese through contact oxidation:
(1) The manganese removal by adsorption coupling catalytic oxidation is carried out in a filter 5;
the filter 5 is a filter column with the diameter of 6cm, a modified zeolite manganese removal filter material is used as a filter material, the thickness of the filter material layer 6 is 700mm, a supporting layer 7 and a water distribution system 8 are arranged below the filter material layer 6, the filtering speed is 6m/h, the filtering time is 24h, and the backwashing strength is 10L/(s.m.m) 2 ) And the backwashing time is 3min.
The operation method for removing manganese by adsorption coupling catalytic oxidation comprises the following steps: closing a backwashing valve 12 and a circulating drain valve 14, opening a filter outlet valve 10, feeding raw water with the manganese concentration of 0.9-1.1 mg/L into a raw water tank 1, aerating the raw water by an aeration pump 3, feeding the fully aerated raw water into a filter 5 by a raw water pump 2 through a filter inlet pipe 4, filtering by a filter material layer 6, continuously intercepting divalent manganese in the raw water in the filter material layer 6 under the adsorption coupling catalytic oxidation action of the modified zeolite manganese removal filter material, feeding the filtered water into a water distribution system 8 through a supporting layer 7, and feeding the filtered water into a clear water tank 11 through a filter outlet pipe 9; after the filtration is finished, closing the water outlet valve 10 of the filter, opening the backwashing valve 12 and the backwashing pump 13, allowing the filtered water in the clean water tank 11 to enter from the bottom of the filter 5, and backwashing the filter material layer 6 from bottom to top; with the periodic progress of filtration-backwashing, the adsorption capacity of the filter material layer 6 on the divalent manganese is gradually exhausted, the concentration of the manganese in the effluent water is gradually increased, when the operation time reaches 216h and the concentration of the manganese in the effluent water is increased to 0.1mg/L, the adsorption coupling catalytic oxidation manganese removal is finished, and the manganese removal is performed by potassium permanganate enhanced oxidation.
(2) The potassium permanganate enhanced oxidation demanganization is carried out in a circulating system consisting of the filter 5, a circulating water tank 17 and a circulating pump 16, and the operation method of the potassium permanganate enhanced oxidation demanganization comprises the following steps:
firstly, a raw water pump 2, a backwashing valve 12 and a filter outlet valve 10 are closed, raw water filtration is stopped, and the potassium permanganate adding amount is calculated according to the following formula:
W 1 ＝1.149nSVt＝1.149×1.0×2.86×10 -3 ×6×120＝4.062g
4.062g of permanganic acid was mixed with pure waterPotassium was dissolved and formulated into 1% KMnO 4 And adding the solution into a circulating water tank 17, then opening a circulating water drain valve 14 and a circulating pump 16, adding the potassium permanganate solution into the filter 5 from the upper part of the filter material layer 6, and circularly filtering for 4 hours through the filter material layer 6 at a filtering speed of 3m/h to finish the manganese removal by potassium permanganate enhanced oxidation, closing the circulating water drain valve 14 and the circulating pump 16, and entering a contact oxidation manganese removal stage.
(3) The contact oxidation demanganization is carried out in the filter 5, in the process of the contact oxidation demanganization, bivalent manganese in the fully aerated raw water is oxidized and removed by dissolved oxygen in the water under the catalytic action of a manganese active filter membrane formed on the surface of a filter material, filtered water with the manganese concentration lower than 0.1mg/L is obtained, and a new manganese active filter membrane is formed, so that the starting process of the demanganization filter is accelerated, the manganese concentration of the effluent water is always lower than 0.1mg/L after the filter is continuously operated for 60 days, and the completion of the starting of the contact oxidation demanganization filter is indicated.

Claims (4)

1. The preparation method of the modified zeolite demanganization filter material is characterized by comprising the following specific steps:
A. washing zeolite with pure water, draining, and oven drying;
B. weighing the zeolite, adding 0.5-2% (preferably 1%) NaOH solution by mass, shaking and contacting at room temperature for 24h, cleaning with pure water until pH is neutral, draining, and oven drying;
C. to the zeolite obtained above is added 2-6% (preferably 4%) by mass of MnCl 2 ·4H 2 The solution O is vibrated and contacted for 24 hours at room temperature, and then is drained and dried;
D. to the zeolite obtained above is added 1-5% (preferably 2%) by mass of KMnO 4 And (3) vibrating and contacting the solution at room temperature for 12 hours, and then draining and drying to obtain the modified zeolite manganese removal filter material.
2. The process of claim 1 wherein in step a, the zeolite has a particle size in the range of 0.8mm to 1.5mm and a non-uniformity coefficient in the range of 1.4 to 1.6; in the step B, the mass/volume of the zeolite and the NaOH solution is 1kg/L; in the step (C), the step (D) is carried out,zeolite and MnCl 2 ·4H 2 The mass/volume of the O solution is 2kg/L; in step D, zeolite is reacted with KMnO 4 The mass/volume of the solution is 2kg/L; the drying temperature is 100-110 ℃ (preferably 105 ℃), and the drying time is not less than 4h.
3. The modified zeolite demanganization filter material prepared according to the method of any one of claims 1-2.
4. A quick start method for a contact oxidation manganese removal filter tank when a modified zeolite manganese removal filter material is used is characterized by comprising the following steps: the modified zeolite demanganization filter material is prepared by the method of any one of claims 1-2;
the rapid starting method is realized by sequentially and alternately performing adsorption coupling catalytic oxidation manganese removal, potassium permanganate enhanced oxidation manganese removal, contact oxidation manganese removal or contact oxidation manganese removal and potassium permanganate enhanced oxidation manganese removal, and specifically comprises the following steps:
(1) Firstly, carrying out adsorption coupling catalytic oxidation manganese removal in a filter tank, feeding fully aerated raw water into the filter tank, adopting periodic operation of filtration and backwashing until the manganese concentration of the outlet water of the filter tank is increased to 0.1mg/L, finishing the adsorption coupling catalytic oxidation manganese removal, and feeding the outlet water into potassium permanganate to enhance oxidation manganese removal;
the structure of the filter is the same as that of a conventional contact oxidation manganese removal filter, the thickness of a filter material layer is 700-1000 mm, a supporting layer and a water distribution system are arranged below the filter material layer, and the difference is that the modified zeolite manganese removal filter material provided by the invention is adopted as a filter material, the particle size range is 0.8-1.5 mm, the non-uniform coefficient is 1.4-1.6, the filtering speed is 5-8 m/h, and the filtering time is 24h; the back washing strength is 10 to 12L/(s.m) 2 ) The back washing time is 3-5 min;
the operation method for removing manganese by adsorption coupling catalytic oxidation comprises the following steps: raw water is fully aerated in a raw water tank, then the fully aerated raw water is filtered by a filter material layer at a certain filtering speed, divalent manganese in the raw water is continuously intercepted by the filter material layer under the adsorption action of the modified zeolite manganese removal filter material, in addition, the modified zeolite manganese removal filter material has a certain catalytic manganese removal action, partial adsorbed divalent manganese can be further oxidized into high-valence manganese oxide, a manganese active filter membrane with the catalytic manganese removal capacity is gradually formed on the surface of the filter material, and under the adsorption coupling catalytic oxidation action of the modified zeolite manganese removal filter material, effluent with manganese reaching the standard can be obtained at the initial stage of the operation of the filter. The formation of the manganese active filter membrane is a slow process, the concentration of manganese in the effluent water is gradually increased along with the gradual exhaustion of the adsorption capacity of the filter material layer, when the concentration of manganese in the effluent water is increased to 0.1mg/L, the filtration process is stopped, the adsorption coupling catalytic oxidation manganese removal is finished, and the manganese removal is strengthened by potassium permanganate oxidation;
(2) After the step (1), performing potassium permanganate enhanced oxidation and manganese removal, wherein the potassium permanganate enhanced oxidation and manganese removal is realized by performing downward circulating filtration on a potassium permanganate solution from a filter material layer in the step (1) for a period of time in a circulating system consisting of the filter tank in the step (1), a circulating water tank and a circulating pump after the filter tank stops filtering, and the specific operation method comprises the following steps:
a. the required potassium permanganate dosage was calculated according to the following formula:
W 1 ＝1.149nSVt,
wherein, the first and the second end of the pipe are connected with each other,
W 1 the potassium permanganate dosage, g, required for the first manganese removal by potassium permanganate-enhanced oxidation; the first time refers to the overall first time of potassium permanganate enhanced oxidation;
n-average concentration of bivalent manganese in raw water, mg/L;
filtration area, m, of S-filter 2 ；
V-filtration speed, m/h;
t-accumulated filtering time of the filter chamber, h, before the manganese removal by potassium permanganate enhanced oxidation for the first time;
b. quantitatively weighing the potassium permanganate W required for the first time of manganese removal by potassium permanganate enhanced oxidation according to the calculation result of the step a 1 And preparing 1 percent KMnO by pure water 4 A solution;
c. mixing KMnO 4 Adding the solution into a circulating water tank, and starting a circulating pump to increase the volumeAdding a potassium permanganate solution from the upper part of the filter tank in the step (1), filtering the potassium permanganate solution from top to bottom through a filter material layer at a filtering speed of 3m/h, returning filtered effluent to a circulating water tank, feeding the effluent into the filter tank by a circulating pump again for circulating filtration, performing enhanced oxidation on bivalent manganese adsorbed in the filter material layer by potassium permanganate in the circulating filtration process, intercepting generated high-valence manganese oxide in the filter material layer until the circulating filtration time reaches 4-6 h, completing the removal of manganese by potassium permanganate enhanced oxidation, and then entering a contact oxidation manganese removal stage;
(3) The manganese removal by contact oxidation is carried out in the filter tank treated in the step (2), fully aerated raw water is introduced into the filter tank treated in the step (2), divalent manganese in the raw water is oxidized by dissolved oxygen in water under the catalytic action of a manganese active filter membrane formed on the surface of a filter material, so that the manganese concentration of the outlet water of the filter tank is lower than 0.1mg/L, a new manganese active filter membrane is further formed on the surface of the filter material, the starting process of the manganese removal filter tank is accelerated, and if the manganese concentration of the outlet water of the filter tank is kept lower than 0.1mg/L for a long time and reaches more than 60 days, the starting of the contact oxidation manganese removal filter tank is finished;
(4) If the manganese concentration of the effluent is increased to 0.1mg/L again after the operation of the step (3) for a period of time, repeating the operations of removing manganese by potassium permanganate enhanced oxidation and the removal of manganese by contact oxidation in the step (2) until the manganese concentration of the effluent of the filter tank which is contacted with the removal of manganese by oxidation is continuously lower than 0.1mg/L and reaches more than 60 days, and finishing the rapid start of the filter tank which is contacted with the removal of manganese by oxidation;
the operation method for removing manganese by potassium permanganate enhanced oxidation in the repeated step (2) is completely the same as the operation method for removing manganese by potassium permanganate enhanced oxidation in the step (2) except that the required calculation method of the potassium permanganate dosage is different;
the potassium permanganate dosage required for the second and subsequent manganese removal by potassium permanganate enhanced oxidation is calculated according to the following formula:
W m ＝0.8 m-1 W m-1 (m is more than or equal to 2), wherein m refers to the m-th intensified oxidation of potassium permanganate in the whole process;
W m the high manganese required by the strengthened oxidation and manganese removal of the potassium permanganate in the mth time (m is more than or equal to 2)Potassium dosage, g.
CN202211022655.XA 2022-08-24 Preparation and quick starting method of modified zeolite manganese removal filter material Active CN115318245B (en)

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CN113426471A (en) * 2021-06-28 2021-09-24 哈尔滨工业大学 Dynamic preparation method and enhanced oxidation filtration application of nascent-state nano-layered manganese catalyst
CN113877304A (en) * 2021-09-07 2022-01-04 哈尔滨工业大学 Preparation method and application of functionalized deep manganese removal filter material
CN114163025A (en) * 2021-12-11 2022-03-11 北京工业大学 Enhanced starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation
CN114560517A (en) * 2022-03-08 2022-05-31 西安工程大学 Rapid starting method for realizing filter tank for synchronously removing ammonia nitrogen and manganese in water by catalysis

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CN113426471A (en) * 2021-06-28 2021-09-24 哈尔滨工业大学 Dynamic preparation method and enhanced oxidation filtration application of nascent-state nano-layered manganese catalyst
CN113877304A (en) * 2021-09-07 2022-01-04 哈尔滨工业大学 Preparation method and application of functionalized deep manganese removal filter material
CN114163025A (en) * 2021-12-11 2022-03-11 北京工业大学 Enhanced starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation
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