CN108706745B - Method for treating high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water - Google Patents
Method for treating high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water Download PDFInfo
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Abstract
The invention discloses a method for treating high-iron-manganese-ammonia-nitrogen combined pollution low-temperature underground water, which is characterized in that natural zeolite is used as a raw material, a zeolite-based material is loaded with manganese oxide, the material is loaded with microorganisms such as nitrobacteria, iron-manganese oxidizing bacteria and the like through impregnation of an enrichment culture solution, a multifunctional composite material of the zeolite-loaded manganese oxide and the microorganisms is prepared and filled into a filter column, the operation is carried out in a sequencing batch mode according to four stages of water inlet adsorption, water evacuation, air blowing biological regeneration and nitrate washing, simultaneously, iron-manganese-ammonia nitrogen in the low-temperature underground water is purified, and the outlet water reaches the quality standard of drinking water.
Description
Technical Field
The invention relates to a method for treating high-iron-manganese-ammonia-nitrogen combined pollution low-temperature underground water, and belongs to the technical field of water treatment and utilization of non-metal mineral resources.
Background
Underground water in the three north area of China is generally anoxic at low temperature (lower than 10 ℃), and Fe in the underground water is caused by pollution of nitrogen to the underground water caused by chemical weathering of rocks, reduction of microorganisms and agricultural planting and breeding2+、Mn2+、NH4 +The phenomenon that-N exceeds the standard at the same time is very common, wherein Fe2+5～20mg/L，Mn2+2-5mg/L，NH4 +-N1-15 mg/L and standard for domestic drinking water NH4 +Concentration of-N<0.5mg/L, total iron concentration<0.3mg/L、Mn2+Concentration of<0.1 mg/L. The development of economic technical methods for treating the poor-quality underground water and the guarantee of the water quality of the water supply for residents are urgent technical requirements for solving the current civil problems.
Zeolites are a family of aluminosilicate minerals having a framework silica-based structure, and a number of natural zeolites 40 have been found, the most common of which are clinoptilolite, mordenite, chabazite, erionite, phillipsite, heulandite, laumontite, stilbite, analcime, and the like. The zeolite minerals belong to different crystal systems, and the crystals are mostly in the form of fibers, hairs and columns, and the crystals are few in the form of plates or short columns. The zeolite has developed crystal microporous pore canal and structure charge, and possesses great inner surface area and excellent ion exchange characteristic, so that it has wide application in adsorption, ion exchange, molecular sieve, catalysis and other fields.
Zeolites on various metal cations (K)+、Na+、Ca2+、NH4 +Heavy metal ions, etc.), the zeolite can be widely applied to various wastewater treatment processes, in particular to the treatment of wastewater deep deamination and denitrification. The methods disclosed by CN201710296211.8, CN201710293189.1, CN201210020674.9, CN201110162569.4 and the like all use zeolite as a basic raw material to prepare a water treatment material for adsorbing and purifying ammonia nitrogen; CN201610368672.7, CN201610368468.5 and CN201610368466.6 use zeolite to prepare hydraulic construction materials for adsorbing ammonia nitrogen in water; CN201710878345.0 discloses a preparation method and application of modified zeolite molecular sieve adsorption particles, which are adsorbent particles prepared by crosslinking zeolite powder serving as a main raw material in a solution of chitosan, zinc acetate and sodium alginate and are used for adsorbing and removing ammonia nitrogen in low-temperature water.
Since zeolite adsorbs ammonia nitrogen and is easily saturated, regeneration is a critical problem. In the early days, salt solution ion exchange regeneration technology was developed, but the generated high-concentration salt solution containing ammonia nitrogen is relatively difficult to dispose, and the zeolite regeneration is not complete. Biological zeolite technology is developed from the last 90 th century, namely nitrifying bacteria are loaded in zeolite-based materials to convert adsorbed ammonia nitrogen into nitrate so as to realize biological regeneration. CN201710865502.4 discloses a biological treatment device for micro-polluted source water, wherein a suspended filler layer, a modified zeolite layer and a cobble layer are arranged in the device to strengthen the attachment of microorganisms and increase the diversity of biological species of a system, thereby strengthening the removal of nitrogen and organic matters in the micro-polluted source water, reducing the blockage of the system, and reducing the aeration and back-washing energy consumption of the system, namely combining the adsorption of zeolite with the biological regeneration. CN201110134948.2, CN201110134017.2 and CN201110106007.8 further develop the zeolite application technology, porous materials are prepared by zeolite to load nitrobacteria, and an aeration biological filter or four stages of adsorption, water emptying, air blowing biological regeneration and nitrate washing are adopted to operate in a sequencing batch mode, so that the deep deammoniation and nitrogen treatment of wastewater are well achieved.
CN201510051879.7 discloses a ferro-manganese oxide composite modified zeolite, a preparation method and an application thereofFirstly, natural zeolite is pulverized, sieved and pretreated by acid and alkali, and then the zeolite and FeCl with a certain concentration are mixed3Mixing the solution for reaction to prepare iron oxide modified zeolite material, and mixing the obtained iron oxide modified zeolite with certain concentration MnSO4The solution is mixed and reacted, and then the adsorbing material with high Cr (VI) adsorbing capacity and large specific surface area can be prepared after cleaning and drying at low temperature, and is particularly suitable for the treatment of low-concentration industrial wastewater and drinking water in sudden Cr (VI) pollution events.
Although zeolite has been widely applied to wastewater treatment and zeolite-based materials are diversified, no material and technical method capable of simultaneously removing iron, manganese, ammonia nitrogen in low-temperature underground water exist. The existing difficulties and difficulties are that the zeolite has weak adsorption capacity to iron and manganese ions in underground water and has poor purification effect; although zeolite can adsorb and remove ammonia nitrogen in water, the low-temperature underground water with high iron, manganese and ammonia nitrogen has low water temperature and is anoxic, and even if microorganisms exist, ammonia nitrogen nitration is difficult to occur due to low metabolic activity of the microorganisms to realize biological regeneration, so that the zeolite can easily adsorb ammonia nitrogen to be saturated. The invention aims to solve the problem of simultaneous purification of high-iron, manganese, ammonia nitrogen in low-temperature underground water at present.
Disclosure of Invention
In order to avoid the problems in the prior art, the invention aims to provide a method for treating high-iron-manganese ammonia nitrogen composite polluted low-temperature underground water.
The invention takes natural zeolite as a raw material, manganese oxide is loaded on a zeolite-based material through oxidation reduction of permanganate and divalent manganese ions or hydrolysis, precipitation and oxidation of manganese sulfate, the material is loaded with microorganisms such as nitrobacteria, iron and manganese oxidizing bacteria and the like through impregnation of an enrichment culture solution, a multifunctional composite material of the zeolite-loaded manganese oxide and the microorganisms is prepared and is filled into a filter column, and the operation is carried out in a sequential batch mode according to four stages of water inlet adsorption, water drainage, biological regeneration of air blowing and nitrate washing. The zeolite exchange and ammonium ion adsorption function is exerted, simultaneously, the biological zeolite filler is endowed with the functions of removing iron and manganese by catalytic oxidation, the biological carrier and the loaded microorganisms such as nitrifying bacteria, iron and manganese oxidizing bacteria and the like to adsorb Fe2+、Mn2+And the zeolite regeneration is realized by ammonia nitrogen biological oxidation, and the problem of simultaneous purification of iron, manganese, ammonia nitrogen composite pollution in low-temperature underground water is solved.
The invention relates to a method for treating high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water, which comprises the following steps:
step 1: loading of oxides of manganese
Crushing and screening natural zeolite to obtain zeolite particles with the particle size of 0.8-1.2 mm; adding the obtained zeolite particles into 0.5-1M manganese sulfate solution, adding 0.5-1M potassium permanganate solution under stirring, and continuously stirring for reaction for 0.5-1 h; after the reaction is finished, taking out the particles, draining, and drying at 150 ℃ to obtain MnOX-a zeolite nanocomposite;
in the step 1, the mass-to-volume ratio of the zeolite particles to the manganese sulfate solution and the potassium permanganate solution is 1g:1mL:1 mL-10 g:1mL:1 mL.
The chemical reaction occurring in this step can be expressed by the following equation:
MnO7 -+Mn2++6H+→2MnO2+3H2O。
step 2: loading of microorganisms
MnO obtained in the step 1X-impregnating the zeolite nanocomposite material with 0.01-0.1M ammonium bicarbonate solution at room temperature for 5h until the adsorbed ammonium ions are saturated, and filling the zeolite nanocomposite material into a filter column; conveying the enrichment culture nitrifying bacteria and the iron-manganese oxidizing bacteria liquid which are 1-10 times of the volume of the filter column into the filter column by using a peristaltic pump, and circulating for 3 days for membrane hanging, wherein the total concentration of the bacteria liquid is more than 109cfu/mL；
And step 3: simultaneous purification of iron, manganese and ammonia nitrogen
3a, conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 2 for adsorption treatment to obtain effluent NH4 +N concentration 0.5mg/L, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
3b, draining water in the filter column, introducing air at 15-40 ℃ into the filter column for 12-24 hours by using an air blower, promoting iron and manganese adsorbed on the surface of the zeolite-based functional material to be oxidized, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize zeolite regeneration;
3c, spraying water from the top of the filter column for 5-10 min, washing nitrate generated by converting nitrifying bacteria into ammonia nitrogen, and discharging leacheate for independent treatment;
the processes 3a to 3c in step 3 constitute a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period. When the adsorption column is blocked, the suspended state of the particles is kept for 5min through gas-water synergistic backwashing, and the particles are accumulated again to rebuild the pores among the particles to recover the normal operation of the adsorption column.
The second treatment method of the high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water comprises the following steps:
step 1: preparation of zeolite porous materials
Crushing natural zeolite and sieving the crushed natural zeolite with a 100-mesh sieve to obtain zeolite powder; adding cement, lime, a surfactant and water into the obtained zeolite powder, and stirring to obtain a paste; adding aluminum powder serving as a foaming agent into the obtained paste, uniformly stirring, pouring into a mold, foaming and initially solidifying for 3-6 hours at 40 ℃, cutting into 2 x 2cm squares by using steel wires, and curing for 8-12 hours in a steam curing chamber at 110-150 ℃ under saturated steam pressure to obtain a zeolite porous material;
in the step 1, the addition amount of cement is 10-15% of the mass of the zeolite powder, the addition amount of lime is 5-10% of the mass of the zeolite powder, the addition amount of a surfactant with a bubble stabilizing function is 0.1-0.5% of the mass of the zeolite powder, the addition amount of aluminum powder is 0.2-1% of the mass of the zeolite powder, and the mass ratio of total solids of water is 50-60%.
Step 2: loading of oxides of manganese
Soaking the zeolite porous material obtained in the step 1 in 0.5M manganese sulfate solution at room temperature for 10min, taking out and draining, and naturally drying or drying to obtain a manganese oxide-loaded zeolite material;
the chemical reaction that occurs in this step can be expressed by the following equation:
Mn2++2O2+4H+→MnO2+2H2O
and step 3: loading of microorganisms
Impregnating the manganese oxide-loaded zeolite material obtained in the step 2 with enrichment culture nitrifying bacteria and iron-manganese oxidizing bacteria liquid with the volume being 1-10 times that of the manganese oxide-loaded zeolite material for 2-8h to load microorganisms, wherein the total concentration of the bacteria liquid is more than 108cfu/mL to obtain a zeolite material loaded with manganese oxide and microorganisms, and filling the zeolite material into a filter column;
and 4, step 4: simultaneous purification of iron, manganese and ammonia nitrogen
4a, conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 3 for adsorption treatment to obtain effluent NH4 +N concentration 0.5mg/L, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
4b, draining water in the filter column, introducing air at 15-40 ℃ into the filter column for 12-24 hours by using an air blower, promoting iron and manganese adsorbed on the surface of the zeolite-based functional material to be oxidized, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize zeolite regeneration;
4c, spraying water from the top of the filter column for 5-10 min, washing nitrate generated by converting nitrifying bacteria into ammonia nitrogen, and discharging eluent for independent treatment;
the processes 4a to 4c in step 4 constitute a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period. And when the adsorption column is blocked, the normal operation of the adsorption column is recovered by gas-water synergistic backwashing for 10 min.
The invention has the beneficial effects that:
the nanometer manganese oxide loaded on the surface of the zeolite enhances the Fe in the low-temperature underground water while not influencing the ion exchange adsorption of ammonia nitrogen by the zeolite2+、Mn2+Can lead the effluent Fe to be adsorbed by the composite material2+、Mn2+、NH4 +the-N concentration reaches the quality standard of drinking water.
Is prepared from natural zeoliteThe multifunctional composite material is prepared by loading manganese oxide and microorganisms on raw materials, and can adsorb Fe2+、Mn2+、NH4 +In addition to the function of-N, the microbial oxidation of Fe2+、Mn2+、NH4 +-function of N.
The operation is carried out in sequence and batch mode according to four stages of water inlet adsorption, water drainage, air blowing biological regeneration and nitrate washing. In the water inlet adsorption stage, the surface of the composite material faces Fe due to low water temperature and oxygen deficiency2+、Mn2+、NH4 +The removal of-N is mainly adsorption, the nitrification is weak, not only ammonia nitrogen is removed, but also the concentration of nitrate in effluent is low, the total nitrogen removal rate is high, and the defects of the prior art are overcome.
In the air blowing biological regeneration stage, because the water in the adsorption column is emptied, the water purification pressure is not available, the air pressure required by air blowing regeneration is low, and the energy consumption is low. To improve microbial oxidation of Fe2+、Mn2+、NH4 +the-N metabolic activity, the blast air temperature is increased by 15-40 ℃, and the problem of low microbial metabolic activity in low-temperature low water is solved.
The method has the advantage of simultaneously removing Fe in the groundwater2+、Mn2+、NH4 +N, and does not require aeration oxygenation of groundwater. The action mechanism is in an adsorption stage, and the zeolite, the loaded iron-manganese (hydrogen) oxide and the microorganism respectively adsorb NH4 +-N、Fe2+、Mn2+In the blast regeneration stage, the adsorption of ammonia nitrogen and the nitrification and the adsorption of Fe are finished by nitrifying bacteria2+、Mn2+Chemical and biological oxidation in the air overcomes the obstacle of insufficient dissolved oxygen in water. Nitrate formed by the nitrification of microorganisms is discharged independently in the washing stage, and NH is not contained in discharged water4 +-N converted nitrate. The improvement of the air inlet temperature in the blast regeneration stage can enhance the metabolic activity of nitrobacteria and iron-manganese oxidizing bacteria, shorten the regeneration time and overcome the obstacle of biological nitrification and deamination of ammonia nitrogen in underground water at low temperature.
Detailed Description
Example 1:
the treatment method of the high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water in the embodiment comprises the following steps:
1. crushing and screening natural clinoptilolite ore to obtain zeolite particles with the particle size of 0.8-1.2 mm;
2. adding 100g of zeolite particles into 0.5M 100mL of manganese sulfate solution, adding 0.5M 100mL of potassium permanganate solution while stirring, and continuously stirring for reaction for 0.5 h; after the reaction is finished, taking out the particles, draining, and drying at 150 ℃ to obtain MnOX-a zeolite nanocomposite;
3. MnO ofX-impregnating the zeolite nanocomposite material with 0.05M ammonium bicarbonate solution at room temperature for 5h to adsorb ammonium ions, and filling into a filter column;
4. enrichment culture of nitrifying bacteria and iron-manganese oxidizing bacteria liquid (total concentration of bacteria liquid is greater than 10) with 10 times of volume of filter column9cfu/mL) is conveyed into a filter column by a peristaltic pump, and the membrane is hung for 3 days in a circulating mode;
5. conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 4 for adsorption treatment to obtain effluent NH4 +N concentration 0.5mg/L, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
6. draining water in the filter column, introducing air of 30 ℃ into the filter column for 24 hours by using an air blower to promote the oxidation of iron and manganese adsorbed on the surface of the zeolite-based functional material, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize the regeneration of the zeolite;
7. spraying water from the top of the filter column for 5min, washing nitrate generated by nitrobacteria converted into ammonia nitrogen, and discharging the eluent for independent treatment;
the processes of steps 5 to 7 form a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period. When the adsorption column is blocked, the pores among the particles are backwashed by the cooperation of gas and water to recover the normal operation of the adsorption column.
The method of the invention is used for treating high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground waterTreatment, the effluent guarantee meets the drinking water standard: NH (NH)4 +-N concentration less than 0.5mg/L, total iron concentration less than 0.3mg/L, Mn2+The concentration is less than 0.1 mg/L.
Example 2:
the treatment method of the high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water in the embodiment comprises the following steps:
1. crushing natural zeolite and sieving the crushed natural zeolite with a 100-mesh sieve to obtain zeolite powder; adding cement, lime, a surfactant and water into the obtained zeolite powder, and stirring to obtain a paste; adding aluminum powder as a foaming agent into the obtained paste, uniformly stirring, pouring into a mold, foaming and initially solidifying for 3 hours at 40 ℃, cutting into 2 x 2cm squares by using steel wires, and curing for 12 hours in a steam curing chamber at 130 ℃ under saturated steam pressure to obtain a zeolite porous material;
in the step 1, the addition amount of the cement is 15% of the mass of the zeolite powder, the addition amount of the lime is 5% of the mass of the zeolite powder, the addition amount of the surfactant is 0.1% of the mass of the zeolite powder, the addition amount of the aluminum powder is 0.2% of the mass of the zeolite powder, and the mass ratio of the total solid of water is 50-60%.
2. Dipping the zeolite porous material obtained in the step 1 by using a 0.5M manganese sulfate solution, taking out and draining, and naturally drying or drying to obtain a manganese oxide-loaded zeolite material;
3. impregnating the manganese oxide-loaded zeolite material obtained in the step 2 with enrichment culture nitrifying bacteria and iron-manganese oxidizing bacteria liquid for 2-8h to load microorganisms, wherein the concentration of the bacteria liquid is more than 108cfu/mL to obtain a zeolite material loaded with manganese oxide and microorganisms, and filling the zeolite material into a filter column;
4. conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 3 for adsorption treatment to obtain effluent NH4 +N concentration 0.5mg/L, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
5. draining water in the filter column, introducing air of 40 ℃ into the filter column for 12h by using an air blower to promote the oxidation of iron and manganese adsorbed on the surface of the zeolite-based functional material, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize the regeneration of the zeolite;
6. spraying water from the top of the filter column for 10min, washing nitrate generated by nitrobacteria converted into ammonia nitrogen, and discharging the eluent for independent treatment;
the processes of steps 4 to 6 form a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period. When the adsorption column is blocked, the pores among the particles are backwashed by the cooperation of gas and water to recover the normal operation of the adsorption column.
The high-iron-manganese-ammonia-nitrogen composite polluted low-temperature underground water is treated by the method, and the effluent guarantees that the drinking water standard is met: NH (NH)4 +-N concentration less than 0.5mg/L, total iron concentration less than 0.3mg/L, Mn2+The concentration is less than 0.1 mg/L.
Claims (8)
1. A method for treating high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water is characterized by comprising the following steps:
step 1: loading of oxides of manganese
Crushing and screening natural zeolite to obtain zeolite particles with the particle size of 0.8-1.2 mm; adding the obtained zeolite particles into 0.5-1M manganese sulfate solution, adding 0.5-1M potassium permanganate solution under stirring, and continuously stirring for reaction for 0.5-1 h; after the reaction is finished, taking out the particles, draining, and drying at 150 ℃ to obtain MnOX-a zeolite nanocomposite;
step 2: loading of microorganisms
MnO obtained in the step 1X-impregnating zeolite nano composite material with 0.01-0.1M ammonium bicarbonate solution at room temperature until the adsorption ammonium ion is saturated, and filling the impregnated zeolite nano composite material into a filter column; conveying the enrichment culture nitrifying bacteria and the iron-manganese oxidizing bacteria liquid which are 1-10 times of the volume of the filter column into the filter column by using a peristaltic pump, and circulating for 3 days to carry out biofilm formation;
and step 3: simultaneous purification of iron, manganese and ammonia nitrogen
3a, conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 2 for adsorption treatment to obtain effluent NH4 +-N concentration 0.5mgPer liter, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
3b, draining water in the filter column, introducing air at 15-40 ℃ into the filter column for 12-24 hours by using an air blower, promoting iron and manganese adsorbed on the surface of the zeolite-based functional material to be oxidized, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize zeolite regeneration;
3c, spraying water from the top of the filter column for 5-10 min, washing nitrate generated by converting nitrifying bacteria into ammonia nitrogen, and discharging leacheate for independent treatment;
the processes 3a to 3c in step 3 constitute a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period.
2. The processing method according to claim 1, characterized in that:
in the step 1, the mass-to-volume ratio of the zeolite particles to the manganese sulfate solution and the potassium permanganate solution is 1g:1mL:1 mL-10 g:1mL:1 mL.
3. The processing method according to claim 2, characterized in that:
in step 2, the total concentration of the nitrifying bacteria and the iron-manganese oxidizing bacteria liquid which are subjected to enrichment culture is more than 109cfu/mL。
4. The processing method according to claim 1, characterized in that:
when the adsorption column is blocked, the suspended state of the particles is kept for 5min through gas-water synergistic backwashing, and the particles are accumulated again to rebuild the pores among the particles to recover the normal operation of the adsorption column.
5. A method for treating high-iron-manganese ammonia nitrogen combined pollution low-temperature underground water is characterized by comprising the following steps:
step 1: preparation of zeolite porous materials
Crushing natural zeolite and sieving the crushed natural zeolite with a 100-mesh sieve to obtain zeolite powder; adding cement, lime, a surfactant and water into the obtained zeolite powder, and stirring to obtain a paste; adding aluminum powder serving as a foaming agent into the obtained paste, uniformly stirring, pouring into a mold, foaming and initially solidifying for 3-6 hours at 40 ℃, cutting into 2 x 2cm squares by using steel wires, and curing for 8-12 hours in a steam curing chamber at 110-150 ℃ under saturated steam pressure to obtain a zeolite porous material;
step 2: loading of oxides of manganese
Soaking the zeolite porous material obtained in the step 1 in 0.5M manganese sulfate solution at room temperature for 10min, taking out and draining, and naturally drying or drying to obtain a manganese oxide-loaded zeolite material;
and step 3: loading of microorganisms
Dipping the manganese oxide-loaded zeolite material obtained in the step (2) for 2-8h by using enrichment culture nitrifying bacteria and iron-manganese oxidizing bacteria liquid with the volume being 1-10 times that of the manganese oxide-loaded zeolite material to obtain a manganese oxide-loaded and microorganism-loaded zeolite material, and filling the manganese oxide-loaded and microorganism-loaded zeolite material into a filter column;
and 4, step 4: simultaneous purification of iron, manganese and ammonia nitrogen
4a, conveying the high-iron-manganese-ammonia-nitrogen combined polluted low-temperature underground water to the filter column in the step 3 for adsorption treatment to obtain effluent NH4 +N concentration 0.5mg/L, total iron concentration 0.3mg/L, Mn2+The concentration of 0.1mg/L is a penetration point, and the operation is stopped when any index exceeds a standard;
4b, draining water in the filter column, introducing air at 15-40 ℃ into the filter column for 12-24 hours by using an air blower, promoting iron and manganese adsorbed on the surface of the zeolite-based functional material to be oxidized, and nitrifying ammonia nitrogen adsorbed by zeolite by microorganisms under the condition of ventilation and oxygen supply to realize zeolite regeneration;
4c, spraying water from the top of the filter column for 5-10 min, washing nitrate generated by converting nitrifying bacteria into ammonia nitrogen, and discharging eluent for independent treatment;
the processes 4a to 4c in step 4 constitute a sequencing batch operation cycle; and conveying the high-iron manganese ammonia nitrogen composite polluted low-temperature underground water to be treated to the filter column for the next operation period.
6. The processing method according to claim 5, characterized in that:
in the step 1, the addition amount of cement is 10-15% of the mass of the zeolite powder, the addition amount of lime is 5-10% of the mass of the zeolite powder, the addition amount of a surfactant with a bubble stabilizing function is 0.1-0.5% of the mass of the zeolite powder, the addition amount of aluminum powder is 0.2-1% of the mass of the zeolite powder, and the mass ratio of total solids of water is 50-60%.
7. The processing method according to claim 5, characterized in that:
in step 3, the total concentration of the nitrifying bacteria and the iron-manganese oxidizing bacteria liquid which are subjected to enrichment culture is more than 108cfu/mL。
8. The processing method according to claim 5, characterized in that:
when the adsorption column is blocked, the normal operation of the adsorption column is recovered through the cooperation of gas and water and back washing.
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