CN114163025B - Enhanced starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation - Google Patents
Enhanced starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
- C02F1/64—Heavy metal compounds of iron or manganese
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
A strengthening starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation belongs to the field of water treatment. The enhanced starting stage adopts a potassium permanganate pre-oxidation technology to shorten the starting period of the gravity type ultrafiltration demanganizing technology, and the gravity type ultrafiltration technology can realize the efficient and stable removal of manganese in polluted surface water under the conditions of no potassium permanganate, no hydraulic back flushing and no chemical cleaning after entering a stable operation stage. Continuously adding potassium permanganate in a moderate adding amount mode to strengthen and accelerate the forming process of a manganese active filter cake layer on the surface of the ultrafiltration membrane in the starting stage until the content of manganese in water filtered by the membrane of the gravity type external pressure ultrafiltration membrane is continuously lower than 0.1mg/L; in the stable operation stage, raw water of manganese-containing surface water can directly enter a membrane pool in a gravity flow mode, and high-efficiency and stable removal of manganese can be realized by means of catalytic oxidation and physical interception of a manganese active filter cake layer on the surface of an ultrafiltration membrane.
Description
Technical Field
The invention relates to the field of pollution removal and water quality purification in the process of natural surface water and water resource utilization, in particular to a reinforced starting method of a gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation, belonging to the field of water treatment.
Background
In recent years, along with the rapid development of fields such as industries, mining industries, construction industries and the like in China, the phenomenon of manganese pollution of various natural surface water is more serious, and the natural surface water has the characteristics of mainly endogenous pollution and seasonality and burstiness. According to investigation, seasonal and sudden manganese exceeding phenomena of different degrees occur in surface water reservoirs, lakes, rivers and the like, wherein the manganese concentration is in the range of 0.2mg/L-4.0mg/L, and the manganese content limit value of 0.1mg/L in the sanitary standard (GB 5749-2006) of the living drinking water is far exceeded. In addition, in the water resource utilization process, the problem of exceeding manganese is often encountered. The excessive manganese content can cause the increase of the chromaticity of water, and serious threat and influence are generated on the safety of water supply, so that efficient purification of manganese-containing surface water is needed.
At present, the demanganization method mainly comprises a natural oxidation method, a chemical oxidation method, a contact oxidation method, a biological oxidation method, a membrane treatment method and the like, and most of the demanganization methods are demanganization processes for the manganese-containing underground water. The natural oxidation method adopts the processes of aeration, precipitation, filtration and the like, and has complex process flow and huge equipment; the contact catalytic oxidation method realizes demanganization by means of catalytic oxidation of mature manganese sand, but the mature manganese sand has long culture period and demanganization effect is easily influenced by water quality; the membrane treatment method is combined with pre-oxidation for removing manganese, but causes serious membrane pollution, frequent back flushing and chemical cleaning are required, and the operation and maintenance cost is high.
The natural water on the surface has the problem of manganese-organic compound pollution, especially in the areas of buildings, communities, villas, holidays, rural areas, villages and the like, and has the characteristics of various source water, simple treatment process, weak technical strength, difficult operation and maintenance and dispersed arrangement, and the existing demanganizing device has the problems of long starting period of demanganizing process, unstable demanganizing effect, complex operation, difficult operation and maintenance and the like, and is difficult to meet the demands of decentralized water supply and water resource utilization. Therefore, there is a need to develop a targeted manganese-containing surface water treatment technology with the characteristics of short starting period, simple and convenient operation, low operation and maintenance cost and suitability for decentralized water supply.
The gravity type ultrafiltration system is a novel membrane filtration process based on the development of the requirements of dispersion type water quality purification and water resource utilization, has the characteristics of low maintenance, low energy consumption and simple operation, and is very suitable for the field of dispersion type water quality purification and water resource utilization. The gravity ultrafiltration process also has certain demanganization capacity, but the demanganization function has a starting period as long as several months, so that the further popularization and the use of the gravity ultrafiltration process are limited. Therefore, it is necessary to establish a gravity type ultrafiltration demanganization process rapid starting method with the demanganization function of natural surface water.
Disclosure of Invention
The invention aims to solve the problems of long starting period, unstable demanganization effect, complex operation and difficult operation and maintenance of the demanganization process of the existing gravity type ultrafiltration process, and aims to establish a reinforced starting method of the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation so as to realize the rapid starting of the gravity type ultrafiltration demanganization function.
The purpose of the invention is that: in the reinforced starting stage, adding a proper amount of potassium permanganate into raw water for pre-oxidation, generating manganese oxide with catalytic oxidation on the surface of an ultrafiltration membrane of a gravity ultrafiltration process, rapidly forming an active manganese filter cake layer, and shortening the starting period of a manganese removal function; after entering a stable operation stage, the efficient and stable demanganization function can be realized under the condition of no need of adding an oxidant by means of the catalytic oxidation and physical interception of the manganese filter cake layer on the surface of the ultrafiltration membrane.
The invention is realized by the following technical scheme:
a strengthening starting method of gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation comprises a raw water tank, a water inlet pipe, a pipeline mixer, a dosing tank, a dosing pump, a dosing pipe, a membrane pool, a gravity type ultrafiltration membrane, a water outlet pipe and a clean water tank; wherein former water tank, inlet tube, pipeline blender, membrane pond link to each other in proper order, and gravity type milipore filter arranges in the membrane pond, and gravity type milipore filter, outlet pipe, clear water tank link to each other in proper order, and dosing tank, dosing pump, dosing pipe, pipeline blender link to each other in proper order, and the pipeline blender that is located on the inlet tube links to each other with dosing pipe.
When the manganese-containing surface water is started, raw water of the manganese-containing surface water entering the raw water tank flows through the water inlet pipe and the pipeline mixer in a gravity flow mode, potassium permanganate liquid medicine in the dosing tank is fed into the pipeline mixer through the dosing pump and the dosing pipe, and is fully mixed with raw water and then enters the membrane tank through the water inlet pipe; after being filtered by a gravity type ultrafiltration membrane in the membrane tank, the membrane filtration water flows into a clean water tank in a gravity flow mode through a water outlet pipe; the method specifically comprises the following steps:
(1) Detecting the manganese content of raw water and the oxygen consumption of permanganate (calculated according to a GB5750-2006 standard method), calculating and evaluating a manganese content exceeding range and a potassium permanganate dosage range, gradually increasing the potassium permanganate dosage in the determined potassium permanganate dosage range, observing the color of water fed into a membrane tank by adopting a visual method until a slight pink phenomenon just appears in the water fed into the membrane tank, stopping the relatively high potassium permanganate dosage at the moment, correspondingly reducing the potassium permanganate dosage, determining the moderate dosage, continuously adding the potassium permanganate under the condition of moderate dosage, avoiding the phenomenon of pink of raw water in the membrane tank, and observing the red brown attachments or filter cake layers on the surface of ultrafiltration membrane filaments by adopting a visual method;
(2) Stopping adding potassium permanganate after continuously adding for 15 days, after completely updating water in the membrane tank into raw water without adding potassium permanganate, detecting the manganese content of membrane filtered water, continuously adding potassium permanganate according to the moderate dosage of the step (1), and repeating the steps every 3-5 days, namely stopping adding potassium permanganate, detecting the manganese content of the membrane filtered water, observing the change trend of the manganese content of the water until the manganese content of the membrane filtered water is always lower than 0.1mg/L, and ending the strengthening starting stage.
Entering a stable operation stage after the strengthening start is finished: after the strengthening start is finished, raw water directly enters a membrane tank from a raw water tank to carry out gravity type ultrafiltration, and enters a stable operation stage, and in the stable operation stage, raw water containing manganese directly enters the membrane tank in a gravity flow mode, and the high-efficiency and stable removal of manganese can be realized by means of the catalytic oxidation and physical interception effects on the surface of an ultrafiltration membrane and the filtration of the ultrafiltration membrane. In the process of strengthening starting and stable operation, the membrane tank does not need any aeration, hydraulic back flushing or chemical cleaning, and only needs to discharge mud at regular time; and stopping adding potassium permanganate in the stable operation stage.
The invention is mainly suitable for surface water with excessive manganese content and polluted surface water, including surface natural water such as reservoir water, lake water, river water and the like, and rainwater, reclaimed water and the like for water resource utilization; when the manganese content of raw water is 0.1-4.0mg/L and the oxygen consumption of permanganate is 2.0-5.0mg/L, the concentration of potassium permanganate in the membrane tank is 0.1-10.0 mg/L. According to the oxygen consumption range of the permanganate of the raw water, the potassium permanganate dosage (mass or weight) range is 0.6-0.9 times of the oxygen consumption of the permanganate. The weight concentration of the potassium permanganate liquor prepared in the dosing tank is 0.1-3.0%.
In the invention, the gravity type ultrafiltration membrane is a curtain type hollow fiber membrane and adopts an external pressure type membrane component; the membrane material is Polyethersulfone (PES), polyvinylidene fluoride (PVDF), polyethylene (PVC) and the like, and the pore diameter of the membrane pores is 0.01-0.1 mu m. The filtration pressure of the gravity type ultrafiltration membrane is 2-9kPa, and the membrane flux in the enhanced starting stage is 5-15L/(m) 2 H) range, membrane flux at steady operation stage of 3-6L/(m) 2 H) range.
The invention has the following characteristics:
1. compared with the natural starting process of the gravity type ultrafiltration process, the cycle of the enhanced starting method is obviously shortened, and the cost during the starting period is greatly saved;
2. the gravity type ultrafiltration process in the enhanced starting stage does not need any aeration, hydraulic back flushing or chemical cleaning, and only needs to discharge mud at regular time;
3. the gravity type ultrafiltration process adopting the enhanced starting method also has the functions of efficiently removing turbidity, ammonia nitrogen, organic matters, algae, bacteria, viruses and the like;
4. the enhanced starting method is little affected by seasons, has low requirements on water quality conditions, low technical difficulty and strong operability;
5. the enhanced starting method does not need to increase process units, has the characteristics of easy operation, simple operation and maintenance and the like, and has wide application prospect and popularization value.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Reference numerals
Raw water tank (1), water inlet pipe (2), pipeline mixer (3), dosing tank (4), dosing pump (5), dosing pipe (6), membrane tank (7), gravity ultrafiltration membrane (8), water outlet pipe (9), clean water tank (10)
Detailed Description
The following is further described in conjunction with the accompanying drawings and specific examples to provide a better understanding of the invention and to enable one skilled in the art to practice it, but these examples are intended to illustrate the invention and are not to be construed as limiting its scope.
Example 1
Taking raw water of a manganese-containing surface reservoir in Hainan as an example, the raw water quality index is as follows: manganese content 0.51mg/L, permanganate oxygen consumption 2.0mg/L, UV 254 0.038cm -1 The ammonia nitrogen content is 0.35mg/L, the turbidity is 3.05NTU, the chlorophyll a is 0.035, and the manganese content is far higher than the limit value of 0.1mg/L in the sanitary standard of drinking water (GB 5749-2006).
The composition of the method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation is shown in figure 1. The specific operation method is as follows:
1) According to the manganese content of raw water and the oxygen consumption of permanganate, determining the potassium permanganate dosage range to be 1.1-1.4mg/L, gradually increasing the potassium permanganate dosage in the determined dosage range, wherein each time of increase is 0.1mg/L, observing the color of effluent of the membrane tank by adopting a visual method, stopping increasing the potassium permanganate dosage when the water in the membrane tank has slight pink phenomenon just, and properly reducing the potassium permanganate dosage to be 1.1mg/L at the moment, thereby determining the moderate dosage to be 1.1mg/L.
2) Stopping adding potassium permanganate after continuously adding for 15 days under the moderate dosage of 1.1mg/L, and detecting the manganese content of the membrane filtered water; at the moment, the manganese content of the membrane filtered water still does not reach the standard, and potassium permanganate is continuously added according to a proper dosage; and repeating the above operation every 3-5 days. After stopping dosing on day 25, the manganese content of the membrane filtered water was continuously below 0.1mg/L, and the enhanced start-up phase could be ended. At this time, it was visually observed that a reddish brown manganese active cake layer was formed on the surface of the ultrafiltration membrane.
3) In the stable operation stage, raw water of the manganese-containing surface water directly enters the membrane pool through the water inlet pipe in a gravity flow mode, and the manganese can be efficiently and stably removed by means of catalytic oxidation and physical interception of the manganese active filter cake layer on the surface of the ultrafiltration membrane, wherein the manganese content of the water is about 0.02mg/L.
4) In the process of strengthening starting and stable running, no aeration, hydraulic back flushing or chemical cleaning is carried out, and the sludge discharge is carried out only once a week for about 3min.
5) The gravity type ultrafiltration membrane adopted in the experiment is a curtain type hollow fiber membrane, and an external pressure type membrane component is adopted; the membrane material is Polyethersulfone (PES), the pore diameter of the membrane is 0.03 mu m, and the filtration pressure is 6kPa.
After 120 days of continuous operation according to the process shown in FIG. 1, the stable membrane flux of the gravity type ultrafiltration demanganization process is still maintained at 3.32-3.35L/(m) 2 h) A. The invention relates to a method for producing a fibre-reinforced plastic composite The pollution indexes of the membrane filtered water are respectively manganese content of 0.02mg/L and permanganate oxygen consumption of 1.2mg/L, UV 254 Content of 0.015cm -1 The ammonia nitrogen content is 0.03mg/L, the turbidity is 0.25NTU, and the chlorophyll a content is 0.003, which all meet sanitary standards for domestic drinking water (GB 5749-2006).
Claims (7)
1. The intensified starting method of the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation is characterized in that the equipment comprises a raw water tank, a water inlet pipe, a pipeline mixer, a dosing tank, a dosing pump, a dosing pipe, a membrane pool, a gravity type ultrafiltration membrane, a water outlet pipe and a clean water tank; wherein the raw water tank, the water inlet pipe, the pipeline mixer and the membrane tank are sequentially connected, the gravity ultrafiltration membrane is arranged in the membrane tank, the gravity ultrafiltration membrane, the water outlet pipe and the clean water tank are sequentially connected, the dosing tank, the dosing pump, the dosing pipe and the pipeline mixer are sequentially connected, and the pipeline mixer on the water inlet pipe is connected with the dosing pipe;
when the manganese-containing surface water is started, raw water of the manganese-containing surface water entering the raw water tank flows through the water inlet pipe and the pipeline mixer in a gravity flow mode, potassium permanganate liquid medicine in the dosing tank is fed into the pipeline mixer through the dosing pump and the dosing pipe, and is fully mixed with raw water and then enters the membrane tank through the water inlet pipe; after being filtered by a gravity type ultrafiltration membrane in the membrane tank, the membrane filtration water flows into a clean water tank in a gravity flow mode through a water outlet pipe; the method specifically comprises the following steps:
(1) Detecting the manganese content of raw water, calculating the oxygen consumption of potassium permanganate according to a GB5750-2006 standard method, calculating and evaluating an exceeding range of the manganese content and an addition range of the potassium permanganate, gradually increasing the addition of the potassium permanganate in the determined addition range of the potassium permanganate, observing the color of water fed into the membrane tank by adopting a visual method until a slight pink phenomenon just appears in the water fed into the membrane tank, stopping the relatively high addition of the potassium permanganate at the moment, correspondingly reducing the addition of the potassium permanganate, determining the moderate addition amount, continuously adding the potassium permanganate under the condition of the moderate addition amount, avoiding the pink phenomenon of the raw water in the membrane tank, and observing the red brown attachments or filter cake layers on the surface of the ultrafiltration membrane wire by adopting a visual method;
(2) Stopping adding potassium permanganate after continuously adding for 15 days, after completely updating water in the membrane tank into raw water without adding potassium permanganate, detecting the manganese content of membrane filtered water, continuously adding potassium permanganate according to the moderate dosage of the step (1), and repeating the steps every 3-5 days, namely stopping adding potassium permanganate, detecting the manganese content of the membrane filtered water, observing the change trend of the manganese content of the water until the manganese content of the membrane filtered water is always lower than 0.1mg/L, and ending the strengthening starting stage.
2. The method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation according to claim 1, wherein the method enters a stable operation stage after strengthening and starting is finished: after the strengthening start is finished, raw water directly enters a membrane tank from a raw water tank to carry out gravity ultrafiltration, and enters a stable operation stage, wherein in the stable operation stage, manganese-containing raw water directly enters the membrane tank in a gravity flow mode, and the high-efficiency and stable removal of manganese can be realized by means of the catalytic oxidation and physical interception effects on the surface of an ultrafiltration membrane and the filtration of the ultrafiltration membrane; in the process of strengthening starting and stable operation, the membrane tank does not need any aeration, hydraulic back flushing or chemical cleaning, and only needs to discharge mud at regular time; and stopping adding potassium permanganate in the stable operation stage.
3. The method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation according to claim 1, wherein the method is suitable for surface water with standard exceeding manganese content and pollution, including surface natural water of reservoir water, lake water and river water, rainwater and reclaimed water for water resource utilization.
4. The method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation according to claim 1, wherein when the manganese content of raw water is 0.1-4.0mg/L and the oxygen consumption of potassium permanganate is 2.0-5.0mg/L, the concentration of potassium permanganate in a membrane tank is 0.1-10.0 mg/L.
5. The method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation according to claim 1, wherein the potassium permanganate dosage range is 0.6-0.9 times of the potassium permanganate oxygen consumption according to the potassium permanganate oxygen consumption range of raw water; the weight concentration of the potassium permanganate liquor prepared in the dosing tank is 0.1-3.0%.
6. The method for strengthening and starting the gravity type ultrafiltration demanganization process based on potassium permanganate pre-oxidation according to claim 1, wherein the gravity type ultrafiltration membrane is a curtain type hollow fiber membrane and an external pressure type membrane component is adopted; the membrane material is Polyethersulfone (PES), polyvinylidene fluoride (PVDF) or Polyethylene (PVC), and the pore diameter of the membrane pore is 0.01-0.1 μm.
7. The method for strengthening and starting the gravity type ultrafiltration demanganizing technology based on potassium permanganate pre-oxidation according to claim 1, wherein the filtration pressure of the gravity type ultrafiltration membrane is 2-9kPa, and the membrane flux in the strengthening and starting stage is 5-15L/(m) 2 H) range, membrane flux at steady operation stage of 3-6L/(m) 2 H) range.
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