CN109095565A - A kind of water depth processing unit - Google Patents

A kind of water depth processing unit Download PDF

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Publication number
CN109095565A
CN109095565A CN201811057301.2A CN201811057301A CN109095565A CN 109095565 A CN109095565 A CN 109095565A CN 201811057301 A CN201811057301 A CN 201811057301A CN 109095565 A CN109095565 A CN 109095565A
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China
Prior art keywords
water
plate
pipeline
processing unit
carbon nanomaterial
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CN201811057301.2A
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CN109095565B (en
Inventor
钱飞跃
高仕谦
沈耀良
王俊霞
黄慧敏
盛嘉逸
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Suzhou University of Science and Technology
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Suzhou University of Science and Technology
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Priority to CN201811057301.2A priority Critical patent/CN109095565B/en
Publication of CN109095565A publication Critical patent/CN109095565A/en
Application granted granted Critical
Publication of CN109095565B publication Critical patent/CN109095565B/en
Priority to PCT/CN2019/098806 priority patent/WO2020052361A1/en
Priority to US17/041,421 priority patent/US11840463B2/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/14Maintenance of water treatment installations
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00Specific treatment goals
    • C02F2303/16Regeneration of sorbents, filters
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/023Reactive oxygen species, singlet oxygen, OH radical

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention relates to a kind of water depth processing units, including the plate and frame membrane reactor with water inlet pipe and outlet pipe, the raw water transfer being connected with the water inlet pipe of the plate and frame membrane reactor, the clear water reserviors being connected with the outlet pipe of the plate and frame membrane reactor, the water depth processing unit further includes the oxidant dosing system being connected with the water inlet pipe of the plate and frame membrane reactor or the raw water transfer, the plate and frame membrane reactor further includes carbon nanomaterial composite membrane, the carbon nanomaterial composite membrane includes the carbon nanomaterial layer being successively set between the water inlet pipe and the outlet pipe, load has the basement membrane layer of the carbon nanomaterial layer, the raw material of the carbon nanomaterial layer includes single layer redox graphene and multi-walled carbon nanotube.The purification efficiency of water depth processing unit of the invention is high, low energy consumption for processing, heavy metal free secondary pollution, applied widely.

Description

A kind of water depth processing unit
Technical field
The invention belongs to environmental technology fields, and in particular to a kind of water depth processing unit.
Background technique
With a large amount of uses of artificial synthesized chemicals (such as drug and personal care articles, detergent, pesticide), middle part Branch is discharged into natural water body by urban drainage system, brings potential ecology and environmental risk.The pollutant usually has There are the features such as concentration low (< 1mg/L), molecular weight small (< 500Dalton), strong solubility height and persistence, also referred to as micro- pollution Object.Some researches show that, the tradition water treatment technology such as coagulation, precipitating, filtering and biodegrade to the removal efficiency of micropollutants compared with It is low, it is unable to satisfy the requirement of drinking water deep purification.Currently, membrane separation technique and advanced oxidation processes are considered as that control is organic micro- The effective means of pollutant.
The effects of by steric effect, electrostatic repulsion, dissolution diffusion, with nanofiltration (NF), the film that reverse osmosis (RO) is representative Isolation technics can each pollutant in effectively catching water, have it is easy to operate quickly, target adapts to wide, device and is easy to automatic The advantages that change, but its transmembrane pressure need to be controlled in NF 10-20bar, RO 20-100bar, and the energy consumption of processing unit water is higher, Producing water ratio is usually less than 75%, is still to carry out subsequent processing to condensed water.Further, since being pure physical separating process, pollutant Be attached in film surface and duct and cause fouling membrane, the system of will lead to produce it is aqueous can significant decrease, even if using backwash and Chemical cleaning also can only partially be restored.In contrast, advanced oxidation processes, which mainly pass through, generates a certain amount of OH, SO4 ·-Equal Strong oxdiatives Free love base, degradation, mineralising pollutant, for example, ultraviolet light or visible light catalytic oxidation, catalytic ozonation, persulfate are urged Change oxidation, Fenton (Fenton) reaction etc..In the above system, often make using all kinds of transition-metals and their oxides as catalyst With.Currently, how effectively fixed, separate and regenerated catalyst, realize and reuse, and stringent prevention and control digestion of metallic ion is still Limit the main problem of such methods engineering application.
As a kind of nonmetal nano material, graphene oxide (GO) thin slice has the two-dimensional layer close to single carbon atom thickness Shape structure, mainly by sp2The hexa-atomic carboatomic ring of hydridization and great amount of hydroxy group, carboxyl and epoxy-functional composition.With graphene phase Than the hydrophily of GO is stronger, is easier to realize functionalization, and cost is relatively low, is well suited for being used to prepare novel film materials.Have The study found that GO Surface oxygen-containing groups will obtain partial reduction under the conditions of strong basicity and certain temperature, it can shape in carbon atomic layer At zigzag defect, formed redox graphene (rGO).This not only makes rGO obtain stronger persulfate to urge with ozone Change activity, produces a large amount of SO4 ·-Or OH free radical, also significantly reduce hydrone in the frictional force of carbon material surface, favorably In the excessively aqueous energy for improving GO membrane material, transmembrane pressure is reduced.If can have the function of catalysis oxidation using the foundation of rGO thin slice Film separation system, will effectively overcome the inherent defect of traditional membrane separation technique and advanced oxidation processes, become control water in micro- dirt Contaminate a kind of new method of object.
It should be noted that reaction unit is the place for carrying out water process, and determine the key factor for the treatment of effect.It is existing Some treatment reaction devices and its control method not can be implemented simultaneously UF membrane and catalysis oxidation function, and reason includes: that (1) exists In existing apparatus, NF and RO membrane module can be used in efficiently separating for pollutant, but oxidant is added in raw water, not only cannot The pollutant for generating enough strong oxidative free radical degradation retentions, can also do great damage to membrane structure, lead to its separation effect It can significantly reduce;(2) in existing apparatus, in order to give full play to catalyst efficiency, frequently with reduction catalyst ruler during reaction The methods of very little, raising mixing intensity.It when after reaction, and needs to carry out lock out operation to catalyst, to obtain processing water outlet. It is difficult that aforesaid operations method is realized in industrialization continuous operation;(3) in existing apparatus, do not have to decaying catalyst Carry out in-situ regeneration function, can only pass through periodic replacement catalyst, it is ensured that the operation of device, this will certainly improve its operation at This.
Therefore, the design of reaction unit configuration and its control method how are innovated, reduction-oxidation graphite is farthest played The separation of alkene film and catalysis, it has also become the key of micropollutants in water removal is efficiently gone using this water process new technology.
Summary of the invention
Technical problem to be solved by the invention is to provide the catalysis that one kind can give full play to carbon nanomaterial composite membrane Oxidation and separation retention functions, and the structure of carbon nanomaterial composite membrane will not be caused at the water depth of non-renewable damage Manage device and method.
In order to solve the above technical problems, the present invention adopts the following technical scheme that:
It is an object of the present invention to provide a kind of water depth processing units, including the sheet frame with water inlet pipe and outlet pipe Formula membrane reactor, the raw water transfer being connected with the water inlet pipe of the plate and frame membrane reactor and the plate and frame The clear water reserviors that the outlet pipe of membrane reactor is connected, the water depth processing unit further include and the plate and frame film reaction The oxidant dosing system that the water inlet pipe of device or the raw water transfer are connected, the plate and frame membrane reactor also wrap Include carbon nanomaterial composite membrane, the carbon nanomaterial composite membrane includes being successively set on the water inlet pipe and described going out Carbon nanomaterial layer, load between water pipe have the basement membrane layer of the carbon nanomaterial layer, the carbon nanomaterial layer Raw material include single layer redox graphene and multi-walled carbon nanotube.
The present invention by the single layer redox graphene that is mutually coupled in carbon nanomaterial layer and multi-walled carbon nanotube with Oxidant effect in oxidant dosing system, catalysis form the strong oxidizing property free radical of degradation of contaminant, meanwhile, oxidant is not The structure of basement membrane layer can be damaged.The mixed liquor of raw water and oxidant to be processed is in the micro- of carbon nanomaterial composite membrane It sees in layer structure and does Tortuous flow, and catalysis oxidation and separation retention occur simultaneously, to effectively remove organic micro- in water Pollutant.In addition, the present invention is by the way that carbon nanomaterial layer to be carried in basement membrane layer, basement membrane layer can play the work of support With to improve the compound film strength of carbon nanomaterial.
Preferably, redox graphene (rGO) described in the carbon nanomaterial layer and the multi wall carbon are received The mass ratio of mitron (MWCNT) is 2~4:1.
Preferably, the redox graphene is flaky, and a diameter of 2~5 μm, with a thickness of 0.8~1.2nm, Carbon oxygen atom ratio is 3~4:1, single layer rate > 95%.
Wherein, the redox graphene be using the graphene oxide of commercially available acquisition as raw material, it is auxiliary using ultrasonic wave Dispersion method is helped to obtain graphene oxide dispersion, ultrasonic power density is 4~6WmL-1, ultrasonic time is 20~30min, Then, it is that 10% ammonia spirit adjusts pH > 10, and is made after 120 DEG C of 3~4h of airtight heating that mass fraction, which is added dropwise,.
In the present invention, the test method of ultrasonic power density is ultrasound intensity divided by dispersion liquid volume.
Preferably, the internal diameter of the multi-walled carbon nanotube is 2~5nm, and outer diameter < 8nm, length is 1~2 μm, specific surface Product > 500m2/g。
Wherein, the multi-walled carbon nanotube passes through commercially available acquisition.
Preferably, carbon nanomaterial layer described in the carbon nanomaterial composite membrane is on the basement membrane layer surface Load capacity be 8~32g/m2
Preferably, the pure water flux of the carbon nanomaterial composite membrane is 30~90L (m2·h·bar)-1
In the present invention, the test method of the pure water flux of carbon nanomaterial composite membrane is in 25 DEG C of room temperatures and 1bar constant pressure item Under part, pure water volume that analytical unit time, per membrane area pass through.
Preferably, the resistivity of the carbon nanomaterial composite membrane is 1.0~2.0 × 1018m-2
In the present invention, the test method of the resistivity of carbon nanomaterial composite membrane is according to Carman equation calculation constant-pressure conditions Under compound membrane resistance, then by membrane resistance and carbon nanomaterial thickness degree, the resistance of unit of account thickness carbon nanomaterial layer, i.e., Resistivity.
Preferably, the effective filtration area of the carbon nanomaterial composite membrane is not less than 0.1m2
In the present invention, the test method of the effective filtration area of carbon nanomaterial composite membrane is anti-according to the plate and frame film The diameter calculation of the circular open of filter plate side in device is answered to obtain.
Preferably, the basilar memebrane of the basement membrane layer is the polytetrafluoro of nylon membrane, PVDF membrane, hydrophilic modifying One of vinyl film is a variety of;The pore size filter of the basilar memebrane is 0.45 μm or less.
In the present invention, the commercially available acquisition of the basilar memebrane.
In the present invention, the carbon nanomaterial composite membrane passes through redox graphene and multi-walled carbon nanotube is uniform The surface for being carried on basilar memebrane is made, specifically, preparing multi-walled carbon nanotube dispersion liquid and oxygen reduction using ultrasonic wave auxiliary law Graphite alkene dispersion liquid, ultrasonic power density are 4~6WmL-1, ultrasonic time is 20~30min;The multi wall carbon is received Mitron dispersion liquid and the redox graphene dispersion liquid are mixed according to the mass ratio of two kinds of carbon nanomaterials, repeat ultrasound behaviour Make, ultrasonic power density is 4~6WmL-1, ultrasonic time is 10~20min;Finally use vacuum filtration method by two kinds of carbon Nanomaterial loadings are on basilar memebrane.
Preferably, the plate and frame membrane reactor further includes that the water inlet pipe and the carbon nanomaterial is arranged in Layer between water conservancy diversion web plate, be arranged between the water conservancy diversion web plate and the carbon nanomaterial layer silica gel sealing ring, set Set the orifice plate between the basement membrane layer and the outlet pipe.
It is further preferred that the orifice plate includes substrate, the multiple diversion trenches being provided on the substrate, is provided with Multiple deflector holes in the diversion trench.
It is further preferred that the water conservancy diversion web plate, the silica gel sealing ring, the carbon nanomaterial composite membrane and The orifice plate constitutes a membrane separation assemblies, and the plate and frame membrane reactor includes multiple films arranged side by side point From component.
It is further preferred that after the plate and frame membrane reactor further includes thrust plate, the thrust plate is arranged in The front baffle of side, pressure plate, be arranged in the pressure plate front side rear bulkhead, the front baffle and described is set Multiple filter plates between rear bulkhead, the intermediate bulkhead being arranged between the two neighboring filter plate, for by the sheet frame Each component of formula membrane reactor fixed top plate and fastener;Between the front baffle and the filter plate, the filter plate The membrane separation assemblies are respectively arranged between filter plate and the rear bulkhead between the intermediate bulkhead, described; Front baffle, the intermediate bulkhead, the rear bulkhead and the filter plate is respectively provided with internal cavities, and described Front baffle and the rear bulkhead offer the opening with connects with the internal cavities, the centre close to the side of the filter plate The two sides of partition and the filter plate offer the opening with connects with the internal cavities;The front baffle, the middle interval The lower part of plate and the rear bulkhead passes through respectively to be connected to the internal cavities with the water inlet pipe the first communicating pipe;Institute The internal cavities by being connected to the second communicating pipe by the top for the filter plate stated with the outlet pipe.
It is further preferable that effective filtering of the area of section of the internal cavities and the carbon nanomaterial composite membrane Area is identical.
According to a kind of specific and be preferably carried out mode, the circular cross section of the internal cavities.
It is further preferable that the front baffle, the intermediate bulkhead, the size of the rear bulkhead are identical, it is described 1.2~1.5 times with a thickness of the intermediate bulkhead thickness of filter plate.
Wherein, the front baffle, the identical shape for referring to appearance of size of the intermediate bulkhead, the rear bulkhead The size of shape and internal cavities is identical.
In the present invention, the number of the membrane separation assemblies can require flexible setting according to raw water flow, it is preferable that institute The number for the membrane separation assemblies stated is 4~16, i.e., the quantity of filter plate is 2~8 pieces, and the quantity of intermediate bulkhead is 1~7 piece.
Preferably, the first pipe that the raw water transfer includes raw water water tank, is connected with the raw water water tank Road, the force (forcing) pump being connected with the first pipe, be connected respectively with the force (forcing) pump and the water inlet pipe Two pipelines, the first valve being arranged in the first pipe and first flowmeter are arranged on the second pipe Second valve;The third pipe that the oxidant dosing system includes oxidant reservoir, is connected with the oxidant reservoir Road, is respectively connected with the dosing pump and the first pipe at the dosing pump being connected with the third pipeline 4th pipeline, the third valve being arranged on the third pipeline, the second flowmeter being arranged on the 4th pipeline.
Preferably, the oxidant that the oxidant dosing system is added is persulfate solution or ozone water solution.
Preferably, the water depth processing unit further includes the pressure gauge being arranged on the water inlet pipe.
Preferably, the water depth processing unit further includes film functional regeneration system, the film functional regeneration system The 5th pipeline and the 5th pipe for stirring sealing storage tank including ammonium hydroxide, being connected with the ammonium hydroxide stirring sealing storage tank Water circulating pump that road is connected, is connected at the 6th pipeline that is connected with the water circulating pump with the 6th pipeline Heat exchanger, the 7th pipeline being connected respectively with the heat exchanger and the water inlet pipe, respectively with the water outlet Manage the 8th pipeline being connected with the bottom of ammonium hydroxide stirring sealing storage tank, the be arranged on the 5th pipeline the 4th Valve and third flowmeter, the 5th valve being arranged on the 7th pipeline, be arranged on the 8th pipeline Six valves, the water depth processing unit further include be arranged in the 8th pipeline and the outlet pipe junction and The 7th valve on the outlet pipe between the clear water reserviors.
Due to passing through long-play, the catalytic performance of carbon nanomaterial and it is excessively aqueous can all can be due to surface-active point Consumption, masking and decrease.Carbon nanomaterial catalytic activity may be implemented by setting film functional regeneration system in the present invention It is significant to extend composite membrane service life with the in-situ regeneration of surface hydrophobic, avoid the prior art need to add catalyst collection, The additional process such as regeneration and recycling.
It is further preferred that the mass concentration of the ammonium hydroxide stored in the ammonium hydroxide stirring sealing storage tank is 4%~10%, PH is not less than 10.
Preferably, the organic micro-pollutants concentration in raw water to be processed stored in the raw water transfer is For 0.5mg/L hereinafter, organic carbon concentration is lower than 1mg/L, no suspended substance, pH is 6~9.
A second object of the present invention is to provide a kind of method for carrying out water process using the water depth processing unit, Include the following steps:
(1) raw water to be processed being stored in raw water water tank and the oxidant being stored in oxidant reservoir are mixed and is added It is delivered to after pressure in the plate and frame membrane reactor, the mixed liquor of the raw water and the oxidant is received in the carbon Catalysis oxidation and separation retention occur under the action of rice Material cladding film, treated, and water outlet is discharged through outlet pipe;
(2) when the reading of pressure gauge is close to 5bar, stop being passed through into the plate and frame membrane reactor it is described to The raw water of processing and the oxidant convey the ammonium hydroxide being stored in ammonium hydroxide stirring sealing storage tank after heat exchanger heats In-situ regeneration processing is carried out to the carbon nanomaterial composite membrane in the plate and frame membrane reactor, when the reading of pressure gauge After number is down to 4~8h of 1.5bar or less or operation, stop the in-situ regeneration processing.
Preferably, in step (1), the flow of raw water to be processed is controlled by the first valve.
Preferably, in step (1), by the dosage for adjusting oxidant described in the revolving speed control of dosing pump.
Preferably, when the oxidant is persulfate solution, the temperature of the oxidant is controlled lower than 30 DEG C; When the oxidant is ozone solution, the temperature for controlling the oxidant is 0~4 DEG C.
Preferably, it when the oxidant is persulfate solution, controls persulfate in the mixed liquor and has The initial molar concentration ratio of machine micropollutants is 50~200:1;When the oxidant is ozone solution, described mix is controlled Closing the initial mass concentration ratio of ozone and organic micro-pollutants in liquid is 10~50:1.
Preferably, it is 0.5-5.0Lmin that the flow for controlling the raw water to be processed, which corresponds to membrane flux,-1·m-2, control The flow of the system oxidant is not more than the 5% of the flow of the raw water to be processed.
Wherein, the flow of the raw water to be processed corresponds to the flow and sheet frame that membrane flux refers to raw water to be processed The ratio of total effective filtration area in formula membrane reactor.
Preferably, in step (1), the reading of pressure gauge is controlled no more than 5bar.
Preferably, it is 0.1~0.4Lmin that the flow for controlling the ammonium hydroxide, which corresponds to membrane flux,-1·m-2
Wherein, the flow of the ammonium hydroxide correspond to membrane flux refer to the flow of ammonium hydroxide with it is total in plate and frame membrane reactor The ratio of effective filtration area.
Preferably, the temperature for controlling the ammonium hydroxide at the heat exchanger outlet is 120~150 DEG C.
Except Parameter adjustables such as oxidant type, oxidant dosage, raw water flow, nanometer carbon material supported amounts in the present invention Outside, filter plate quantity can also be according to processing water, water quality situation flexible setting, effective mistake of membrane module in plate and frame membrane reactor Filtering surface is long-pending and catalyst amount also changes therewith.In addition, the SO with strong oxidizing property4 ·-(standard oxidizing potential 2.5-3.1V) Or OH (standard oxidizing potential 2.7V) plays central role in micropollutants remove, the oxidation pair of both free radicals Most organic pollutants are effective.Therefore, the present invention has good water, water quality adaptability.
Due to the implementation of above technical scheme, the invention has the following advantages over the prior art:
(1) carbon nanomaterial functions simultaneously as catalyst and separating medium, is urged with tradition using the dispersing type containing metal component Agent is compared, and during reaction, there is no heavy metals to dissolve out the problem of influencing water quality treatment, and does not need in addition to add catalyst point From step, process flow is shorter, and device composition is simpler;
(2) the characteristics of giving full play to carbon nanomaterial composite membrane lower resistance, high catalytic activity, in the processing comparable feelings of water Under condition, transmembrane pressure is far below tradition NF, RO film.Using membrane separating process as the reaction platform of catalysis oxidation, on the one hand, can By generating SO4 ·-Or the strong oxidizing properties free radical such as OH, micropollutants in water are effectively removed, on the other hand, are also mentioned for composite membrane Reliable self-cleaning ability has been supplied, has effectively reduced fouling membrane situation, and condensed water will not be generated;Above-mentioned function is traditional UF membrane Not available for component;
(3) purification efficiency of water depth processing unit of the invention is high, low energy consumption for processing, heavy metal free secondary pollution, fits It is wide with range.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the water depth processing unit of specific embodiment;
Fig. 2 is the electronic photo of carbon nanomaterial composite membrane;
Fig. 3 is the stereoscan photograph of carbon nanomaterial layer;
Fig. 4 is the sectional view of the plate and frame membrane reactor of specific embodiment;
Fig. 5 is the side view of the intermediate bulkhead of specific embodiment;
Fig. 6 is the side view of the filter plate of specific embodiment;
Fig. 7 is the side view of the water conservancy diversion web plate of specific embodiment;
Fig. 8 is the side view of the orifice plate of specific embodiment;
Fig. 9 is removal rate and separate run times of the 1 recycled water advanced treatment device of embodiment to low concentration sulfamethoxazole Relational graph;
Figure 10 is removal rate and regeneration times of the water depth processing unit in embodiment 1 to low concentration sulfamethoxazole Relational graph;
Figure 11 is water depth processing unit in embodiment 2 to the removal rate of low concentration phenols and the pass of separate run times System's figure;
Figure 12 is water depth processing unit in embodiment 2 to the removal rate of low concentration phenols and the relationship of regeneration times Figure;
Wherein, 1, plate and frame membrane reactor;2, clear water reserviors;3, the 7th valve;4, pressure gauge;11, thrust plate;12, it is preceding every Plate;13, filter plate;14, silica gel sealing ring;15, water conservancy diversion web plate;16, carbon nanomaterial composite membrane;17, orifice plate;18, intermediate bulkhead; 19, rear bulkhead;20, pressure plate;21, water inlet pipe;22, outlet pipe;23, top plate;24, fastener;25, internal cavities;26, first Communicating pipe;27, the second communicating pipe;31, raw water water tank;32, first pipe;33, force (forcing) pump;34, second pipe;35, the first valve Door;36, first flowmeter;37, the second valve;41, oxidant reservoir;42, third pipeline;43, dosing pump;44, the 4th pipeline; 45, third valve;46, second flowmeter;51, ammonium hydroxide stirring sealing storage tank;52, the 5th pipeline;53, water circulating pump;54, the 6th Pipeline;55, heat exchanger;56, the 7th pipeline;57, the 8th pipeline;58, the 4th valve;59, third flowmeter;60, the 5th valve Door;61, the 6th valve;171, substrate;172, diversion trench;173, deflector hole.
Specific embodiment
The present invention will be further described in detail in the following with reference to the drawings and specific embodiments, but the present invention is not limited to Lower embodiment.When specific experimental method being not specified in embodiment, carried out in accordance with national standard method and condition.
Water depth processing unit as shown in Figure 1, including plate and frame membrane reactor 1, raw water transfer, oxidant add System, film functional regeneration system, clear water reserviors 2 etc..Raw water transfer, oxidant dosing system are connected by pipeline, and and film Be connected to the water inlet pipe 21 of plate and frame membrane reactor 1 after functional regeneration system is in parallel, the outlet pipe 22 of plate and frame membrane reactor 1 with Clear water reserviors 2 are connected to.
Raw water transfer includes raw water water tank 31, the first pipe being connected with raw water water tank 31 32 and first pipe 32 be connected force (forcing) pump 33, be connected respectively with force (forcing) pump 33 and water inlet pipe 21 second pipe 34, be arranged in first pipe The first valve 35 and first flowmeter 36 on 32, the second valve 37 being arranged on second pipe 34.First flowmeter 36 Between the first valve 35 and force (forcing) pump 33.
Oxidant dosing system includes oxidant reservoir 41, is connected with oxidant reservoir 41 third pipeline 42, with the Dosing pump 43 that three pipelines 42 are connected, the 4th pipeline 44 being connected respectively with dosing pump 43 and first pipe 32, setting exist Third valve 45 on third pipeline 42, the second flowmeter 46 being arranged on the 4th pipeline 44.Oxidant dosing system is thrown The oxidant added is persulfate solution or ozone water solution.
The junction of 4th pipeline 44 and first pipe 32 is between first flowmeter 36 and force (forcing) pump 33.From first The raw water of pipeline 32 and oxidant from the 4th pipeline 44 are passed through force (forcing) pump 33, after pressurized 33 pressurization of pump, through second pipe 34 are passed through in water inlet pipe 21.
Film functional regeneration system includes that ammonium hydroxide stirring seals storage tank 51, stirs the sealing storage tank 51 is connected the 5th with ammonium hydroxide Pipeline 52, the water circulating pump 53 being connected with the 5th pipeline 52, the 6th pipeline 54 being connected with water circulating pump 53 and the 6th pipe Heat exchanger 55 that road 54 is connected, respectively and goes out the 7th pipeline 56 being connected respectively with heat exchanger 55 and water inlet pipe 21 Water pipe 22 is stirred with ammonium hydroxide seals the 8th pipeline 57 that the bottom of storage tank 51 is connected, the 4th valve being arranged on the 5th pipeline 52 Door 58 and third flowmeter 59, the 5th valve 60 being arranged on the 7th pipeline 56, the 6th valve that is arranged on the 8th pipeline 57 Door 61.Third flowmeter 59 is between the 4th valve 58 and water circulating pump 53.
Water depth processing unit further includes being arranged between the 8th pipeline 57 and the junction and clear water reserviors 2 of outlet pipe 22 The 7th valve 3 on outlet pipe 22.
Water depth processing unit further includes the pressure gauge 4 being arranged on water inlet pipe 21.Raw water and the pressurized pump 33 of oxidant Plate and frame membrane reactor 1 is entered by pressure gauge 4 after pressurization, ammonium hydroxide enters plate through excess pressure table 4 after the heating of heat exchanger 55 Frame membrane reactor 1.
Water inlet pipe 21, outlet pipe 22, first pipe 32, second pipe 34, third pipeline 42, the 4th pipeline the 44, the 5th pipe Road 52, the 6th pipeline 54, the 7th pipeline 56, the 8th pipeline 57 are all made of 304 stainless steel tubes.
As shown in Fig. 2, plate and frame membrane reactor 1 further include 1 thrust plate, 11,1 front baffles 12, it is muti-piece filter plate 13, more A silica gel sealing ring 14, multiple water conservancy diversion web plates 15, multiple carbon nanomaterial composite membranes 16, multiple orifice plates 17, muti-piece intermediate bulkhead 18,1 top plate 23 and 1 fastener 24 of outlet pipe 22,1 of water inlet pipe 21,1 of pressure plate 20,1 of rear bulkhead 19,1.
Thrust plate 11 is placed in front end, is followed by front baffle 12, is then spaced apart filter plate 13 (304 stainless steel) and centre Partition 18 (304 stainless steel) places rear bulkhead 19 on rear side of last 1 piece of filter plate 13, and by pressure plate 20, top plate 23 and fastening Part 24 fixes each component, it is ensured that sealing.
Water inlet pipe 21, outlet pipe 22 are respectively arranged at 1 lower part of plate and frame membrane reactor and top, pass through entire reactor.
Be equipped with inside front baffle 12, rear bulkhead 19 section be circular internal cavities 25 (25 area of section of internal cavities= The effective filtration area of carbon nanomaterial composite membrane 16), it closes on 13 side of filter plate and offers the opening being connected to internal cavities 25, Opening covers water conservancy diversion web plate 15, and other side closing, lower end is by the first communicating pipe 26 connecting internal cavities 25 and water inlet pipe 21 It is logical.
Appearance, the cavity size of intermediate bulkhead 18 are identical as front baffle 12, rear bulkhead 19, but the two sides of intermediate bulkhead 18 are equal The opening being connected to internal cavities 25 is offered, opening is covered with water conservancy diversion web plate 15, and lower end will be interior by the first communicating pipe 26 Portion's cavity 25 is connected to water inlet pipe 21.
For filter plate 13 with a thickness of 1.5 times of 18 thickness of intermediate bulkhead, it is that circular internal cavities 25 are (internal that inside, which is equipped with section, 25 areas of section of cavity=carbon nanomaterial composite membrane 16 effective filtration area), the two sides of filter plate 13 offer and inside The opening that cavity 25 is connected to, opening cover abacus 17, and upper end passed through for the second communicating pipe 27 for internal cavities 25 and outlet pipe 22 connections.
Orifice plate 17 includes substrate 171, the multiple diversion trenches 172 being provided on substrate 171, is provided in diversion trench 172 Multiple deflector holes 173, diversion trench 172 is annular in shape, collects convenient for filtrate.Carbon nanomaterial composite membrane 16 is placed on orifice plate 17, Silica gel sealing ring 14 is inlaid on water conservancy diversion web plate 15, silica gel sealing ring 14 is located at water conservancy diversion web plate 15 and carbon nanomaterial composite membrane 16 Between, carbon nanomaterial composite membrane 16 is between water conservancy diversion web plate 15 and orifice plate 17.In the case where each component is fixed and clamped, lead Drift net plate 15, silica gel sealing ring 14, carbon nanomaterial composite membrane 16 and orifice plate 17 constitute a membrane separation assemblies.
Carbon nanomaterial composite membrane 16 is by redox graphene (rGO) and multi-walled carbon nanotube (MWCNT) according to matter Amount is than being that 2~4:1 uniform load is prepared in the surface of basilar memebrane, to be formed by redox graphene (rGO) and more The carbon nanomaterial layer and basement membrane layer that wall carbon nano tube (MWCNT) is constituted.Wherein, carbon nanomaterial layer is located at water conservancy diversion web plate 15 Between basement membrane layer, so that the mixed liquor come in from water inlet pipe 21 is by entering front baffle 12, centre the first communicating pipe 26 In the cavity of partition 18 and rear bulkhead 19, in flow process from bottom to top, water distribution uniformity is extremely after 15 water conservancy diversion of water conservancy diversion web plate The surface of carbon nanomaterial layer, mixed liquor do Tortuous flow in the microcosmic layer structure of carbon nanomaterial composite membrane 16, and same Shi Fasheng catalysis oxidation and separation retention, effectively remove the organic micro-pollutants in water, treated water after the collection of orifice plate 17, The internal cavities 25 of filter plate 13 are converged into, then enter outlet pipe 22 through the second communicating pipe 27, water is delivered to clearly by outlet pipe 22 In pond 2.
Redox graphene is flaky, and a diameter of 2~5 μm, with a thickness of 0.8~1.2nm, carbon oxygen atom ratio is 3~4:1, single layer rate > 95%.Wherein, redox graphene is using the graphene oxide of commercially available acquisition as raw material, using super Sound wave aid dispersion method obtains graphene oxide dispersion, and ultrasonic power density is 4~6WmL-1, ultrasonic time be 20~ 30min is then added dropwise 10% ammonia spirit and adjusts pH > 10, and be made in 120 DEG C of 3~4h of airtight heating.Multi-walled carbon nanotube Internal diameter be 2~5nm, outer diameter < 8nm, length be 1~2 μm, specific surface area > 500m2/g.The basilar memebrane of basement membrane layer is Buddhist nun Imperial film, PVDF membrane, hydrophilic modifying one of polytetrafluoroethylene film or a variety of;The filter hole of the basilar memebrane Diameter is 0.45 μm or less.
Load capacity of the carbon nanomaterial layer on basement membrane layer surface is 8~32g/m in carbon nanomaterial composite membrane 162, carbon The pure water flux of nano material complex film 16 is 30~90L (m2·h·bar)-1., resistivity is 1.0~2.0 × 1018m-2, have It imitates filter area and is not less than 0.1m2
The method for carrying out water process using above-mentioned apparatus, includes the following steps:
(1) the 4th valve 58, the 5th valve 60, the 6th valve 61 and water circulating pump 53 are closed, the first valve 35, the are opened Two valves 37, third valve 45, the 7th valve 3, dosing pump 43 and force (forcing) pump 33;
(2) raw water to be processed is stored in raw water water tank 31, is stirred by blender to keep homogeneous state, so It is delivered to force (forcing) pump 33 by first pipe 32, the flow of raw water is controlled by adjusting the first valve 35, controls original to be processed It is 0.5-5.0Lmin that the flow of water, which corresponds to membrane flux,-1·m-2
(3) oxidant is stored in oxidant reservoir 41, oxidant reservoir 41 covers, and is stirred by blender to protect Homogeneous state is held, oxidant is delivered to dosing pump 43 through third pipeline 42, is then delivered to first pipe 32 through the 4th pipeline 44 Enter force (forcing) pump 33 after mixing with the raw water in first pipe 32, adjust the dosage of the revolving speed control oxidant of dosing pump 43, The flow of control oxidant is not more than the 5% of the flow of raw water to be processed;When oxidant is persulfate solution, oxygen is controlled The temperature of agent is lower than 30 DEG C;When oxidant is ozone solution, the temperature for controlling oxidant is 0~4 DEG C;
(4) by second pipe 34, to be delivered to plate and frame film anti-after pressurized 33 pressurization of pump of the mixed liquor of raw water and oxidant The water inlet pipe 21 for answering device 1 controls persulfate and organic micro-pollutants in mixed liquor when oxidant is persulfate solution Initial molar concentration ratio is 50~200:1;When oxidant is ozone solution, ozone and organic micro-pollutants in mixed liquor are controlled Initial mass concentration ratio be 10~50:1;
(5) mixed liquor by water inlet pipe 21 by be evenly distributed to the first communicating pipe 26 front baffle 12, intermediate bulkhead 18 and after In the internal cavities 25 of partition 19, in flow process from bottom to top, water distribution uniformity to carbon is received after 15 water conservancy diversion of water conservancy diversion web plate The surface of rice material layer, mixed liquor is cooked Tortuous flow in the microcosmic layer structure of carbon nanomaterial composite membrane 16, and is sent out simultaneously Raw catalysis oxidation and separation retention, effectively remove the organic micro-pollutants in water, and treated water is after the collection of orifice plate 17, confluence To the internal cavities 25 of filter plate 13, then enter outlet pipe 22 through the second communicating pipe 27, water is delivered to clear water reserviors 2 by outlet pipe 22 In;
(6) when the reading of pressure gauge 4 is close to 5bar, the first valve 35, the second valve 37, third valve 45, the are closed Seven valves 3, dosing pump 43 and force (forcing) pump 33 open the 4th valve 58, the 5th valve 60, the 6th valve 61 and water circulating pump 53, It is that ammonium hydroxide of 4%~10%, pH not less than 10 is stored in ammonium hydroxide stirring sealing storage tank 51 by mass concentration, ammonium hydroxide is through the 5th pipe Road 52 is delivered to water circulating pump 53, is then delivered to after heat exchanger 55 heated through the 6th pipeline 54, through the 7th pipeline 56 It is delivered to water inlet pipe 21, ammonium hydroxide is by water inlet pipe 21 by being evenly distributed to front baffle 12,18 and of intermediate bulkhead the first communicating pipe 26 In the internal cavities 25 of rear bulkhead 19, in flow process from bottom to top, water distribution uniformity is to carbon after 15 water conservancy diversion of water conservancy diversion web plate The surface of layer of nanomaterial, and Tortuous flow is done to carbon nanomaterial in the microcosmic layer structure of carbon nanomaterial composite membrane 16 Carry out in-situ immobilization, then through orifice plate 17 collection after, converge into the internal cavities 25 of filter plate 13, then through the second communicating pipe 27 into Enter outlet pipe 22, then is delivered to ammonium hydroxide stirring sealing storage tank 51 through the 8th pipeline 57;Wherein, the flow for controlling ammonium hydroxide corresponds to film and leads to Amount is 0.1~0.4Lmin-1·m-2;The thermal medium that heat exchanger 55 uses is conduction oil, conduction oil and ammonium hydroxide counter current contacting, The temperature for ensuring the ammonium hydroxide in 55 exit of heat exchanger is 120~150 DEG C;When the reading of pressure gauge 4 be down to 1.5bar or less or After person runs 4~8h, stop the in-situ regeneration processing.
Processing unit and processing method in present embodiment is especially suitable for organic micro- in raw water to be processed Pollutant concentration is 0.5mg/L hereinafter, organic carbon concentration is lower than 1mg/L, no suspended substance, the raw water that pH is 6~9.
Embodiment 1
The design parameter for the above-mentioned processing unit that the present embodiment uses is provided that
Carbon nanomaterial composite membrane 16: nanometer carbon material supported is 16gm-2, rGO and MWCNT mass ratio are 3:1, pure water Flux is about 39L (m2·h·bar)-1, unit resistivity is preferably 1.8 × 1018m-2, the effective filtration area of monolithic membrane is 0.1m2;RGO wafer diameters are at 2-5 μm, and for thickness in 0.8-1.2nm, carbon oxygen atom ratio is 3.3:1, single layer rate > 95%; MWCNT internal diameter is in 2-5nm, and outer diameter<8nm, length is at 1-2 μm, specific surface area>500m2·g-1;Substrate selects diameter 400mm's Nylon membrane, pore size filter are preferably 0.22 μm;
Plate and frame membrane reactor 1: 13 quantity of filter plate is 6 pieces, and 18 quantity of intermediate bulkhead is 5 pieces, and total effective filtration area is about For 1.2m2
The raw water for using the present embodiment to handle: for 0.05mg/L, background organic carbon concentration is about sulfamethoxazole concentration 0.3mg/L, no suspended substance, pH are about 6.8;
Oxidant: sodium persulfate aqueous solution;
Regenerative agent: 4% ammonia spirit.
Specific processing step includes micropollutants removal and composite membrane functional regeneration step, specific as follows:
(1) micropollutants remove: raw water flow is about 0.6Lmin-1, corresponding membrane flux about 0.5Lmin-1·m-2;It crosses Sodium sulphate concentrated solution temperature is controlled at 25 DEG C, and control oxidizer flow rate is about the 2% of raw water flow, and sodium peroxydisulfate and sulfalene are disliked The initial molar concentration ratio of azoles is 100:1;4 initial reading of pressure gauge is 1.7bar.With the extension of processing time, pressure gauge 4 Reading gradually rises, and reaches 4.6bar after 72h is handled.
(2) composite membrane functional regeneration: ammonia circulation flow about 0.24Lmin-1, corresponding membrane flux is 0.2Lmin-1· m-2;It is about 122 DEG C that heat exchanger 55, which exports ammonia spirit concentration,.4 initial reading of pressure gauge is 3.9bar, is then gradually decreased, After running 6h, 4 stable reading of pressure gauge stops in-situ regeneration operation in 1.1bar.
It reprocesses-regenerates 7 times using the present embodiment, operating condition is as shown in attached drawing 9 and 10.The result table of embodiment 1 It is bright, it is still fine to the removal effect of sulfamethoxazole after 7 processing regeneration.
Embodiment 2
The design parameter for the above-mentioned processing unit that the present embodiment uses is provided that
Carbon nanomaterial composite membrane 16: nanometer carbon material supported is 32gm-2, rGO and MWCNT mass ratio are 2:1, pure water Flux is about 52L (m2·h·bar)-1, unit resistivity is preferably 1.5 × 1018m-2, the effect filter area of monolithic membrane is 0.1m2;RGO wafer diameters are at 2-5 μm, and for thickness in 0.8-1.2nm, carbon oxygen atom ratio is 3.7:1, single layer rate > 95%; MWCNT internal diameter is in 2-5nm, and outer diameter<8nm, length is at 1-2 μm, specific surface area>500m2·g-1;Substrate selects diameter 400mm's Pvdf membrane, pore size filter are preferably 0.45 μm;
Plate and frame membrane reactor 1: 13 quantity of filter plate is 8 pieces, and 18 quantity of intermediate bulkhead is 7 pieces, and total effective filtration area is about For 1.6m2
The raw water for using the present embodiment to handle: for phenol concentration for 0.03mg/L, background organic carbon concentration is about 0.6mg/L, No suspended substance, pH are about 7.4;
Oxidant: ozone water solution;
Regenerative agent: 8% ammonia spirit.
Specific processing step includes micropollutants removal and composite membrane functional regeneration step, specific as follows:
(1) micropollutants remove: raw water flow is about 1.6Lmin-1, corresponding membrane flux about 1.0Lmin-1·m-2;It is smelly Oxygen concentrated solution temperature is controlled at 0 DEG C, and control oxidizer flow rate is about the 5% of raw water flow, the initial mass concentration of ozone and phenol Than for 50:1;4 initial reading of pressure gauge is 1.4bar.With the extension of processing time, the reading of pressure gauge 4 is gradually risen, and is passed through Reach 4.9bar after 48h processing.
(2) composite membrane functional regeneration: ammonia circulation flow about 0.5Lmin-1, corresponding membrane flux is 0.3Lmin-1·m-2;It is about 121 DEG C that heat exchanger 55, which exports ammonia spirit concentration,.4 initial reading of pressure gauge is 4.4bar, is then gradually decreased, and is transported After row 6h, 4 stable reading of pressure gauge stops in-situ regeneration operation in 1.2bar.
Using continuous processing-regeneration 9 times of the present invention, operating condition is as shown figs. 11 and 12.The result table of embodiment 2 It is bright, it is still fine to the removal effect of phenol after 9 processing regeneration.
The present invention is described in detail above, its object is to allow the personage for being familiar with this field technology that can understand this The content of invention is simultaneously implemented, and it is not intended to limit the scope of the present invention, all Spirit Essence institutes according to the present invention The equivalent change or modification of work, should be covered by the scope of protection of the present invention.

Claims (12)

1. a kind of water depth processing unit, including with water inlet pipe (21) and outlet pipe (22) plate and frame membrane reactor (1), with The raw water transfer and the plate and frame film reaction that the water inlet pipe (21) of the plate and frame membrane reactor (1) is connected The clear water reserviors (2) that the outlet pipe (22) of device (1) is connected, it is characterised in that: the water depth processing unit further includes and institute The oxidant dosing system that the water inlet pipe (21) or the raw water transfer for the plate and frame membrane reactor (1) stated are connected, The plate and frame membrane reactor (1) further includes carbon nanomaterial composite membrane (16), the carbon nanomaterial composite membrane (16) Described in having including the carbon nanomaterial layer that is successively set between the water inlet pipe (21) and the outlet pipe (22), load Carbon nanomaterial layer basement membrane layer, the raw material of the carbon nanomaterial layer includes single layer redox graphene and multi wall Carbon nanotube.
2. water depth processing unit according to claim 1, it is characterised in that: described in the carbon nanomaterial layer The mass ratio of redox graphene and the multi-walled carbon nanotube is 2~4:1;The redox graphene is in thin slice Shape, a diameter of 2~5 μm, with a thickness of 0.8~1.2nm, carbon oxygen atom ratio is 3~4:1, single layer rate > 95%;Described is more The internal diameter of wall carbon nano tube is 2~5nm, and outer diameter < 8nm, length is 1~2 μm, specific surface area > 500m2/g。
3. water depth processing unit according to claim 1, it is characterised in that: the carbon nanomaterial composite membrane (16) Described in carbon nanomaterial layer the basement membrane layer surface load capacity be 8~32g/m2, the carbon nanomaterial The pure water flux of composite membrane (16) is 30~90L (m2·h·bar)-1, unit resistivity is 1.0~2.0 × 1018m-2, effectively Filter area is not less than 0.1m2
4. water depth processing unit according to claim 1, it is characterised in that: the basilar memebrane of the basement membrane layer is Buddhist nun Imperial film, PVDF membrane, hydrophilic modifying one of polytetrafluoroethylene film or a variety of;The filter hole of the basilar memebrane Diameter is 0.45 μm or less.
5. water depth processing unit according to claim 1, it is characterised in that: the plate and frame membrane reactor (1) is also Including be arranged between the water inlet pipe (21) and the carbon nanomaterial layer water conservancy diversion web plate (15), be arranged in it is described The basement membrane layer and institute is arranged in silica gel sealing ring (14) between water conservancy diversion web plate (15) and the carbon nanomaterial layer The orifice plate (17) between outlet pipe (22) stated.
6. water depth processing unit according to claim 5, it is characterised in that: the orifice plate (17) includes substrate (171), multiple diversion trenches (172) for being provided on the substrate (171), be provided with it is more in the diversion trench (172) A deflector hole (173).
7. water depth processing unit according to claim 5, it is characterised in that: the water conservancy diversion web plate (15), described Silica gel sealing ring (14), the carbon nanomaterial composite membrane (16) and the orifice plate (17) constitute a membrane separation assemblies, The plate and frame membrane reactor (1) includes multiple membrane separation assemblies arranged side by side.
8. water depth processing unit according to claim 7, it is characterised in that: the plate and frame membrane reactor (1) is also Including thrust plate (11), the front baffle (12) for the rear side that the thrust plate (11) is set, pressure plate (20), it is arranged described Pressure plate (20) front side rear bulkhead (19), be arranged between the front baffle (12) and the rear bulkhead (19) Multiple filter plates (13), the intermediate bulkhead (18) being arranged between the two neighboring filter plate (13), for by the sheet frame Each component of formula membrane reactor (1) fixed top plate (23) and fastener (24);The front baffle (12) and the filter plate (13) between, between the filter plate (13) and the intermediate bulkhead (18), the filter plate (13) and the rear bulkhead (19) membrane separation assemblies are respectively arranged between;It is the front baffle (12), the intermediate bulkhead (18), described Rear bulkhead (19) and the filter plate (13) are respectively provided with internal cavities (25), and the front baffle (12) and it is described after every Plate (19) offers the opening being connected to internal cavities (25), the intermediate bulkhead close to the side of the filter plate (13) (18) and the two sides of the filter plate (13) offer the opening being connected to internal cavities (25);The front baffle (12), The lower part of the intermediate bulkhead (18) and the rear bulkhead (19) passes through the first communicating pipe (26) for the inside respectively Cavity (25) is connected to the water inlet pipe (21);The top of the filter plate (13) will be described by the second communicating pipe (27) Internal cavities (25) are connected to the outlet pipe (22).
9. water depth processing unit according to claim 8, it is characterised in that: the section face of the internal cavities (25) Product is identical as the effective filtration area of carbon nanomaterial composite membrane (16);The front baffle (12), the centre Partition (18), the size of the rear bulkhead (19) are identical, the filter plate (13) with a thickness of the intermediate bulkhead (18) 1.2~1.5 times of thickness.
10. water depth processing unit according to claim 1, it is characterised in that: the raw water transfer includes original Water tank (31), the first pipe (32) being connected with the raw water water tank (31) are connected with the first pipe (32) Logical force (forcing) pump (33), the second pipe (34) being connected respectively with the force (forcing) pump (33) and the water inlet pipe (21), The second pipe is arranged in the first valve (35) and first flowmeter (36) that are arranged on the first pipe (32) (34) the second valve (37) on;The oxidant dosing system includes that oxidant reservoir (41) and the oxidant store up Third pipeline (42) that pond (41) is connected, the dosing pump (43) being connected with the third pipeline (42), respectively with it is described Dosing pump (43) be connected with the first pipe (32) the 4th pipeline (44), the third pipeline (42) is set On third valve (45), the second flowmeter (46) that is arranged on the 4th pipeline (44).
11. water depth processing unit according to claim 1, it is characterised in that: the water depth processing unit is also wrapped Include the pressure gauge (4) being arranged on the water inlet pipe (21).
12. water depth processing unit according to claim 1, it is characterised in that: the water depth processing unit is also wrapped Film functional regeneration system is included, the film functional regeneration system includes that ammonium hydroxide stirring seals storage tank (51), stirs with the ammonium hydroxide Mix sealing storage tank (51) be connected the 5th pipeline (52), be connected with the 5th pipeline (52) water circulating pump (53), The 6th pipeline (54) being connected with the water circulating pump (53), the heat exchanger being connected with the 6th pipeline (54) (55), the 7th pipeline (56) that is connected respectively with the heat exchanger (55) and the water inlet pipe (21), respectively with institute The outlet pipe (22) stated stirs the 8th pipeline (57) for sealing the bottom of storage tank (51) and being connected with the ammonium hydroxide, is arranged in institute The 4th valve (58) on the 5th pipeline (52) and third flowmeter (59) stated are arranged on the 7th pipeline (56) 5th valve (60), the 6th valve (61) being arranged on the 8th pipeline (57), the water depth processing unit is also Including being arranged between the junction and the clear water reserviors (2) of the 8th pipeline (57) and the outlet pipe (22) The 7th valve (3) on the outlet pipe (22).
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CN111514856A (en) * 2020-05-20 2020-08-11 清华大学 Graphene oxide adsorption film, preparation method thereof and water treatment method

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CN111514856A (en) * 2020-05-20 2020-08-11 清华大学 Graphene oxide adsorption film, preparation method thereof and water treatment method

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