CN115745293B - Catalytic reduction dechlorination device containing load type PVDF membrane - Google Patents
Catalytic reduction dechlorination device containing load type PVDF membrane Download PDFInfo
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- CN115745293B CN115745293B CN202211504476.XA CN202211504476A CN115745293B CN 115745293 B CN115745293 B CN 115745293B CN 202211504476 A CN202211504476 A CN 202211504476A CN 115745293 B CN115745293 B CN 115745293B
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a catalytic reduction dechlorination device containing a load type PVDF (polyvinylidene fluoride) membrane, which comprises a catalytic reduction zone, a mixed reaction zone and a precipitation zone which are sequentially connected, wherein the top of the catalytic reduction zone is provided with a water inlet and a water distributor which are mutually connected, and a first packing layer is arranged below the water distributor and used for treating sewage; the bottom of the mixing reaction zone is provided with an aeration device, the middle part of the mixing reaction zone is provided with a second filler layer, and the top of the mixing reaction zone is connected with a dosing device and is used for carrying out coagulation reaction; the first packing layer and the second packing layer are uniformly distributed with a load type PVDF film; the sedimentation zone comprises a water producing port, an inclined plate zone and a mud discharging port from top to bottom, and the sewage is subjected to mud-water separation in the sedimentation zone to obtain produced water.
Description
Technical Field
The invention belongs to the technical field of chlorine-containing organic wastewater treatment, and particularly relates to a catalytic reduction dechlorination device containing a load-type PVDF membrane.
Background
The waste water discharged from the industries of pesticides, dyes, plastics, synthetic rubber, chemical industry, chemical fiber and the like contains a large amount of chlorinated organic matters. Chlorinated organics have hydrophobicity, are difficult to biodegrade, degrade slowly under natural conditions, can be continuously enriched in the environment and biosphere, and become one of the most common pollutants in soil and surface water systems. Most chlorinated organic compounds have the characteristics of high toxicity, difficult degradation and bioaccumulation, and have the effects of carcinogenesis, teratogenesis and mutagenesis. The chlorinated organic matters enter the environment, so that the ecological environment is directly damaged, and the harm to human beings and other organisms in the ecological environment is also generated.
The method for treating the chlorinated organic compound mainly comprises the physical method: can only transfer chlorinated organic matters, cannot achieve the actual removal, and is difficult to reach the standard for emission; biological method: chlorinated organics are extraneous compounds, and are generally difficult to digest and degrade by microorganisms, which is highly likely to cause microbial poisoning; chemical method: the method mainly comprises an oxidation method and a reduction method, wherein the oxidation method comprises an incineration method, a wet oxidation method, a photocatalytic oxidation method, an ozone oxidation method and the like, but the methods have the problems of high energy consumption, secondary pollution generation, incapability of being applied to a real water treatment process and the like; the reduction methods comprise an electrocatalytic oxidation method and a zero-valent iron reduction method, and the problems of high energy consumption, severe use conditions, high large-scale application cost and the like exist in the methods.
Disclosure of Invention
In order to solve one of the problems, the invention provides a catalytic reduction dechlorination device containing a supported PVDF membrane, wherein a catalytic reduction zone and a mixed reaction zone of the device are both provided with filler layers, the filler layers are PVDF membranes loaded with nano palladium-iron bimetallic particles, and the PVDF membranes have the advantages of excellent plasticity, strong acid and alkali resistance, high temperature resistance, high strength and the like. The device is suitable for treating acid, alkali and neutral chlorine-containing wastewater, solves the problem of secondary pollution in the treatment process of chlorinated organic matters, has lower cost and is convenient to popularize and apply.
The catalytic reduction dechlorination device comprises a catalytic reduction zone, a mixed reaction zone and a precipitation zone which are sequentially connected, wherein the top of the catalytic reduction zone is provided with a water inlet and a water distributor which are mutually connected, and a first filler layer is arranged below the water distributor and used for treating sewage;
the bottom of the mixing reaction zone is provided with an aeration device, the middle part of the mixing reaction zone is provided with a second filler layer, and the top of the mixing reaction zone is connected with a dosing device and is used for carrying out coagulation reaction; the first packing layer and the second packing layer are uniformly distributed with a load type PVDF film;
the sedimentation zone comprises a water producing port, an inclined plate zone and a mud discharging port from top to bottom, and the sewage is subjected to mud-water separation in the sedimentation zone to obtain produced water.
Optionally, the first filler layer includes a plurality of first membrane modules that the level was arranged, and every first membrane module is wave and vertically places, and first membrane module includes a plurality of first diaphragm of slope and second diaphragm promptly, and first diaphragm and second diaphragm set up in turn, and the angle that takes between adjacent first diaphragm and the second diaphragm about all is 60-150 within the scope, can be the same, also can be different, and can change in real time.
Optionally, a first supporting frame is arranged in the area of the first packing layer, the first supporting frame comprises a plurality of groups of vertically arranged first brackets which are parallel to each other, each group of first brackets is horizontally arranged and comprises a plurality of first positioning rods which are parallel to each other and two first supporting rods at two ends of each first positioning rod, the first positioning rods and the first supporting rods are all at the same horizontal height, the two first supporting rods are parallel to each other, and the first positioning rods are perpendicular to the first supporting rods, namely, a plurality of I-shaped structures are formed; two ends of the first supporting rod are connected with two side walls of the catalytic reduction zone;
the upper side edge and the lower side edge of the first diaphragm or the second diaphragm are respectively fixed on the first positioning rods of the two groups of first brackets which are adjacent up and down, and the first positioning rods above and below the connection of the same first diaphragm or the second diaphragm are not on the same vertical line so as to ensure that the first diaphragm or the second diaphragm is obliquely arranged.
In order to make the included angle between the first membrane and the second membrane changeable, further optional, the singular first support of the first support frame may be movable, or the plural first supports may be movable. Taking the case that the first support in the singular number is movable and the first supports in the plural number are fixed as an example, sliding rails are arranged on the two side wall surfaces of the catalytic reduction area corresponding to the first support rods, namely, two vertical sliding rails which are parallel to each other are arranged on one side wall surface, the two ends of all the first support rods are clamped in the corresponding sliding rails, the two ends of the first support rods in the singular number are provided with sliding blocks and can move up and down in the sliding rails, and the first support rods in the plural number are fixed in the sliding rails and play a limiting role on the upper and lower first support rods so as to prevent overlapping winding of upper and lower diaphragms;
the first support rod of the first singular support is of a sleeve structure and comprises an inner tube and an outer tube, two ends of the first positioning rod are fixedly connected to the corresponding outer tube, and two ends of the inner tube are clamped in the sliding rail.
Optionally, the catalytic reduction zone is further provided with a circulation port, the circulation port is arranged below the packing layer and is connected with a water inlet of the catalytic reduction zone through a circulation pump, and the circulation port is used for partially refluxing the sewage treated by the supported PVDF membrane and adjusting the water inlet state of the catalytic reduction zone;
the water outlet of the catalytic reduction zone is arranged at the bottom of the catalytic reduction zone and is communicated with the catalytic reduction zone and the mixed reaction zone, and the sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
Optionally, the mixing reaction area is connected with an external dosing device through a dosing pipe, the dosing device comprises a dosing pipe and a dosing pump, the dosing pipe is connected with the dosing pipe through the dosing pump and is used for inputting coagulant or flocculant into the mixing reaction area, and the coagulant or flocculant fully reacts under the stirring action of the aeration device;
the water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and is communicated with the mixed reaction zone and the sedimentation zone, and the sewage treated by the mixed reaction zone is input into the sedimentation zone.
Optionally, the second filler layer includes a plurality of second membrane assemblies horizontally arranged, and the structure of the second membrane assemblies is the same as that of the first membrane assemblies, which is different from the first membrane assemblies in that all angles between the upper and lower adjacent third membrane sheets and the fourth membrane sheets are in the range of 60-180 degrees, which may be the same or different, and may be changed in real time, i.e. the second membrane assemblies may be in a wave shape or a straight line shape at some time.
The second filler layer area is provided with a second supporting frame, the structure of the second supporting frame is the same as that of the first supporting frame, and the difference is that the up-down movement range of a second bracket of the second supporting frame and the left-right movement range of an outer tube of the second supporting rod are larger, so that the second membrane component can be changed into a straight shape from wave deformation.
The supported PVDF film of the invention is loaded with nano palladium and nano iron particles, and the preparation method is as follows:
(1) Preparing KOH solution, and redissolving KMnO 4 Obtaining KMnO 4 -KOH solution; configuration H 2 SO 4 Solution, re-dissolving NaHSO 3 Obtaining NaHSO 3 -H 2 SO 4 A solution; preparing KOH solution, and redissolving KBH 4 Obtaining KBH 4 -KOH solution; preparing ethanol solution, and redissolving Pd (O) 2 CCH 3 ) 2 Pd (O) is obtained 2 CCH 3 ) 2 -an ethanol solution;
(2) Cleaning PVDF film with deionized water, soaking in KMnO 4 In KOH solution, alkali washing and dechlorination reaction are carried out to obtain an intermediate film I;
(3) Washing the intermediate film I with deionized water, soaking in NaHSO 3 -H 2 SO 4 Hydrophilic modification is carried out in the solution to obtain a modified PVDF membrane;
(4) Immersing the modified PVDF film into FeSO 4 In the solution, then vacuum drying is carried out to obtain the loaded Fe 2+ A PVDF membrane of (C); will be loaded with Fe 2+ Is immersed in KBH in PVDF film 4 Performing oxidation-reduction reaction in KOH solution to obtain a PVDF film loaded with zero-valent iron;
(5) Immersing zero-valent iron-loaded PVDF film in Pd (O 2 CCH 3 ) 2 And (3) in ethanol solution, carrying out chemical deposition to obtain the supported PVDF film.
Optionally, in the step (1), the mass concentration of the KOH solution is 16-20%, KMnO 4 KMnO in KOH solution 4 The mass concentration of (2) is 8-10%;
H 2 SO 4 the mass concentration of the solution is 40-45%, naHSO 3 -H 2 SO 4 NaHSO in solution 3 The mass concentration of (2) is 18-20%;
the mass concentration of KOH solution is 15-20%, KBH 4 KBH in KOH solution 4 The mass concentration of (2) is 11-15%;
the concentration of the ethanol solution is 70-75wt% and Pd (O) 2 CCH 3 ) 2 Pd (O) in ethanol solution 2 CCH 3 ) 2 The mass concentration of (2) was 10%.
Optionally, in the step (2), the temperature of the alkaline leaching and dechlorination reaction is 18-20 ℃ and the time is 1-2h; PVDF molecule in KMnO 4 In the strong alkaline oxidizing environment of KOH solution, part of HF is removed and double bonds are generated, and the film body turns from white to brown. The PVDF film in step (2) may be prepared or may be purchased as a finished product.
Optionally, in the step (3), the hydrophilic modification temperature is 20-28 ℃ and the hydrophilic modification time is 4-6h; under acidic conditions, nucleophilic addition reaction is carried out on the double bond on the intermediate membrane I, polyol is generated, and hydrophilic group-hydroxyl (-OH) is generated on the membrane, so that the PVDF membrane has hydrophilicity.
Optionally, in step (4), the modified PVDF membrane is immersed in FeSO 4 The FeSO is carried out in the solution for 15-20min 4 The mass concentration of the solution is 10-13%, and then the solution is placed in a drying oven at 115 ℃ for vacuum drying for 2-3h;
the Fe is loaded 2+ Is immersed in KBH in PVDF film 4 The zero-valent iron particles just generated are extremely easy to oxidize by oxygen in the air after 15-20min in KOH solution, so that the PVDF film loaded with zero-valent iron is quickly put into absolute ethyl alcohol for preservation after being washed by absolute ethyl alcohol.
Optionally, in the step (5), the PVDF film loaded with zero-valent iron is immersed in Pd (O2 CCH 3) 2-ethanol solution for 10-15min, and nano palladium particles are loaded by chemical deposition, and the specific reaction is Pd 2+ +Fe→Pd↓+Fe 2+ 。
After the PVDF film is subjected to hydrophilic modification, the PVDF film is easy to wet by water, and is favorable for loading nano particles. The sewage passes through the packing layer from top to bottom, chlorinated organic matters in the sewage react with nano palladium/iron in the supported PVDF membrane to generate inorganic chlorine, and the zero-valent iron part on the supported PVDF membrane is oxidized into Fe 2+ And into the sewage. Then the sewage enters a mixed reaction zone, and under the aeration effect, oxygen in the air drives Fe 2+ Oxidation to Fe 3+ ，Fe 3+ Coagulation reaction with Polyacrylamide (PAM) to form flocculate, the flocculated water enters a sedimentation zone, the flocculate is sedimented to a bottom zone through an inclined plate to form sludge, and the sludge is discharged through a sludge discharge pump.
Drawings
FIG. 1 is a schematic diagram of the overall structure of a catalytic reduction dechlorination apparatus containing a supported PVDF membrane;
FIG. 2 is a schematic diagram of a first filler layer;
FIG. 3 is a schematic perspective view of a first filler layer;
fig. 4 is a schematic view of a sliding track of the first filler layer.
In the drawing, a 1-water distributor, a 2-first packing layer, a 3-aeration device, a 4-second packing layer, a 5-water producing port, a 6-sloping plate area, a 7-mud discharging port, an 8-first membrane component, a 9-first membrane, a 10-second membrane, a 11-first bracket, a 12-first positioning rod, a 13-first supporting rod, a 14-sliding rail, a 15-inner pipe, a 16-outer pipe and a 17-dosing pipe.
Detailed Description
The embodiment provides a catalytic reduction dechlorination device containing a supported PVDF membrane, which comprises a catalytic reduction zone, a mixed reaction zone and a precipitation zone which are sequentially connected, wherein the top of the catalytic reduction zone is provided with a water inlet and a water distributor 1 which are mutually connected, and a first packing layer 2 is arranged below the water distributor 1 and used for treating sewage;
the bottom of the mixed reaction zone is provided with an aeration device 3, the middle part of the mixed reaction zone is provided with a second filler layer 4, and the top of the mixed reaction zone is connected with a dosing device and is used for carrying out coagulation reaction; the first packing layer 2 and the second packing layer 4 are uniformly distributed with a load type PVDF film;
the sedimentation zone comprises a water producing port 5, an inclined plate zone 6 and a mud discharging port 7 from top to bottom, and the sewage is subjected to mud-water separation in the sedimentation zone to obtain produced water.
Optionally, the first filler layer 2 includes a plurality of first membrane assemblies 8 arranged horizontally, each first membrane assembly 8 is wavy and placed vertically, that is, the first membrane assemblies 8 include a plurality of inclined first membranes 9 and second membranes 10, the first membranes 9 and the second membranes 10 are alternately arranged, and angles between all the upper and lower adjacent first membranes 9 and second membranes 10 are within a range of 60-150 degrees, which may be the same or different and may be changed in real time.
Optionally, the area of the first filler layer 2 is provided with a first supporting frame, the first supporting frame includes a plurality of groups of vertically arranged first brackets 11 parallel to each other, each group of first brackets 11 is horizontally arranged and includes a plurality of first positioning rods 12 parallel to each other and two first supporting rods 13 at two ends of the first positioning rods 12, the first positioning rods 12 and the first supporting rods 13 are all at the same horizontal height, the two first supporting rods 13 are parallel to each other, and the first positioning rods 12 are perpendicular to the first supporting rods 13, i.e. a plurality of "i" shapes are formed; two ends of the first supporting rod 13 are connected with two side walls of the catalytic reduction zone;
the upper and lower sides of the first membrane 9 or the second membrane 10 are respectively fixed on the first positioning rods 12 of the upper and lower adjacent two groups of first brackets 11, and the first positioning rods 12 above and below the connection of the same first membrane 9 or the second membrane 10 are not on the same vertical line, so as to ensure that the first membrane 9 or the second membrane 10 is obliquely arranged. The bottom edge of the first membrane 9 and the top edge of the second membrane 10, which are adjacent to each other above and below the same first membrane module 8, may be fixed to the same first positioning rod 12.
Because the first membrane modules 8 are wavy, namely, have wave crests and wave troughs, when a plurality of first membrane modules 8 are horizontally arranged at certain intervals, the wave crests of the left and right adjacent first membrane modules 8 are close to each other, the wave troughs are also close to each other, namely, the wave crests on the left side are blown into the wave crests on the right side, the wave troughs on the right side are sunk into the wave troughs on the left side, but the wave troughs and other positions of the left and right adjacent first membrane modules 8 are kept at the same intervals and are not overlapped with each other.
In order to make the included angle between the first membrane 9 and the second membrane 10 changeable, further optionally, the single first support 11 of the first support frame may be movable, or the plural first supports 11 may be movable, and the first membrane assembly 8 of the present invention has a wave structure, and the inclination angle of the membrane may be changed by only moving the top edge or the bottom edge of the membrane without moving all the first supports 11.
Taking the single first support 11 as an example, the first supports 11 are movable and the first supports 11 are fixed, the two side wall surfaces of the catalytic reduction area are provided with slide rails 14 corresponding to the first support rods 13, namely, one side wall surface is provided with two vertical slide rails 14 which are parallel to each other, two ends of all the first support rods 13 are clamped in the corresponding slide rails 14, two ends of the first support rods 13 of the single first support 11 are provided with sliding blocks and can move up and down in the slide rails 14, the first support rods 13 of the first supports 11 are fixed in the slide rails 14, the limiting effect on the upper and lower first support rods 13 is achieved, and overlapping winding of upper and lower diaphragms is prevented;
the first supporting rod 13 of the singular first bracket 11 is of a sleeve structure and comprises an inner tube 15 and an outer tube 16, two ends of the first positioning rod 12 are fixedly connected to the corresponding outer tube 16, and two ends of the inner tube 15 are clamped in the sliding rail 14.
For example, when it is necessary to change the angle between the first pair of first diaphragms 9 and the second diaphragm 10, the second first support 11 is fixed, the first support rod 13 of the first support 11 moves downward on the slide rail 14, and at the same time the outer tube 16 moves leftward, and the angle between the first diaphragm 9 and the second diaphragm 10 becomes smaller; the first support rod 13 moves upwards on the slide rail 14, and the outer tube 16 moves rightwards, so that the included angle between the first membrane 9 and the second membrane 10 is increased; the movement of the first support bar 13 on the slide rail 14 may be controlled by a driving means (e.g. hydraulic cylinder) outside the catalytic reduction zone and the movement of the sleeve may be provided with push-pull means on the side walls to push the outer tube 16 to move.
The water distributor 1 of the invention can be a conventional water distributor 1 in the market. When the catalytic reduction zone operates normally, the liquid level of the sewage to be treated is higher than the top surface of the first packing layer 2, the sewage passes through the first packing zone from top to bottom, and organic chlorine in the sewage fully contacts with the surface of the membrane and the palladium-iron catalyst loaded on the surface of the membrane to degrade the organic chlorine. The stacked wavy first membrane assemblies 8 can enlarge the contact membrane area, play a role in disturbing water flow and promote the contact of sewage and the membrane surface. The wave-shaped included angle of the first membrane component 8 is adjustable, so that the water flow state in the first filler layer 2, such as the water flow speed and direction, is adjusted according to the water inlet state, and the treatment efficiency is improved; in addition, the adjustment is performed in real time during the operation, which is helpful to remove the sludge or solid impurities accumulated in the membrane gap by means of the change of the water flow, so as to clean the first packing layer 2. Because the diaphragm is inclined, the distance between the upper and lower first brackets 11 and the horizontal distance between the first positioning rods 12 at the top and bottom of the same diaphragm are changed to ensure that the diaphragm is always straightened and not bent.
The invention designs the first membrane component 8 into a stacked wave shape, so that sewage can flow down along the two sides of the membrane, and the supported catalysts of the two layers of the membrane are fully utilized. Specifically, the sewage first falls on the upper surface of the first membrane 9, and flows down along the surface, during the flowing down process, part of the sewage may permeate into the lower surface of the first membrane 9 through the membrane hole, and flows down along the surface, the sewage on the lower surface of the first membrane 9 may drop on the upper surface of the first membrane 9 of the adjacent first membrane assembly 8 (because the peak of the adjacent first membrane assembly 8 is blown into the peak of the first membrane assembly 8, the two parts are in an upper-lower relationship), and so on, the upper surface, the lower surface and the supported catalyst in the membrane hole channel of the membrane can be utilized, thereby improving the utilization of the membrane material.
Optionally, the catalytic reduction zone is further provided with a circulation port, the circulation port is arranged below the packing layer and is connected with a water inlet of the catalytic reduction zone through a circulation pump, and the circulation port is used for partially refluxing the sewage treated by the supported PVDF membrane and adjusting the water inlet state of the catalytic reduction zone;
the water outlet of the catalytic reduction zone is arranged at the bottom of the catalytic reduction zone and is communicated with the catalytic reduction zone and the mixed reaction zone, and the sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
Optionally, the mixing reaction area is connected with an external dosing device through a dosing pipe 17, the dosing device comprises a dosing pipe 17 and a dosing pump, the dosing pipe 17 is connected with the dosing pipe 17 through the dosing pump, and is used for inputting coagulant or flocculant into the mixing reaction area, and fully reacts under the stirring action of the aeration device 3;
the water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and is communicated with the mixed reaction zone and the sedimentation zone, and the sewage treated by the mixed reaction zone is input into the sedimentation zone.
Optionally, the second filler layer 4 includes a plurality of second membrane assemblies horizontally arranged, and the second membrane assemblies have the same structure as the first membrane assemblies 8, with the difference that all the angles between the third membrane and the fourth membrane, which are adjacent up and down, are in the range of 60-180 degrees, and may be the same or different, and may be changed in real time, that is, the second membrane assemblies may be in a wave shape or a straight shape at some time.
The second filler layer 4 is provided with a second supporting frame, and the structure of the second supporting frame is the same as that of the first supporting frame, and the difference is that the up-down movement range of the second bracket of the second supporting frame and the left-right movement range of the outer tube 16 of the second supporting rod are larger, so that the second membrane assembly can be changed into a straight shape from wave shape.
Specifically, the second filler layer 4 includes a plurality of second membrane assemblies arranged horizontally, each of the second membrane assemblies is in a wave shape and is placed vertically, that is, the second membrane assemblies include a plurality of inclined third membranes and fourth membranes, the third membranes and the fourth membranes are alternately arranged, and angles between all the upper and lower adjacent third membranes and fourth membranes are in a range of 60-180 degrees, which can be the same or different and can be changed in real time.
Optionally, the area of the second packing layer 4 is provided with a second supporting frame, the second supporting frame comprises a plurality of groups of second brackets which are vertically arranged and are parallel to each other, each group of second brackets is horizontally arranged and comprises a plurality of second positioning rods which are parallel to each other and two second supporting rods at two ends of each second positioning rod, the second positioning rods and the second supporting rods are all at the same horizontal height, the two second supporting rods are parallel to each other, and the second positioning rods are perpendicular to the second supporting rods, namely, a plurality of I-shaped structures are formed; two ends of the second supporting rod are connected with two side walls of the mixed reaction zone;
the upper side edge and the lower side edge of the third diaphragm or the fourth diaphragm are respectively fixed on the second positioning rods of the two groups of the second brackets which are adjacent up and down. The bottom edge of the third diaphragm and the top edge of the fourth diaphragm which are adjacent to each other from top to bottom of the same second diaphragm assembly can be fixed on the same second positioning rod.
The sewage treated by the catalytic reduction zone enters the mixed reaction zone, continuously contacts with the membrane while passing through the second filler layer 4 from bottom to top, degrades residual organic chlorine in the sewage, and simultaneously the sewage in the mixed reaction zone needs to react with a coagulant or a flocculant, and the second filler layer 4 can be matched with the aeration device 3 to disturb sewage flow so as to promote reaction. Because more flocs or sludge can be generated in the mixed reaction area, when the second membrane component in the second filler layer 4 is in a wave shape, the sludge is easier to accumulate in the gaps, so that the movement range of the second support frame is larger, the second membrane component can be changed into a straight line shape, thus the wave crest and the wave trough of the sludge accumulation can be eliminated, the sewage is facilitated to bring most of the sludge into the sedimentation area, and the second filler layer 4 is cleaned.
Optionally, a plurality of inclined plates which are parallel to each other and are obliquely arranged are arranged in the inclined plate area 6, after coagulation or flocculation reaction, most of sewage enters the sedimentation area, and firstly enters the inclined plate area 6 for mud-water separation, supernatant is discharged from the water producing port 5, namely produced water, the sewage is sedimented to the bottom of the sedimentation area and is discharged through the mud discharging port 7, the mud discharging port 7 is connected with an external mud discharging pump, and the sewage is treated according to the traditional method of the sludge in the field after being discharged.
Optionally, the bottom of sedimentation zone can back taper to set up the scraper, be convenient for mud discharge. The mud scraping plate is a mud scraping plate which is conventional in the art.
The supported PVDF membrane of the embodiment supports nano palladium and nano iron particles, and the preparation method is as follows:
(1) Preparing a KOH solution with the weight percent of 20 percent, and then dissolving KMnO 4 Obtaining KMnO 4 KMnO 10wt% 4 -KOH solution; 45wt% of H is configured 2 SO 4 Solution, re-dissolving NaHSO 3 Obtaining NaHSO 3 20wt% NaHSO 3 -H 2 SO 4 A solution; preparing a KOH solution with 20wt percent, and redissolving KBH 4 Obtaining KBH 4 KBH of 15wt% 4 -KOH solution; preparing 75wt% alcohol solution, and dissolving Pd (O) 2 CCH 3 ) 2 Pd (O) is obtained 2 CCH 3 ) 2 10wt% Pd (O) 2 CCH 3 ) 2 -an ethanol solution;
(2) Cleaning PVDF film with deionized water, soaking in KMnO 4 In KOH solution, alkali washing and dechlorination reaction is carried out, and reaction is carried out for 2 hours at 20 ℃ to obtain an intermediate film I;
(3) Washing the intermediate film I with deionized water, soaking in NaHSO 3 -H 2 SO 4 Hydrophilic modification is carried out in the solution, and the reaction is carried out for 5 hours at 25 ℃ to obtain a modified PVDF membrane;
(4) Immersing the modified PVDF film into 10wt% FeSO 4 The solution is placed in the state of 15min, and then vacuum drying is carried out for 3h at 115 ℃ to obtain the loaded Fe 2+ A PVDF membrane of (C); will be loaded with Fe 2+ Is immersed in KBH in PVDF film 4 In KOH solution, redox is carried outReacting for 15min to obtain a PVDF film loaded with zero-valent iron; washing the PVDF film loaded with zero-valent iron by absolute ethyl alcohol, and then rapidly placing the PVDF film into the absolute ethyl alcohol for preservation;
(5) Immersing zero-valent iron-loaded PVDF film in Pd (O 2 CCH 3 ) 2 And (3) carrying out chemical deposition in an ethanol solution for 10min to obtain the supported PVDF film.
The PVDF film in the step (2) is prepared by the following steps:
0.05g of PVDF powder is added into 5ml of N, N-dimethylacetamide (DMAc) solvent, stirred and dissolved at 60 ℃, then 0.25g of pore-forming agent polyvinylpyrrolidone (PVP) is added, and stirring is continued until no precipitate exists; sealing and preserving the obtained casting film liquid, and standing for 20 hours at room temperature in a dark place to remove all bubbles in the casting film liquid;
pouring the defoamed casting film liquid on a smooth glass plate at room temperature under the condition of 60% humidity, and scraping a liquid film with uniform thickness by using a scraper;
immersing the glass sheet carrying the liquid film in a 20vol.% ethanol solution, at which time DMAc as a solvent phase slowly transfers to the solvent phase resulting in the formation of a porous PVDF film; after the liquid film on the glass plate is completely changed into a solid PVDF film and is completely separated from the glass plate, taking out the glass plate, and keeping the just-formed PVDF raw film in a fixed liquid for continuous soaking for 24 hours so as to completely release a solvent phase into a non-solvent phase; taking out the prepared PVDF raw film, cleaning the PVDF raw film with distilled water, and then putting the PVDF raw film into distilled water for standby.
Claims (7)
1. The catalytic reduction dechlorination device containing the supported PVDF membrane is characterized by comprising a catalytic reduction zone, a mixed reaction zone and a precipitation zone which are connected in sequence, wherein the top of the catalytic reduction zone is provided with a water inlet and a water distributor which are connected with each other, and a first filler layer is arranged below the water distributor and used for treating sewage;
the bottom of the mixing reaction zone is provided with an aeration device, the middle part of the mixing reaction zone is provided with a second filler layer, and the top of the mixing reaction zone is connected with a dosing device and is used for carrying out coagulation reaction; the first packing layer and the second packing layer are uniformly distributed with a load type PVDF film;
the sedimentation zone comprises a water producing port, an inclined plate zone and a mud discharging port from top to bottom, and the sewage is subjected to mud-water separation in the sedimentation zone to obtain produced water;
the first filler layer comprises a plurality of first membrane assemblies which are horizontally arranged, and each first membrane assembly is wavy and vertically arranged;
the first membrane component comprises a plurality of inclined first membranes and second membranes, the first membranes and the second membranes are alternately arranged, and angles between all the upper and lower adjacent first membranes and second membranes are within the range of 60-150 degrees and can be changed in real time;
the second filler layer comprises a plurality of second membrane assemblies which are horizontally arranged, each second membrane assembly is wavy and vertically arranged, each second membrane assembly comprises a plurality of inclined third membranes and fourth membranes, the third membranes and the fourth membranes are alternately arranged, and angles between all the upper and lower adjacent third membranes and fourth membranes are within the range of 60-180 degrees and can be changed in real time.
2. The catalytic reduction dechlorination device according to claim 1, characterised in that the area of the first packing layer is provided with a first support frame comprising several groups of first supports arranged vertically and parallel to each other;
each group of first supports are horizontally arranged and comprise a plurality of first positioning rods which are parallel to each other and two first support rods at two ends of each first positioning rod, the first positioning rods and the first support rods are all at the same horizontal height, the two first support rods are parallel to each other, and the first positioning rods are perpendicular to the first support rods to form a plurality of I-shaped structures; two ends of the first supporting rod are connected with two side walls of the catalytic reduction zone;
the upper side edge and the lower side edge of the first diaphragm or the second diaphragm are respectively fixed on the first positioning rods of the two groups of first brackets which are adjacent up and down, and the first positioning rods above and below the connection of the same first diaphragm or the second diaphragm are not on the same vertical line so as to ensure that the first diaphragm or the second diaphragm is obliquely arranged.
3. The catalytic reduction dechlorination device according to claim 2, characterised in that the first support frame is movable in the singular or in the plural;
the two side wall surfaces of the catalytic reduction area are respectively provided with a sliding rail corresponding to the first supporting rods, one side wall surface is provided with two vertical sliding rails which are parallel to each other, two ends of all the first supporting rods are clamped in the corresponding sliding rails, two ends of the first supporting rods of the first single-number support are respectively provided with a sliding block and can move up and down in the sliding rails, the first supporting rods of the first multiple supports are fixed in the sliding rails, the limiting effect on the upper and lower first supporting rods is achieved, and overlapping winding of upper and lower diaphragms is prevented;
the first support rod of the first singular support is of a sleeve structure and comprises an inner tube and an outer tube, two ends of the first positioning rod are fixedly connected to the corresponding outer tube, and two ends of the inner tube are clamped in the sliding rail.
4. The catalytic reduction dechlorination device according to claim 1, wherein the catalytic reduction zone is further provided with a circulation port, the circulation port is arranged below the packing layer and is connected with a water inlet of the catalytic reduction zone through a circulation pump, and the circulation port is used for partially refluxing sewage treated by the supported PVDF membrane and adjusting the state of water inflow of the catalytic reduction zone;
the water outlet of the catalytic reduction zone is arranged at the bottom of the catalytic reduction zone and is communicated with the catalytic reduction zone and the mixed reaction zone, and the sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
5. The catalytic reduction dechlorination device according to claim 1, wherein the mixing reaction zone is connected with an external dosing device through a dosing pipe, the dosing device comprises a dosing pipe and a dosing pump, the dosing pipe is connected with the dosing pipe through the dosing pump, and is used for inputting coagulant or flocculant into the mixing reaction zone, and fully reacts under the stirring action of the aeration device;
the water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and is communicated with the mixed reaction zone and the sedimentation zone, and the sewage treated by the mixed reaction zone is input into the sedimentation zone.
6. The catalytic reduction dechlorination device according to claim 1, characterised in that the region of the second packing layer is provided with a second support frame comprising several groups of second supports arranged vertically and parallel to each other,
each group of second brackets are horizontally arranged and comprise a plurality of second positioning rods which are parallel to each other and two second supporting rods at two ends of each second positioning rod, the second positioning rods and the second supporting rods are all at the same horizontal height, the two second supporting rods are parallel to each other, and the second positioning rods are perpendicular to the second supporting rods to form a plurality of I-shaped structures; two ends of the second supporting rod are connected with two side walls of the mixed reaction zone;
the upper side edge and the lower side edge of the third diaphragm or the fourth diaphragm are respectively fixed on the second positioning rods of the two groups of the second brackets which are adjacent up and down.
7. The catalytic reduction dechlorination device according to claim 1, wherein the supported PVDF membrane is loaded with nano palladium and nano iron particles, and the preparation method is as follows:
(1) Preparing KOH solution, and redissolving KMnO 4 Obtaining KMnO 4 -KOH solution; configuration H 2 SO 4 Solution, re-dissolving NaHSO 3 Obtaining NaHSO 3 -H 2 SO 4 A solution; preparing KOH solution, and redissolving KBH 4 Obtaining KBH 4 -KOH solution; preparing ethanol solution, and redissolving Pd (O) 2 CCH 3 ) 2 Pd (O) is obtained 2 CCH 3 ) 2 -an ethanol solution;
(2) Cleaning PVDF film with deionized water, soaking in KMnO 4 In KOH solution, alkali washing and dechlorination reaction are carried out to obtain an intermediate film I;
(3) Washing the intermediate film I with deionized water, soaking in NaHSO 3 -H 2 SO 4 Hydrophilic modification is carried out in the solution to obtain a modified PVDF membrane;
(4) Immersing the modified PVDF film into FeSO 4 In the solution, then vacuum drying is carried out to obtain the loaded Fe 2+ A PVDF membrane of (C); will be loaded with Fe 2+ Is immersed in KBH in PVDF film 4 Performing oxidation-reduction reaction in KOH solution to obtain a PVDF film loaded with zero-valent iron;
(5) Immersing zero-valent iron-loaded PVDF film in Pd (O 2 CCH 3 ) 2 And (3) in ethanol solution, carrying out chemical deposition to obtain the supported PVDF film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11192795B2 (en) * | 2019-05-01 | 2021-12-07 | Imam Abdulrahman Bin Faisal University | ZnO-porous graphite composites, their use and manufacture |
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| JP2627397B2 (en) * | 1994-07-04 | 1997-07-02 | 市川 武 | Automatic lake purification system |
| JP2014131784A (en) * | 2013-01-07 | 2014-07-17 | Swing Corp | Sludge dryer |
| CN107973402A (en) * | 2017-11-28 | 2018-05-01 | 华夏碧水环保科技有限公司 | Pulling flow type AO reactors |
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