CN115745293A - 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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- CN115745293A CN115745293A CN202211504476.XA CN202211504476A CN115745293A CN 115745293 A CN115745293 A CN 115745293A CN 202211504476 A CN202211504476 A CN 202211504476A CN 115745293 A CN115745293 A CN 115745293A
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Abstract
The invention relates to a catalytic reduction dechlorination device containing a load type PVDF membrane, which comprises a catalytic reduction area, a mixed reaction area and a precipitation area which are sequentially connected, wherein the top of the catalytic reduction area 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 is used for treating sewage; the bottom of the mixed reaction zone is provided with an aeration device, the middle part of the mixed reaction zone is provided with a second packing layer, and the top of the mixed reaction zone is connected with a dosing device and is used for coagulation reaction; the first packing layer and the second packing layer are uniformly provided with load type PVDF films; the settling zone comprises a water producing port, an inclined plate zone and a sludge discharge port from top to bottom, and the sewage is subjected to sludge-water separation in the settling 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 (polyvinylidene fluoride) membrane.
Background
The waste water discharged by the industries of pesticide, dye, plastic, synthetic rubber, chemical industry, chemical fiber and the like contains a large amount of chlorinated organic matters. Chlorinated organic compounds are hydrophobic, difficult to biodegrade, slow to degrade under natural conditions, and 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 carcinogenic, teratogenic and mutagenic effects. Chlorinated organic matters enter the environment, which not only directly damages the ecological environment, but also harms human beings and other organisms in the ecological environment.
The method for treating chlorinated organic compounds mainly comprises a physical method: only the chlorinated organic matters can be transferred, the actual removal can not be achieved, and the standard discharge is difficult to reach; the biological method comprises the following steps: chlorinated organic compounds are foreign compounds, and are generally difficult to digest and degrade by microorganisms, so that microorganism poisoning is possibly caused; the chemical method comprises the following steps: 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 practical water treatment process and the like; the reduction method comprises an electrocatalytic oxidation method and a zero-valent iron reduction method, and the methods also have the problems of high energy consumption, harsh use conditions, high large-scale application cost and the like.
Disclosure of Invention
In order to solve one of the problems, the invention provides a catalytic reduction dechlorination device containing a supported PVDF (polyvinylidene fluoride) film, wherein packing layers are arranged in a catalytic reduction region and a mixed reaction region of the device, the packing layers are all PVDF films loaded with nano palladium-iron bimetallic particles, and the PVDF film has the advantages of excellent plasticity, strong acid and alkali resistance, high temperature resistance, high strength and the like. The device is suitable for the treatment of acid, alkali and neutral chlorine-containing wastewater, solves the problem of secondary pollution generated in the treatment process of chlorinated organic compounds, and has the advantages of low cost and convenient popularization and application.
The catalytic reduction dechlorination device comprises a catalytic reduction area, a mixed reaction area and a precipitation area which are sequentially connected, wherein a water inlet and a water distributor which are mutually connected are arranged at the top of the catalytic reduction area, and a first packing layer is arranged below the water distributor and used for treating sewage;
the bottom of the mixed reaction zone is provided with an aeration device, the middle part of the mixed reaction zone is provided with a second packing layer, and the top of the mixed reaction zone is connected with a dosing device and is used for coagulation reaction; the first packing layer and the second packing layer are uniformly provided with load type PVDF films;
the settling zone comprises a water producing port, an inclined plate zone and a sludge discharge port from top to bottom, and the sewage is subjected to sludge-water separation in the settling zone to obtain produced water.
Optionally, the first packing layer includes a plurality of first membrane modules arranged horizontally, each first membrane module is waved and vertically placed, that is, the first membrane module includes a plurality of inclined first membranes and second membranes, the first membranes and the second membranes are alternately arranged, and angles formed between all the first membranes and the second membranes adjacent to each other up and down are in a range of 60 to 150 degrees, and may be the same or different, and may be changed in real time.
Optionally, a first support frame is arranged in the area of the first packing layer, the first support frame includes a plurality of groups of vertically arranged and mutually parallel first supports, each group of first supports is horizontally arranged and includes a plurality of mutually parallel first positioning rods and two first support rods at two ends of the first positioning rod, the first positioning rod and the first support rod are both at the same horizontal height, the two first support rods are mutually parallel, and the first positioning rod is perpendicular to the first support rod, so that a plurality of "i" shapes are formed; two ends of the first supporting rod are connected with two side walls of the catalytic reduction area;
the upper side and the lower side of the first membrane or the second membrane are respectively fixed on the first positioning rods of the two groups of first supports which are adjacent from top to bottom, and the first positioning rods above and below the same first membrane or the same second membrane are not on the same vertical line so as to ensure that the first membrane or the second membrane is obliquely arranged.
In order to make the angle between the first membrane and the second membrane variable, it is further optional that a singular first support of the first support frame is movable, or that a plurality of first supports is movable. The odd first supports can move, the plurality of first supports are fixed as an example, sliding rails are arranged on the two side wall surfaces of the catalytic reduction zone 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, sliding blocks are arranged at the two ends of the first support rods of the odd first supports and can move up and down in the sliding rails, and the first support rods of the plurality of first supports are fixed in the sliding rails to play a role in limiting the upper and lower first support rods and prevent the upper and lower diaphragms from being wound in an overlapped mode;
the first bracing piece of odd number first support is the bushing structure, including inner tube and outer tube, the both ends fixed connection of first locating lever is on the outer tube that corresponds, and the both ends joint of inner tube is in the slide rail.
Optionally, the catalytic reduction region is further provided with a circulation port, the circulation port is arranged below the packing layer and connected with a water inlet of the catalytic reduction region through a circulation pump, and the circulation port is used for refluxing a part of sewage treated by the load type PVDF membrane and adjusting the water inlet state of the catalytic reduction region;
the water outlet of the catalytic reduction zone is arranged at the bottom of the catalytic reduction zone and communicated with the catalytic reduction zone and the mixed reaction zone, and sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
Optionally, 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 a coagulant or a flocculant into the mixing reaction zone to fully react under the stirring action of the aeration device;
and a water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and communicated with the mixed reaction zone and the precipitation zone, and sewage treated by the mixed reaction zone is input into the precipitation zone.
Optionally, the second packing layer includes a plurality of second membrane modules arranged horizontally, and the second membrane modules have the same structure as the first membrane modules, except that angles formed between all vertically adjacent third and fourth membrane modules are in the range of 60-180 °, and may be the same or different, and may change in real time, that is, the second membrane modules may be wavy or linear at some time.
The second support frame is arranged in the second filling layer area, the structure of the second support frame is the same as that of the first support frame, and the difference is that the vertical moving range of a second support of the second support frame and the horizontal moving range of an outer tube of the second support rod are larger, so that the second membrane assembly can be changed into a straight line from a wave shape.
The load type PVDF membrane of the invention loads nano palladium and nano iron particles, and the preparation method comprises the following steps:
(1) Preparing KOH solution, and dissolving KMnO 4 Obtaining KMnO 4 -a KOH solution; configuration H 2 SO 4 Solution, redissolving NaHSO 3 To obtain NaHSO 3 -H 2 SO 4 A solution; preparing KOH solution, and dissolving KBH 4 To obtain KBH 4 -a KOH solution; preparing ethanol solution, and dissolving Pd (O) 2 CCH 3 ) 2 To obtain Pd (O) 2 CCH 3 ) 2 -an ethanol solution;
(2) Washing PVDF membrane with deionized water, soaking in KMnO 4 Carrying out alkali washing dechlorination reaction in a KOH solution to obtain an intermediate film I;
(3) Cleaning the intermediate film I with deionized water, and soaking in NaHSO 3 -H 2 SO 4 Carrying out hydrophilic modification 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 load Fe 2+ The PVDF film of (1); will carry Fe 2+ PVDF membrane immersion in KBH 4 Carrying out oxidation-reduction reaction in a KOH solution to obtain a PVDF film loaded with zero-valent iron;
(5) Immersing the PVDF membrane loaded with zero-valent iron into Pd (O) 2 CCH 3 ) 2 And (4) carrying out chemical deposition in an ethanol solution to obtain the supported PVDF membrane.
Optionally, in the step (1), the mass concentration of the KOH solution is 16-20%, and KMnO is adopted 4 KMnO in KOH solution 4 The mass concentration of (A) is 8-10%;
H 2 SO 4 the mass concentration of the solution is 40-45%, and the solution is NaHSO 3 -H 2 SO 4 NaHSO in solution 3 The mass concentration of (A) is 18-20%;
the mass concentration of KOH solution is 15-20 percent, and KBH 4 KBH in KOH solution 4 The mass concentration of (A) is 11-15%;
the ethanol solution has a concentration of 70-75wt% and Pd (O) 2 CCH 3 ) 2 Pd (O) in ethanol solution 2 CCH 3 ) 2 The mass concentration of (2) is 10%.
Optionally, in the step (2), the temperature of the alkali washing dechlorination reaction is 18-20 ℃, and the time is 1-2h; PVDF molecule in KMnO 4 In a strong alkaline strong oxidation environment of the KOH solution, part of HF is removed, double bonds are generated, and the membrane body is changed from white to brown. The PVDF membrane in the step (2) can be prepared or a finished product can be purchased.
Optionally, in the step (3), the temperature of the hydrophilic modification is 20-28 ℃, and the time is 4-6h; under acidic conditions, the double bond on the intermediate membrane I generates nucleophilic addition reaction to generate polyol, and hydrophilic groups-hydroxyl (-OH) are generated on the membrane, so that the PVDF membrane has hydrophilicity.
Optionally, in step (4), the modified PVDF membrane is immersed in FeSO 4 Adding FeSO into 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 with the temperature of 115 ℃ for vacuum drying for 2-3h;
the load of Fe 2+ PVDF membrane immersion in KBH 4 And (2) in a KOH solution for 15-20min, the just generated zero-valent iron particles are very easily oxidized by oxygen in the air, so that the PVDF film loaded with the zero-valent iron is quickly put into absolute ethyl alcohol for storage after the PVDF film is cleaned by the absolute ethyl alcohol.
Optionally, in the step (5), the PVDF membrane loaded with zero-valent iron is immersed in a Pd (O2 CCH 3) 2-ethanol solution for 10-15min, and loaded with nano-palladium particles by chemical deposition, specifically, the reaction is Pd 2+ +Fe→Pd↓+Fe 2+ 。
According to the invention, the PVDF membrane is subjected to hydrophilic modification, so that the PVDF membrane is easily wetted by water and is beneficial to loading nano particles. The sewage passes through the filler layer from top to bottom, chlorinated organic matters in the sewage react with the nano palladium/iron in the load type PVDF membrane to generate inorganic chlorine, and the zero-valent iron part on the load type PVDF membrane is oxidized into Fe 2+ And into the wastewater. Then, the sewage enters a mixed reaction zone, and under the action of aeration, the oxygen in the air converts Fe 2+ Oxidation to Fe 3+ ，Fe 3+ Forming floc through coagulation reaction with Polyacrylamide (PAM), allowing flocculated water to enter a settling zone, settling the floc to a bottom zone through an inclined plate to form sludge, and discharging the sludge through a sludge discharge pump.
Drawings
FIG. 1 is a schematic diagram showing the overall structure of a catalytic reduction dechlorination apparatus including a supported PVDF membrane;
FIG. 2 is a schematic view of a first packing layer;
FIG. 3 is a schematic perspective view of a first packing layer;
FIG. 4 is a schematic diagram of a sled of the first packing layer.
In the attached drawing, 1-a water distributor, 2-a first packing layer, 3-an aeration device, 4-a second packing layer, 5-a water producing port, 6-an inclined plate area, 7-a sludge discharging port, 8-a first membrane component, 9-a first membrane, 10-a second membrane, 11-a first bracket, 12-a first positioning rod, 13-a first supporting rod, 14-a sliding rail, 15-an inner tube, 16-an outer tube and 17-a medicine feeding tube.
Detailed Description
The embodiment provides a catalytic reduction dechlorination device containing a supported PVDF (polyvinylidene fluoride) membrane, which comprises a catalytic reduction area, a mixed reaction area and a precipitation area which are sequentially connected, wherein a water inlet and a water distributor 1 which are mutually connected are arranged at the top of the catalytic reduction area, 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 is provided with a second packing layer 4, and the top part is connected with a dosing device and used for coagulation reaction; the first packing layer 2 and the second packing layer 4 are uniformly provided with load type PVDF films;
the settling zone comprises a water producing port 5, an inclined plate zone 6 and a sludge discharge port 7 from top to bottom, and the sewage is subjected to sludge-water separation in the settling zone to obtain produced water.
Optionally, the first packing layer 2 includes a plurality of horizontally arranged first membrane modules 8, each first membrane module 8 is waved and vertically placed, that is, the first membrane module 8 includes 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 formed between all the upper and lower adjacent first membranes 9 and second membranes 10 are in a range of 60 to 150 degrees, and may be the same or different, and may be changed in real time.
Optionally, a first supporting frame is arranged in the area of the first packing layer 2, the first supporting frame includes a plurality of groups of first supports 11 which are vertically arranged and parallel to each other, each group of first supports 11 is horizontally arranged, and includes a plurality of first positioning rods 12 which are 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 both 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, so that 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 region;
the upper side and the lower side of the first membrane 9 or the second membrane 10 are respectively fixed on the first positioning rods 12 of the two groups of first supports 11 which are adjacent up and down, and the first positioning rods 12 above and below which the same first membrane 9 or the second membrane 10 is connected 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 sheet 9 and the top edge of the second membrane sheet 10, which are adjacent to each other above and below the same first membrane module 8, may be fixed to the same first positioning bar 12.
Because the first membrane modules 8 are wavy, that is, have peaks and troughs, when a plurality of first membrane modules 8 are horizontally arranged at a certain interval, the peaks and troughs of the left and right adjacent first membrane modules 8 are close to each other, that is, the left peak bulges into the right peak, and the right trough sinks into the left trough, but the left and right adjacent first membrane modules 8 maintain the same spacing at the peaks, troughs and other positions, and do not overlap each other.
In order to make the included angle between the first membrane 9 and the second membrane 10 changeable, further alternatively, the single first support 11 of the first support frame may be movable, or the plurality of first supports 11 may be movable, and the first membrane module 8 of the present invention has a wave-shaped structure, and the inclination angle of the membrane can be changed by moving the top edge or the bottom edge of the membrane without moving all the first supports 11.
The odd first supports 11 are movable, and the plural first supports 11 are fixed as an example, the positions, corresponding to the first support rods 13, on the two side wall surfaces of the catalytic reduction zone are respectively provided with a slide rail 14, that is, two vertical slide rails 14 which are parallel to each other are arranged on one side wall surface, the two ends of all the first support rods 13 are clamped in the corresponding slide rails 14, the two ends of the first support rods 13 of the odd first supports 11 are respectively provided with a slide block and can move up and down in the slide rails 14, the first support rods 13 of the plural first supports 11 are fixed in the slide rails 14, so that the limiting effect on the upper and lower first support rods 13 is achieved, and the upper and lower diaphragms are prevented from being overlapped and wound;
For example, when the angle between the first pair of first diaphragms 9 and the second diaphragm 10 needs to be changed, the second first bracket 11 is fixed, the first supporting rod 13 of the first bracket 11 moves downwards on the sliding rail 14, the outer tube 16 moves leftwards at the same time, and the included angle between the first diaphragm 9 and the second diaphragm 10 becomes smaller; the first supporting rod 13 moves upwards on the sliding rail 14, and simultaneously the outer tube 16 moves rightwards, so that the included angle between the first diaphragm 9 and the second diaphragm 10 is increased; the movement of the first support rod 13 on the skid 14 can be controlled by a driving device (e.g. a hydraulic cylinder) outside the catalytic reduction zone, and the movement of the sleeve can be provided with a push-pull device on the side wall to push the outer pipe 16 to move.
The water distributor 1 of the invention can be a conventional water distributor 1 on the market. When the catalytic reduction area is in normal operation, 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 area from top to bottom, and organic chlorine in the sewage is fully contacted with the surface of the membrane and the supported palladium-iron catalyst for degradation. The stacked wave-shaped first membrane components 8 can increase the area of the membrane which can be contacted, and simultaneously play a role in disturbing water flow and promote the contact of sewage and the membrane. The included angle of the wave shape of the first membrane component 8 is adjustable, so that the water flow state inside the first packing layer 2 is adjusted according to the water inlet state, for example, the water flow speed and direction are adjusted, and the treatment efficiency is improved; in addition, adjust in real time in the operation process, help getting rid of the mud or the solid impurity that accumulate in the membrane clearance with the help of the change of rivers self, realize clean first packing layer 2. Because the diaphragm is inclined, the distance between the upper first support 11 and the lower first support 11 and the horizontal distance between the first positioning rods 12 at the top and the bottom of the same diaphragm are required to be changed to ensure that the diaphragm is always stretched straight and not bent.
The first membrane component 8 is designed into a stacked wave shape, so that sewage can flow down along two surfaces of the membrane, and the supported catalysts of two layers of the membrane are fully utilized. Specifically, the sewage firstly 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 holes and flow down along the surface, and the sewage on the lower surface of the first membrane 9 may drip on the upper surface of the first membrane 9 of the adjacent first membrane module 8 (because the wave crests of the adjacent first membrane module 8 bulge into the wave crests of the first membrane module 8, the two parts are in an up-and-down relationship), so by analogy, the supported catalysts on the upper surface and the lower surface of the membrane and in the membrane hole channels can be utilized, and the utilization of the membrane material is improved.
Optionally, the catalytic reduction region is further provided with a circulation port, the circulation port is arranged below the packing layer and connected with a water inlet of the catalytic reduction region through a circulation pump, and the circulation port is used for refluxing a part of sewage treated by the load type PVDF membrane and adjusting the water inlet state of the catalytic reduction region;
the water outlet of the catalytic reduction zone is arranged at the bottom of the catalytic reduction zone and communicated with the catalytic reduction zone and the mixed reaction zone, and sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
Optionally, the mixing reaction zone 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 a coagulant or a flocculant into the mixing reaction zone to fully react under the stirring action of the aeration device 3;
and a water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and communicated with the mixed reaction zone and the precipitation zone, and sewage treated by the mixed reaction zone is input into the precipitation zone.
Optionally, the second packing layer 4 includes a plurality of second membrane modules arranged horizontally, and the second membrane modules have the same structure as the first membrane modules 8, except that angles formed between all vertically adjacent third and fourth membranes are within a range of 60 to 180 °, and may be the same or different, and may be changed in real time, that is, the second membrane modules may be wavy or linear at some time.
The area of the second packing layer 4 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 moving range of a second support of the second supporting frame and the left-right moving range of an outer tube 16 of the second supporting rod are larger, so that the second membrane assembly can be changed from wave shape to linear shape.
Specifically, the second packing layer 4 includes a plurality of second membrane modules horizontally arranged, each second membrane module is waved and vertically disposed, that is, the second membrane module includes a plurality of inclined third membranes and fourth membranes, the third membranes and the fourth membranes are alternately arranged, and angles formed between all the third membranes and the fourth membranes adjacent to each other up and down are in a range of 60 to 180 degrees, and may be the same or different, and may be changed in real time.
Optionally, a second support frame is arranged in the area of the second packing layer 4, the second support frame includes a plurality of groups of vertically arranged and mutually parallel second supports, each group of second supports is horizontally arranged and includes a plurality of mutually parallel second positioning rods and two second support rods at two ends of the second positioning rods, the second positioning rods and the second support rods are all at the same horizontal height, the two second support rods are mutually parallel, and the second positioning rods are perpendicular to the second support rods, so that a plurality of "i" shapes are formed; two ends of the second support rod are connected with two side walls of the mixed reaction zone;
and the upper side and the lower side of the third membrane or the fourth membrane are respectively fixed on the second positioning rods of the two groups of second supports which are adjacent up and down. The bottom edge of the third membrane and the top edge of the fourth membrane which are vertically adjacent to each other of the same second membrane component can be fixed on the same second positioning rod.
The sewage that is handled through the catalytic reduction district gets into the mixed reaction district, from the supreme second packing layer 4 of passing through down, continues to contact with the membrane, degrades remaining organic chlorine in the sewage, and the mixed reaction is distinguished interior sewage of water simultaneously and needs react with coagulant or flocculating agent, and second packing layer 4 can cooperate aeration equipment 3 carries out the disturbance to sewage rivers, promotes the reaction. Because the mixed reaction zone can produce more flocs or sludge, when the second membrane module inside the second packing layer 4 is wavy, the clearance is easier to accumulate sludge, so the moving range of the second supporting frame is wider, the second membrane module can be changed into a straight line shape, the wave crests and the wave troughs accumulated by sludge can be eliminated, the sewage is favorably brought into the settling zone, and the cleaning of the second packing layer 4 is realized.
Optionally, a plurality of inclined plates which are parallel to each other and are obliquely arranged are arranged in the inclined plate area 6, sewage carries most sludge to enter the settling area after coagulation or flocculation reaction, the sewage firstly enters the inclined plate area 6 to be subjected to mud-water separation, supernatant is discharged from the water production port 5 to be water production, the sludge is settled to the bottom of the settling area and discharged from the sludge discharge port 7, the sludge discharge port 7 is connected with an external sludge discharge pump, and the sludge is discharged and then is treated according to the traditional method of sludge in the field.
Optionally, the bottom of the settling zone can be inverted conical, and a mud scraper is arranged, so that sludge can be discharged conveniently. The scraper can be a scraper which is conventional in the art.
The supported PVDF membrane described in this embodiment supports nano palladium and nano iron particles, and the preparation method is as follows:
(1) Preparing 20wt% KOH solution, and dissolving KMnO 4 Obtaining KMnO 4 Is 10wt% of KMnO 4 -a KOH solution; preparation of 45wt% H 2 SO 4 Solution, redissolving NaHSO 3 To obtain NaHSO 3 20% by weight of NaHSO 3 -H 2 SO 4 A solution; preparing 20wt% KOH solution, and dissolving KBH 4 To obtain KBH 4 KBH of 15wt% 4 -a KOH solution; preparing 75wt% ethanol solution, and dissolving Pd (O) 2 CCH 3 ) 2 To obtain Pd (O) 2 CCH 3 ) 2 10wt% Pd (O) 2 CCH 3 ) 2 -an ethanol solution;
(2) Washing PVDF membrane with deionized water, soaking in KMnO 4 Carrying out alkali washing dechlorination reaction in a KOH solution, and reacting for 2h at 20 ℃ to obtain an intermediate film I;
(3) Cleaning the intermediate film I with deionized water, and soaking in NaHSO 3 -H 2 SO 4 Carrying out hydrophilic modification in the solution, and reacting for 5 hours at 25 ℃ to obtain a modified PVDF membrane;
(4) Immersing the modified PVDF film into 10wt% of FeSO 4 The solution is put for 15min and then dried for 3h in vacuum at 115 ℃ to obtain the load Fe 2+ The PVDF membrane of (1); will carry Fe 2+ PVDF membrane immersion in KBH 4 Carrying out oxidation-reduction reaction in a KOH solution for 15min to obtain a zero-valent iron loaded PVDF film; after the PVDF membrane loaded with zero-valent iron is cleaned by absolute ethyl alcohol, the PVDF membrane is quickly put into the absolute ethyl alcohol for preservation;
(5) Immersing a zero-valent iron-loaded PVDF membrane in Pd (O) 2 CCH 3 ) 2 -performing chemical deposition in an ethanol solution for 10min to obtain the supported PVDF membrane.
Wherein the preparation method of the PVDF membrane in the step (2) is as follows:
adding 0.05g of PVDF powder into 5ml of N, N-dimethylacetamide (DMAc) solvent, stirring at 60 ℃ to dissolve, adding 0.25g of pore-forming agent polyvinylpyrrolidone (PVP), and continuing stirring until no precipitate exists; sealing and storing the obtained casting solution, and standing for 20 hours at room temperature in a dark place to remove all bubbles in the casting solution;
pouring the defoamed casting solution on a smooth glass plate under the conditions of room temperature and humidity of 60%, and scraping a liquid film with uniform thickness by using a scraper;
immersing the glass plate carrying the liquid membrane in a 20vol.% ethanol solution, while the slow phase transfer of DMAc as solvent phase to the solvent phase results in the formation of a porous PVDF membrane; after the liquid film on the glass plate is completely changed into the solid PVDF film and is completely separated from the glass plate, taking out the glass plate and leaving the just-formed PVDF original film in the fixing liquid to continue soaking for 24 hours so as to completely release the solvent phase into the non-solvent phase; and taking out the prepared PVDF original membrane, cleaning the PVDF original membrane by using distilled water, and then putting the PVDF original membrane into the distilled water for later use.
Claims (9)
1. A catalytic reduction dechlorination device containing a load type PVDF membrane is characterized by comprising a catalytic reduction area, a mixed reaction area and a precipitation area which are sequentially connected, wherein a water inlet and a water distributor which are mutually connected are arranged at the top of the catalytic reduction area, and a first packing layer is arranged below the water distributor and is used for treating sewage;
the bottom of the mixed reaction zone is provided with an aeration device, the middle part of the mixed reaction zone is provided with a second packing layer, and the top of the mixed reaction zone is connected with a dosing device and is used for coagulation reaction; the first packing layer and the second packing layer are uniformly provided with load type PVDF films;
the settling zone comprises a water producing port, an inclined plate zone and a sludge discharge port from top to bottom, and the sewage is subjected to sludge-water separation in the settling zone to obtain produced water.
2. The catalytic reduction dechlorination apparatus according to claim 1, wherein the first packing layer comprises a plurality of first membrane modules which are horizontally arranged, and each first membrane module is waved and vertically arranged;
the first membrane assembly comprises a plurality of inclined first membranes and second membranes, the first membranes and the second membranes are alternately arranged, and the angles formed between all the vertically adjacent first membranes and second membranes are within the range of 60-150 degrees and can be changed in real time.
3. The catalytic reduction dechlorination apparatus according to claim 2, wherein the area of the first packing layer is provided with a first supporting frame, and the first supporting frame comprises a plurality of groups of first brackets which are vertically arranged and parallel to each other;
each group of first supports 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 positioned 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 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 area;
the upper side and the lower side of the first membrane or the second membrane are respectively fixed on the first positioning rods of the two groups of first supports which are adjacent from top to bottom, and the first positioning rods above and below the same first membrane or the same second membrane are not on the same vertical line so as to ensure that the first membrane or the second membrane is obliquely arranged.
4. The catalytic reductive dechlorination apparatus of claim 3, wherein the singular first support of the first support frame is movable or the plural first supports are movable;
the two side wall surfaces of the catalytic reduction zone are provided with slide rails corresponding to the positions of the first support rods, one side wall surface is provided with two vertical slide rails which are parallel to each other, the two ends of all the first support rods are clamped in the corresponding slide rails, the two ends of the first support rods of the odd-number first supports are provided with slide blocks and can move up and down in the slide rails, the first support rods of the plurality of first supports are fixed in the slide rails to play a role in limiting the upper and lower first support rods, and the upper and lower diaphragms are prevented from being overlapped and wound;
the first bracing piece of odd number first support is the bushing structure, including inner tube and outer tube, the both ends fixed connection of first locating lever is on the outer tube that corresponds, and the both ends joint of inner tube is in the slide rail.
5. 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 the water inlet of the catalytic reduction zone through a circulation pump, and the circulation port is used for refluxing the sewage part 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 communicated with the catalytic reduction zone and the mixed reaction zone, and sewage treated by the catalytic reduction zone is input into the mixed reaction zone.
6. 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 a coagulant or a flocculant into the mixing reaction zone to fully react under the stirring action of the aeration device;
and a water outlet of the mixed reaction zone is arranged at the top of the mixed reaction zone and communicated with the mixed reaction zone and the precipitation zone, and sewage treated by the mixed reaction zone is input into the precipitation zone.
7. The catalytic reduction dechlorination device according to claim 1, wherein the second packing layer comprises a plurality of second membrane assemblies which are horizontally arranged, each second membrane assembly is waved and vertically arranged, each second membrane assembly comprises a plurality of inclined third membranes and inclined fourth membranes, the third membranes and the fourth membranes are alternately arranged, and angles formed between every two adjacent third membranes and every adjacent fourth membranes are within the range of 60-180 degrees and can be changed in real time.
8. The catalytic reduction dechlorination apparatus according to claim 7, wherein the area of the second packing layer is provided with a second supporting frame, the second supporting frame comprises a plurality of groups of second brackets which are vertically arranged and parallel to each other,
each group of second supports 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 positioned 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 bodies; two ends of the second support rod are connected with two side walls of the mixed reaction zone;
and the upper side and the lower side of the third membrane or the fourth membrane are respectively fixed on the second positioning rods of the two groups of second supports which are adjacent up and down.
9. The catalytic reductive dechlorination apparatus 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 dissolving KMnO 4 Obtaining KMnO 4 -a KOH solution; configuration H 2 SO 4 Solution, redissolving NaHSO 3 To obtain NaHSO 3 -H 2 SO 4 A solution; preparing KOH solution, and dissolving KBH 4 To obtain KBH 4 -a KOH solution; preparing ethanol solution, and dissolving Pd (O) 2 CCH 3 ) 2 To obtain Pd (O) 2 CCH 3 ) 2 -an ethanol solution;
(2) Washing PVDF membrane with deionized water, soaking in KMnO 4 Carrying out alkali washing dechlorination reaction in a KOH solution to obtain an intermediate film I;
(3) Cleaning the intermediate film I with deionized water, and soaking in NaHSO 3 -H 2 SO 4 Carrying out hydrophilic modification in the solution to obtain a modified PVDF membrane;
(4) Immersing the modified PVDF membrane into FeSO 4 In the solution, and then vacuum drying is carried out to obtain the load Fe 2+ The PVDF membrane of (1); will carry Fe 2+ PVDF membrane immersion in KBH 4 Carrying out oxidation-reduction reaction in a KOH solution to obtain a zero-valent iron loaded PVDF film;
(5) Immersing the PVDF membrane loaded with zero-valent iron into Pd (O) 2 CCH 3 ) 2 -carrying out chemical deposition in an ethanol solution to obtain the supported PVDF membrane.
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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 |
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