Electrochemical membrane module for selectively removing pollutants and preparation method thereof

Abstract

An electrochemical membrane module for selectively removing pollutants and a preparation method thereof are provided. A Ti/SnO.sub.2—Sb substrate electrode is coated with a MI—TiO.sub.2 sol-gel by means of a dip-coating method, and then sintered to obtain a molecular imprinting type Ti/MI—TiO.sub.2/SnO.sub.2—Sb coated electrode; the coated electrode is adhered to a ceramic micro-filtration membrane using epoxy resin glue to obtain a Ti/MI—TiO.sub.2/SnO.sub.2—Sb MI-anodic conductive composite membrane; the MI-anodic conductive composite membrane is used as an anode, and a titanium mesh is used as a cathode, so that the electrochemical membrane module capable of selectively removing pollutants is obtained. The invention effectively combines an electrochemical micro-filtration membrane and a molecular imprinting technique. When the electrochemical membrane module is used, suspended particles and refractory organics in the sewage are removed, and a highly selective removal of certain refractory pollutants can be achieved.

Claims

1. An electrochemical membrane module for selectively removing pollutants, comprising a membrane bracket, MI-anodic composite membranes, and a titanium mesh, wherein the membrane bracket is provided with a suction port connecting with an inner cavity of the membrane bracket, the inner cavity of the membrane bracket is internally provided with the titanium mesh as a cathode, and both outer sides of the membrane bracket are provided with the MI-anodic composite membranes, and each of the MI-anodic composite membranes comprises a Ti—SnO.sub.2—Sb substrate electrode and a ceramic micro-filtration membrane, wherein the Ti—SnO.sub.2—Sb substrate electrode is opposite to the inner cavity of the membrane bracket, and the Ti—SnO.sub.2—Sb substrate electrode is coated with a MI—TiO.sub.2 sol-gel coating; wherein the Ti—SnO.sub.2—Sb substrate electrode is obtained by preparing a sol-gel having a Sn:Sb of 9:1, coating the sol-gel on the titanium mesh having a pore diameter of 100 μm and a thickness of 200 μm, and sintering the titanium mesh.

2. A method for preparing the electrochemical membrane module according to claim 1, comprising the steps of: (1) immersing the Ti—SnO.sub.2—Sb substrate electrode in the MI—TiO.sub.2 sol-gel, removing the Ti—SnO.sub.2—Sb substrate electrode from the MI—TiO.sub.2 sol-gel and sintering the Ti—SnO.sub.2—Sb substrate electrode to obtain a coated electrode coated with the MI—TiO.sub.2 sol-gel coating on a surface of the coated electrode, and then adhering the coated electrode to a surface of the ceramic micro-filtration membrane by epoxy resin, to obtain the MI-anodic composite membranes; (2) vertically disposing the titanium mesh m the membrane bracket as the cathode, and adhering two of the MI-anodic composite membranes obtained in the step (1) to the both outer sides of the membrane bracket directly opposite to the cathode, wherein the Ti—SnO.sub.2—Sb substrate electrode is placed opposite to the inner cavity of the membrane bracket.

3. The method according to claim 2, wherein the MI—TiO.sub.2 sol-gel is prepared by adding titanium alkoxide and a template molecule into first absolute ethanol and stirring to obtain a molecular imprinting precursor solution, then mixing water, second absolute ethanol and glacial acetic acid under stirring to obtain a reaction medium solution, and finally adding the reaction medium solution to the molecular imprinting precursor solution dropwise under stirring.

4. The method according to claim 3, wherein the titanium alkoxide is at least one of tetrabutyl titanate, isopropyl titanate and titanium isopropoxide.

5. The method according to claim 3, wherein the template molecule is at least one of 2,4-dichlorophenoxyacetic acid, 3,4-dichlorophenoxyacetic acid, 2,3-dichlorophenoxy acetic acid and p-chlorophenol.

6. The method according to claim 3, wherein a molar ration of the template molecule, the titanium alkoxide, a sum of the first absolute ethanol and the second absolute ethanol, the glacial acetic acid, and to the water is 0.5:1:18:2:8.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic diagram of the preparation process of the electrochemical membrane module of the present invention;

(2) FIG. 2 is a schematic diagram of the membrane reactor structure of the present invention.

REFERENCE NUMBERS

(3) 10. inlet pipe 20. reactor casing 30. electrochemical membrane module 31. membrane bracket 32. MI-anodic composite membrane 321. Ti—SnO.sub.2—Sb substrate electrode 322. ceramic micro-filtration membrane 323. TiO.sub.2 sol-gel coating 33. titanium mesh 40. power supply 50. aeration system 51. aeration tube 52. gas flowmeter 53. air pump 60. outlet pipe 61. peristaltic pump 62. pressure gauge 63. flowmeter

DETAILED DESCRIPTION OF THE EMBODIMENTS

(4) The features of the present invention are further described by the following embodiments, but the claims of the present invention are not limited thereby.

Embodiment 1

(5) An electrochemical membrane module for selectively removing pollutants includes a membrane bracket, MI-anodic composite membranes, and a titanium mesh, wherein the membrane bracket is provided with a suction port connecting with the inner cavity of the membrane bracket, the inner cavity of the membrane bracket is internally incorporated with the titanium mesh as a cathode, and both outer sides of the membrane bracket are integrated with the MI-anodic composite membranes, the MI-anodic composite membrane includes a Ti—SnO.sub.2—Sb substrate electrode and a ceramic micro-filtration membrane, wherein the substrate electrode is placed opposite to the inner cavity of the membrane bracket, and the substrate electrode is coated with a MI—TiO.sub.2 sol-gel coating.

(6) As shown in FIG. 1, the preparation method of the above electrochemical membrane module for selectively removing pollutants includes the steps of:

(7) (1) Preparation of Ti—SnO.sub.2—Sb substrate electrode: according to the literature [Zheng, J.; Wang, Z.; Ma, J.; Xu, S.; Wu, Z. Development of an electrochemical ceramic membrane filtration system for efficient contaminant removal from waters. Environ. Sci. Technol. 2018, 52(7), 4117-41261.], a sol-gel with a Sn:Sb of 9:1 was prepared, which was then coated on the titanium mesh having a pore size of 100 μm, a thickness of 200 μm, and a size of 5 cm*8 cm, and the Ti—SnO.sub.2—Sb substrate electrode was obtained after sintering the coated titanium mesh;

(8) (2) Preparation of MI—TiO.sub.2 sol-gel: titanium source (tetrabutyl titanate) and template molecule (2,4-dichlorophenoxyacetic acid) were added into absolute ethanol and stirred to obtain the molecular imprinting precursor solution A, and then water, absolute ethanol and glacial acetic acid were mixed under stirring to obtain the reaction medium solution B, finally, B was added into A dropwise under stirring to obtain the MI—TiO.sub.2 sol-gel; wherein the molar ratio of 2,4-dichlorophenoxyacetic acid:tetrabutyl titanate:absolute ethanol:glacial acetic acid:water was 0.5:1:18:2:8; the titanium mesh had a pore diameter of 100 μm and a thickness of 200 μm; the ceramic micro-filtration membrane consisted of ZrO.sub.2 and Al.sub.2O.sub.3, and the pore size of the ceramic micro-filtration membrane was 0.25 μm;

(9) (3) Preparation of MI-anodic composite membrane: the Ti—SnO.sub.2—Sb substrate electrode was immersed in the MI—TiO.sub.2 sol-gel, then sintered to obtain an electrode coated with the TiO.sub.2 sol-gel, and then the electrode was adhered to the surface of the ceramic micro-filtration membrane by epoxy resin, to obtain the MI-anodic composite membrane;

(10) (4) Preparation of electrochemical membrane module: the titanium mesh was vertically inserted in the membrane bracket as a cathode, and two MI-anodic composite membranes obtained in the step (3) were adhered to both outer sides of the membrane bracket directly opposite to the cathode, wherein the distance between the anode and the cathode was set at 1.0 cm, the substrate electrode was placed opposite to the inner cavity of the membrane bracket, to obtain the electrochemical membrane module for selectively removing pollutants (labeled as C1).

(11) As shown in FIG. 2, the membrane bioreactor employing the above electrochemical membrane module includes inlet pipe 10, reactor casing 20, electrochemical membrane module 30, power supply 40, aeration system 50, and outlet pipe 60; one end of inlet pipe 10 is placed in reactor casing 20; electrochemical membrane module 30 is placed in reactor casing 20, and electrochemical membrane module 30 includes membrane bracket 31, MI-anodic composite membranes 32, and titanium mesh 33, membrane bracket 31 is provided with a suction port connecting with the inner cavity of the membrane bracket, and the suction port is connected with outlet pipe 60, titanium mesh 33 is inserted in the inner cavity of the membrane bracket as a cathode, and titanium mesh 33 is connected to the negative pole of the power supply by a wire, both outer sides of the membrane bracket are provided with MI-anodic composite membranes 32, MI-anodic composite membranes 32 are connected to the positive pole of power supply 40 through wires, and MI-anodic composite membrane 32 includes Ti—SnO.sub.2—Sb substrate electrode 321 and ceramic micro-filtration membrane 322, wherein substrate electrode 321 is placed opposite to the inner cavity of the membrane bracket, and substrate electrode 321 is coated with MI—TiO.sub.2 sol-gel coating 323, and ceramic micro-filtration membrane 322 is placed facing the water; power supply 40 is a regulated DC power supply, and the voltage range of power supply 40 is from 0.5 to 4 V; aeration system 50 includes aeration tube 51, gas flowmeter 52, and air pump 53, aeration tube 51 is located below electrochemical membrane module 30, and gas flowmeter 52 is used to regulate the flow rate of intake air; outlet pipe 60 is provided with peristaltic pump 61, pressure gauge 62 and flowmeter 63.

(12) A low-concentration sewage containing 2,4-dichlorophenoxyacetic acid and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were set as: the concentrations of influent pollutants (2,4-dichlorophenoxyacetic acid and sulfamethoxazole) were 1 mg/L, pH=7.0, the hydraulic retention time was 4 h, and the voltage of the regulated DC power supply was 3 V. The results showed that the removal rate of the target pollutant 2,4-dichlorophenoxyacetic acid by the electrochemical membrane module C1 was 89%, and the selectivity coefficient was 4.5.

Embodiment 2

(13) An electrochemical membrane module for selectively removing pollutants includes a membrane bracket, MI-anodic composite membranes, and a titanium mesh, the membrane bracket is provided with a suction port connecting with the inner cavity of the membrane bracket, the inner cavity of the membrane bracket is internally incorporated with the titanium mesh as a cathode, and both outer sides of the membrane bracket are integrated with the MI-anodic composite membranes, the MI-anodic composite membrane includes a Ti—SnO.sub.2—Sb substrate electrode and a ceramic micro-filtration membrane, wherein the substrate electrode is placed opposite to the inner cavity of the membrane bracket, and the substrate electrode is coated with a MI—TiO.sub.2 sol-gel coating.

(14) The preparation method of the above electrochemical membrane module for selectively removing pollutants includes the steps of:

(15) (1) Preparation of Ti—SnO.sub.2—Sb substrate electrode: according to the literature [Zheng, J.; Wang, Z.; Ma, J.; Xu, S.; Wu, Z. Development of an electrochemical ceramic membrane filtration system for efficient contaminant removal from waters. Environ. Sci. Technol. 2018, 52, (7), 4117-4126.], a sol-gel with a Sn:Sb of 9:1 was prepared, which was then coated on the titanium mesh having a pore size of 100 μm, a thickness of 200 μm, and a size of 5 cm*8 cm, the Ti/SnO.sub.2—Sb substrate electrode was obtained after sintering the coated titanium mesh;

(16) (2) Preparation of MI—TiO.sub.2 sol-gel: titanium source (isopropyl titanate) and template molecule (3,4-dichlorophenoxyacetic acid) were added into absolute ethanol and stirred to obtain the molecular imprinting precursor solution A, and then water, absolute ethanol and glacial acetic acid were mixed under stirring to obtain the reaction medium solution B, finally B was added into A dropwise under stirring to obtain the MI—TiO.sub.2 sol-gel; wherein the molar ratio of 3,4-dichlorophenoxyacetic acid:isopropyl titanate:absolute ethanol:glacial acetic acid:water was 0.5:1:18:2:8; the titanium mesh had a pore diameter of 100 μm and a thickness of 200 μm; the ceramic micro-filtration membrane consisted of ZrO.sub.2 and Al.sub.2O.sub.3, and the membrane pore size of the ceramic micro-filtration membrane was 0.25 μm;

(17) (3) Preparation of MI-anodic composite membrane: the Ti—SnO.sub.2—Sb substrate electrode was immersed in the MI—TiO.sub.2 sol-gel, then sintered to obtain an electrode coated with the TiO.sub.2 sol-gel, and then the electrode was adhered to the surface of the ceramic micro-filtration membrane by epoxy resin, to obtain the MI-anodic composite membrane;

(18) (4) Preparation of electrochemical membrane module: the titanium mesh was vertically inserted in the membrane bracket as a cathode, and two MI-anodic composite membranes obtained in the step (3) were adhered to the both outer sides of the membrane bracket directly opposite to the cathode, wherein the distance between the anode and the cathode was set at 1.0 cm, the substrate electrode was placed opposite to the inner cavity of the membrane bracket, to obtain the electrochemical membrane module for selectively removing pollutants (labeled as C2).

(19) The membrane bioreactor employing the above electrochemical membrane module includes inlet pipe 10, reactor casing 20, electrochemical membrane module 30, power supply 40, aeration system 50, and outlet pipe 60; one end of inlet pipe 10 is inserted in reactor casing 20; electrochemical membrane module 30 is placed in reactor casing 20, and electrochemical membrane module 30 includes membrane bracket 31, MI-anodic composite membranes 32, and titanium mesh 33, membrane bracket 31 is provided with a suction port connecting with the inner cavity of the membrane bracket, and the suction port is connected with outlet pipe 60, titanium mesh 33 is inserted in the inner cavity of the membrane bracket as a cathode, and titanium mesh 33 is connected to the negative pole of the power supply by a wire, both outer sides of the membrane bracket are provided with MI-anodic composite membranes 32, MI-anodic composite membranes 32 are connected to the positive pole of power supply 40 through wires, and MI-anodic composite membrane 32 includes Ti—SnO.sub.2—Sb substrate electrode 321 and ceramic micro-filtration membrane 322, wherein substrate electrode 321 is placed opposite to the inner cavity of the membrane bracket, and substrate electrode 321 is coated with MI—TiO.sub.2 sol-gel coating 323, and ceramic micro-filtration membrane 322 was placed facing the water; power supply 40 is a regulated DC power supply, and the voltage range of power supply 40 is from 0.5 to 4 V; aeration system 50 includes aeration tube 51, gas flowmeter 52, and air pump 53, aeration tube 51 is located below electrochemical membrane module 30, and gas flowmeter 52 is used to regulate the flow rate of intake air; outlet pipe 60 is provided with peristaltic pump 61, pressure gauge 62 and flow meter 63.

(20) A low-concentration sewage containing 3,4-dichlorophenoxyacetic acid and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were set as: the concentrations of influent pollutants were 1 mg/L, pH=7.0, the hydraulic retention time was 4 h, and the voltage of the regulated DC power supply was 3 V. The results showed that the removal rate of the target pollutant 3,4-dichlorophenoxyacetic acid by the electrochemical membrane module C2 was 90%, and the selectivity coefficient was 4.8.

Embodiment 3

(21) An electrochemical membrane module for selectively removing pollutants includes a membrane bracket, MI-anodic composite membranes, and a titanium mesh, wherein the membrane bracket is provided with a suction port connecting with the inner cavity of the membrane bracket, the inner cavity of the membrane bracket is internally provided with the titanium mesh as a cathode, and both outer sides of the membrane bracket are provided with the MI-anodic composite membranes, the MI-anodic composite membrane includes a Ti—SnO.sub.2—Sb substrate electrode and a ceramic micro-filtration membrane, wherein the substrate electrode is placed opposite to the inner cavity of the membrane bracket, and the substrate electrode is coated with a MI—TiO.sub.2 sol-gel coating.

(22) The preparation method of the above electrochemical membrane module for selectively removing pollutants includes the steps of:

(23) (1) Preparation of Ti—SnO.sub.2—Sb substrate electrode: according to the literature [Zheng, J.; Wang, Z.; Ma, J.; Xu, S.; Wu, Z. Development of an electrochemical ceramic membrane filtration system for efficient contaminant removal from waters. Environ. Sci. Technol. 2018, 52, (7), 4117-4126.], a sol-gel with a Sn:Sb of 9:1 was prepared, which was then coated on the titanium mesh having a pore size of 100 μm, a thickness of 200 μm, and a size of 5 cm*8 cm, and, the Ti/SnO.sub.2—Sb substrate electrode was obtained after sintering the coated titanium mesh;

(24) (2) Preparation of MI—TiO.sub.2 sol-gel: titanium source (titanium isopropoxide) and template molecule (p-chlorophenol) were added into absolute ethanol and stirred to obtain the molecular imprinting precursor solution A, and then water, absolute ethanol and glacial acetic acid were mixed under stirring to obtain the reaction medium solution B, finally B was added into A dropwise under stirring to obtain the MI—TiO.sub.2 sol-gel; wherein the molar ratio of p-chlorophenol:titanium isopropoxide:absolute ethanol:glacial acetic acid:water was 0.5:1:18:2:8; the titanium mesh had a pore diameter of 100 μm and a thickness of 200 μm; the ceramic micro-filtration membrane consisted of ZrO.sub.2 and Al.sub.2O.sub.3, and the membrane pore size of the ceramic micro-filtration membrane was 0.25 μm;

(25) (3) Preparation of MI-anodic composite membrane: the Ti—SnO.sub.2—Sb substrate electrode was immersed in the MI—TiO.sub.2 sol-gel, then removed and sintered to obtain an electrode coated with the TiO.sub.2 sol-gel, and then the electrode was adhered to the surface of the ceramic micro-filtration membrane by epoxy resin, to obtain the MI-anodic composite membrane;

(26) (4) Preparation of electrochemical membrane module: the titanium mesh was vertically inserted in the membrane bracket as a cathode, and two MI-anodic composite membranes obtained in the step (3) were adhered to both outer sides of the membrane bracket directly opposite to the cathode, wherein the distance between the anode and the cathode was set at 1.0 cm, the substrate electrode was placed opposite to the inner cavity of the membrane bracket, to obtain the electrochemical membrane module for selectively removing pollutants (labeled as C3).

(27) The membrane bioreactor employing the above electrochemical membrane module includes inlet pipe 10, reactor casing 20, electrochemical membrane module 30, power supply 40, aeration system 50, and outlet pipe 60; one end of inlet pipe 10 is placed in reactor casing 20; electrochemical membrane module 30 is placed in reactor casing 20, and t electrochemical membrane module 30 includes membrane bracket 31, MI-anodic composite membranes 32, and titanium mesh 33, membrane bracket 31 is provided with a suction port connecting with the inner cavity of the membrane bracket, and the suction port is connected with outlet pipe 60, titanium mesh 33 is inserted in the inner cavity of the membrane bracket as a cathode, and titanium mesh 33 is connected to the negative pole of the power supply by a wire, both outer sides of the membrane bracket are provided with MI-anodic composite membranes 32, MI-anodic composite membranes 32 are connected to the positive pole of power supply 40 through wires, and MI-anodic composite membrane 32 includes Ti—SnO.sub.2—Sb substrate electrode 321 and ceramic micro-filtration membrane 322, wherein substrate electrode 321 is placed opposite to the inner cavity of the membrane bracket, and substrate electrode 321 is coated with MI—TiO.sub.2 sol-gel coating 323, and ceramic micro-filtration membrane 322 is placed facing the water; power supply 40 is a regulated DC power supply, and the voltage range of power supply 40 is from 0.5 to 4 V; aeration system 50 includes aeration tube 51, gas flowmeter 52, and air pump 53, aeration tube 51 is located below electrochemical membrane module 30, and gas flowmeter 52 is used to regulate the flow rate of intake air; outlet pipe 60 is provided with peristaltic pump 61, pressure gauge 62 and flow meter 63.

(28) A low-concentration sewage containing p-chlorophenol and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were set as: the concentrations of influent pollutants were 1 mg/L, pH=7.0, the hydraulic retention time was 4 h, and the voltage of the regulated DC power supply was 1 V. The results showed that the removal rate of the target pollutant p-chlorophenol by the electrochemical membrane module C3 was 87%, and the selectivity coefficient was 4.0.

Comparative Example 1

(29) An electrochemical membrane module (labeled as D) was prepared in the same manner as in Embodiment 1 except that 2,4-dichlorophenoxyacetic acid was not added in the preparation step (2) of the electrochemical membrane module.

(30) A membrane bioreactor employing the above electrochemical membrane module was also prepared, in which the only part different from membrane bioreactor of Embodiment 1 is the electrochemical membrane modules used.

(31) A low-concentration sewage containing 2,4-dichlorophenoxyacetic acid and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were the same as those in Embodiment 1. The results showed that the removal rate of the target pollutant 2,4-dichlorophenoxyacetic acid by the electrochemical membrane module D was 51%, and the selectivity coefficient was 0.9.

Comparative Example 2

(32) An electrochemical membrane module (labeled as E) was prepared in the same manner as in Embodiment 1, except that the molar ratio of 2,4-dichlorophenoxyacetic acid, tetrabutyl titanate, absolute ethanol, glacial acetic acid and water added in the electrochemical membrane module preparation step (2) was changed to 0.4:1:18:2:8.

(33) A membrane bioreactor employing the above electrochemical membrane module was also prepared, in which the only part different from membrane bioreactor of Embodiment 1 is the electrochemical membrane modules used.

(34) A low-concentration sewage containing 2,4-dichlorophenoxyacetic acid and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were the same as those in Embodiment 1. The results showed that the removal rate of the target pollutant 2,4-dichlorophenoxyacetic acid by the electrochemical membrane module E was 78%, and the selectivity coefficient was 2.94.

Comparative Example 3

(35) An electrochemical membrane module (labeled as F) was prepared in the same manner as in Embodiment 1, except that the molar ratio of 2,4-dichlorophenoxyacetic acid, tetrabutyl titanate, absolute ethanol, glacial acetic acid and water added in the electrochemical membrane module preparation step (2) was changed to 0.5:1:19:2:9.

(36) A membrane bioreactor employing the above electrochemical membrane module was also prepared, in which the only part different from membrane bioreactor of Embodiment 1 is the electrochemical membrane modules used.

(37) A low-concentration sewage containing 2,4-dichlorophenoxyacetic acid and sulfamethoxazole (interfering substance) was treated by the above membrane bioreactor, and the experimental conditions were the same as those in Embodiment 1. The results showed that the removal rate of the target pollutant 2,4-dichlorophenoxyethyl by the electrochemical membrane module F was 81.5%, and the selectivity coefficient was 3.1.

(38) It is to be understood that the foregoing detailed description of the present invention is intended to illustrate the invention rather than limit the present invention. It will be understood by those skilled in the art that the present invention may be modified or equivalently substituted to achieve the same technical effects; as long as the application requirements are met, it is also within the scope of the present invention.