CN111717966B - Sulfate reducing bacteria electro-filtration sterilization device, graphene nanofiber non-woven fabric and preparation method of graphene nanofiber non-woven fabric - Google Patents
Sulfate reducing bacteria electro-filtration sterilization device, graphene nanofiber non-woven fabric and preparation method of graphene nanofiber non-woven fabric Download PDFInfo
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- CN111717966B CN111717966B CN201910214198.6A CN201910214198A CN111717966B CN 111717966 B CN111717966 B CN 111717966B CN 201910214198 A CN201910214198 A CN 201910214198A CN 111717966 B CN111717966 B CN 111717966B
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Abstract
The invention relates to the field of environmental protection and sterilization, and discloses a sulfate reducing bacteria electric filtration sterilization device, a graphene nanofiber non-woven fabric and a preparation method thereof, wherein the electric filtration sterilization device comprises a filter layer, the filter layer sequentially comprises a cathode, an anode and a filter element from top to bottom, the filter element is the graphene nanofiber non-woven fabric, and the preparation method of the graphene nanofiber non-woven fabric comprises the following steps: 1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid; 2) under the stirring condition, blending the graphene dispersion liquid and polyvinylidene fluoride to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene; 3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric. According to the invention, the graphene nanofiber non-woven fabric is used as the filter element, so that chlorine and chlorine-containing byproducts are not generated in a water body under the action of high voltage.
Description
Technical Field
The invention relates to the technical field of environmental protection sterilization, and particularly relates to a sulfate reducing bacteria electro-filtration sterilization device and a preparation method of graphene nanofiber non-woven fabric.
Background
Microbial corrosion is a bioelectrochemical process and can seriously endanger industries such as petroleum, power generation and the like. Among them, Sulfate Reducing Bacteria (SRB) are considered to be the most important corrosive microorganisms, and widely exist in electric field circulating cooling water and oil field reinjection water, causing extensive corrosion to pipelines, well drilling, pumping machinery, storage tanks, and the like. Corrosion products of SRB can also cause plugging of the formation, resulting in reduced crude oil production. Therefore, in order to enable the water quality control index to meet the requirement, the effective killing of the SRB has important significance on the treatment and the reinjection long-term operation of a circulating cooling water system and oil extraction wastewater.
At present, the most widely used method for killing SRB bacteria is to add bactericide, but the adding of the bactericide has the following problems: firstly, the price is high, and the unit price of a plurality of bactericides is more than ten thousand yuan/ton; secondly, the sterilization effect is unstable, the water quality of the oil field is complex, a certain neutralization effect is realized on effective radicals on the bactericide, and the bacteria have high variation speed and easily generate drug resistance; finally, the use of bactericides is liable to cause harm to the environment. Therefore, more and more research is being directed towards physicochemical sterilization.
For example, CN102372386A discloses a method for sterilizing oil field sewage by combining electrochemical oxidation with ultraviolet and ultrasonic techniques, which utilizes an electrochemical method to generate effective chlorine for sterilization, and simultaneously uses residual chlorine for further sterilization in combination with ultrasonic cavitation and ultraviolet irradiation. However, in the petrochemical industry, metal pipelines are more, and chlorine can cause serious corrosion to production equipment and harm to human health; and the method has longer process flow and larger equipment volume.
Chinese patent CN205953734U discloses a treatment device for ultraviolet composite sterilization of oilfield injection water, which consists of an ozone sterilization component and an ultrasonic-ultraviolet sterilization component, wherein the treatment device effectively avoids the harm of chlorine gas to production, but adds equipment such as an ozone generator and the like, the whole process is still longer, and the operation cost is higher; meanwhile, the ozone smell threshold value is low, so that discomfort of operators is easily caused.
Disclosure of Invention
The invention aims to solve the problems of long process flow, high operation cost, no harm to human health and the like in the prior art, provides a sulfate reducing bacteria electric filtration sterilization device, and provides a preparation method of graphene nanofiber non-woven fabric on the basis.
In order to achieve the above object, a first aspect of the present invention provides a sulfate reducing bacteria electric filtration sterilization apparatus, which includes a filter layer, the filter layer sequentially includes a cathode, an anode and a filter element from top to bottom, the filter element is a graphene nanofiber non-woven fabric;
the preparation method of the graphene nanofiber non-woven fabric comprises the following steps:
1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid;
2) under the stirring condition, blending the graphene dispersion liquid with polyvinylidene fluoride with the number average molecular weight of 80000-120000 to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene;
3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric.
The second aspect of the invention provides a preparation method of a graphene nanofiber non-woven fabric, which comprises the following steps:
1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid;
2) under the stirring condition, blending the graphene dispersion liquid with the polyvinylidene fluoride with the number average molecular weight of 80000-120000 to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene;
3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric.
The third aspect of the present invention provides a graphene nanofiber nonwoven fabric in the above sulfate-reducing bacteria electro-filtration sterilization apparatus or a graphene nanofiber nonwoven fabric obtained by the above preparation method.
According to the technical scheme, the graphene nanofiber non-woven fabric is used as the filter element, so that chlorine and chlorine-containing byproducts can not be generated under the action of voltage, and the filter element is used as an anode material, so that harm to the bodies of operators can be avoided. Meanwhile, the sterilization method disclosed by the invention has the advantages of high sterilization efficiency, simple process, low operation cost, no harm to human health and environmental friendliness.
Drawings
FIG. 1 is a sectional view (a) and a sectional view (b) of 1-1 of an electric sterilizing apparatus for sulfate-reducing bacteria according to the present invention.
Description of the reference numerals
1 filtering the shell; 2, a water inlet pipe; 3, discharging a water pipe; 4, a filter layer; 5 a cathode; 6 insulating water distribution plate; 7 an anode; 8, a filter element; 9 a bearing layer; 10, supporting frames; 11 a direct current stabilized power supply; 12 water distribution tank.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a sulfate reducing bacteria electric filtration sterilization device, as shown in fig. 1, the electric filtration sterilization device comprises a filter layer 4, the filter layer 4 comprises a cathode 5, an optional insulating water distribution plate 6, an anode 7, a filter element 8 and an optional supporting layer 9 from top to bottom in sequence, and the filter element 8 is the graphene nanofiber non-woven fabric;
the preparation method of the graphene nanofiber non-woven fabric comprises the following steps:
1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid;
2) under the stirring condition, blending the graphene dispersion liquid with polyvinylidene fluoride with the number average molecular weight of 80000-120000 to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene;
3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric.
The sterilization device disclosed by the invention is based on the principle of electric filtration, when in use, the cathode and the anode are electrically connected with the direct-current power supply, the direct-current power supply can conveniently and flexibly adjust the voltage between the cathode and the filter element, can change from 1V to 4V, and the filter element can enable free radicals generated by water (such as oilfield reinjection water) containing sulfate reducing bacteria to be mainly hydroxyl free radicals, superoxide free radicals and sulfate free radicals in a working range from 1V to 4V through dye dyeing and fluorescence migration, so that the sterilization device is green, healthy and environment-friendly, and the whole sterilization device is simple, compact and efficient.
In the invention, the sulfate reducing bacteria are widely existed in anoxic environments such as soil, seawater, river water, underground pipelines, oil-gas wells and the like. In the present invention, the water containing sulfate-reducing bacteria may be various common water bodies (e.g., oilfield reinjection water) containing sulfate-reducing bacteria. The sulfate-reducing bacteria may be selected from microorganisms such as those in the genera Desulfurvibrio, Desulfuromonas, Desulfurophytum, Desulfobacter, Desulfurococcus and Desulfornia.
In the invention, the insulating water distribution plate 6 which is selectively arranged can be further provided with a water distribution groove 12 with the upper surface and the lower surface communicated with each other. The cathode 5 is connected to the inside of the water distribution tank 12. The anode 7 is attached to the upper surface of the filter element 8. The selectively arranged supporting layer 9 is used for supporting the cathode 5, the insulating water distribution plate 6, the anode 7 and the filter element 8. The insulating water-distributing plate 6 and the anode 7 are in contact with the edge of the filter element 8, so that a hollow space is formed between the cathode 5 and the filter element 8.
As mentioned above, the filter layer 4 may further include an insulating water-distribution plate 6 and a support layer 9. In a preferred embodiment of the present invention, as shown in fig. 1, the filter layer 4 comprises, from top to bottom, a cathode 5, an insulating water-distributing plate 6, an anode 7, a filter element 8 and a support layer 9; the water distribution tank 12 with the upper surface and the lower surface communicated with each other is arranged on the insulating water distribution plate 6, the cathode 5 is connected to the inner side of the water distribution tank 12, the anode 7 is attached to the upper surface of the filter element 8, and a hollow space is formed between the cathode 5 and the filter element 8.
In the present invention, the material of the cathode may be various conventional cathode materials in the art. For example, the cathode 5 may be a stainless steel sheet or a copper sheet, preferably a round stainless steel sheet.
In the present invention, the insulating water distribution plate 6 mainly serves to guide water containing sulfate-reducing bacteria to a narrow space formed by the cathode and the filter element. For example, the insulating water distribution plate 6 may be a tetrafluoroethylene insulating water distribution plate, preferably an annular tetrafluoroethylene insulating water distribution plate.
In the present invention, the shape of the water distribution groove 12 may be various conventional shapes in the art. For example, the water distribution grooves 12 may be arc-shaped, and the number of the grooves is 2 to 6, which is beneficial to increasing the water passing amount.
In the present invention, the material of the anode 7 may be various anode materials conventional in the art. For example, the anode 7 may be a ceramic anode or a graphite anode, preferably an annular graphite anode, which facilitates the formation of a narrow hollow space between the cathode and the filter element.
In the present invention, the support layer 9 not only can support but also needs a large amount of water, thereby facilitating the filtration of a large amount of water containing sulfate-reducing bacteria (for example, oilfield reinjection water, etc.). For example, the supporting layer 9 is a porous quartz supporting layer, preferably a circular porous quartz supporting layer.
In the invention, the height-diameter ratio of the hollow space is 1:10-12, so that the sterilization of water containing sulfate reducing bacteria can be effectively ensured.
In a preferred embodiment of the present invention, as shown in fig. 1, the present invention further includes a filtering housing 1, the filtering housing 1 includes a water inlet pipe 2, a water outlet pipe 3 and a support frame 10, the top of the filtering housing 1 is open, the water inlet pipe 2 and the water outlet pipe 3 are respectively disposed at the upper portion and the lower portion of the outer side of the filtering housing 1, the support frame 10 is disposed at the middle portion of the inner side of the filtering housing 1, and the filtering layer 4 is disposed on the support frame 10.
In the invention, the connection modes of the water inlet pipe 2, the water outlet pipe 3 and the support frame 10 with the filtering shell 1 are respectively heat setting welding or one-time hot press molding.
In the invention, the cathode 5 and the insulating water distribution plate 6 are connected by a nut.
In the present invention, the filter housing may be made of various conventional materials in the art. For example, the material of the filter housing 1 may be engineering plastic or insulating and corrosion resistant material.
Preferably, the main body of the filter housing 1 is cylindrical.
In a preferred embodiment of the present invention, the electric filter sterilization device further comprises a centrifugal pump arranged in front of the outside of the filter housing 1, which not only can provide the power for filtration, but also can use a pressure gauge to monitor the filtration resistance during the filtration process, and if necessary, clean the filter layer.
The second aspect of the invention provides a preparation method of a graphene nanofiber non-woven fabric, which comprises the following steps:
1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid;
2) under the stirring condition, blending the graphene dispersion liquid with the polyvinylidene fluoride with the number average molecular weight of 80000-120000 to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene;
3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric.
The graphene nanofiber non-woven fabric prepared by the invention can generate hydroxyl free radicals, superoxide free radicals and sulfate free radicals in a water body containing sulfate reducing bacteria under the action of voltage, and does not generate chlorine-related free radicals, so that chlorine and chlorine-containing byproducts are not generated, and the harm to the bodies of operators can be avoided by using the filter element as an anode material.
The inventors of the present invention also found that N, N-dimethylformamide and dimethylsulfoxide solvent in the nonwoven fabric are chemically bonded to graphene and polyvinylidene fluoride, and thus remain in the nonwoven fabric even during subsequent use.
In the present invention, graphene can be prepared by the following steps: (1) firstly, preparing a graphene oxide primary product by adopting a traditional Hummers method, cleaning, adding deionized water for ultrasonic treatment, and then freeze-drying to prepare graphene oxide, so that the performance of the graphene oxide is enhanced; (2) and preparing the prepared graphene oxide into graphene by adopting a low-temperature thermal reduction method.
In the invention, the proper amount of polyvinylidene fluoride is selected, so that the graphene dispersion liquid and the polyvinylidene fluoride have good interfacial compatibility, the spatial distribution condition of the graphene dispersion liquid in a polyvinylidene fluoride matrix is effectively regulated and controlled, the graphene dispersion liquid forms a good conductive network, the percolation threshold of the composite material is effectively improved, and the water containing sulfate reducing bacteria can be prevented from generating chlorine radicals. For example, the polyvinylidene fluoride may be used in an amount of 0.2g, 0.3g, 0.4g, 0.5g, or any two of these values, relative to 1g of graphene.
In step 1) of the present invention, the amount of N, N-dimethylformamide and dimethylsulfoxide is 2 to 5g, relative to 1g of graphene; not only can better dispersion of graphene in the subsequent electrospinning process be realized, but also the combination of the N, N-dimethylformamide and the dimethyl sulfoxide can prevent the water containing sulfate reducing bacteria from generating chlorine free radicals.
Preferably, the mass ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 2.0-2.5: 1. For example, it may be 2.0: 1,2.1: 1,2.2: 1,2.3: 1,2.4: 1,2.5: 1 and any two of these point values.
In the present invention, the stirring conditions may be designed in accordance with various conventional conditions in the art. For example, in the step 2), the stirring conditions include a stirring temperature of 40-60 ℃ and a stirring time of 5-8 h.
In the present invention, the process parameters for electrospinning may be of various designs conventional in the art. For example, in the step 3), the parameter control of the electrospinning comprises electrostatic voltage of 15-30kV, receiving distance of 10-30cm and injection rate of 2-5 mL/h.
The third aspect of the invention provides a graphene nanofiber non-woven fabric prepared by the method. Preferably, the thickness of the prepared graphene nanofiber non-woven fabric is 150 μm, the fiber diameter is 150nm and the pore diameter is 0.2-0.35 μm, so that the thorough electro-filtration sterilization and permeation quantity of the water body containing the sulfate reducing bacteria can be fully ensured.
In the invention, the thickness, the fiber diameter and the pore average diameter of the graphene nanofiber non-woven fabric are measured after being calculated by an image shot by an SEM (scanning electron microscope).
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the sulfate reducing bacteria are measured by a method determined by SY/T0532-2012 Absolute dilution method for bacteria analysis method of oil field injection water.
Polyvinylidene fluoride is a commercially available product having a sigma-aldrich trade designation 427144.
The water containing sulfate reducing bacteria is oilfield reinjection water, water samples are taken from three different sewage combined treatment stations of the Shengli oilfield, namely oilfield reinjection water No. 1, oilfield reinjection water No. 2 and oilfield reinjection water No. 3,
wherein, the number of SRB of the oilfield reinjection water No. 1 is 47000/mL, the total mineral content is 65231mg/L, and the pH value is 6.0;
the number of SRB of the oilfield reinjection water No. 2 is 15000/mL, the total mineral content is 36172mg/L, and the pH value is 5.5;
the number of SRB of oilfield reinjection water No. 3 is 4000/mL, the total mineral content is 44854mg/L, and the pH value is 5.7.
Other raw materials were commercially available products unless otherwise specified.
In the present invention, room temperature means 25. + -. 5 ℃.
Example 1
The preparation of the graphene comprises the following steps:
(1) weighing 5g of 300-mesh crystalline flake graphite and 2g of NaNO3Mixing, 120mL of concentrated H was added2SO4Stirring in ice bath, and adding 20g KMnO after 30min4After reacting for 60min, moving the mixture into a warm water bath at 40 ℃ for further reaction for 30min, then slowly adding 230mL of deionized water, keeping the reaction temperature at 98 ℃, stirring for 5min, and then adding a proper amount of H2O2Filtering when bubbles are not generated, washing the solution for many times by using deionized water and 5% hydrochloric acid until the solution is neutral, adding the deionized water, carrying out ultrasonic treatment for 1 hour at the ultrasonic frequency of 25kHz, and then freeze-drying the solution at the temperature of-30 ℃ to obtain graphene oxide;
(2) ultrasonically dispersing the prepared graphene oxide in dimethylacetamide (DMAc) to prepare 0.2mg/L graphene oxide solution, reacting for 15min at 165 ℃, filtering by using a tetrafluoroethylene filter membrane after the reaction is finished and the temperature of the solution is reduced to room temperature, and drying at 60 ℃ to obtain the graphene.
Example 2
The preparation method of the graphene nanofiber non-woven fabric comprises the following steps:
1) ultrasonically dispersing 5g of the prepared graphene into a mixed solution of 8g of N, N-Dimethylformamide (DMF) and 4g of dimethyl sulfoxide (DMSO) under the ultrasonic frequency of 25kHz to obtain a graphene dispersion liquid;
2) blending the obtained graphene dispersion with 1.5g of polyvinylidene fluoride (PVDF, number average molecular weight of 107000) under stirring to obtain a blend; wherein the stirring conditions comprise that the stirring temperature is 50 ℃ and the stirring time is 6 hours;
3) carrying out electrospinning on the obtained blend to obtain graphene nanofiber non-woven fabric; wherein the parameter control of the electrospinning comprises electrostatic voltage of 20kV, receiving distance of 20cm, injection rate of 3mL/h, thickness of the prepared graphene nanofiber non-woven fabric of 128 μm, fiber diameter of 140nm and pore diameter of 0.28 μm.
Example 3
A graphene nanofiber nonwoven fabric was prepared as in example 2, except that 1.7g of polyvinylidene fluoride (number average molecular weight 107000) was used, and the graphene nanofiber nonwoven fabric was prepared to have a thickness of 137 μm, a fiber diameter of 138nm and a pore diameter of 0.29. mu.m.
Example 4
The graphene nanofiber nonwoven fabric was prepared according to the method of example 2, except that the parameter control of electrospinning included an electrostatic voltage of 15kV, a receiving distance of 10cm, and an injection rate of 5mL/h, and the prepared graphene nanofiber nonwoven fabric had a thickness of 143 μm, a fiber diameter of 132nm, and a pore diameter of 0.32 μm.
Comparative example 1
Graphene nanofiber nonwoven fabrics were prepared according to the method of example 2, except that the solvent was 12g of N, N-Dimethylformamide (DMF), and the prepared graphene nanofiber nonwoven fabrics had a thickness of 165 μm, a fiber diameter of 155nm, and a pore diameter of 0.28 μm.
Comparative example 2
Graphene nanofiber nonwoven fabrics were prepared according to the method of example 2, except that the mass of polyvinylidene fluoride added was 5g, and the prepared graphene nanofiber nonwoven fabrics had a thickness of 188 μm, a fiber diameter of 172nm and a pore diameter of 0.37 μm.
Example 5
The sulfate reducing bacteria electric filtering sterilization device comprises a filtering shell 1, a filtering layer 4 and a direct current power supply 11, wherein the filtering shell 1 comprises a water inlet pipe 2, a water outlet pipe 3 and a support frame 10, the top of the filtering shell 1 is provided with an opening, the water inlet pipe 2 and the water outlet pipe 3 are respectively arranged at the upper part and the lower part of the outer side of the filtering shell 1, the support frame 10 is arranged at the middle part of the inner side of the filtering shell 1, and the filtering layer 4 sequentially comprises a cathode 5, an insulating water distribution plate 6, an anode 7, a filter element 8 and a support layer 9 from top to bottom; the filter element 8 is the graphene nanofiber non-woven fabric prepared in embodiment 2, the insulating water distribution plate 6 is provided with a water distribution groove 12 with the upper surface and the lower surface communicated with each other, the cathode 5 is connected to the inner side of the water distribution groove 12, the anode 7 is attached to the upper surface of the filter element 8, the edge of the anode 7 is attached to the filter shell 1, a hollow space is formed between the cathode 5 and the filter element 8, the height of the space is 1.2cm, and the bearing layer 9 is arranged on the support frame 10; the cathode 5 and the graphite anode 7 are connected with a direct current stabilized voltage power supply 11 through leads.
Wherein, the connection modes of the water inlet pipe 2, the water outlet pipe 3 and the support frame 10 with the filtering shell 1 are respectively one-time hot press molding.
Wherein, the filtering shell 1 is made of engineering plastics, and the main body is cylindrical.
The cathode 5 is connected with the insulating water distribution plate 6 through a nut, the cathode 5 is a round stainless steel sheet, and the insulating water distribution plate 6 is an annular tetrafluoroethylene insulating water distribution plate.
As shown in FIG. 1 (b), the water distribution grooves 12 are arc-shaped, the number of the water distribution grooves is 4, and water enters the reaction zone from the four grooves and stays in the reaction zone for 0.5 to 1 s.
Wherein the anode 7 is an annular graphite anode.
Wherein, the supporting layer 9 is a circular porous quartz supporting layer.
Example 6
The sulfate reducing bacteria electric filtration sterilization device is different from that in the embodiment 5, the filter element 8 is the graphene nano fiber non-woven fabric prepared in the embodiment 3.
Example 7
The sulfate reducing bacteria electric filtration sterilization device is different from that in the embodiment 5, the filter element 8 is the graphene nano fiber non-woven fabric prepared in the embodiment 4.
Comparative example 3
The sulfate reducing bacteria electric filtration sterilization device is different from that in the embodiment 5, the filter element 8 is the graphene nano fiber non-woven fabric prepared in the comparative example 1.
Comparative example 4
The sulfate reducing bacteria electric filtration sterilization device is different from that in the embodiment 5, the filter element 8 is the graphene nano fiber non-woven fabric prepared in the comparative example 2.
Test example 1
The oil field reinjection water 1#, 2# and 3# was sterilized at different operating voltages (1V, 2V and 3V) using the sulfate-reducing bacteria electro-filtration sterilization apparatuses of examples 5 to 7, comparative example 3 and comparative example 4, respectively, and the residence time of water in the hollow space, the operating voltage and the sterilization effect evaluation are shown in table 1. Meanwhile, the effluent of the 1#, 2# and 3# reinjection water under the 3V operating voltage is detected by using dye dyeing and fluorescence shift reaction, and no chlorine free radical is found, so that the device does not generate chlorine gas and chlorine-containing products under the actual operating condition, and is beneficial to the health of operators.
TABLE 1
From the results in table 1, it can be seen that, for oilfield reinjection water with different water quality, according to the preferred embodiments of the present invention (examples 5-7), the apparatus of the present invention can effectively remove SRB with a removal rate as high as 99.5% or more, and meets the technical requirements of oilfield reuse of bactericide. At present, the absolute standard of most oil fields executed in the actual production process is that the SRB does not exceed 100/mL, except that the 1# oil field reinjection water with poor water quality is under the condition of lower voltage (1V), the effluent SRB is higher, and the other operation conditions can meet the requirement; and when the voltage is more than or equal to 2V, the sterilization rate of all oilfield reinjection water treated by the device reaches 100 percent. Therefore, the voltage can be controlled to be about 2V by an operator, the voltage is operated according to the practical reasonable condition of the quality of the reinjection water, and the energy consumption is reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (22)
1. The electric filtration sterilization device for the sulfate reducing bacteria is characterized by comprising a filter layer (4), wherein the filter layer (4) sequentially comprises a cathode (5), an anode (7) and a filter element (8) from top to bottom, the anode (7) electrically connected under the condition that a direct-current power supply is 1V-4V is attached to the upper surface of the filter element (8), a hollow space is formed between the cathode (5) and the filter element (8), and the filter element (8) is graphene nanofiber non-woven fabric;
the preparation method of the graphene nanofiber non-woven fabric comprises the following steps:
1) ultrasonically dispersing graphene into N, N-dimethylformamide and dimethyl sulfoxide to obtain a graphene dispersion liquid;
2) under the stirring condition, blending the graphene dispersion liquid with polyvinylidene fluoride with the number average molecular weight of 80000-120000 to obtain a blend; wherein the dosage of the polyvinylidene fluoride is 0.2-0.5g relative to 1g of graphene;
3) and (3) carrying out electrospinning on the blend to obtain the graphene nanofiber non-woven fabric.
2. The sulfate reducing bacteria electric filtration sterilization device according to claim 1, wherein the filter layer (4) further comprises an insulating water distribution plate (6) and a supporting layer (9); and the insulating water distribution plate (6) is provided with a water distribution tank (12) with the upper surface and the lower surface communicated with each other, and the cathode (5) is connected to the inner side of the water distribution tank (12).
3. The sulfate reducing bacteria electro-filtration sterilization apparatus according to claim 1 or 2, wherein the cathode (5) is a stainless steel sheet or a copper sheet.
4. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 3, wherein the cathode (5) is a circular stainless steel sheet.
5. The sulfate reducing bacteria electric filtration sterilization device according to claim 2, wherein the insulating water distribution plate (6) is a tetrafluoroethylene insulating water distribution plate.
6. The sulfate reducing bacteria electric filtration sterilization device according to claim 5, wherein the insulating water distribution plate (6) is an annular tetrafluoroethylene insulating water distribution plate.
7. The sulfate-reducing bacteria electro-filtration sterilization device of claim 1 or 2, wherein the anode (7) is a graphite anode or a ceramic anode.
8. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 7, wherein the anode (7) is a ring-shaped graphite anode.
9. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 2, wherein the support layer (9) is a porous quartz support layer.
10. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 9, wherein the support layer (9) is a circular porous quartz support layer.
11. The sulfate reducing bacteria electro-filtration sterilization apparatus according to claim 2, wherein the water distribution tank (12) is arc-shaped, and the number of the water distribution tanks is 2-6.
12. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 2, wherein the height-to-diameter ratio of the hollow space is 1: 10-12.
13. The sulfate reducing bacteria electric filtration sterilization device according to claim 1 or 2, wherein the sulfate reducing bacteria electric filtration sterilization device further comprises a filtration shell (1), the filtration shell (1) comprises a water inlet pipe (2), a water outlet pipe (3) and a support frame (10), the top of the filtration shell (1) is open, the water inlet pipe (2) and the water outlet pipe (3) are respectively arranged at the upper part and the lower part of the outer side of the filtration shell (1), the support frame (10) is arranged at the middle part of the inner side of the filtration shell (1), and the filtration layer (4) is arranged on the support frame (10).
14. The sulfate reducing bacteria electric filtration sterilization device according to claim 13, wherein the connection modes of the water inlet pipe (2), the water outlet pipe (3) and the support frame (10) and the filtration shell (1) are respectively heat setting welding or one-time hot press molding.
15. The sulfate reducing bacteria electric filtration sterilization apparatus according to claim 13, wherein the material of the filtration housing (1) is engineering plastic or an insulating corrosion resistant material.
16. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 15, wherein the main body of the filter housing (1) is cylindrical.
17. The sulfate reducing bacteria electro-filtration sterilization apparatus according to claim 13, wherein the apparatus further comprises a centrifugal pump disposed in front of the outside of the filtration housing (1).
18. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 1 or 2, wherein in the step 1), the amount of the N, N-dimethylformamide and the dimethyl sulfoxide is 2 to 5g relative to 1g of graphene.
19. The sulfate-reducing bacteria electro-filtration sterilization apparatus according to claim 18, wherein the mass ratio of the N, N-dimethylformamide to the dimethyl sulfoxide is 2.0-2.5: 1.
20. the sulfate reducing bacteria electric filtration sterilization apparatus according to claim 1 or 2, wherein in the step 2), the stirring conditions include a stirring temperature of 40-60 ℃ and a stirring time of 5-8 h.
21. The sulfate reducing bacteria electric filtration sterilization apparatus according to claim 1 or 2, wherein in the step 3), the parameter control of the electrospinning comprises an electrostatic voltage of 15-30kV, a receiving distance of 10-30cm, and an injection rate of 2-5 mL/h.
22. The sulfate reducing bacteria electric filtration sterilization device according to claim 1 or 2, wherein the graphene nanofiber non-woven fabric has a thickness of 120-150 μm, a fiber diameter of 100-150nm and a pore size of 0.2-0.35 μm.
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