CN111762926A - Method for treating industrial wastewater by electrocatalysis-low-pressure reverse osmosis - Google Patents
Method for treating industrial wastewater by electrocatalysis-low-pressure reverse osmosis Download PDFInfo
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- CN111762926A CN111762926A CN202010517849.1A CN202010517849A CN111762926A CN 111762926 A CN111762926 A CN 111762926A CN 202010517849 A CN202010517849 A CN 202010517849A CN 111762926 A CN111762926 A CN 111762926A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention relates to a method for treating industrial wastewater by electrocatalysis-low-pressure reverse osmosis, which comprises the following steps: s1, placing the industrial wastewater to be treated in a reactor with an electrocatalysis system; s2, applying current between the cathode and the anode of the electro-catalysis system, and continuously stirring the industrial wastewater in the reactor; s3, standing and precipitating the industrial wastewater treated by the electro-catalysis system, and then performing sand filtration to obtain electro-catalysis wastewater; s4, carrying out low-pressure reverse osmosis membrane filtration on the electrocatalysis wastewater to obtain a recovered solution. According to the industrial wastewater treatment method, the electro-catalysis system is combined with the low-pressure reverse osmosis method, so that the removal rate of TOC can be effectively improved; the electro-catalysis system is used as pretreatment, so that the occurrence of membrane pollution can be effectively reduced, and the membrane flux is improved.
Description
Technical Field
The invention relates to a wastewater treatment method, in particular to a method for treating regenerated papermaking wastewater by adopting an electrocatalysis and low-pressure reverse osmosis system.
Background
Industrial waste water often contains toxic organic pollutants, and the toxic chemical pollutants have the properties of bioaccumulation, difficult biological decomposition and carcinogenicity, can also destroy the internal circulation system of organisms, and have serious harm to the environment and human bodies. In the face of the existing treatment technology which can not effectively remove pollutants and the requirement of enterprises on wastewater reuse, the advanced treatment technology of wastewater is urgently needed to be developed. From the current literature, no research on the removal of organic matters and the removal of papermaking pollutants by the low-pressure reverse osmosis process is reported.
Disclosure of Invention
The invention aims to solve the technical problems that the existing industrial wastewater treatment method can not effectively remove pollutants and is difficult to recycle.
The technical scheme for solving the technical problems is as follows: a method for treating industrial wastewater by electrocatalysis-low pressure reverse osmosis comprises the following steps:
s1, placing the industrial wastewater to be treated in a reactor with an electrocatalysis system;
s2, applying current between the cathode and the anode of the electro-catalysis system, and continuously stirring the industrial wastewater in the reactor;
s3, standing and precipitating the industrial wastewater treated by the electro-catalysis system, and then performing sand filtration to obtain electro-catalysis wastewater;
s4, carrying out low-pressure reverse osmosis membrane filtration on the electrocatalysis wastewater to obtain a recovered solution.
The invention has the beneficial effects that: the electro-catalysis is an efficient advanced wastewater treatment technology, and has the advantages of easy process control, high treatment efficiency, environmental friendliness and the like. The electrocatalytic reaction mechanism is specifically as follows: electric energy is applied to the soluble metal electrode plate through the outside to generate an electric field effect, finally the metal anode plate generates a large amount of metal cations, and a series of polynuclear hydroxyl complexes and hydroxides are generated through reactions such as hydrolysis, polymerization and the like, so that pollutants in water are adsorbed and flocculated, and are removed. The electrocatalysis can effectively remove organic pollutants, inorganic pollutants and heavy metals in the wastewater, is an ideal wastewater deep treatment means, and can also be coupled with a tail-end membrane process to carry out deep purification on the wastewater. The low pressure reverse osmosis has excellent performance in wastewater treatment with low energy consumption, low running cost, high pollutant removal rate and pollution resistance. The low pressure reverse osmosis membrane has tough and durable properties for effective filtration and separation of brackish, surface water and other waste waters.
According to the industrial wastewater treatment method, the electro-catalysis system is combined with the low-pressure reverse osmosis method, so that the removal rate of TOC can be effectively improved; the electro-catalysis system is used as pretreatment, so that the occurrence of membrane pollution can be effectively reduced, and the membrane flux is improved.
On the basis of the technical scheme, the invention can be further improved as follows.
Furthermore, the anode of the electro-catalytic system is an electrode of rare earth doped titanium-based ruthenium iridium.
Further, the electrode material of the rare earth doped titanium-based ruthenium-iridium is cerium, lanthanum or neodymium doped titanium-based ruthenium-iridium, and the anode of the electrocatalysis system is in a plate, net or cylinder shape.
Further, the cathode of the electro-catalytic system is a stainless steel metal electrode.
Further, the cathode material of the electrocatalysis system is stainless steel, a graphite plate, a graphite felt and a carbon felt; the cathode of the electro-catalysis system is in a plate shape, a net shape or a cylinder shape.
Further, in S2, the current density applied between the cathode and the anode of the electrocatalytic system is 10-40mA/cm2The stirring speed is 80-200 rpm.
Further, in S2, the reaction time of the electrocatalytic system is 3-60 min.
Further, in S3, the pore size specification of the sand filtration is 2 to 5 μm.
Further, in S4, the operating pressure of the low-pressure reverse osmosis is 0.3-0.6 Mpa; the molecular weight cut-off of the low-pressure reverse osmosis is 70-120Da, and the pure water flux of the low-pressure reverse osmosis is 25-30L m-2h-1。
Further, obtaining the wastewater quality suitable for the reuse standard
Drawings
FIG. 1 is a chart of the effect of electrocatalysis on TOC removal by a low pressure reverse osmosis membrane of the present invention;
FIG. 1 shows that the wastewater is subjected to an electrocatalysis experiment, then the low-pressure reverse osmosis membrane is filtered on the basis, 96% of total organic carbon can be removed by the low-pressure reverse osmosis membrane when the wastewater is subjected to the electrocatalysis pretreatment, organic pollutants are gradually removed along with the increase of the electrocatalysis pretreatment time, and 24.6%, 38.2%, 44.1%, 51.2% and 62.4% of the organic pollutants can be removed by the electrocoagulation at 3 min, 5 min, 10 min, 20min and 30 min. Therefore, the electro-catalysis effectively reduces the content of pollutants before entering the membrane and provides conditions for slowing down the membrane pollution. The experimental conditions were chosen to be the most preferred conditions described in the invention (example 1).
FIG. 2 is a graph of the effect of electrocatalysis on the flux of low pressure reverse osmosis membrane of the present invention.
FIG. 2 is a graph showing the effect of electrocatalysis on the flux of low pressure reverse osmosis membrane effluent, which was 25%, 42%, 50%, 65% and 80% higher than the flux of the membrane produced without electrocatalysis pretreatment, when the electrocatalysis pretreatment time was 3, 5, 10, 20 and 30 min. The experimental conditions were chosen to be the most preferred conditions described in the invention (example 1).
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The invention provides an electrocatalysis-low pressure reverse osmosis wastewater treatment method, which comprises the following steps:
s1, placing the industrial wastewater to be treated in a reactor with an electrocatalysis system;
s2, applying current between the cathode and the anode of the electro-catalysis system, and continuously stirring the industrial wastewater in the reactor;
s3, standing and precipitating the industrial wastewater treated by the electro-catalysis system, and then performing sand filtration to obtain electro-catalysis wastewater;
s4, carrying out low-pressure reverse osmosis membrane filtration on the electrocatalysis wastewater to obtain a recovered solution.
The source of the industrial wastewater to be treated is not particularly limited, the method provided by the invention is suitable for all wastewater containing organic matters, preferably refractory industrial wastewater containing organic matters, and the wastewater is not subjected to acidity and alkalinity adjustment.
In the invention, the wastewater to be treated further comprises, before treatment: the wastewater is filtered. In the present invention, the filtration preferably removes suspended matter having a particle size of 1mm or more. The operation of the filtration is not particularly limited in the present invention, and a technical scheme of wastewater filtration known to those skilled in the art can be adopted. In the present invention, the filtration is preferably a grid filtration. The specification of the grating is not specially limited, and suspended matters within the particle size range can be filtered.
After the filtration is finished, the invention preferably adjusts the water quality and the water quantity of the filtered product. The operation of regulating the water quality and the water quantity is not particularly limited, and the technical scheme of regulating the water quality and the water quantity of the wastewater, which is well known by the technical personnel in the field, can be adopted. In the present invention, the water quality and water amount are preferably adjusted in an adjusting tank.
The obtained filtered wastewater is the industrial wastewater subjected to electrocatalysis-low pressure reverse osmosis treatment. In the invention, the treatment process comprises the following steps: and (3) taking the rare earth doped titanium-based ruthenium iridium electrode as an anode and an inert electrode as a cathode, and electrifying direct current to the industrial wastewater to carry out electrocatalytic reaction for removal. In the invention, the treatment time of the industrial wastewater is 3-60min (the influence of different electrocatalysis times on the effluent flux of the low-pressure reverse osmosis membrane is shown in figure 2), more preferably 5-40 min, and most preferably 10-30 min. In the invention, the current density in the wastewater is preferably 10-40mA/cm2More preferably 15 to 35mA/cm2Most preferably 20 to 30mA/cm2。
In the embodiment of the invention, the electrocatalytic reaction tank is provided with a stirring system. The present invention is not particularly limited in terms of the structure and type of the stirring system, and a stirring system known to those skilled in the art may be used. The stirring speed in the wastewater is preferably 80-200 rpm, more preferably 100-180 rpm, and most preferably 120-150 rpm.
The material and the shape of the rare earth doped titanium-based ruthenium iridium electrode and the inert electrode are not particularly limited, and the electrode for the electro-catalysis method, which is well known to those skilled in the art, can be adopted. In the invention, the material of the rare earth doped titanium-based ruthenium iridium electrode is preferably cerium doped titanium-based ruthenium iridium; the shape of the electrode is preferably plate-like, mesh-like or cylindrical. In the embodiment of the invention, the rare earth doped titanium-based ruthenium iridium electrode is specifically plate-shaped. In the invention, the inert electrode is preferably made of stainless steel, graphite or activated carbon; the inert electrode is preferably in the shape of a plate, a mesh, or a cylinder. In an embodiment of the present invention, the inert electrode is specifically a stainless steel plate.
In the present invention, one or more sets of electrodes are preferably disposed within the electrocatalytic reactor. In the invention, the distance between each group of electrodes is preferably 3-15 mm, and more preferably 5-10 mm. In the embodiment of the invention, a slag scraping system is arranged on the electrocatalytic reaction tank. The structure and the type of the slag scraping system are not particularly limited by the invention, and the slag scraping system known by the person skilled in the art can be adopted. In the present invention, scum generated during the wastewater pollutant removal treatment process is scraped by a scum system.
After the electrocatalytic wastewater is obtained, the invention carries out flocculation precipitation treatment on the electrocatalytic wastewater. In the invention, the time of the flocculation precipitation treatment is preferably 30-120 min, and more preferably 45-90 min. The device for flocculation precipitation treatment in the present invention is not particularly limited, and may be any device known to those skilled in the art. In the present invention, the flocculation precipitation treatment is preferably performed in a sedimentation tank.
In the present invention, it is preferable that the precipitation treatment further comprises: and (3) performing sand filtration on the supernatant after precipitation, wherein the size of the pore diameter of the sand filtration is 2-5 μm, preferably 2.5-4.5 μm, and more preferably 3-4 μm. The sand filtration and separation apparatus of the present invention is not particularly limited, and may be any apparatus known to those skilled in the art. It will be appreciated that in the present invention, the precipitation treatment preferably also includes: and sequentially concentrating and dehydrating the sludge obtained by the electrocatalysis precipitation treatment.
In the invention, the electro-catalysis wastewater after sand filtration is subjected to low-pressure reverse osmosis membrane filtration, wherein the operating pressure of the low-pressure reverse osmosis membrane is 0.3-0.6MPa, more preferably 0.35-0.55 MPa, and most preferably 0.4-0.5 MPa. In the embodiment of the present invention, the low pressure reverse osmosis filtration is provided with a waste pressurizing system, and the structure and the kind of the waste pressurizing system are not particularly limited in the present invention, and a pressurizing system well known to those skilled in the art may be used.
In the invention, the electro-catalysis wastewater after sand filtration is subjected to low-pressure reverse osmosis membrane filtration, and the cutoff molecular weight of the low-pressure reverse osmosis membrane is 70-120Da, more preferably 80-110 Da, and most preferably 90-100 Da. The structure and the material of the low-pressure reverse osmosis membrane are not particularly limited, and a membrane component well known to those skilled in the art can be adopted.
In the invention, the electro-catalysis wastewater after sand filtration is subjected to low-pressure reverse osmosis membrane filtration, and the specification of pure water flux of the low-pressure reverse osmosis membrane is 25-30L m-2h-1More preferably 26 to 29L m-2h-1Most preferably 27 to 28L m-2h-1. The structure and the material of the low-pressure reverse osmosis membrane are not particularly limited, and a membrane component well known to those skilled in the art can be adopted.
In order to further illustrate the present invention, the following examples are provided to describe the method for treating wastewater by electrocatalysis-low pressure reverse osmosis, but they should not be construed as limiting the scope of the present invention.
Example 1:
taking the second precipitation treated effluent of certain paper making enterprises, and determining the TOC 59.10-60.5mg/L, the turbidity 0.85-1.01NTU, and the conductivity 1980-.
The method of the invention is adopted to treat the effluent of the secondary sedimentation treatment, the anode of the electro-catalysis system adopts rare earth doped titanium-based ruthenium iridium, the cathode adopts a stainless steel plate, and the distance between every two groups of electrodes is 10 mm. The experimental power supply adopts a constant current mode, and the current density is 30mA/cm2Simultaneously, stirring the wastewater by a stirring paddle, wherein the stirring speed is 150rpm, and the treatment time of the electro-catalysis system on the papermaking wastewater is 30 min; after the electrocatalysis reaction is finished, the wastewater is settled in a sedimentation tank for 60min, and then the supernatant is filtered by using sand filtration with the specification of 3.5 mu m to obtain the electrocatalysis wastewater.
After the sand filtration is finished, the electro-catalysis wastewater is filtered by low-pressure reverse osmosis under the operation pressure of 0.4MPa, in the invention, the specification of the molecular weight cut-off of the low-pressure reverse osmosis membrane is 100Da, and the specification of the pure water flux of the low-pressure reverse osmosis membrane is 27L m-2h-1。
After the reaction, the supernatant was filtered through a 0.45 μm filter to measure other water quality parameters such as TOC (Total organic carbon). Experimental results show that the removal rate of TOC by electrocatalysis can reach 62.4% only after 30min of treatment, the removal rate of TOC by combining a low-pressure reverse osmosis membrane reaches 96%, as shown in figure 1, and the electrocatalysis is used as pretreatment to effectively reduce the occurrence of membrane pollution, after 30min of electrocatalysis treatment, the membrane flux is increased by 80%, and the effluent quality meets the industrial water reuse standard (GB19923-2005), as shown in Table 1.
TABLE 1 comparison of electrocatalysis-Low pressure reverse osmosis effluent quality with Industrial wastewater reuse Standard
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The method for treating industrial wastewater by electrocatalysis-low pressure reverse osmosis is characterized by comprising the following steps:
s1, placing the industrial wastewater to be treated in a reactor with an electrocatalysis system;
s2, applying current between the cathode and the anode of the electro-catalysis system, and continuously stirring the industrial wastewater in the reactor;
s3, standing and precipitating the industrial wastewater treated by the electro-catalysis system, and then performing sand filtration to obtain electro-catalysis wastewater;
s4, carrying out low-pressure reverse osmosis membrane filtration on the electrocatalysis wastewater to obtain a recovered solution.
2. The method according to claim 1, characterized in that the anode of the electrocatalytic system is an electrode of titanium-based ruthenium iridium doped with rare earths.
3. The method according to claim 2, wherein the electrode material of the rare earth doped titanium-based ruthenium-iridium is cerium, lanthanum or neodymium doped titanium-based ruthenium-iridium, and the electrode morphology of the anode of the electrocatalytic system is plate-like, net-like or cylindrical.
4. The method of claim 1, wherein the cathode of the electrocatalytic system is an inert electrode.
5. The method according to claim 4, characterized in that the cathode material of the electrocatalytic system is stainless steel, graphite plate, graphite felt, carbon felt; the cathode of the electro-catalysis system is in a plate shape, a net shape or a cylinder shape.
6. The method of claim 1, wherein in S2, the current density applied between the cathode and the anode of the electrocatalytic system is 10-40mA/cm2The stirring speed is 80-200 rpm.
7. The method of claim 1, wherein in S2, the reaction time of the electrocatalytic system is 3-60 min.
8. The method of claim 1, wherein in S3, the sand filtration has a pore size of 2-5 μm.
9. The method of claim 1, wherein the operating pressure of the low pressure reverse osmosis is 0.3-0.6Mpa in S4.
10. The method of claim 1, wherein the low pressure reverse osmosis has a molecular weight cut-off of 70-120Da and a pure water flux of 25-30L m-2h-1。
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| KR100735546B1 (en) * | 2006-09-19 | 2007-07-06 | 삼정건설 주식회사 | Method for organic wastewater treatments |
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