阅读说明：本技术 一种超声耦合的一体化废水处理装置、方法及系统 (Ultrasonic coupling integrated wastewater treatment device, method and system ) 是由 陈发源 高鹏娜 梁琪 柴云 刘滨 于 2019-10-18 设计创作，主要内容包括：本发明提供一种超声耦合的一体化废水处理装置、方法及系统,一方面由于膜分离与过硫酸盐高级氧化反应集成一体,过硫酸盐高级氧化反应自由基降解有机物、破坏重金属络合物和有机砷、有机磷,金属离子絮体吸附、络合和共沉淀实现多种污染物的去除,降低了过滤膜污堵的概率,并且过滤膜处于容纳腔中,混合器带来的扰动能够同时使得过滤膜上积聚的氢氧化铁絮体不断扰动,零价铁颗粒在过滤膜表面扰动,结合原位生成的自由基氧化剂能起到在线膜清洗作用,进而进一步减轻过滤膜的负担,进一步阻止过滤膜污堵,相较于过硫酸盐高级氧化反应与膜分离非一体化装置,极大地减轻了过滤膜污堵的现象；此外,超声的空化、热解以及机械振动作用能够与过硫酸盐高级氧化反应产生协同作用,可用于连续化废水处理。(The invention provides an ultrasonic coupling integrated wastewater treatment device, method and system, on one hand, because membrane separation and persulfate advanced oxidation reaction are integrated, persulfate advanced oxidation reaction free radicals degrade organic matters, destroy heavy metal complexes, organic arsenic and organic phosphorus, and metal ion floc adsorption, complexation and coprecipitation realize removal of various pollutants, the probability of fouling of a filtering membrane is reduced, the filtering membrane is positioned in a containing cavity, the disturbance brought by a mixer can simultaneously and continuously disturb ferric hydroxide floc accumulated on the filtering membrane, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the in-situ generated free radical oxidizing agent is combined to play a role in online membrane cleaning, so that the burden of the filtering membrane is further reduced, and the fouling of the filtering membrane is further prevented, compared with a persulfate advanced oxidation reaction and membrane separation non-integrated device, the phenomenon of fouling and blocking of the filtering membrane is greatly reduced; in addition, the cavitation, pyrolysis and mechanical vibration effects of the ultrasound can generate synergistic effect with the persulfate advanced oxidation reaction, and can be used for continuous wastewater treatment.)

1. An integrated wastewater treatment device of ultrasonic coupling, comprising:

a device body having a receiving cavity;

the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity;

a second charging device for charging zero-valent iron particles into the accommodating chamber;

a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles;

an ultrasound feeder which feeds ultrasound into the accommodating cavity;

the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide flocs;

the filtering membrane assembly comprises a filtering membrane arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and

and the zero-valent iron particle separator is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, is used for separating the zero-valent iron particles in the ferric hydroxide flocs discharged from the accommodating cavity and throws the separated zero-valent iron particles into the accommodating cavity again.

2. The integrated wastewater treatment apparatus according to claim 1, wherein the first throw-in device comprises:

a persulfate liquid storage tank for storing the persulfate solution;

a wastewater tank for storing the wastewater to be treated; and

the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity; alternatively, the first and second electrodes may be,

the first throw-in device includes:

a persulfate liquid storage tank for storing the persulfate solution;

a wastewater communication pipeline communicated with a wastewater discharge port of a production system; and

and the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity.

3. The integrated wastewater treatment plant of claim 2, wherein the first feeder further comprises:

and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions.

4. The integrated wastewater treatment apparatus according to claim 1, wherein the filtration membrane is a ceramic membrane.

5. The integrated wastewater treatment plant according to claim 1, further comprising: a blowdown assembly;

the soil exhaust assembly includes: the sewage pump and the sludge collector are used for collecting ferric hydroxide flocs and pollutants settled in the accommodating cavity.

6. An ultrasonic coupling integrated wastewater treatment method is characterized by comprising the following steps:

putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;

mixing the persulfate solution, the wastewater to be treated and the zero-valent iron particles in the containing cavity;

feeding ultrasound into the containment chamber;

adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range within a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;

adjusting the pH value of the reaction environment in the containing cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;

collecting liquid penetrating through a filter membrane arranged in the accommodating cavity by suction, wherein the filter membrane is provided with a plurality of pore channels capable of preventing the ferric hydroxide flocs from penetrating;

separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and throwing the separated zero-valent iron particles into the accommodating cavity again;

the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity.

7. The integrated wastewater treatment method according to claim 6, further comprising:

premixing the persulfate solution and the wastewater to be treated;

mixing persulfate solution in the holding chamber, the wastewater to be treated and the zero-valent iron particles, comprising:

and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.

8. The integrated wastewater treatment method according to claim 6, further comprising:

and collecting ferric hydroxide floc settled in the containing cavity.

9. The integrated wastewater treatment method according to claim 6, further comprising:

and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.

10. An ultrasonically-coupled integrated wastewater treatment system comprising the ultrasonically-coupled integrated wastewater treatment apparatus of any one of claims 1 to 5.

Technical Field

The invention relates to the technical field of wastewater treatment, in particular to an ultrasonic coupling integrated wastewater treatment device, method and system.

Background

The persulfate advanced oxidation uses transition metal ions as an activator and uses persulfate (S)₂O₈ ^2-) The wastewater treatment method for chemical oxidation generates sulfate radical through the reaction of transition metal ions and persulfate, and the sulfate radical can destroy organic matters in the wastewater or complexes of the organic matters and heavy metals, thereby achieving the purpose of wastewater degradation. The existing wastewater treatment technology based on persulfate advanced oxidation still has a plurality of defects, and the improvement space exists.

Disclosure of Invention

In order to solve the defects, the wastewater treatment technology of the persulfate advanced oxidation reaction is improved, and the persulfate advanced oxidation reaction is combined with the membrane separation technology and the ultrasonic technology to form an ultrasonic coupling integrated wastewater treatment device, method and system.

An embodiment of an aspect of the present invention provides an integrated wastewater treatment apparatus with ultrasonic coupling, comprising:

a device body having a receiving cavity;

the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity;

a second charging device for charging zero-valent iron particles into the accommodating chamber;

a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles;

an ultrasound feeder which feeds ultrasound into the accommodating cavity;

the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide flocs;

the filtering membrane assembly comprises a filtering membrane arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and

and the zero-valent iron particle separator is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, is used for separating the zero-valent iron particles in the ferric hydroxide flocs discharged from the accommodating cavity and throws the separated zero-valent iron particles into the accommodating cavity again.

In a preferred embodiment, the first investor includes:

a persulfate liquid storage tank for storing the persulfate solution;

a wastewater tank for storing the wastewater to be treated; and

the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity; alternatively, the first and second electrodes may be,

the first throw-in device includes:

a persulfate liquid storage tank for storing the persulfate solution;

a wastewater communication pipeline communicated with a wastewater discharge port of a production system; and

and the premixer is used for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating cavity.

In a preferred embodiment, the first injector further comprises:

and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions.

In a preferred embodiment, the filter membrane is a ceramic membrane.

In a preferred embodiment, further comprising: a blowdown assembly;

the soil exhaust assembly includes: the sewage pump and the sludge collector are used for collecting ferric hydroxide flocs and pollutants settled in the accommodating cavity.

The embodiment of the second aspect of the invention provides an ultrasonic coupling integrated wastewater treatment method, which comprises the following steps:

putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;

mixing the persulfate solution, the wastewater to be treated and the zero-valent iron particles in the containing cavity;

feeding ultrasound into the containment chamber;

adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range within a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;

adjusting the pH value of the reaction environment in the containing cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;

collecting liquid penetrating through a filter membrane arranged in the accommodating cavity by suction, wherein the filter membrane is provided with a plurality of pore channels capable of preventing the ferric hydroxide flocs from penetrating;

separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and throwing the separated zero-valent iron particles into the accommodating cavity again;

the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity.

In a preferred embodiment, further comprising:

premixing the persulfate solution and the wastewater to be treated;

mixing persulfate solution in the holding chamber, the wastewater to be treated and the zero-valent iron particles, comprising:

and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.

In a preferred embodiment, further comprising:

and collecting ferric hydroxide floc settled in the containing cavity.

In a preferred embodiment, further comprising:

and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.

In a third aspect, the present invention provides an integrated wastewater treatment system with ultrasound coupling, which includes the integrated wastewater treatment device with ultrasound coupling as described above.

The invention has the beneficial effects that:

the invention provides an ultrasonic coupling integrated wastewater treatment device, method and system, which are formed by combining persulfate advanced oxidation reaction, membrane separation technology and ultrasonic technology and integrating the membrane separation technology in the same accommodating cavity in which persulfate advanced oxidation reaction occurs. On one hand, the membrane separation and the persulfate advanced oxidation reaction are integrated, free radicals formed by the persulfate advanced oxidation reaction can oxidize organic matters, metal complexes and inorganic matters, metal hydroxide flocs can remove various pollutants simultaneously due to the adsorption, complexation, codeposition and other actions, the irreversible pollution penetrating through the filter membrane can be greatly reduced, the probability of fouling and blocking of the filter membrane is reduced, the filter membrane is positioned in the accommodating cavity, and the ferric hydroxide flocs accumulated on the filter membrane can be continuously disturbed by disturbance brought by the mixer, so that the fouling and blocking of the filter membrane are further prevented; on the other hand, the cavitation of the ultrasound can generate a synergistic effect with the persulfate advanced oxidation reaction, the pyrolysis or cavitation of the ultrasound can generate free radicals, and then the organic matters are oxidized and degraded, the ultrasonic wave can also promote the decomposition of the persulfate, the utilization rate of the persulfate is improved, further, the ultrasonic wave can promote the uniform distribution of ferrous ions of a homogeneous catalyst, so that the persulfate advanced oxidation reaction is strengthened, meanwhile, the mechanical effect of the ultrasound also plays roles of stirring and mass transfer, the flocculent ferric hydroxide generates the disturbance of molecular level, the pollution and blockage phenomenon of a filtering membrane is further reduced, and ferric salt or ferrous salt also can play a certain role of catalysis in the process of generating sulfate radicals by the ultrasonic cavitation; furthermore, the zero-valent iron is in a flowing state and the active sites are timely updated under the action of ultrasound, the reaction activity is improved compared with that of the traditional heterogeneous persulfate advanced oxidation, the vibration frequency of the flowing zero-valent iron is further enhanced by ultrasound, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the online membrane cleaning effect can be realized by combining with a free radical oxidizing agent generated in situ, so that the pollution of the filtering membrane is further reduced, and the phenomenon of pollution and blockage of the filtering membrane is reduced; finally, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 shows a schematic structural diagram of an ultrasonic-coupled integrated wastewater treatment device in an embodiment of the invention.

FIG. 2 is a schematic flow chart of an ultrasonic coupling integrated wastewater treatment method in an embodiment of the invention.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

Various schematic diagrams in accordance with the disclosed embodiments of the invention are shown in the figures. The figures are not drawn to scale, wherein certain details are exaggerated and possibly omitted for clarity of presentation. The shapes of various regions, layers, and relative sizes and positional relationships therebetween shown in the drawings are merely exemplary, and deviations may occur in practice due to manufacturing tolerances or technical limitations, and a person skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions, as actually required.

The process of the higher oxidation of persulfates is persulfate (S)₂O₈ ^2-) Mixing with zero-valent iron, persulfate can be decomposed to generate sulfate radical (SO) at normal temperature₄ ^-Sulfuric acid radical (SO)₄ ^2-) And further, many known organic compounds such as carboxylic acids, alcohols, esters are oxidized to inorganic states. The capability of efficiently mineralizing refractory organic pollutants, oxidizing low-valence inorganic matters and destroying heavy metal complexes in reaction, and the method is widely applied to the treatment of printing and dyeing wastewater, oily wastewater, phenol-containing wastewater, coking wastewater, nitrobenzene-containing wastewater, diphenylamine-containing wastewater and other wastewater.

Zero-valent iron can be converted to divalent iron ions, either under aerobic or anaerobic regulation, the principle of which can be expressed by the following formula:

aerobic conditions: fe⁰+H₂O+1/2O₂→Fe²⁺+2OH^-

Anaerobic condition: : fe⁰+2H₂O→Fe²⁺+2OH^-+H₂

Then reacts with persulfate in persulfate to produce sulfate radical, the principle of which can be expressed by the following formula:

Fe²⁺+S₂O₈ ^2-→Fe³⁺+SO₄ ^-(free radical) + SO₄ ^2-

It is the presence of sulfate radicals which confer a strong oxidizing power. But the prior advanced oxidation based on persulfate simply utilizes persulfate advanced oxidation, and a deep wastewater treatment technology based on persulfate advanced oxidation, namely a deep coupling treatment technology based on persulfate advanced oxidation and a reliable deep coupling multistage wastewater treatment technology are lacked.

Based on this, this application has improved current persulfate advanced oxidation reaction, the degree of depth has coupled persulfate advanced oxidation reaction, membrane separation technique and ultrasonic technology, through combining persulfate advanced oxidation reaction and membrane separation technique, and with the membrane separation technique integration in taking place persulfate advanced oxidation reaction's same chamber that holds, and then form ultrasonic coupling's integrated effluent treatment plant, and then formed reliable degree of depth coupling's second grade waste water treatment integration technique, the efficiency of waste water treatment has been improved greatly, and the coupling degree is higher.

FIG. 1 illustrates an integrated wastewater treatment device coupled by ultrasound provided by an embodiment of an aspect of the present application, as shown in FIG. 1, including: a device body 1 having a housing chamber; the first feeder is used for feeding persulfate solution and wastewater to be treated into the accommodating cavity; a second charging device for charging zero-valent iron particles into the accommodating chamber; a mixer that mixes a persulfate solution, the wastewater to be treated, and the zero-valent iron particles; an ultrasound feeder which feeds ultrasound into the accommodating cavity; the pH value regulator regulates the pH value of the reaction environment in the accommodating cavity to be in a first pH range in a first time period so as to convert the zero-valent iron particles into ferrous ions and further activate persulfate, and regulates the pH value of the reaction environment in the accommodating cavity to be in a second pH range in a second time period after the first time period so as to generate ferric hydroxide or other metal ion flocs; the filtering membrane component comprises a filtering membrane 8 arranged in the accommodating cavity and a collector for collecting liquid penetrating through the filtering membrane 8, and the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through; and a zero-valent iron particle separator 21 which is arranged outside the accommodating cavity, is communicated with the discharge port of the accommodating cavity, and is used for separating and discharging zero-valent iron particles in the ferric hydroxide flocs and throwing the separated zero-valent iron particles into the accommodating cavity again.

The ultrasonic coupling integrated wastewater treatment device in the aspect integrates membrane separation and persulfate advanced oxidation reaction, organic matters, metal complexes and inorganic matters can be oxidized by free radicals formed by persulfate advanced oxidation reaction, and various pollutants can be removed simultaneously due to the effects of adsorption, complexation, coprecipitation and the like of metal hydroxide floc, so that irreversible pollution of a filter membrane can be greatly reduced, the probability of fouling and blocking of the filter membrane is reduced, the filter membrane is positioned in a containing cavity, ferric hydroxide floc accumulated on the filter membrane can be continuously disturbed by disturbance brought by a mixer, and fouling and blocking of the filter membrane are further prevented, and compared with a persulfate advanced oxidation reaction and membrane separation non-integrated device, the phenomenon of fouling and blocking of the filter membrane is greatly reduced; on the other hand, the cavitation of the ultrasound can generate a synergistic effect with the persulfate advanced oxidation reaction, the pyrolysis or cavitation of the ultrasound can generate free radicals, and then the organic matters are oxidized and degraded, the ultrasonic wave can also promote the decomposition of the persulfate, the utilization rate of the persulfate is improved, further, the ultrasonic wave can promote the uniform distribution of ferrous ions of a homogeneous catalyst, so that the persulfate advanced oxidation reaction is strengthened, meanwhile, the mechanical effect of the ultrasound also plays roles of stirring and mass transfer, the flocculent ferric hydroxide generates the disturbance of molecular level, the pollution and blockage phenomenon of a filtering membrane is further reduced, and ferric salt or ferrous salt also can play a certain role of catalysis in the process of generating sulfate radicals by the ultrasonic cavitation; furthermore, zero-valent iron is in a flowing state, active sites are updated in time, the reaction activity is improved compared with that of the traditional heterogeneous persulfate advanced oxidation, the vibration frequency of the flowing zero-valent iron is further enhanced by ultrasound, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the online membrane cleaning effect can be realized by combining with a free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced; finally, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.

Compared with the input of ferrous salt, the application adopts zero-valent iron as an iron source, so that the utilization rate of iron is higher, and the pH range of advanced oxidation reaction is wider; because ferrous salt does not produce ferrous iron in situ, when the ferrous salt enters into the solution, the ferrous salt is directly dissolved and cannot be disturbed on the surface of the filtering membrane, and simultaneously the ferrous salt is directly dissolved and cannot bring the updating of a phase interface, so that the online membrane cleaning effect cannot be realized.

In the embodiment shown in fig. 1, the first investor includes: a persulfate liquid storage tank 3 for storing the persulfate solution; a wastewater communication pipeline 2 communicated with a wastewater discharge port of a production system; and a premixer 4 for premixing the persulfate solution and the wastewater to be treated and pumping the premixed mixed solution into the accommodating chamber. The embodiment directly communicates the device with a wastewater discharge port of a production system, and further can realize continuous online wastewater treatment.

In an embodiment not shown in fig. 1, the first investor comprises: a persulfate liquid storage tank for storing the persulfate solution; a wastewater tank for storing the wastewater to be treated; and the premixer is used for premixing the persulfate solution and the wastewater to be treated, and the premixed mixed solution can be pumped into the accommodating cavity.

Depending on the throughput, pumps of different sizes may be selected, such as micro pumps, peristaltic pumps, plunger pumps, etc., and the application is not limited thereto.

The mixer may be a paddle type mixer or may be a mixer that uses gas not participating in the reaction to create agitation, such as an aerator 16, in this embodiment, the mixer includes: an aerator 16, an air pipeline 15 communicated with the aerator, and an air compressor 14 connected to the air pipeline 15, or an air blower, so as to suck the external air or prepared inert gas (such as nitrogen) into the accommodating cavity, wherein the air or the inert gas forms a plurality of bubbles 23 in the reaction liquid, thereby forming an agitation and disturbance environment.

The ultrasonic feeder specifically comprises a plurality of ultrasonic probes 18 and an ultrasonic generator 17, wherein the ultrasonic probes 18 are uniformly distributed on the side wall of the device body 1, ultrasonic waves are generated through the ultrasonic generator 17, and the ultrasonic probes are used for feeding the ultrasonic waves into the accommodating cavity.

The ultrasonic wave has the functions of pyrolysis, cavitation and mechanical vibration, the pyrolysis or cavitation of the ultrasonic wave can generate free radicals, and then the organic matter is oxidized and degraded, the ultrasonic wave can also promote the decomposition of persulfate, the utilization rate of the persulfate is improved, further, the ultrasonic wave can promote the uniform distribution of ferrous ions of a homogeneous catalyst, so as to strengthen the advanced oxidation reaction of the persulfate, meanwhile, the mechanical effect of the ultrasonic wave also plays roles of stirring and mass transfer, the flocculent ferric hydroxide generates disturbance of molecular level, the pollution and blockage phenomenon of a filtering membrane is further reduced, and ferric salt or ferrous salt also can play a certain role of catalysis in the process of generating sulfate radical free radical by ultrasonic cavitation, and simultaneously, the zero-valent iron in a flowing state can continuously vibrate, the zero-valent iron particles disturb on the surface of the filtering membrane, and the function of cleaning the online membrane can be played by combining with the, further reducing the burden of the filtering membrane and reducing the phenomenon of dirt and blockage of the filtering membrane.

Further, in order to improve the efficiency of the persulfate advanced oxidation reaction, the first injector further comprises: and the cation liquid storage tank is communicated with the premixer pipeline and stores at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions, so that a complex persulfate advanced oxidation reaction system is formed, and the oxidation effect of the persulfate advanced oxidation reaction is further enhanced by the complex persulfate advanced oxidation reaction system.

In this embodiment, in order to reduce noise interference of the reaction apparatus to the outside, a sound insulation member 19, such as a sound insulation board, may be coated on the outer side wall of the apparatus body 1, but the present application is not limited thereto.

The ph adjuster can adjust the ph by adding an acidic substance and a basic substance, and in the embodiment shown in fig. 1, the ph adjuster includes: an acid adding pipeline (not shown in the figure), an alkali adding pipeline (not shown in the figure), an acid liquid tank 5 and a corresponding power pump (not shown in the figure) which are connected to the acid adding pipeline, an alkali liquid tank 6 and a corresponding power pump (not shown in the figure) which are connected to the alkali adding pipeline, and an acid-alkali detector 7, wherein the flow controllers (not shown in the figure) are correspondingly connected to the acid adding pipeline and the alkali adding pipeline.

The filtering membrane 8 in the filtering membrane module can be a ceramic membrane with a set aperture, and the ceramic membrane has various excellent material properties such as high temperature resistance, acid and alkali resistance, high mechanical strength and the like, and is increasingly applied to the field of water treatment. And with the continuous maturity and perfection of the ceramic membrane preparation process, the preparation cost of the ceramic membrane can be continuously reduced, and the ceramic membrane is developed in the field of water treatment. The ceramic membrane can remove colloidal suspended matters, macromolecular organic matters and the like, thereby ensuring the stability of the effluent quality. In the oil gas field, the ceramic membrane also can have better removal effect to grease waste water.

The ceramic membrane is easy to block, the ferric hydroxide floc formed in the embodiment of the invention can reduce transmembrane pressure drop and increase membrane flux, the ferric hydroxide floc can complex and adsorb heavy metal ions, silicon, phosphorus and the like in sewage, and meanwhile, the mixer can continuously disturb the floc accumulated on the ceramic membrane, so that the blocking is further prevented; furthermore, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the on-line membrane cleaning effect can be realized by combining with the free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced.

The ceramic membrane may be fixed by the membrane holder 9, and may be fixed obliquely or vertically, but the present invention is not limited thereto.

The filtering membrane component further comprises a water outlet pipeline 10, a pressure gauge 11, a vacuum pump 12 and a collector 13, the vacuum pump 12 creates suction force, so that liquid in the accommodating cavity penetrates through the filtering membrane 8, the ferric hydroxide floc is blocked by the filtering membrane 8, and the filtering membrane 8 has sewage filtering capacity and is matched with the ferric hydroxide floc to achieve the purpose of two-stage deep treatment. Experiments prove that the transmembrane pressure difference of the device is reduced by 50 percent, and the device is stable for a long time; membrane flux can be increased; the COD removal rate can reach more than 70 percent, and the turbidity is lower than 1 NTU.

In one embodiment, a heat exchanger (not shown) is disposed on the outer side wall or the inner side wall of the apparatus body 1 for adjusting the temperature of the whole reaction system, so that the reaction can be performed at a preferred temperature.

Further, in some embodiments, in order to collect the ferric hydroxide flocs after adsorbing the heavy metal ions, silicon and phosphorus in the wastewater, fig. 1 shows an embodiment in which the apparatus further comprises a wastewater discharge assembly, wherein the wastewater discharge assembly comprises: a dredge pump 22 and a sludge collector for collecting ferric hydroxide flocs and pollutants settled in the containing chamber.

Sludge collector is a long-pending mud fill 20, and long-pending mud fill 20 is the back taper, can make the ferric hydroxide floc can concentrate the pipeline entrance under the effect of gravity like this, and then draws out through dredge pump 22 and holds the chamber outside.

The device is in the use, at first throw into the ware through first throw-in ware and second and throw into the ware respectively to holding in the chamber and throw into needs persulfate solution and pending waste water, throw into zero valent iron particle simultaneously, zero valent iron is the mobile state, active site is in time updated, the higher oxidation of the heterogeneous persulfate of reaction activity ratio tradition improves, after zero valent iron forms the bivalent iron, under the catalytic action of bivalent iron ion, the persulfate decomposes and produces the sulfate radical free radical, mix the back with waste water, the sulfate radical destroys the difficult degradation organic matter in sewage/waste water, or the complex that forms heavy metal and organic matter, organic phosphorus and organic arsenic destroy, here simultaneously, ferrous ion is in the process that generates the sulfate radicalConverting into ferric ion, mixing for a while, and adjusting pH to 6-7.5 (9.5-10.5 for partial system) via pH adjuster^-So far) to provide sufficient OH^-The ferric hydroxide floc reacts with ferric iron in a solution to generate ferric hydroxide floc, and the ferric hydroxide floc is complexed and adsorbs heavy metal ions, silicon, phosphorus and the like in sewage, and the whole reaction is in the same accommodating cavity, the ferric hydroxide floc has low density and large gaps among particles, so that transmembrane pressure drop is reduced, the membrane flux is improved, free radical oxidants generated by iron particles on the surface of a ceramic membrane and in situ can play a role in cleaning an on-line membrane, the pollution and blockage of a filtering membrane can be effectively reduced, continuous disturbance is realized under the action of a mixer on the other hand, the possibility of pollution and blockage is further reduced, a synergistic effect is further generated under an ultrasonic environment, and a secondary wastewater treatment technology of deep coupling of persulfate advanced oxidation reaction and membrane separation technology and ultrasonic technology is further formed. Zero-valent iron is used as an iron source, the optimal pH generated by the advanced oxidation reaction is wide, and the utilization rate of iron is high; compared with the ferrous salt, the ferrous salt does not generate ferrous iron in situ, the ferrous salt is directly dissolved when entering a solution, the ferrous salt cannot be disturbed on the surface of a filtering membrane, and meanwhile, the ferrous salt is directly dissolved and cannot bring updating of a phase interface, and the online membrane cleaning effect cannot be achieved.

Based on the same reason of the foregoing embodiment, the second aspect of the present invention provides an integrated wastewater treatment method by ultrasonic coupling, specifically as shown in fig. 2, including:

s100, putting a mixed solution of persulfate solution and wastewater to be treated and zero-valent iron particles into a containing cavity of a wastewater treatment device;

s200, mixing persulfate solution, the wastewater to be treated and the zero-valent iron particles in the accommodating cavity;

s300, feeding ultrasound into the accommodating cavity;

s400, adjusting the pH value of the reaction environment in the accommodating cavity to be in a first acid-base range in a first time period so as to convert the zero-valent iron particles into ferrous iron ions and further activate persulfate;

s500, adjusting the pH value of the reaction environment in the accommodating cavity to be in a second acid-base range in a second time period after the first time period to generate ferric hydroxide flocs;

s600, collecting liquid penetrating through a filtering membrane arranged in the accommodating cavity by suction, wherein the filtering membrane is provided with a plurality of pore passages capable of preventing the ferric hydroxide flocs from penetrating through;

s700, separating zero-valent iron particles in the ferric hydroxide floc discharged from the accommodating cavity through a zero-valent iron particle separator, and adding the separated zero-valent iron particles into the accommodating cavity again;

the zero-valent iron particle separator is arranged outside the accommodating cavity and communicated with the discharge port of the accommodating cavity.

According to the ultrasonic coupling integrated wastewater treatment method, the persulfate advanced oxidation reaction and the membrane separation technology are combined, and the membrane separation technology is integrated in the same accommodating cavity in which the persulfate advanced oxidation reaction occurs, so that the ultrasonic coupling integrated wastewater treatment device is formed. On one hand, the membrane separation and the persulfate advanced oxidation reaction are integrated, free radicals formed by the persulfate advanced oxidation reaction can oxidize organic matters, metal complexes and inorganic matters, metal hydroxide flocs can remove various pollutants simultaneously due to the adsorption, complexation, codeposition and other actions, the irreversible pollution penetrating through the filter membrane can be greatly reduced, the probability of fouling and blocking of the filter membrane is reduced, the filter membrane is positioned in the accommodating cavity, and the ferric hydroxide flocs accumulated on the filter membrane can be continuously disturbed by disturbance brought by the mixer, so that the fouling and blocking of the filter membrane are further prevented; on the other hand, the cavitation of the ultrasound can generate a synergistic effect with the persulfate advanced oxidation reaction, the pyrolysis or cavitation of the ultrasound can generate free radicals, and then the organic matters are oxidized and degraded, the ultrasonic wave can also promote the decomposition of the persulfate, the utilization rate of the persulfate is improved, further, the ultrasonic wave can promote the uniform distribution of ferrous ions of a homogeneous catalyst, so that the persulfate advanced oxidation reaction is strengthened, meanwhile, the mechanical effect of the ultrasound also plays roles of stirring and mass transfer, the flocculent ferric hydroxide generates the disturbance of molecular level, the pollution and blockage phenomenon of a filtering membrane is further reduced, and ferric salt or ferrous salt also can play a certain role of catalysis in the process of generating sulfate radicals by the ultrasonic cavitation; furthermore, zero-valent iron is in a flowing state, active sites are updated in time, the reaction activity is improved compared with that of the traditional heterogeneous persulfate advanced oxidation, the vibration frequency of the flowing zero-valent iron is further enhanced by ultrasound, zero-valent iron particles are disturbed on the surface of the filtering membrane, and the online membrane cleaning effect can be realized by combining with a free radical oxidizing agent generated in situ, so that the burden of the filtering membrane is further reduced, and the phenomenon of fouling and blocking of the filtering membrane is reduced; finally, the invention is not easy to be polluted and blocked, can be used for continuous online wastewater treatment, and the integrated device can further reduce the process cost, the manufacturing cost and the occupied volume.

Compared with the input of ferrous salt, the optimal pH generated by the advanced oxidation reaction is wide, and the utilization rate of iron is high; because ferrous salt is not ferrous iron generated in situ, ferrous salt is directly dissolved when entering a solution, the ferrous salt cannot be disturbed on the surface of a filtering membrane, and meanwhile, the ferrous salt is directly dissolved and cannot bring updating of a phase interface, and the effect of online membrane cleaning cannot be achieved.

For the same reason, the method further comprises:

s001, premixing the persulfate solution and the wastewater to be treated;

in this embodiment, step S100 includes: and pumping the zero-valent iron particles and the premixed mixed solution into the accommodating cavity.

The wastewater treatment method in this aspect may be combined with the persulfate advanced oxidation reaction and the membrane separation technology, and may also be combined with the membrane separation technology, where the method further includes, based on the foregoing embodiment:

and introducing at least one of ferrous ions, ruthenium ions, cerium ions, cobalt ions, manganese ions, vanadium ions and nickel ions into the accommodating cavity.

In addition, in some embodiments, in order to collect iron hydroxide flocs after adsorbing heavy metal ions, silicon, and phosphorus in the wastewater, the wastewater treatment method of the present aspect further includes:

and S800, collecting ferric hydroxide flocs settled in the accommodating cavity.

The invention further provides an ultrasonic-coupled integrated wastewater treatment system, which comprises the ultrasonic-coupled integrated wastewater treatment device and a wastewater or sewage discharge device, wherein a wastewater discharge port of the wastewater or sewage discharge device is communicated with the ultrasonic-coupled integrated wastewater treatment device, so that the online continuous wastewater treatment is realized.

The wastewater discharge device can be a sub-device in a complete industrial production system, such as a printing and dyeing wastewater discharge device of a printing and dyeing system, so that the ultrasonic coupling integrated wastewater treatment device is directly integrated in the production process, and the process flow of wastewater treatment is simplified.

The above embodiments of the present application will be described in detail with reference to several specific scenarios.

Scene one: the organophosphorus waste water has COD 1120mg/L and total phosphorus 89 mg/L. Preparing a persulfate advanced oxidation reagent, wherein the amount of persulfate is 800-1000mg/L, the input amount of iron ions is 5g/L, adjusting the pH value to 6.5-7.5 after mixing for 120 minutes, starting ceramic membrane filtration, reducing the COD of effluent to within 300mg/L, and reducing the total phosphorus to be less than 10 mg/L. Under the same condition, the optimal pH range of the advanced oxidation of ferrous ions is 2-3.5, and the consumed acid and alkali agent amount is increased; in addition, the ferrous consumption and the sludge amount are increased by 30 percent; the cleaning frequency of the ceramic membrane is increased by 1 time.

Scene two: the electroplating waste water has COD 500mg/L, copper ion concentration 30mg/L and nickel ion content 10 mg/L. Preparing a persulfate high-grade oxidation reagent, wherein the amount of persulfate is 250-500mg/L, the input amount of iron ions is 3g/L, the pH of the wastewater is increased to 6.5-7.5, the reaction is carried out for 90 minutes, and the pH is adjusted to 9.5-10.5; the ceramic membrane filtration is started, the COD of the effluent is reduced to be within 120mg/L, the concentration of copper ions is lower than 0.3mg/L, and the concentration of nickel ions is lower than 0.1 mg/L.

Scene three: printing and dyeing wastewater with COD of 320 mg/L. Preparing a persulfate high-grade oxidation reagent, wherein the amount of persulfate is 150-400mg/L, the input amount of iron ions is 3g/L, the pH value of the wastewater is increased to 6.5-7.5, and the reaction is carried out for 60 minutes; the ceramic membrane filtration is started, and the COD of the effluent is reduced to be within 90 mg/L. Under the same condition, the optimal pH range of the advanced oxidation of ferrous ions is 2-3.5, and the consumed acid and alkali agent amount is increased; in addition, the ferrous consumption and the sludge amount are increased by 30 percent; the cleaning frequency of the ceramic membrane is increased by 1 time.

According to the scene, the ultrasonic coupling integrated wastewater treatment device, method and system provided by the invention are not easy to block, can further improve the wastewater treatment efficiency, and have important guiding significance, and the COD removal rate can reach more than 70%.

It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.