CN104291451A - Electrochemical water scale removal device - Google Patents
Electrochemical water scale removal device Download PDFInfo
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- CN104291451A CN104291451A CN201410522689.4A CN201410522689A CN104291451A CN 104291451 A CN104291451 A CN 104291451A CN 201410522689 A CN201410522689 A CN 201410522689A CN 104291451 A CN104291451 A CN 104291451A
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- incrustation scale
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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
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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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
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides an electrochemical water scale removal device. The device comprises a water scale crystal nucleus generating unit used for electrochemical water treatment, wherein the water scale crystal nucleus generating unit comprises a tank body, diaphragms, cathodes and an anode; a water inlet and a drain outlet are formed in the bottom of the tank body; the diaphragms are arranged inside the tank body and divide the tank body into cathode chambers and an anode chamber; the cathodes are arranged inside the cathode chambers; the anode is arranged inside the anode chamber; a catholyte water outlet and an anolyte water outlet are formed in the top end of the tank body. The electrochemical water scale removal device provided by the invention has the beneficial effects that anode electrochemical products and cathode electrochemical products do not interfere with each other via the diaphragms in the device; the catholyte containing plenty of crystal nuclei is generated in the cathode chambers and the plenty of crystal nuclei provide super-large crystal growth surfaces and crystal active growth points for scaling ions in the solution; as the surface areas of plenty of tiny crystal nuclei are many times larger than the surface areas of the cathodes, the probability of separation of the scaling ions by crystallization is greatly increased and the descaling efficiency is also improved.
Description
Technical field
The invention belongs to incrustation scale removal device field, particularly relate to a kind of electrochemistry incrustation scale removal device.
Background technology
Electrochemical techniques, as a kind of clean incrustation scale and bacterium algae control techniques, in refrigeration cycle water treatment, have passed through practical application for many years.Electrochemistry removes incrustation scale multiple advantage: environmental friendliness, can not bring environmental pollution; Do not need dispose and add chemical; Automatization and more convenient technology controlling and process can be realized.And main difficulty be most of incrusted deposit at cathode surface, cause resistance raise and current efficiency decline.Several negative electrode scale treatment methods of current employing comprise polarity inversion and ultrasonic cleaning.
Application number be 200620032114.5 Chinese patent disclose a kind of electrochemical reactor of the operation of falling pole, by pole, negative electrode incrustation scale is come off, frequently pole-reversing scale removal, the anode loss of catalytic activity of electrolyzer will be made, electrode is caused to produce very high overvoltage, current efficiency declines, and then reduces scale removal ability.
China Patent Publication No. CN101585569A discloses circulating water electrolytic descaling device and descaling method, this device adopts ultrasonic wave to carry out automatic desludging cleaning, when the thickness of incrustation scale increases, resistance on the loop that test electrode and reaction chamber are formed increases, when this resistance value reaches set(ting)value, automatically enter cleaning and descaling process.Above-mentioned negative electrode incrusted deposit cleans to certain thickness again, and making resistance increase increases energy consumption, reduces scale removal ability.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of electrochemistry incrustation scale removal device, electrochemistry incrustation scale removal device provided by the invention has higher electrochemistry scale removing ability.
This application provides a kind of electrochemistry incrustation scale removal device, comprise for electro-chemical water process incrustation scale nucleus generation unit, described incrustation scale nucleus generation unit comprises cell body;
The bottom of described cell body is provided with water-in and sewage draining exit;
Negative electrode with the inside of described cell body is set;
Anode with the inside of described cell body is set;
Barrier film with the inside of described cell body is set;
Cell body is divided into cathode compartment and anolyte compartment by described barrier film;
The top of described cell body is provided with catholyte water outlet and anolyte water outlet.
Preferably, described barrier film is cationic membrane.
Preferably, described barrier film is fixed together with described anode.
Preferably, described negative electrode is carbon steel cathodes, stainless steel cathode, Ti cathode, titanium alloy negative electrode or aluminium alloy negative electrode.
Preferably, described negative electrode is cylindric.
Preferably, the inside of described cell body also comprises negative electrode scraper;
The two ends up and down of described cell body are end plate, and upper head plate is equipped with draw-in groove;
Described negative electrode scraper is fixed on separately on the draw-in groove of the upper head plate of described cell body.
Preferably, described incrustation scale nucleus generation unit also comprises supporting electrode;
Described supporting electrode is positioned at cathode compartment.
Preferably, described barrier film is fixed together with supporting electrode.
Preferably, described supporting electrode is net-shaped stability supporting electrode.
Preferably, described negative electrode is tubular, and described anode arrangement is within the cylindrical chamber of negative electrode.
This application provides a kind of electrochemistry incrustation scale removal device, comprise for electro-chemical water process incrustation scale nucleus generation unit, described incrustation scale nucleus generation unit comprises cell body; The bottom of described cell body is provided with water-in and sewage draining exit; Be arranged at the barrier film of the inside of described cell body; Described barrier film is divided into cathode compartment and anolyte compartment by corresponding for cell body; Be arranged at the negative electrode of the inside of described cathode compartment; Be arranged at the anode of the inside of described anolyte compartment; The top of described cell body is provided with catholyte water outlet and anolyte water outlet.In the electrochemistry incrustation scale removal device that the application provides, pending water is entered incrustation scale nucleus generation unit from water-in bottom cell body, carries out electrochemical treatment, near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Chlorion is oxidized near anode simultaneously, and generate chlorine, chlorine is combined with water further and generates hypochlorous acid and hydrochloric acid; Near negative electrode, aqueous electrolysis produces OH
-near negative electrode, interfacial layer obtains strong alkali solution, the existence of barrier film, by catholyte and anolyte shunting, mutually do not disturb between anode electrochemical product and electrochemical cathode product, the catholyte of pH value more than 9.5 is obtained in cathode compartment, in interfacial layer near cathode surface and cathode surface, pH value reaches more than 14, scale-forming ion degree of supersaturation in high ph-values environment like this is very high, oversaturated scale-forming ion forms nucleus fast, and the catholyte containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt generated in incrustation scale nucleus generation unit is then discharged by the sewage draining exit of cell body bottom.Barrier film in the electrochemistry incrustation scale removal device that the application provides makes mutually not disturb between anode electrochemical product and electrochemical cathode product, generate the catholyte containing a large amount of fouling nucleus in cathode compartment, a large amount of fouling nucleus is crystal growing surface and the crystal Active Growth point that scale-forming ion in solution provides super large; Due to much larger times of the surface area ratio cathodic surface area of a large amount of small nucleus, the probability of scale-forming ion crystallization increases greatly, and scale removal efficiency also just increases.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
The structural representation of the electrochemistry incrustation scale nucleus generation unit that Fig. 1 provides for the embodiment of the present invention;
The structural representation of the electrochemistry incrustation scale nucleus generation unit that Fig. 2 provides for the embodiment of the present invention;
The decomposition texture schematic diagram of the barrier film that Fig. 3 provides for the embodiment of the present invention, supporting electrode and plastic wire;
The packaging assembly schematic diagram of the barrier film that Fig. 4 provides for the embodiment of the present invention, supporting electrode and plastic wire;
The decomposing schematic representation of the installation site of the negative electrode scraper that Fig. 5 provides for the embodiment of the present invention;
The assembling schematic diagram of the installation site of the negative electrode scraper that Fig. 6 provides for the embodiment of the present invention;
The electrochemistry incrustation scale removal device schematic diagram that Fig. 7 provides for the embodiment of the present application.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
With reference to figure 1 ~ Fig. 6,1 is cell body, and 2 is negative electrode, and 3 is anode, 4 is supporting electrode, and 5 is negative electrode scraper, and 6 is drive-motor, and 7 is anode terminal, 8 is copper ring, and 9 is supporting electrode terminal stud, and 10 is water-in, and 11 is catholyte outlet, 12 is anolyte outlet, and 13 is carbon brush, and 14 is sewage draining exit, and 15 is Anode chamber inlets, 16 fix ear for scraper, and 17 is cathode compartment, and 18 is anolyte compartment, 19 is coupling shaft, and 20 is barrier film, and 21 is plastic wire.
The incrustation scale removal device that the application provides comprises incrustation scale nucleus generation unit, and described incrustation scale nucleus generation unit comprises cell body 1.The nucleus of electrochemistry incrustation scale is created in cell body 1 and carries out.In the embodiment of the application, described cell body 1 can be cylindric, also can be square; The top and bottom of described cell body 1 are preferably end plate; Upper head plate is provided with draw-in groove.
In this application, the bottom of described cell body 1 is provided with water-in 10, and pending water enters in cell body 1 by water-in 10, carries out electrochemical treatment.
In this application, described incrustation scale nucleus generation unit comprises the anode 3 being arranged at described cell body 1 inside.In the embodiment of the application, in described cell body 1, at least one anode 3 is set; When described negative electrode 2 is tubular, described anode 3 is arranged within negative electrode 2 chamber, as shown in Figure 1, and the structural representation of the electrochemistry incrustation scale nucleus generation unit that Fig. 1 provides for the embodiment of the present invention; Or when negative electrode 2 is cylindric, negative electrode 2 by least one anode 3 around, as shown in Figure 2, the structural representation of the electrochemistry incrustation scale nucleus generation unit that Fig. 2 provides for the embodiment of the present invention.Near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water, maintains the sterile environment that cell body is inner stronger, and part chlorion is oxidized to chlorine simultaneously, thus forms hypochlorite (ClO
-), hypochlorite has lasting anti-bacteria and grows ability.In the embodiment of the application, the anode that the application adopts can be net-shaped stability electrode (DSA), at 200A/m
2under the density conditions of above electric current, work-ing life is more than 5 years.
In this application, described incrustation scale nucleus generation unit comprises the negative electrode 2 arranged with described cell body 1 inside.In this application, described negative electrode 2 can with the circular frequency continuous rotation of 30rpm ~ 1500rpm, and also can rotate with the circular frequency of 5rpm ~ 30rpm intermittence, the intermittent time is 5min ~ 30min; Described negative electrode 2 is preferably cylindric; Described negative electrode 2 is preferably carbon steel cathodes, stainless steel cathode, Ti cathode, titanium alloy negative electrode or aluminium alloy negative electrode.Near negative electrode, aqueous electrolysis produces OH
-, near negative electrode, interfacial layer obtains the basic solution of pH value more than 14, and calcium carbonate and magnesium hydroxide are in hypersaturated state at interfacial layer, and calcium carbonate and magnesium hydroxide rapid crystallization in cathode surface and interfacial layer, part incrustation scale is at cathode surface crystallization.The OH of high density is produced near negative electrode
-the rotation of negative electrode enhances mass transfer process, scale-forming ion degree of supersaturation in this alkaline environment is very high, and oversaturated scale-forming ion forms nucleus fast, and a large amount of nucleus is crystal growing surface and the crystal Active Growth point that scale-forming ion in solution provides super large; Due to much larger times of the surface area ratio cathodic surface area of a large amount of small nucleus, the probability of scale-forming ion crystallization increases greatly, and scale removal efficiency also just increases.
In this application, the rotatory power field technique personnel of described negative electrode 2 realize preferably by the mode such as drive unit and gear driven; Described drive unit comprises coupling shaft 19 and drive-motor 6; Described coupling shaft is positioned at the bottom of cell body 1; Described drive-motor is positioned at the below of cell body 1; Described negative electrode 2 is connected with drive-motor 6 by coupling shaft, and coupling shaft is simultaneously as the wire of negative electrode, and the fixing copper ring 8 on coupling shaft is directly connected to the negative pole of direct supply by carbon brush 13.The positive pole of direct supply is connected with anode terminal 7 and supporting electrode terminal stud 9.
In this application, described incrustation scale nucleus generation unit comprises barrier film 20, and described barrier film is arranged between anode 3 and negative electrode 2, is divided into anolyte compartment 18 and cathode compartment 17 by corresponding for cell body 1.In this application, anode 3 is arranged in anolyte compartment, and negative electrode 2 is arranged in cathode compartment.In this application, described barrier film 20 is preferably cationic membrane; In the embodiment of the application, described cationic membrane can be specially perfluorinated cation film, the N966 of the Nafion series of such as E.I.Du Pont Company.In some embodiment of the application, described barrier film 20 can be fixed separately, also can fix together with anode 3, also can select to fix together with supporting electrode 4.
In the specific embodiment of the application, cell body 1 is divided into anolyte compartment and cathode compartment by barrier film 20, there are two water outlets accordingly, the top of described cell body 1 is provided with catholyte outlet 11 and anolyte outlet 12, after the electrochemical reaction in incrustation scale nucleus generation unit terminates, anolyte is discharged from anolyte outlet 12, catholyte is discharged from catholyte outlet 11.The bottom of described cell body 1 is provided with sewage draining exit 14, discharges by it incrustation scale produced.
In the electrochemistry incrustation scale removal device that the application provides, pending water is entered incrustation scale nucleus generation unit from water-in bottom cell body, carries out electrochemical treatment, near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Chlorion is oxidized generation chlorine near anode, and chlorine is combined with water further and generates hypochlorous acid and hydrochloric acid, hypochlorite (ClO
-) there is long-term bacteriostatic action; Near negative electrode, aqueous electrolysis produces OH
-near negative electrode, interfacial layer obtains strong alkali solution, the existence of barrier film, by catholyte and anolyte shunting, mutually do not disturb between anode electrochemical product and electrochemical cathode product, the catholyte of pH value more than 9.5 is obtained in cathode compartment, in interfacial layer near cathode surface and cathode surface, pH value reaches more than 14, scale-forming ion degree of supersaturation in high ph-values environment like this is very high, oversaturated scale-forming ion forms nucleus fast, and the catholyte containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt generated in incrustation scale nucleus generation unit is then discharged by the sewage draining exit of cell body bottom.Barrier film in the electrochemistry incrustation scale removal device that the application provides makes mutually not disturb between anode electrochemical product and electrochemical cathode product, generate the catholyte containing a large amount of nucleus in cathode compartment, a large amount of nucleus is crystal growing surface and the crystal Active Growth point that scale-forming ion in solution provides super large; Due to much larger times of the surface area ratio cathodic surface area of a large amount of small nucleus, the probability of scale-forming ion crystallization increases greatly, and scale removal efficiency also just increases.
In this application, described incrustation scale nucleus generation unit preferably also comprises supporting electrode 4, and described supporting electrode 4 is arranged in cathode compartment.In some embodiment of the application, described incrustation scale nucleus generation unit preferably also comprises plastic wire 21, and described plastic wire 21 is set to bag-shaped, and barrier film is placed among mesh bag, protects the damages such as barrier film is not punctured; In this application, the decomposing schematic representation of described barrier film 20, supporting electrode 4 and plastic wire 21, as shown in Figure 3, supporting electrode 4 is in the cathode compartment side of barrier film 20, and plastic wire 21 is in the side, anolyte compartment of barrier film 20; Supporting electrode 4, barrier film 20 and plastic wire 21 are fitted together, as shown in Figure 4, Fig. 4 is the assembling schematic diagram of embodiment septation 20 provided by the invention, supporting electrode 4 and plastic wire 21.
In this application, described incrustation scale nucleus generation unit preferably also comprises negative electrode scraper 5, and described negative electrode scraper 5 can directly be fixed on the draw-in groove of the upper head plate of cell body 1, as shown in Figure 2.In this application, incrustation scale nucleus generation unit preferably also comprises supporting electrode 4, and described supporting electrode is between negative electrode 2 and anode 3; Described supporting electrode 4 is preferably net-shaped stability supporting electrode; Negative electrode scraper 5 is provided with between described supporting electrode 4 and negative electrode 2, described supporting electrode 4 is provided with scraper and fixes ear 16, the scraper that described negative electrode scraper 5 also can be arranged on supporting electrode 4 is fixed on ear 16, scheme of installation as shown in Figure 5 and Figure 6, the decomposing schematic representation of the installation site of the negative electrode scraper that Fig. 5 provides for the embodiment of the present invention; The assembling schematic diagram of the installation site of the negative electrode scraper that Fig. 6 provides for the embodiment of the present application.When negative electrode scraper is fixed together with supporting electrode, in an embodiment of the present invention, the rotation of negative electrode scraper can drive negative electrode scraper to rotate by rotating supporting electrode, is wiped off by the incrustation scale that cathode surface generates; Described negative electrode scraper can carry out intermittence with the circular frequency of 5rpm ~ 30rpm and rotate, and the intermittent time is 5min ~ 30min.In this application, the material of described negative electrode scraper 5 is for strengthening polymkeric substance or pottery, and described enhancing polymkeric substance is preferably reinforced plastics; The shape of described negative electrode scraper can be rectangular shape, and length can be consistent with the length of negative electrode, also can need to regulate with the length adjustment of negative electrode according to processing power.In the embodiment of the application, described negative electrode scraper is preferably 4, and 4 negative electrode scrapers preferably according to square pitch arrangement, and are preferably fixed as the caged thing of self stabilization by three circular supports; Described circular support reinforced plastics is made; Caged thing can be fixed on the end plate of one end of cell body 1, as shown in Figure 1; Also can be fixed on the end plate at two ends up and down of cell body 1, as shown in Figure 2.In this application, the incrustation scale that negative electrode 2 generates on the surface, by elastic device and described negative electrode 2 and surface elasticity close contact, strikes off by described negative electrode scraper 5; Described close contact physical significance, for contact is apart from the smaller the better, is infinite approach.In this application, be provided with elastic device in the side of negative electrode scraper, described elastic device one end acts on negative electrode scraper, and the other end acts on scraper and fixes on ear, and negative electrode scraper can move horizontally under the promotion of elastic device; When between negative electrode scraper is due to negative electrode during frictionloss, elastic device can promote negative electrode scraper to be continued to keep and negative electrode close contact.In the embodiment of the present application, described elastic device can be specially spring.In electrochemical process, a part of nucleus sticks to cathode surface, and a part of nucleus is diffused in cathode compartment by the relative movement between negative electrode scraper and negative electrode.
The cell body of the below correspondence of the supporting electrode 4 of the electrochemistry incrustation scale removal device that the application provides is provided with Anode chamber inlets 15, described Anode chamber inlets 15 is provided with unidirectional facility, only allow the aqueous solution to flow into anolyte compartment 18, do not allow anolyte to flow out anolyte compartment 18 from Anode chamber inlets 15.
In this application, when electrochemical cell normally works, anode 3 is in conducting state, and supporting electrode 4 is in off-state; During electrochemical cell cleaning and regeneration, anode 3 is in off-state, and supporting electrode 4 is in conducting state, and negative electrode 2 is when electrochemical cell normally works with cleaning and regeneration, is in conducting state all the time.
The electrochemistry incrustation scale removal device that the application provides preferably also comprises incrustation scale nucleus growth separating unit, the structure of described incrustation scale nucleus growth separating unit as shown in Figure 7, the electrochemistry incrustation scale removal device schematic diagram that Fig. 7 provides for the embodiment of the present application.In the figure 7, 2 is negative electrode, 3 is anode, 17 is cathode compartment, 18 is anolyte compartment, 20 is barrier film, 22 is accurate filter, 23 is clean water basin, 24 is detritus pool, 25 is detritus pool supernatant liquor reflux pump, 26 is under meter, 27 is negative electrode water inlet storage tank, 28 is mud-removing bucket outlet, 29 is body refuse, 30 is electrolysis power, 31 is cathode compartment service pump, 32 is anode water inlet storage tank, 33 is anolyte compartment's service pump, 34 is hydrocyclone separation technology district, 35 is commutating zone, 36 is sloping plate deposition district, 37 is filtrating area, 38 is mud-removing bucket, 39 is catholyte pH value on-line detector, 40 is circulating water inlet road, 41 is cathode compartment inlet channel, 42 is cathode compartment service pump reflux line, 43 is anolyte compartment's inlet channel, 44 is catholyte outlet conduit, 45 is anolyte outlet conduit, 46 is circulatior clarifier outlet conduit, 47 is acid-base neutralisation pond outlet conduit, 48 is filter outlet pipe road, 49 is detritus pool supernatant liquor reflux line, 50 is flocculant concentration mouth, 51 is the anolyte in anolyte compartment's outlet conduit, 52 is acid-base neutralisation pond water outlet pH value on-line detector, 53 is automatic regulating valve door, 54 is acid-base neutralisation pond, .
Pending water is entered into negative electrode water inlet storage tank 27 and anode water inlet storage tank 32 by inlet channel 40 by the application respectively; The output terminal of negative electrode water inlet storage tank 27 is connected with cathode compartment inlet channel 41, described cathode compartment inlet channel is provided with cathode compartment service pump 31, negative electrode water inlet storage tank 27 is under the effect of cathode compartment service pump 31, by cathode compartment inlet channel 41, recirculated water is transported to cathode compartment 17, cathode compartment inlet channel is provided with under meter 26, described under meter 26 measures flooding quantity, if flooding quantity is too much, by cathode compartment service pump reflux line 42, superfluous water is back to negative electrode water inlet storage tank 27; The output terminal of anode water inlet storage tank 32 is connected with anolyte compartment's inlet channel 43, described anolyte compartment inlet channel is provided with anolyte compartment's service pump 33, pending water, under the effect of anolyte compartment's service pump 33, is transported to anolyte compartment 18 by anolyte compartment's inlet channel 43 by described anode water inlet storage tank 32; Anode 3 is connected with the positive pole of electrolysis power 30, and negative electrode 2 is connected with the negative pole of electrolysis power 30, starts electrolysis power, and start electrochemical reaction, electrochemical reaction process, as described in technique scheme, does not repeat them here.
The incrustation scale nucleus growth separating unit that the application provides is connected by the water outlet of pipeline with the incrustation scale nucleus generation unit described in technique scheme.The incrustation scale nucleus growth separating unit that the application provides comprises hydrocyclone separation technology district 34, commutating zone 35, sloping plate deposition district 36, filtrating area 37 and sludge discharging area bucket 38.
The incrustation scale nucleus growth separating unit that the application provides comprises hydrocyclone separation technology district 34, and described hydrocyclone separation technology district 34 is connected with cathode compartment 17 by catholyte outlet conduit 44.In this application, the pH value of the catholyte of discharging from cathode compartment is measured by catholyte pH value on-line detector 39, together with the flocculation agent that the catholyte containing a large amount of incrustation scale nucleus of alkalescence and flocculant concentration mouth 50 are injected, hydrocyclone separation technology district is entered by tangential direction, incrustation ion in nucleus and catholyte is in hydrocyclone separation technology district spiral, collide between the nucleus generated in scale-forming ion in water and nucleus generation unit, scale-forming ion grows in the basic conditions further on nucleus, and crystal is grown up further; Mutually collide between crystal, class occurs and reunites, the crystal grain of growing up or the larger alumen ustum formed under flocculation agent effect enter sludge discharging area under the influence of centrifugal force, also have the slightly little crystal grain of part to rise to commutating zone 35.
The incrustation scale nucleus growth separating unit that the application provides comprises commutating zone 35, and described commutating zone is above hydrocyclone separation technology district.In this application, less crystal grain then further growth and the reunion in commutating zone 35 is entered.In commutating zone 35, catholyte smooth flow, then enters sloping plate deposition district 36.
The incrustation scale nucleus growth separating unit that the application provides comprises sloping plate deposition district 36, and described sloping plate deposition district 36 is above commutating zone 35.In this application, crystal grows with reunion or flocculates into slightly large scale crystal in described sloping plate deposition district 36, and precipitates under gravity.
The incrustation scale nucleus growth separating unit that the application provides comprises mud-removing bucket 38, and described mud-removing bucket 38 is in the below of hydraulic cyclone area 34.The application does not have special restriction to described mud-removing bucket, adopts mud-removing bucket well known to those skilled in the art.In this application, described incrustation scale nucleus growth separating unit preferably also comprises body refuse pond 24, and described body refuse pond 24 is connected with mud-removing bucket 38 by mud-removing bucket outlet 28; Body refuse is discharged in body refuse pond 24 by described mud-removing bucket 38 together with water, and the body refuse 29 depositing to bottom is disposed separately.Supernatant liquor in detritus pool, then under the effect of detritus pool supernatant liquor reflux pump 25, enters into pending water by detritus pool supernatant liquor backflow 49.
The incrustation scale nucleus growth separating unit that the application provides preferably also comprises filtrating area 37, and described filtrating area 37 is above sloping plate deposition district 36.In this application, the incrustation scale nucleus formed under electrolytic action mostly is aragonite crystallization, mostly is the crystal cluster of porous, slightly larger than the proportion of water, and filtrating area 37 is for tackling the scale crystal of escape.In the embodiment of the application, described filtrating area 37 can be specially filtering net; Described filtering net can be metal net, also can be nylon monofilament net; The aperture of described filtering net can be 10 μm ~ 120 μm, also can be 90 μm ~ 100 μm.
In this application, the output terminal of filtrating area 37 is connected with acid-base neutralisation pond 54 by circulatior clarifier outlet conduit 46; Water after filtrating area 37 processes enters into acid-base neutralisation pond 54 by circulatior clarifier outlet conduit 46, pH value in acid-base neutralisation pond is regulated and can be regulated by anolyte, the pH value in described acid-base neutralisation pond is measured by acid-base neutralisation pond water outlet pH value on-line detector 52, and described acid-base neutralisation pond water outlet pH value on-line detector 52 is arranged on the output terminal in acid-base neutralisation pond; Anolyte outlet conduit 45 is provided with variable valve 53, and the anolyte 51 in anolyte compartment's outlet conduit is used for adjust ph by a part for anolyte outlet conduit 45 by described variable valve 53; Described variable valve 53 is controlled by online pH detector; The pH value of the water outlet in described acid-base neutralisation pond controls between 7 ~ 8.
In this application, the water outlet in acid-base neutralisation pond is transported in accurate filter 22 by acid-base neutralisation pond outlet conduit 47, and the water side of described accurate filter 22 is connected with clean water basin 23 by filter outlet pipe road 48.The application does not have special restriction to described accurate filter, adopts accurate filter well known to those skilled in the art.Directly enter into clean water basin 23 through the water of accurate filter to store, complete the dirty removing processing of water, for subsequent use.
Particularly, in the embodiment of the application, the process that electrochemistry removes incrustation scale is as follows:
Pending water is entered into cell body 1 from the water-in of cell body 1, anode terminal 7 and supporting electrode terminal stud 9 are connected to the positive pole of electrolysis power, negative electrode 2 is connected with drive-motor by coupling shaft, coupling shaft, as the wire of negative electrode, coupling shaft is fixed copper ring 8 is connected to direct supply negative pole by carbon brush 13; The line of the aqueous solution in cell body 1, anode 3, negative electrode 2 and electrolysis power, form closing current loop, barrier film 20 is divided into cathode compartment and anolyte compartment by corresponding for cell body, will start electrolysis power, starts electrochemical reaction occurs near anode and negative electrode; In the anode compartment, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water, maintains the sterile environment that reaction chamber is inner stronger; Chlorion is oxidized generation chlorine near anode, and chlorine and water are further combined with generating hypochlorous acid and hydrochloric acid, and hypochlorite (ClO-) has lasting bacteriostatic action; In the cathodic compartment, near negative electrode interfacial layer obtain pH value up to 14 strong alkali solution, calcium carbonate and magnesium hydroxide are in hypersaturated state in interfacial layer, calcium carbonate and magnesium hydroxide possess the condition generating nucleus fast in cathode surface and interfacial layer, cathode surface is departed from and interfacial layer is diffused in catholyte in the hydroxide radical that negative electrode produces and the relative movement of established nucleus between scraper and negative electrode, nucleus is generated further in catholyte, the then further growth of existing nucleus, along with the carrying out of reaction, obtain the catholyte containing a large amount of nucleus; Subsequently the tangential direction that catholyte is exported by catholyte is entered nucleus growth separating unit together with flocculation agent, scale-forming ion in nucleus and catholyte rotates in eddy flow hybrid reaction district spirrillum, nucleus further growth, nucleus are reunited, and the nucleus particle after growing up or the throw out of flocculation enter mud-removing bucket under the influence of centrifugal force and be removed; Part scale crystal then through eddy flow mixing and precipitation catholyte behind commutating zone, enter the further precipitate and separate in tube settling district, complete the dirty removing processing of high hardness water.
Electrochemistry incrustation scale removal device provided by the invention can be used in circulating water treatment, be arranged in cooling circulating water system with the form of by-pass flow, circulating water system is constantly evaporated by cooling tower, mineral substance in recirculated water is concentrated, concentrated degree represents with cycles of concentration, often adopt the cycles of concentration of cycles of concentration as this circulating water system of more stable certain ion calculating, such as potassium ion, chlorion.Such as, if in addition comparatively cycles of concentration is low, illustrates that calcium ion has crystallization, calcium ion and bicarbonate ion for the ratio ratio of (ionic concn in recirculated water with this ionic concn in make up water) that calculates of ion.
According to different moisturizing water quality and circulating water system feature, usually can control different cycles of concentration, to ensure that the mineral substance in recirculated water can not work the mischief to circulating water system, such as fouling causes heat exchange efficiency decline, chlorine ion concentration is too high causes corrosion etc.
The water quality of the present invention to the Inlet and outlet water of the electrochemistry incrustation scale removal device through providing is analyzed, and detailed process is:
Pending water is introduced electrochemistry incrustation scale removal device, cathode diameter is 200mm, and cathode length is 800mm, and flow is 5m
3/ h, strength of current is 15A, water temp is 20 DEG C, every half hour respectively from import and outlet sampling analysis calcium ion hardness, methyl orange alkalinity, magnesium ion hardness, the chlorine ion concentration of this device, analysis water-like 40 altogether, average result as following table 1, the water quality detection average result that the incrustation scale removal device that table 1 provides for the embodiment of the present invention is imported and exported.
The water quality detection average result that the incrustation scale removal device that table 1 provides for the embodiment of the present invention is imported and exported
Note: total hardness, basicity and calcium hardness are all with CaCO
3meter.
In order to furtherly with bright the present invention, below in conjunction with embodiment, a kind of electrochemistry incrustation scale removal device provided by the invention is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
Be arranged in cooling circulating water system by two electrochemistry incrustation scale removal devices with the form of by-pass flow, quantity of circulating water is 1200m
3/ h, adopt the electrochemistry incrustation scale nucleus generation unit device two shown in Fig. 1 to overlap, total treatment capacity of this electrochemistry incrustation scale nucleus generation unit is 40m
3/ h, be that the pending water of 15 ~ 35 DEG C enters into cell body by the water-in of cell body by temperature, barrier film is provided with in described cell body, cell body is divided into cathode compartment and anolyte compartment by barrier film, rotating cathode is arranged in cathode compartment, the diameter of rotating cathode is 500mm, and length is 800mm, and the angular velocity of rotation of rotating cathode is 10rpm; Anode is in anolyte compartment, and the aqueous solution in rotating cathode, anode, cell body and electrolysis power form closing current loop; Start electrolysis power, size of current is 30A, starts electrochemical reaction occurs near anode and rotating cathode; Near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Near rotating cathode, aqueous electrolysis produces OH
-, near rotating cathode, interfacial layer obtains strong alkali solution, and the incrustation scale nucleus formed on rotating cathode surface in electrochemical process and in interfacial layer is diffused in solution by rotating electrode, and the solution containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt that in incrustation scale nucleus generation unit, negative electrode scraper scrapes then is discharged by the sewage draining exit of cell body bottom;
Catholyte containing a large amount of nucleus is discharged by the pipeline be connected with catholyte water outlet, enters incrustation scale nucleus growth separating unit; Scale-forming ion in nucleus and catholyte rotates in eddy flow hybrid reaction district spirrillum, nucleus further growth, nucleus are reunited, nucleus major part after growing up comes together in mud-removing bucket zone center and is removed, through eddy flow mixing and precipitation catholyte behind commutating zone, enter the further precipitate and separate in tube settling district; Water behind tube settling district is the filtering net interception scale crystal of 90 μm again through aperture; Adjust ph after water after filtering net mixes with the anolyte of above-mentioned generation, is transported to pond of cooling tower by water, completes the dirty removing processing of water;
This device runs 6 months continuously, and detect weekly the water quality of moisturizing and recirculated water, average result is listed in the table below 2, and table 2 is the Analysis Results of Water Quality of the embodiment of the present invention 1.
Table 2 is the Analysis Results of Water Quality of the embodiment of the present invention 1
As can be seen from Table 2, from ionic concn ratio calculation result, the cycles of concentration of recirculated water counts 3.6 times with potassium ion; Wherein methyl orange alkalinity is the result adding sulfuric acid neutralization, and some is stripping in cooling tower, and cycles of concentration can not illustrate electrochemical appliance removal efficiency; And open circulating water system inspection interchanger and pipeline, do not find obvious incrusted deposit, illustrate that the loss of calcium hardness and total alkalinity is that electrochemistry incrustation scale removal device is removed.Calculate according to cycles of concentration, the calcium hardness in recirculated water is with CaCO
3meter should be 322.5mg/L, and actual calcium hardness is with CaCO
3meter is only 139.0mg/L, and accumulative removal efficiency is 56.9%; The cycles of concentration of magnesium hardness is 2.4, and accumulative removal efficiency is 34.0%.
Embodiment 2
Be arranged in cooling circulating water system by two electrochemistry incrustation scale removal devices with the form of by-pass flow, quantity of circulating water is 1150m
3/ h, adopt the electrochemistry incrustation scale nucleus generation unit device two shown in Fig. 2 to overlap, total treatment capacity of this electrochemistry incrustation scale nucleus generation unit is 40m
3/ h, be that the pending water of 20 ~ 40 DEG C enters into cell body by the water-in of cell body by temperature, the aqueous solution in rotating cathode, anode, cell body and electrolysis power form closing current loop, described rotating cathode diameter is 500mm, rotating cathode length is 800mm, and the angular velocity of rotation of rotating cathode is 30rpm; Start electrolysis power, size of current is 40A, starts electrochemical reaction occurs near anode and rotating cathode; Near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Near rotating cathode, aqueous electrolysis produces OH
-, near rotating cathode, interfacial layer obtains strong alkali solution, and the incrustation scale nucleus formed on rotating cathode surface in electrochemical process and in interfacial layer is diffused in solution by rotating electrode, and the solution containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt generated in incrustation scale nucleus generation unit is then discharged by the sewage draining exit of cell body bottom;
Catholyte containing a large amount of nucleus is discharged by the pipeline be connected with catholyte water outlet, enters incrustation scale nucleus growth separating unit; Scale-forming ion in nucleus and catholyte rotates in eddy flow hybrid reaction district spirrillum, nucleus further growth, nucleus are reunited, nucleus major part after growing up comes together in mud-removing bucket and is removed, through eddy flow mixing and precipitation catholyte behind commutating zone, enter the further precipitate and separate in tube settling district; Water behind tube settling district is the filtering net interception scale crystal of 100 μm again through aperture; Water after filtering net and above-mentioned anolyte compartment produce water and mix adjust ph, and direct water is transported to pond of cooling tower, completes the dirty removing processing of water; In cooling tower pH value adopt further add sulfuric acid regulate reach service requirements;
This device runs 12 months continuously, and detect weekly the water quality of moisturizing and recirculated water, average result is listed in the table below 3, and table 3 is the Analysis Results of Water Quality of the embodiment of the present invention 2.
Table 3 is the Analysis Results of Water Quality of the embodiment of the present invention 2
As can be seen from Table 3, from ionic concn ratio calculation result, the cycles of concentration of recirculated water is 5.9 times with chloride ion.And open circulating water system inspection interchanger and pipeline, do not find obvious incrusted deposit, illustrate that the loss of calcium hardness and total alkalinity is that electrochemistry incrustation scale removal device is removed.Calculate according to cycles of concentration, the calcium hardness in recirculated water should be that 264.9mg/L is (with CaCO
3meter), and actual calcium hardness is only 78.5mg/L (with CaCO
3meter), accumulative removal efficiency is 70.4%; The cycles of concentration of magnesium hardness is 4.3, and accumulative removal efficiency is 27.9%.
Embodiment 3
Be arranged in cooling circulating water system by four electrochemistry incrustation scale removal devices with the form of by-pass flow, quantity of circulating water is 3000m
3/ h, adopt the electrochemistry incrustation scale nucleus generation unit device four shown in Fig. 1 to overlap, total treatment capacity of this electrochemistry incrustation scale nucleus generation unit is 100m
3/ h, be that the pending water of 20 ~ 35 DEG C enters into cell body by the water-in of cell body by temperature, barrier film is provided with in described cell body, cell body is divided into cathode compartment and anolyte compartment by barrier film, rotating cathode is arranged in cathode compartment, the diameter of rotating cathode is 500mm, and length is 800mm, and the angular velocity of rotation of rotating cathode is 15rpm; Anode is in anolyte compartment, and the aqueous solution in rotating cathode, anode, cell body and electrolysis power form closing current loop; Start electrolysis power, size of current is 72A, starts electrochemical reaction occurs near anode and rotating cathode; Near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Near rotating cathode, aqueous electrolysis produces OH
-, near rotating cathode, interfacial layer obtains strong alkali solution, and the incrustation scale nucleus formed on rotating cathode surface in electrochemical process and in interfacial layer is diffused in solution by rotating electrode, and the solution containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt that in incrustation scale nucleus generation unit, negative electrode scraper scrapes then is discharged by the sewage draining exit of cell body bottom;
Catholyte containing a large amount of nucleus is discharged by the pipeline be connected with catholyte water outlet, enters incrustation scale nucleus growth separating unit; Scale-forming ion in nucleus and catholyte rotates in eddy flow hybrid reaction district spirrillum, nucleus further growth, nucleus are reunited, nucleus major part after growing up comes together in mud-removing bucket zone center and is removed, through eddy flow mixing and precipitation catholyte behind commutating zone, enter the further precipitate and separate in tube settling district; Water behind tube settling district is the filtering net interception scale crystal of 50 μm again through aperture; Water after filtering net is transported to pond of cooling tower, completes the dirty removing processing of water;
This device runs 6 months continuously, and detect weekly moisturizing and detect the water quality of recirculated water every day, average result is listed in the table below 4, and table 4 is the Analysis Results of Water Quality of the embodiment of the present invention 3.
Table 4 is the Analysis Results of Water Quality of the embodiment of the present invention 3
As can be seen from Table 4, from ionic concn ratio calculation result, the cycles of concentration of recirculated water is 3.1 times with chloride ion; And open circulating water system inspection interchanger and pipeline, do not find obvious incrusted deposit, illustrate that the loss of calcium hardness and total alkalinity is that electrochemistry incrustation scale removal device is removed.Calculate according to cycles of concentration, the calcium hardness in recirculated water is with CaCO
3meter should be 1085mg/L, and actual calcium hardness is with CaCO
3meter is only 487mg/L, and accumulative removal efficiency is 55%; The cycles of concentration of magnesium hardness is 2.6, and accumulative removal efficiency is 15%.
Comparative example
Be arranged in cooling circulating water system by commercially available two cover electrochemistry incrustation scale removal devices with the form of by-pass flow, quantity of circulating water is 1400m
3/ h, the treatment capacity of two cover electrochemistry incrustation scale removal devices is 50m
3/ h, Faradaic current intensity is 36A, and water temp is 28 ~ 32 DEG C; This electrochemistry incrustation scale removal device is the columned container that a carbon steel manufactures, and diameter is approximately 600mm, and be 900mm deeply, this cylindrical container doubles as the negative electrode of electrolytic reaction; Be fixed on carbon steel lid and have three anodes and a Pneumatic scraper, anode and scraper are all placed in cylindrical container, do not separate between negative electrode and positive electrode; Anode posts diameter is approximately 25mm, directly reaches container bottom; Titanium electrode nickel oxide is made, so that the low pH environment in tolerance local, is used for wiping inwall preliminary precipitation mineral substance out when circular plastic spatula cleans at every turn.
Cleaning interval is 6 hours, and scavenging period is 2 minutes, and when each cleaning starts, two electrical ball valves control the flow direction of the water flowed in this device; The first step of cleaning, imported valve is closed, and the sewage draining valve of this bottom of device is opened; Scraper moves from top to bottom under the promotion of piston in reaction chamber, wipes the incrustation scale be precipitated out in advance that inwall is soft off, and discharges from bottom together with wash-down water; When blowdown, inlet valve is opened, to rinse discharge areas; After about 2 minutes, sewage draining valve is closed, and the top of reaction chamber got back to by scraper, and flowing water Valve is opened, and this device is reworked.
When starting electrolytic process, start electrochemical reaction occurs near anode and rotating cathode; Near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Near cylindrical container inwall negative electrode, aqueous electrolysis produces OH
-, near negative electrode, interfacial layer obtains strong alkali solution, and incrustation scale is separated out in cathodic deposition, and regular cylinder starts discoid scraper, wipes incrustation scale off, outside bottom blow-down valve discharge system.Water after this device electrochemical treatment directly gets back to pond of cooling tower, completes the dirty removing processing of water;
This device runs 12 months continuously, and detect weekly the water quality of moisturizing and recirculated water, average result is listed in the table below 5, and table 5 is the Analysis Results of Water Quality of comparative example of the present invention.Basicity throws the result after acid neutralization, and cycles of concentration can not the removal efficiency of devices illustrated.
The Analysis Results of Water Quality that table 5 is comparative example of the present invention
As can be seen from Table 5, from ionic concn ratio calculation result, the cycles of concentration of recirculated water counts 3.6 times with potassium ion.And open circulating water system inspection interchanger and pipeline, do not find obvious incrusted deposit, illustrate that the loss of calcium hardness and total alkalinity is that electrochemistry incrustation scale removal device is removed.Calculate according to cycles of concentration, the calcium hardness in recirculated water should be that 909.0mg/L is (with CaCO
3meter), and actual calcium hardness is only 645.6mg/L (with CaCO
3meter), accumulative removal efficiency is 29.0%; The cycles of concentration of magnesium hardness is 3.3, and accumulative removal efficiency is 9.4%.
As seen from the above embodiment, this application provides a kind of electrochemistry incrustation scale removal device, comprise the incrustation scale nucleus generation unit for electro-chemical water process, described incrustation scale nucleus generation unit comprises cell body; The bottom of described cell body is provided with water-in and sewage draining exit; Negative electrode with the inside of described cell body is set; Anode with the inside of described cell body is set; Barrier film with the inside of described cell body is set; Described barrier film is divided into cathode compartment and anolyte compartment by corresponding for cell body; The top of described cell body is provided with anolyte water outlet and catholyte water outlet.In the electrochemistry incrustation scale removal device that the application provides, pending water is entered incrustation scale nucleus generation unit from water-in bottom cell body, carries out electrochemical treatment, near anode, water electrolysis produces oxygen and oxyradical, generates hydrogen peroxide and ozone with the dissolved oxygen in water and water; Chlorion is oxidized to chlorine near anode, and chlorine is combined with water further and generates hypochlorous acid and hydrochloric acid, and hypochlorite (ClO-) has lasting bacteriostatic action; Near negative electrode, aqueous electrolysis produces OH
-near negative electrode, interfacial layer obtains strong alkali solution, the existence of barrier film, by catholyte and anolyte shunting, mutually do not disturb between anode electrochemical product and electrochemical cathode product, the catholyte of pH value more than 9.5 is obtained in cathode compartment, in interfacial layer near cathode surface and cathode surface, pH value reaches more than 14, scale-forming ion degree of supersaturation in high ph-values environment like this is very high, oversaturated scale-forming ion forms nucleus fast, and the catholyte containing a large amount of incrustation scale nucleus discharges cell body from the water outlet on cell body top; The dirt generated in incrustation scale nucleus generation unit is then discharged by the sewage draining exit of cell body bottom.Barrier film in the electrochemistry incrustation scale removal device that the application provides makes mutually not disturb between anode electrochemical product and electrochemical cathode product, generate the catholyte containing a large amount of nucleus in cathode compartment, a large amount of nucleus is crystal growing surface and the crystal Active Growth point that scale-forming ion in solution provides super large; Due to much larger times of the surface area ratio cathodic surface area of a large amount of small nucleus, the probability of scale-forming ion crystallization increases greatly, and scale removal efficiency also just increases.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. an electrochemistry incrustation scale removal device, comprise for electro-chemical water process incrustation scale nucleus generation unit, described incrustation scale nucleus generation unit comprises cell body;
The bottom of described cell body is provided with water-in and sewage draining exit;
Be arranged at the barrier film of the inside of described cell body;
Cell body is divided into cathode compartment and anolyte compartment by described barrier film;
Be arranged at the negative electrode of the inside of described cathode compartment;
Be arranged at the anode of the inside of described anolyte compartment;
The top of described cell body is provided with catholyte water outlet and anolyte water outlet.
2. electrochemistry incrustation scale removal device according to claim 1, is characterized in that, described barrier film is cationic membrane.
3. electrochemistry incrustation scale removal device according to claim 1, it is characterized in that, described barrier film is fixed together with described anode.
4. electrochemistry incrustation scale removal device according to claim 1, is characterized in that, described negative electrode is carbon steel cathodes, stainless steel cathode, Ti cathode, titanium alloy negative electrode or aluminium alloy negative electrode.
5. electrochemistry incrustation scale removal device according to claim 1, is characterized in that, described negative electrode is cylindric.
6. electrochemistry incrustation scale removal device according to claim 1, is characterized in that, the inside of described cell body also comprises negative electrode scraper;
The two ends up and down of described cell body are end plate, and upper head plate is provided with draw-in groove;
Described negative electrode scraper is fixed on separately on the draw-in groove of the upper head plate of described cell body.
7. the electrochemistry incrustation scale removal device according to claim 5 or 6, is characterized in that, described incrustation scale nucleus generation unit comprises and also comprises supporting electrode;
Described supporting electrode is positioned at cathode compartment.
8. electrochemistry incrustation scale removal device according to claim 7, it is characterized in that, described barrier film is fixed together with supporting electrode.
9. electrochemistry incrustation scale removal device according to claim 8, is characterized in that, described supporting electrode is net-shaped stability supporting electrode.
10. electrochemistry incrustation scale removal device according to claim 1, is characterized in that, described negative electrode is tubular, and described anode arrangement is within the cylindrical chamber of negative electrode.
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