CN1246869C - Flow-through capacitor and method - Google Patents

Flow-through capacitor and method Download PDF

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CN1246869C
CN1246869C CN 00812144 CN00812144A CN1246869C CN 1246869 C CN1246869 C CN 1246869C CN 00812144 CN00812144 CN 00812144 CN 00812144 A CN00812144 A CN 00812144A CN 1246869 C CN1246869 C CN 1246869C
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capacitor
electrode
surface area
electrode material
gram
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CN1371521A (en
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马奇·D·安德曼
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BAIO RESOURCE Co
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Molecular Biology (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

A flow-through capacitor and method for the purification of fluids, like soft water. The capacitor includes anode-cathode electrodes (3) composed of a low surface area electrode material having a surface area between 10 to 1000 square meter per gram BET (Brunauer Emmett Teller method) to form one or more cells.

Description

Circulated capacitor and method
In first to file:
The application's basis and priority are the U.S. temporary patent applications, and sequence number is 60/146,397, and the applying date is 1999.7.30, is hereby incorporated by.
Background technology:
Circulation (flow-through) capacitor of use high surface area electrode is used for water purification and has obtained commercial confirmation and a lot of patent applications are arranged, for example, Andelman U.S. patent 5,192,432, open day is 1993.3.9; Patent 5,196,115, open day is 1993.3.23; Patent 5,200,068, open day is 1993.4.6; Patent 5,360,540, open day is 1994.11.1; Patent 5,415,768, open day is 1995.5.16; Patent 5,547,581, open day is 1996.8.20; Patent 5,620,597, open day is 1997.4.15; Patent 5,748,437, open day is 1998.5.5; Patent 5,779,891, open day is 1998.7.14; Otowa U.S. patent 5,538,611, open day is 1996.7.23; Farmer U.S. patent 5,425,858, open day is 1995.6.20; BenakU.S patent 3,658,674, open day is 1972.4.25, they have all described the use of high surface area material.These materials have the high surface that is formed by the carbon that comprises activated carbon powder, active carbon cloth and aeroge usually.For example; Otowa U.S. patent 5,538,611 claimed surface areas (are seen the 6th hurdle greater than the use of the activated carbon of about 1000B.E.T usually; 29-33 is capable); and the use that Andelman U.S. patent 5,620,597 has been described 2000 square metres of in circulated capacitor every gram activated carbon (is seen the 14th hurdle; 8-10 is capable); U.S. patent 6,620, and 597 have described in fact by any corrosion-resistant, circulated capacitor electrode (seeing that the 4th hurdle the 51st walks to the 5th hurdle the 16th row) that high surface area material is formed.U.S. patent 5,196, and 115,5,192,432,5,200,068 has all described the use of high surface area material.U.S. patent 5,547, and 581 have narrated every gram greater than about 1000 square metres high surface area material (seeing the 14th hurdle the 7th row).U.S. patent 5,425,858 have stipulated to use high surface coefficient aeroge (seeing that the 5th hurdle 66-69 is capable) and described the use with high especially surface coefficient silica aerogel electrode in the circulated capacitor structure, for example, and 400 to 1000 square metres of every grams (seeing that the 5th hurdle the 66th walks to the 6th hurdle the 1st row).
The example that the circulated capacitor of many use low surface areas and high resistance electrode is equally also arranged.Thereby this may be owing to use inherent insulating material or influenced the bulk conductivity characteristic unfriendly owing to added the inert material or the adhesive of enough insulation.For example, Electrochemical Demineralizatin of Water with Carbon Electrodes (the U.S.Department of the Interior Research and Development Progress ReportNo.188 that delivers by Danny D.Caudel etc., in May, 1996) use of the circulated capacitor with carbon electrode described in a literary composition.Table III in this publication has been described the demineralisation as a kind of function of surface area.This works has mainly been described the use of the carbon black electrode of listing backing material in, and this backing material adds considerable insulating material in electrode, and has therefore produced high resistance.The carbon of all uses is low surface area, and promptly every gram is lower than 1000 square metres but all combine the inertia high-resistance material.All anode-cathodes of listing are to comprising that at least a kind of to have low surface area be that every gram is lower than 310 square metres material.
Yet the straight-through resistance of listing to the Table III in Table I (through resistance) is very high, promptly surpasses 0.5 ohm, and normally above 1 ohm.Although the publication of Caudle uses high conductivity carbon black and graphite in electrode, because (for example, Caudle has described a kind of calendared DARCRON in conjunction with conductive carbon black from powdery conductive carbon black material The use of (E.I.duPont de Nemours and Company of Wilmington, the registered trade mark of Delaware) (seeing the 66th page)) use of a large amount of inert binder materials of the single electrode of making is so the electrode of making has high resistance.
Summary of the invention:
The present invention relates to a kind of circulated capacitor, the electrode that in this capacitor, uses, and a kind of method of making and operating this circulated capacitor.
The present invention relates to a kind of circulated capacitor that is used to purify a kind of liquid, this capacitor comprises: a shell; In this shell, be used to introduce an inlet of liquid to be clean; An and outlet of the liquid after in this shell, being used to discharge purification.The present invention also comprises a plurality of electrodes of being made up of electrode material, so that be formed for one or more unit of decontaminating liquid, wherein, described electrode comprises an anode layer and a cathode layer.These layers are arranged and constructed to make liquid to flow between these layers and by described unit; And comprising a capacitor, the series resistance of each individual unit of this capacitor is approximately 0.03 ohm or littler; And comprise surface area and have the electrode material that every gram electric capacity surpasses about 1 farad electric capacity with about 10-1000 square metre of every gram B.E.T (Brunauer Emmett Teller method).
The present invention also provides a kind of circulated capacitor system that comprises above-mentioned capacitor, and this circulated capacitor system comprises power supply, and wherein, the resistance voltage from this power supply to this capacitor is reduced to 4 volts.
The invention provides a kind of method that is used to purify the water that comprises ionic contamination, wherein, this method comprises the following steps: a) to provide aforesaid circulated capacitor; B) water to be clean is incorporated in the inlet; C) discharge the water that ionic soil is crossed from outlet; D) get rid of the ionic contamination of collecting from capacitor.
An object of the present invention is to utilize low resistance, low surface area, high-capacitance material so that provide flow velocity with raising, higher energy efficiency and the better circulated capacitor of corrosion resistance.
Another object of the present invention provides the circulated capacitor that has low surface area and have the high conductive material that is lower than about 0.3 ohm of series resistance.
High resistance has limited the magnitude of current that can flow into capacitor.By the restriction electric current, high resistance also can limit the flow velocity of the water that may purify in circulated capacitor.Low resistance provides has the more circulated capacitor of macro-energy efficient, and this capacitor has the flow velocity faster of the employed capacitance material of every gram.Required underflow speed to should be every gram low surface area material per minute to surpass 1ml by obtaining 90% purification, preferably every gram low surface area material per minute surpasses 4ml.This should be applied to one and stride the concentration wide region, reaches 0.02N at least.Many low surface area materials are inherent conductions, so they do not need current-collector or to the contact that compresses of their current-collectors, so have reduced by a resistive element.
Because the electric capacity that material internal increases, thereby these high surface area materials of use prior art.The high surface area material of prior art need have high porosity or high texture, and these structures have reduced the bulk conductivity of material.Yet the high porosity of high surface area material inherence has increased volume resistivity.Therefore, the flow velocity of the material of each specified rate and energy efficiency have also reduced.Because the high resistance of those materials, the circulated capacitor of making of high surface area material requires higher operating voltage to come compensated voltage drop usually.Because therefore the oxidation or the corrosion of high surface area material have been emphasized material and have been reduced electrode life.Usually, when operation under voltage more than 1 volt and low surface area material when also coming in handy, the charging of low surface area material is faster and can utilize the higher amperage of every gram material, therefore can make circulated capacitor work.
Therefore, because the voltage drop that is caused by resistance during charge cycle is littler, relative with power end, the mean value of measured operating voltage will be lower in capacitor self.For example, power end can be powered 2 volts, and the inner voltage that is born of capacitor itself is preferably lower than 1 volt according to averaging between charge period.The residual electricity pressure drop drops in the lead that flows to capacitor and can not be used for the long-pending electrode material of oxidized surface or it is produced adverse influence.Owing to reduced oxidation and corrosion, thereby the harmonic(-)mean that provides operation charge cycle voltage has improved electrode life.Harmonic(-)mean operation cycle voltage of the present invention also makes energy utilize more fully.
In corrosion is not very important occasion, low resistance, low surface area material also can be worked under bigger electric current and voltage, therefore the flow velocity faster faster and that provide about every grams per minute to surpass 1ml that charges purifies, when requiring to increase flow velocity, preferably the electrode material per minute is approximately 4ml concerning 90% purification, and preferably operates circulated capacitor at every gram electrode material above under 50 milliamperes the situation.
High surface, high resistance capacitor that each given weight or volume of electrode material is had than slug flow speed prior art that purify, that charging is slower need move under the voltage that energy efficiency is lower in that numerical value is higher, so that the compensation high-resistance material.Therefore, however need the circulated capacitor that still has high specific capacitance that surface area reduces, resistance reduces.
For utilization has improved the improvement performance of electric energy efficiency, need the low resistance circulated capacitor.Usually, than the low surface area material, because of the porosity of its reduction and higher bulk density, thus have higher conductivity, unless it combines with a large amount of insulating material.Yet fortunately because their conductivity preferably, thus for low electrical resistant material as electric capacity, its more surface area is useful.Therefore because it has lower resistance, do not sacrifice electric capacity, increased extremely performance of flow velocity, energy efficiency simultaneously so can use than the low surface area material.
The present invention allow to use aeroge with low surface coefficient with utilize low surface area, than the conductivity of the increase in the low-porosity material.For example, the activated carbon powder, active carbon cloth, carbon black, aeroge, foam, glassy carbon, porous or veined graphite, have every gram and be lower than other active carbon materials of 400 square metres surface coefficient, also can be used as the circulated capacitor electrode, so that utilize those higher conductivity than the low surface area material.Yet for high ratio electric capacity is provided, surface area should not be lower than about 10 square metres of every gram.So use closeer, provide the bulk conductivity that strengthens than the low surface area material, therefore have higher performance.
Although be low surface area, because its low resistance and high capacitance, series connection platinum carbon black and conductive oxide still can be used as goodish electrode.Ruthenium-oxide, titanium oxide, other transition metal oxide, nitride, boride, and carbide, or the combination in them is a most preferred embodiment.Magneli phase titanium suboxide (titanium suboxide) is a kind of special electric conducting material, i.e. TiNO 2N-1, wherein (n) is the integer between 4 to 10.The low surface area ceramic electrode no matter be the integral body or the powder of sintering, all is bonded together with a kind of adhesive that comprises the polytetrafluoroethylene (PTFE) adhesive.
In the time of in being used in the bipolar electrode group, electroconductive oxide also covers with electrochemical method and is corrosion-resistant and anti-oxidant.Usually, inert material on the electrochemistry and conductivity ceramics can particulate, fiber, sintering, sheet or monolith forms use.With respect to the high-resistance material of describing in the above-mentioned prior art patent, these materials also have extremely beneficial low resistance.
Usually, the preferably every gram of the surface area of low surface area conductive electrode is lower than 400 square metres, but every gram is not less than 10 square metres.And do not require that surface area is too low, and or sacrifice than electric capacity, low excessively as the surface area of the granulated metal of simple sintering.Conductive electrode material should have enough surface areas to possess high ratio electric capacity, and preferably every gram is above 1 farad.It is selected that surface area between 400 square metres of 10 square metres of every grams and the every grams provides the optimal parameter of high ratio electric capacity and high conductivity.The porosity and the texture structure that match with this surface area values are needs.Between 10 to 400 square metres of every grams and have every cubic centimetre 0.1 gram or more highdensity low surface area close material provides every cubic centimetre high volume electric capacity or high capacitance.
Usually, can use to have high specific capacitance, and any anticorrosive, the high conductivity material of every gram surface area between 10 and 400 square metres.This electric capacity typically may be at every gram more than 1 farad or every cubic centimetre of capacitor volume more than 1 farad.The preferably every gram of this electric capacity is more than 10 farads or every cubic centimetre more than 10 farads.Resistance is lower than 0.03 ohm-cm typically, preferably is lower than 0.01 ohm-cm.The high conductive material that some resistance are lower than 0.03 ohm-cm may have the surface area of 400 square metres of a little higher than every grams, reaches 1000 square metres as every gram.For example, the nanotube of alignment or nanotube electrode usually may be between 100-1000 square metre of every grams, and have higher conductivity and the electric capacity of activated carbon, aeroge or carbon cloth than prior art.The resistance of nano-tube material is 0.001 ohm-cm or lower.The carbon black of some high conductivity such as Monarch1400, its surface area is compared it with the prior art material and is had electric capacity in 560 square metres of every grams, and resistance still is lower than 0.01 ohm-cm, this is than the area carbon material of prior art, and is lower as aeroge, activated carbon and carbon cloth.
Therefore, the capacitor that the nanotube that is lower than 1000 square metres by carbon black and every gram of low relatively surface area is made can provide has the more circulated capacitor of energy-efficient, the size of each given capacitor device or system is had purify flow velocity faster.
What make us feeling surprised is, although specific area is very low mutually than high resistance, the high surface area material of low surface area material and prior art, its electric capacity is very high.This is because utilized surface area better in low surface area, conductivity better material.Therefore, low surface area, low electrical resistant material are useful for the circulated capacitor that improvement in performance is provided.
Titanium foil and ruthenium-oxide material provide a kind of improved circulated capacitor that has low series resistance and each given electrode material measurer is had flow velocity purification faster.These materials may mix and use with independent use, are coated on the substrate or are coated on the current-collector and use.For example, ruthenium-oxide may be by plating, sintering, be coated on the current-collector substrate, comprises tantalum, titanium, graphite.In other words, the powder of these materials may be by sintering or by using a kind of polymeric binder, comprises that to form fibriilar PTFE bonding and form thin slice.U.S. patent 4,153, and 661 have described use PTFE and dusty material making sheeting.Can use surface area between 400 square metres of 10 square metres of every grams and every grams electrical conductivity Carbon black or the graphite of porous aggregate.The total amount of adhesive is lower than 10% in the PTFE electrode, normally is lower than 6%, so adhesive is encased in conductivity powdery electrode material in the electrode thin slice, and does not influence bulk conductivity significantly.
The electrode thin slice can be used as to be collector electrode or to use with the current-collector of conductive foil, polymer, graphite foil, metal or other conductions.May use every gram 10 to 400 square metres nanotube filler, comprise the nanotube of alignment.Present current-collector and electrode can be thin slice, lead or rod, or any geometry, thereby make it can be towards right by the separated anode-cathode of partition.This partition may be to have ionic conductivity and any material of being still electric insulation.For example, this partition comprises little outstanding, the insulator that web plate is printed of insulation, maybe may be independent sheeting, for example the polyolefin of nonwoven, have and spin or polymeric lattice material, the NAFION of nonwoven The glass fibre of (E.I.du Pont deNemous and Company of Wilmington, the registered trade mark of Delaware), pottery, mineral microparticle or the like are formed.In other words, electrode may be used in and divide the pad or the supporter that split to separate in the box-like bearing, as long as electrode is low surface area, low resistance.Usually, 400 square metres of every grams enough for the circulated capacitor of improvement in performance provides the low resistance electrode, for example, are lower than 1 ohm-cm to the surface area between 10 square metres of every grams, preferably are lower than 0.3 ohm-cm.It is long-pending that these electrodes should have minimal surface, so that high ratio electric capacity is provided, and for example vitreous carbon, foam-like and the porous metals electrode that utilizes the powder metallurgy art to make.Yet, unless having minimal surface, amass these materials, preferably every gram surpasses 10 square metres, otherwise electrode will have low ratio electric capacity.And because the ion adsorption capacity minimizing is therefore very little to making the circulated capacitor use.If surface area is too high, resistance just increases.The surface area of the granulated metal of sintering should be 10 square metres of every grams between 400 square metres of every grams.
Low surface area, low electrical resistant material with average operation voltage can make the internal part of circulated capacitor be connected in series to the box-like bearing of circulated capacitor electrode, because improved conductivity and lower average operation voltage make from the power supply to the conductive lead wire, the ohmic drop of optional current-collector and electrode for capacitors itself is lower.This voltage drop is preferably lower than 4 volts.The current potential that is no more than the electrolysis nidus falls that permission is connected in series to box-like bearing with internal part and in low-voltage.Each anode and negative electrode are to becoming a single capacitor.
The puncture voltage that the voltage of the less electrode group of loss itself is preferably lower than water in conductive lead wire adds the overvoltage of top electrode.Concerning the aqueous solution preferably 2 volts or lower, concerning organic solution preferably 4 volts or lower.The virtual voltage of each the single capacitor in the electrode group is with the number of electrode group voltage divided by a plurality of electrode pair layers.Each electrode pair is represented a series capacitor.
Being connected in series of electrode by using higher voltage power to improve electric energy efficiency to given amperage.The entire electrode group has the voltage identical with the capacitor that is connected in parallel.Yet this electrode group is made up of a plurality of (n) internal capacitor of series connection.In these capacitors each is owing to this number (n) has reduced voltage.Therefore, compare with the capacitor that is connected in parallel, electrode has an average operation voltage that is reduced for 1/n, therefore demonstrates better corrosion resistance, and lower to the amperage requirement, energy uses more abundant, and the ability of utilizing cheap, lower ampere power.Do not use low resistance, low surface area material, resistance is just too big thereby can not carry out practical application.
To only for the purpose of graphic extension the present invention be described below in conjunction with the embodiment shown in some; Yet, will be appreciated that, under the prerequisite that does not deviate from the spirit and scope of the present invention, also can in these illustrative embodiment, make various changes, change, replenish and improve.
Description of drawings:
Fig. 1 is the schematic, exploded that is used in the multi-layered electrode in the series capacitor; And
Fig. 2 has illustrated a kind of circulation of the present invention, series capacitors.
Embodiment:
Fig. 1 shows the arrangement of the electrode layer of the circulated capacitor that is used to construct a series connection.In this embodiment, in fact have only termination electrode 1 to be used for being connected to power supply.Hole 2 is set so that can connect as shown in Figure 2 screw rod 9 and washer screw device 11, thereby formation is connected with the tight of bolt 10 with conductive lead wire.Layer 3 is low surface area, high conductive electrode; This capacitor also has optional inside collector 5, and the end current-collector 1 of connecting with feedthrough connector hole 2 as shown in Figure 1.High conductivity, low surface area electrode may omit end current-collector 1 and 5 and also play their current-collector, and in this case, the low surface area electrode that can connect is expanded and is provided with a jockey, as hole 2.In other words, some materials may be soldered, crimping or pull out to form a lead-in wire such as electric wire goes between.The number of layer may be any integer, but is preferably lower than 1000.Also may the connection in series-parallel combination.For example, layer as shown in fig. 1 may repeat repeatedly, has leaded electrode that is connected in parallel and the electrode that is connected in series inner, that do not extend of containing of elongation.Be connected in series to mean and connect in electronics perception (electronic sense) mode.Between internal electrode, there is not actual connection, because they are separated by partition 4.
Fig. 2 shows a kind of tandem arrangement 9, bolt device 10 and washer screw device 11 of assembling, their form with termination electrode 1 between tight the electrical connection.Conductive lead wire 1 may be crushed between top board 15 and the bolt and be connected with the tight of washer screw device 11 to form.Entire electrode group 14 is set in the box-like bearing 13 of the locator 8 with entrance and exit 7 and liquid connection.Arrow is represented flow passage, and it flows into top or bottom.For example, in side flow around electrode group 14, between layer 3, flow, if perhaps electrode material porous, flow through electrode material, perhaps flow through the fluid passage that forms by partition, perhaps rise therefrom by the formed internal path 12 of combination by internal electrode, partition or current-collector hole 6 as shown in Figure 1.
The geometry of any circulated capacitor connects the circulated capacitor that internal electrode can be converted into series connection by non-physical property.For example, the spiral of the circulated capacitor of series connection twine distortion can be by a plurality of anode-cathode layers are provided but only prolong or connect and finish from a lead-in wire of termination electrode.By power supply only is connected to termination electrode and cut off simply in the middle of the parallel lead-in wire 4 that is connected, that can use Andelman U.S. patent 5,779,891 shown in Figure 1ly goes out stacked wafer design.AndelmanU.S. patent 5,779, and Figure 12 of 891 shows a kind of geometry of the many stick electrode that are of little use, and all stick electrode all are connected in parallel.Be these electrodes of connecting, the stick electrode of embarking on journey of separating can be connected to the opposite electrode of power supply, and the stick electrode with even number placed in the middle of at least two row does not have and the power supply physical connection.It is right that the inner stick electrode that does not connect forms anode-cathode, serves as single series capacitor.
Circulated capacitor of the present invention can be used to purify waste water, sewage or cooling tower water.In addition, circulated capacitor of the present invention is including, but not limited to the processing of the chemical pretreatment solution of caprolactam, ethylene glycol, sugar and corn syrup stream or eliminate on the ionic impurity of great use.Ionic compound, the electro-catalysis ground that circulated capacitor of the present invention can be used to absorb static decompose organic molecule or electrochemically with metallic solution chemically reactive or plated metal solution.Circulated capacitor of the present invention also can be used for electrochemistry synthetic in.
Embodiment 1
Have a kind of fluorocarbon, as in the 0.01 inch thick thin slice that forms fibriilar PTFE, the RuO with 40-400 per square meter of surface area 2XH 2The O pulverulent material is made into the circulated capacitor of Fig. 1.NALTEX (Nalle Plastics, Inc.of Austin, the registered trade mark of Texas) two-sided screen pack is used as partition, and graphite foil, titanium or other not corrodible materials are used for doing optional current-collector.Surpass 4 milliliters flow velocity with every gram electrode material per minute, the brackish water that will comprise the NaCl of 0.1M purifies 90%, to containing NaCl 0.01M.
Embodiment 2
With RuO 2Be plated on 0.005 inch thick tantalum paper tinsel to make a kind of composite electrode as one 0.005 inches thick flash platings with inherent current-collector, this current-collector has the B.E.T surface area of 400-200 square metre of every gram and the resistance that is lower than 0.001 ohm-cm, RuO 2Be cut into 3 square inches and be assembled into the circulated capacitor that a kind of spiral twines.One DC power supply offers 1.2 volts of voltages of circulated capacitor, and contaminated water is extracted out and is sent to this capacitor from underground water source simultaneously.
The water that contains radiostrontium and caesium is cleaned and surpasses 90% and sent back to underground again.The radioactive dirty water that concentrates is emitted and is fed to be used as in the crystallizer unit further from capacitor and concentrates.
Embodiment 3
Be deposited in molybdenum nitride, boride and carbide thin film on the tantalum paper tinsel of 0.5 mil thick,, described in 292, be made into a kind of series connection circulated capacitor as shown in Figure 2 as in Andelman U.S. patent 5,680.One DC power supply provides 2 volts of voltages for the entire electrode group.This and Andelman U.S. patent 5,620, control system shown in Figure 15 of 597 combines, so that a kind of littler circulated capacitor is provided, this capacitor purifies the solid water of 500ppm dissolving with the volume flow rate of the acceleration of every cubic centimetre of per minute 3ml of the box-like bearing size of capacitor.
Embodiment 4
From Cabot company, has the hydrophily conductive carbon black Monarch1400 of 560 square metres of nitrogen surface areas of every gram TMFormation has 0.02 inch thick sheeting of 5%PTFE adhesive, so that make the composite electrode that is lower than 0.02 to 0.01 ohm-cm.0.05 the thick graphite foil of inch is used as conductive seat.0.02 inch NALTEX with 1 centimetre of wide screen lattice Two-sided screen pack is as partition.This has just made circulated capacitor as described in Figure 1.DC power supply is connected on parallel anode that ties together and the cathode leg and with 1 volt constant voltage driving capacitor.
Be reversed in each charge cycle polarity.2000 microSiemen of municipal water (little Siemens) solution is purified to more than 70%.In case electric dodar is to 600 microSiemen (little Siemens), three-way valve of a relay shunt consumes, and capacitor is short circuit simultaneously.This has just emitted the pollutant that has absorbed, and this pollutant is poured in the gutter.Polarity of capacitor is reversed to carry out next one charging/purification cycle.A kind of sand prefilter (sand prefilter) is used to remove granular substance.Use a kind of cloth post (cloth post) filter so as to stop may from capacitor, discharge and flow into the organic substance that condenses and other granular substance in the product liquid stream.Optional deionization resin or counter-infiltration system fine finishining are from the product water of capacitor.Circulated capacitor of the present invention also can be used in water supply, regeneration or the sewage loop of RO deionization electrodialysis or filtration system.
Embodiment 5
The circulated capacitor of embodiment 4 is used to absorb halogenated hydrocarbons when no-voltage.Therefore capacitor moves 5 minutes under 2 volts of voltages, so that the electro-catalysis ground halogenated hydrocarbons that cracking absorbed.
Embodiment 6
Having under the muriatic situation, the circulated capacitor of embodiment 2 operates under 2 volts of voltages, so that generate chlorine and other redox compounds for the purpose of microbial decontamination in the water.
Embodiment 7
Capacitor among the embodiment 4 be electrically connected in the mode of series connection so as to allow the use high voltage, than the power supply of small amperage.For the DC power supply provides bleeder mechanism.Each unit monitored separately and controlled, so that provide equal voltage for this each unit.

Claims (14)

1, a kind of circulated capacitor that is used for fluid purification is characterized in that this capacitor comprises:
A) shell;
B) in this shell, be used to introduce an inlet of liquid to be clean;
C) outlet of the liquid after in this shell, being used to discharge purification;
D) a plurality of electrodes of forming by electrode material, so that be formed for one or more unit of decontaminating liquid, wherein, described electrode comprises an anode layer and a cathode layer, and these layers are arranged and constructed to make liquid to flow between layer and by described unit; This electrode material has every gram electric capacity and surpasses 1 farad electric capacity; And
Wherein, it is 0.03 ohm or littler series resistance that this circulated capacitor has every individual unit, and wherein, described electrode material has the surface area of 10-1000 square metre of every gram.
2, capacitor as claimed in claim 1, wherein, described electrode material comprises having the long-pending nanotube of 100-1000 square metre of electrode material surface of every gram.
3, capacitor as claimed in claim 1, wherein said electrode material have 0.01 ohm-cm or littler resistivity and every gram surpasses 10 farads electric capacity.
4, capacitor as claimed in claim 1, wherein, described electrode material is from by carbon black, aeroge, activated carbon and carbon cloth, perhaps selects in their group that combination constituted.
5, capacitor as claimed in claim 1, wherein, described electrode material has the surface area of 10 to 400 square metres of every grams.
6, capacitor as claimed in claim 1, wherein, described anode and negative electrode are electrically connected in the mode of series connection.
7, capacitor as claimed in claim 1, it comprises the individual unit of a plurality of series connection, and the operating voltage of this individual unit is that whole series voltage is divided by the resulting value of the quantity of described unit.
8, capacitor as claimed in claim 1, wherein, described electrode material is selected from following group: ruthenium-oxide, form fibriilar fluorocarbon, be coated in ruthenium-oxide, tantalum and graphite material on the titanium, and their combination.
9, capacitor as claimed in claim 1, wherein, described electrode layer be arranged on one stacked in.
10, capacitor as claimed in claim 1 is characterized in that: described each electrode layer has one and is positioned at the hole center, circulating liquid.
11, capacitor as claimed in claim 1, it has when at the charge cycle period average voltage less than 1 volt.
12, capacitor as claimed in claim 1, it is operated under greater than 50 milliamperes situation at every gram electrode material.
13, a kind of circulated capacitor system comprises capacitor as claimed in claim 1, and comprises power supply that wherein, the resistance voltage from this power supply to this capacitor is reduced to 4 volts.
14, a kind of method that is used to purify the water that comprises ionic contamination is characterized in that this method comprises the following steps:
A) provide circulated capacitor as claimed in claim 1;
B) water to be clean is incorporated in the inlet;
C) discharge the water that ionic soil is crossed from outlet;
D) get rid of the ionic contamination of collecting from capacitor.
CN 00812144 1999-07-30 2000-07-29 Flow-through capacitor and method Expired - Fee Related CN1246869C (en)

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US6709560B2 (en) 2001-04-18 2004-03-23 Biosource, Inc. Charge barrier flow-through capacitor
EP1291324A3 (en) * 2001-09-07 2003-10-29 Luxon Energy Devices Corporation Deionizers with energy recovery
CN101624229B (en) * 2008-07-09 2011-06-08 冠亚智财股份有限公司 Capacitor deionizing instrument of mixed type electrodes
CN101811754B (en) * 2010-05-17 2012-02-01 长沙理工大学 Activated carbon washing-resisting electrode and preparation method and application thereof
EP2571818B1 (en) * 2010-05-19 2017-02-22 Voltea B.V. Evaporative Recirculation Cooling Water System, Method of Operating an Evaporative Recirculation Cooling Water System
KR20150059202A (en) * 2013-11-21 2015-06-01 (주) 청연 Permeable hybrid electrode for capacitive deionization using activated carbon fibers
EP3037389B1 (en) 2014-12-24 2018-05-16 IDROPAN DELL'ORTO DEPURATORI S.r.l. Apparatus for purifying a fluid and method for the attainment thereof
KR20180066665A (en) * 2016-12-09 2018-06-19 엘지전자 주식회사 filter module for water treatment apparatus and water treatment apparatus having thereof
SE540976C2 (en) * 2017-06-21 2019-02-12 Stockholm Water Tech Ab Device for capacitive deionization of aqueous media and method of manufacturing such a device
US20210300799A1 (en) * 2020-03-27 2021-09-30 Battelle Memorial Institute Electrocatalytic bio-oil and wastewater treatment

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US3930094A (en) * 1972-08-31 1975-12-30 Westinghouse Electric Corp Hydrophobic mats for gas diffusion electrodes
US5620597A (en) * 1990-04-23 1997-04-15 Andelman; Marc D. Non-fouling flow-through capacitor
US5343156A (en) * 1992-04-15 1994-08-30 Nat Semiconductor Corp IC for producing an output voltage related to fuel composition in a capacitive fuel sensor
US5656915A (en) * 1995-08-28 1997-08-12 Eaves; Stephen S. Multicell battery pack bilateral power distribution unit with individual cell monitoring and control

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