CN105776680B - A kind of new micro- discharge water purification machine - Google Patents
A kind of new micro- discharge water purification machine Download PDFInfo
- Publication number
- CN105776680B CN105776680B CN201610224093.5A CN201610224093A CN105776680B CN 105776680 B CN105776680 B CN 105776680B CN 201610224093 A CN201610224093 A CN 201610224093A CN 105776680 B CN105776680 B CN 105776680B
- Authority
- CN
- China
- Prior art keywords
- water
- barrier film
- source
- water tank
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
Landscapes
- Life Sciences & Earth Sciences (AREA)
- 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)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of new micro- discharge water purification machine, the water purification machine includes electrolysis cells, reverse osmosis membrane processing unit and finished product water tank；Electrolysis cells include paired electrode and source water tank, first, second water penetration barrier film is respectively equipped between the yin, yang electrode of first, second electrode pair, first window and the second window are offered in the relative side wall of source water tank respectively, first and second water penetration barrier film completely covers respectively to be laid on first, second window；The yin, yang electrode of first electrode pair and the positive and negative electrode of second electrode pair are respectively arranged on the inside and outside portion of source water tank；The delivery port of source water tank connects with the water inlet of reverse osmosis membrane processing unit, and the pure water outlet of reverse osmosis membrane processing unit connects with finished product water tank, and the concentrated water outlet of reverse osmosis membrane processing unit connects with source water tank.The water purification machine can improve the effect of source Water warfare and the water outlet efficiency of water purification, and only trace waste water discharges, so as to save source water resource.
Description
Technical field
The present invention relates to a kind of new micro- discharge water purification machine, belong to drinking water terminal water treatment technical field.
Background technology
Currently, water environment is exacerbated, the safe and healthy Frequent Accidents of drinking water quality, seriously jeopardizes the existence of people.Water
Pollution is mainly that the pollutant as caused by mankind's activity causes, and it includes industrial pollution source, agricultural pollution source and domestic pollution source
Three parts.Increasingly the water pollution aggravated, significant threat is formed to the living safety of the mankind, turn into human health, economy and
The major obstacles of social sustainable development.Investigated according to authoritative institution of the world, every year the whole world caused by drinking unhygienic water at least
20000000 people are dead, and therefore, water pollution is referred to as " world's number one killer ".
Domestic and international most of waterworks are so far still using precipitation, filtering, the outmoded process of chlorination, by rivers
Water or underground water are simply processed into drinkable water.However, spread unchecked and pour in face of trade effluent, rural sewage and sanitary sewage wildness
Life water source, waterworks can't bear the heavy load helpless.Along with running water from water factory through water transfer pipe network and high-rise water storage
Case reaches and pollution is added caused by drinking water terminal, and it is health that municipal tap water dare not have been said.Especially, running water adds
Although chlorine can be killed effectively except germ, can also produce more halogenated hydrocarbon compound simultaneously, the contents of these chlorinated organics into
Increase again, be the significant source for causing the mankind to suffer from various diseases.Even boiling tap water, above-mentioned residue still drive no
Go, can also make the increase of the carcinogenic substance such as nitrite and chloroform.That is, even if the safety coefficient of drinking water is also not high
's.
Existing purification of water quality product or drinking water related product, predominantly medium adsorb or used the filter membrane in various apertures by water
Nuisance intercepted the physics mode handling process filtered out.Because activated carbon class sorbing material is easy to saturation failure, and
Various filter membranes are easy to be contaminated by bacterial again or organic matter obstruction or damaged, thus actual conditions be can not be such as Theoretical Design
It is desired to accomplish like that to the sufficiently cleaned up of water pollutant.At the source water pollution of getting worse, existing physics mode
Science and engineering skill far can not ensure water quality reaching standard.But physics mode water treatment technology also has an advantage in that, will not exactly generate
Toxic byproduct.Therefore the water quality of traditional RO membrane reverse osmosis filter method production is the safest, but is exchanged for the generation that ensures safety
Valency is then up to the even more converse concentrated waters of 40%-70% and is wasted be discharged into sewer pipe, cause huge water resource and
Waste of energy, and the cost changed after the blocking of RO films is very high.To reduce or even reaching no effuent discharge, saving water resource,
Various patented technologies are had been developed that so far.Used for example, converse concentrated water is stored into it, or by the pollutant in concentrated water first through molecular sieve
Cleaning blowing time is reduced Deng filtering Posterior circle reuse, or adjustment waste water ratio, or by electrical control, or it is direct through non-return valve
Return and diluted in running water main line, or with " the double water of double films " pattern, water quality based water utilization, etc..The common deficiency of these technologies, one
It is not consider from overall system design, simply local single measure, often makes system overall work unbalance；The second is do not consider
Start with from the water condition that enters for improving membrane component, mitigate the live load of membrane component, it may be said that it is " curing the symptoms, not the disease ", so so far
The product that yet there are no real utility goods comes out.
Comparatively speaking, it is a kind of excellent height although Water Treatment technique has many advantages, such as cheap simple efficient
Level oxidation technology, but there is a series of problems in electrochemical treatments, should not handle occasion list in civilian terminal Drinking Water in itself
Solely use, so far there is not yet in daily life water treatment field and closes extensive use.To find out its cause, one is Water Treatment technique
The enough reaction time is needed, and in daily life water occasion, from start, to water outlet, only several seconds, pollutant exist water purifier
The residence time is too short in water purifier, has little time to complete related chemistry reaction treatment at all；The second is have can for Water Treatment technique
Can be with certain toxic side effect.For example, although chemical oxidation reaction technique can potent inactivation of bacterial, depth degradation organic matter,
Go water removal in various harmful substances, but all kinds of Strong oxdiative factors that chemical oxidization method is generated be substantially non-selectivity, can not
Control, if dealing with the novel substance not having in most probably generating source water improperly, jeopardize safe drinking water on the contrary；Just because of this, in the people
Many daily life drink water purifyings handle occasion, and the application for Water Treatment technique can be described as double cautious.
However, in the unprecedented serious pollution of water environment, conventional physical water purifier today unable to do what one wishes, examine closely again
The possibility that concern Water Treatment is applied in Drinking Water purified treatment, innovative development one kind can efficiently remove dirty in water
Thing non-toxic by-products, highly safe chemical oxidation method for purifying water and device again are contaminated, by physical absorption-filtration treatment technique
It is combined with electrochemical treatments technique, displays one's respective advantages, learn from other's strong points to offset one's weaknesses, it is ensured that people's life drinking water quality safety, is had very
Important realistic meaning.
Although presently commercially available electrolytic ion water dispenser water treatment system substantially can be considered physical absorption-filtration treatment work
Skill is combined with electrochemical treatments technique, but its system architecture is the preposition processing of physical absorption-membrane filtration and electrolysis water unit
Rearmounted combination.Regrettably, for purification of water quality, this " putting the cart before the horse " frame mode, simple physical is not overcome to inhale
The deficiency of attached-membrane filtration disposal ability, such as be commonly used for the activated carbon of pre-treatment, its nonpolar suction of porous high-specific surface area
Attached characteristic, there is preferable deodorization, decolouring, remove chlorine residue, filtering suspension, and filter out the organic matter that molecular weight is more than 3000
Effect.However, the protection to filter membrane is inadequate, the absorption of some organic matters can not decompose on filter membrane causes film to fail, activity
Carbon electrode saturation failure easily by germ contamination, or even become the hotbed of bacteria breed so as to further block filter membrane, etc..Before
Handle unqualified so that reverse osmosis membrane or milipore filter are stained significantly and broken invalid.Rearmounted electrochemical treatments technique also can band
Carry out many new problems, such as cathodic reduction can generate nitrite, heavy metal ion and can not filter out and cause heavy metals exceeding standard
Deng it is not up to standard to ultimately result in water purifier.
The content of the invention
The invention solves technical problem to be：There is provided that a kind of wastewater discharge is few, the pure water of reliable operation service life length
Machine.
In order to solve the above-mentioned technical problem, technical scheme proposed by the present invention is：A kind of micro- discharge water purification machine, the electrolysis
Unit includes the paired electrode of negative and positive, electrolysis power and source water tank for electrode power supply, and the source water tank is provided with first
Water inlet and the first delivery port；The paired anodic-cathodic has two pairs, is first electrode pair and second electrode pair respectively, described
The first water penetration barrier film made of non-conducting material is provided between the yin, yang electrode of first electrode pair, the second electrode pair
Be provided with the second water penetration barrier film made of non-conducting material between yin, yang electrode, the first, second water penetration barrier film it is permeable
The pore diameter range of micropore is less than 2 millimeters and more than 1 nanometer；The first water penetration barrier film by the positive electrode of first electrode pair with
Source water tank separates, and the second water penetration barrier film separates the negative electrode of second electrode pair and source water tank, and the source water tank is relative
Side wall on offer first window and the second window respectively, the first water penetration barrier film, which completely covers, to be laid on first window,
The second water penetration barrier film, which completely covers, to be laid on the second window；The positive electrode and negative electrode of the first electrode pair are respectively arranged on
Outwardly and inwardly, the positive electrode and negative electrode of the second electrode pair are respectively arranged on the inside and outside of source water tank to source water tank；
The reverse osmosis membrane processing unit is provided with the second water inlet, pure water outlet and concentrated water outlet, first delivery port and entered with second
The mouth of a river connects, and the pure water outlet of the reverse osmosis membrane processing unit connects with finished product water tank, the reverse osmosis membrane processing unit
Concentrated water outlet connects with source water tank；When in use, the positive electrode of the negative electrode of the first electrode pair and second electrode pair with
Water in the water tank of source directly contacts, and the positive electrode of the first electrode pair is only with passing through the first water penetration barrier film in the water tank of source
The infiltration water contact oozed out, the negative electrode of the second electrode pair in the water tank of source by the second water penetration barrier film only with being oozed out
Infiltration water contact.
It should be noted that the object that the present invention is handled is that city is provided from water, as described in the background art, present water is dirty
Getting worse is contaminated, city is provided from water and has become a kind of micro-polluted water（Special contamination water in other words）, its pollution sources includes ring
Pollute in border（Such as residues of pesticides）, pollution and pipeline secondary pollution etc. caused by chlorination.
The working mechanism and beneficial effect of technical scheme disclosed in the invention described above are presented below.
The source water tank is using first, second water penetration barrier film as boundary：The first electrode is to setting up separately in the first water penetration
Barrier film both sides, the negative electrode of the first electrode pair is in the water tank of source, and its positive electrode is outside the water tank of source；The second electrode pair
Set up separately in the second water penetration barrier film both sides, the positive electrode of the second electrode pair is in the water tank of source, and its negative electrode is in source water tank
Outside.Certainly, as being provided with cavity inside the water tank of source, the first or second water penetration barrier film is arranged on cavity housing, then is arranged on sky
The negative electrode of the second electrode pair of intracavitary or the positive electrode of first electrode pair, which are considered as, to be arranged on outside the water tank of source.
First by taking first electrode pair as an example, the positive electrode of first electrode pair in the water tank of source only with penetrating through the first water penetration
The infiltration water contact of barrier film（Positive electrode does not contact directly with the water of source water tank）, anode direct oxidation reaction is transferred to source water tank
Outer progress, reaction product of anode are drained outside container, will not return again to polluted water in container.Meanwhile the negative pollution in water
Thing is acted on such as chlorine residue, various harmful anions by anode voltage, can also out of container in water through the first water penetration every
Film, it is outer with infiltration water discharge to move to source water tank.
The structure of the first water penetration barrier film shows as the water passage region of countless permeable micropores on microcosmic in the present invention,
Because the first water penetration barrier film is made of non-conductive material, thus voltage drop is produced in the water passage of permeable micropore, i.e.,
When the decomposition voltage of electrolysis power puts on external electrode（Positive electrode）With interior electrode（Negative electrode）Afterwards, following voltage landing is formed
Relation：The outer positive electrode of first water penetration barrier film（+）The voltage drop U1 of moisture film between → positive electrode and the first water penetration barrier film → thoroughly
The anti-generation of water resistance between negative electrode in the water penetration barrier film of pressure drop U2 caused by water-based barrier film direct impedance → first and source water tank
Voltage drop U3.
And infiltration water of the positive electrode of first electrode pair only with the first water penetration barrier film contacts, the positive electrode of first electrode pair
Press close to the first water penetration barrier film, the liberation of hydrogen, the gas of oxygen evolution reaction generation when being so electrolysed easily enter the mistake of permeable micropore
Bubble is generated in aquaporin and in the water in water passage, in the water passage of the permeable micropore of the first water penetration barrier film
Bubble is easy to broken so as to produce localized hyperthermia's high pressure in narrow and small environment, so with minimum electric shock send efficient water body etc. from
Electron discharge, the oxidation of hydroxyl free base class transient state is generated in the first water penetration barrier film and in the first water penetration barrier film neighboring area water
The plasma of the factor（Plasma is the state of material the 4th that same level is in solid-state, liquid, gaseous state, low-temperature plasma
Body is rich in electronics, ion, free radical and excited state molecule, and electronics has very high reactivity with ion, can make usual conditions
Under be difficult to or chemical reaction that speed is difficult becomes very rapid, discharged generation plasma group by water body, can be significantly
Improve the degradation efficiency of pollutant in water body）, the oxidisability of the hydroxyl radical free radical transient state oxidation factor is extremely strong（More than ozone）, together
Existence time in Shi Shui is again extremely short, therefore can be after generation rapidly to Organic substance in water（Such as bacterium）Formed Deng pollutant
Water is reduced directly to after extremely strong degradation and itself rapid oxidation, does not stay any toxic side effect.
Second electrode pair is with first electrode to similar, but voltage landing is in opposite direction.Therefore likewise, the in the present invention
The negative electrode of two electrode pairs contacts the cell reaction for being to ensure that second electrode pair with the infiltration water of the second water penetration barrier film
It is normally carried out, and great amount of hydroxy group radical type transient state oxidation factor can be produced.
Meanwhile in the presence of second electrode pair, metal cation such as calcium ions and magnesium ions, ferrimanganic in the endogenous water of source water tank etc.
It is lasting to separate out, discharged through the second water penetration barrier film so that the hardness continuous decrease of source Water in Water Tanks, harmful heavy metal in the water of source
Deng progressively removing；And the direct oxidation based on the anode of second electrode pair in the water tank of source acts on, the microorganism in the water of source is gone out
Living, organic matter is degraded.
In addition, the negative electrode of first electrode pair and the positive electrode of second electrode pair the 3rd group of electrode pair of equivalent composition（Yin, yang
Without barrier film between electrode）, the microorganism in the water of source is inactivated under its electric field action, can more preferably play the purification of electrochemistry
Effect.
In the use of the present invention, source water carries out electrochemical treatments through the electrolysis cells first, by calcium ions and magnesium ions in the water of source,
Ferrimanganic and the chlorate of strong oxidizing property, hypochlorite are discharged from the water tank of source, and by hydroxyl free base class transient state oxidation because
Son is sterilized by source water and organic matter degradation, then intercepts and is filtered out in water through the further physics of the reverse osmosis membrane processing unit
Residual harmful substance（Toxic byproduct is only a small amount of H2O2And O3, H2O2And O3Half life of decomposition be usually no more than half an hour, no
The filter assemblies or absorbent module of rear end will not only be produced with harmful effect, and filter component or absorbent module can be entered
Row sterilizing）, so as to obtain the purified water of depth.The present invention is using " preposition electrochemical treatments and membrane filtration postpositive disposal "
Combination, so as to overcome in background technology the group of " the preposition processing of physical absorption-membrane filtration and electrolysis water unit postpositive disposal "
The various defects closed（Such as the easy broken invalid of filter membrane, the heavy metals exceeding standard etc. mentioned in the prior art）, obtain required
Pure water.
Anti-seepage membrane processing unit is pure physical treatment mode in the present invention, it is ensured that effluent quality especially Biological indicators
Tight security, and basic handling is clean before reverse osmosis membrane processing unit is entered for the pollutant in source water of the present invention,
Therefore the live load of reverse osmosis membrane processing unit mitigates significantly, and correspondingly, the service life of reverse osmosis membrane processing unit is significantly
Extend, reach the effect taken stopgap measures and effected a permanent cure（Service life is long and caused purified water water quality is good）.
In addition, reverse osmosis membrane is determined to must have concentrated water discharge ability normal work, and product water by its working mechanism
3 are generally with the ratio of concentrated water:7 or so.But the concentrated water side water outlet of reverse osmosis membrane processing unit is not directly discarded in the present invention,
But it is back in the water tank of source and makees after-treatment with recycling.For whole system, what real outer waste discharge was abandoned, only from
The very small amount sewage of discharge on the outside of the water tank of source.The model machine of the present invention some typical urbans respectively, to work as districts and cities in China
It is source water to be provided from water, makees for a long time, a large amount of post-installation review experimental datas show, in the reliable and stable work of guarantee system and is gone out
On the premise of water purification of water quality safety index, ratio that is controllable and realizing product pure water and efflux wastewater is better than 8:2.With China
Exemplified by Dalian Area（City is provided from the TDS of water in 100 ~ 150mg/L）, actual product pure water and waste water ratio are more than 9:1.Cause
This, the wastewater discharge in the present invention is few, and water outlet efficiency greatly improves.
Because first, second water penetration barrier film obtains the clamping protection of paired electrode in the present invention, experiment proves, first,
Second water penetration barrier film will not be scrapped because of premature failures such as damaged or obstructions in use, remain reliable and stable work
State；It is also scum loosely occasionally to have fouling even in first, second water penetration barrier film and electrode surface, in electrolytic process
The appropriate decomposition voltage polarity for switching the paired electrode for being applied to first, second water penetration barrier film both sides, it is possible to easily
Remove deposition fouling of the anions and canons precipitate in electrode and water penetration membrane surface.
The present invention can also periodically swing to the polarity of two electrode pairs according to being actually needed, now voltage when implementing
Grade can also differ, so that first, second water penetration barrier film alternating degradation of organic substances, discharge harmful heavy metal ions,
Or the chlorine residue of discharge residual, various harmful anions etc., the quality of purified water so not only can be further improved, is given full play to
The catharsis of electrochemistry, and first, second water penetration barrier film can be protected, extend its service life.
In order to further improve plasma discharge characteristic in film, the first water penetration barrier film and the second water penetration can be made
Barrier film all uses hydrophilic barrier film.Hydrophilic film surface energy forms hydrogen bond ordered structure with water, can improve the leaching of fenestra water-filling
Profit state, the plasma discharge process in film that is advantageous to persistently are carried out.
Preferably, the pore size of the permeable micropore of the first water penetration barrier film and shape are essentially identical, and described second
The pore size and shape of the permeable micropore of water penetration barrier film are also essentially identical.
More preferable hydrophily can be made it have by being modified to barrier film, and the aperture size of micropore is uniform, tool
Modifies technique can use known physically or chemically technology, such as shaping of fenestra Regularization, optically catalytic TiO 2, pole
Narrow high-voltage pulse is to film pretreatment, etc..Its meaning is not only in that the raising of efficiency, also effectively prevent because current density is excessive
It is easily caused the deterioration of biological index.
In the present invention, if the aperture of the permeable micropore of first, second water penetration barrier film is excessive（I.e. water passage is excessive）,
It is equivalent to and in a disguised form increases electrode diameter（Electrode curvature radius）Cause discharge in water starting excitation voltage to increase, and make generation
Bubble volume becomes reduces the catalytic specific surface area of gas-liquid two-phase greatly.And if first, second water penetration barrier film it is permeable
The aperture of micropore is too small（I.e. water passage is too small）, it can make that electrolysis aerogenesis can not occur or gas producing efficiency is extremely low, it is small to arrive
Aerogenesis can be electrolysed to a certain degree cannot be introduced into permeable micropore（Also bubble can not just be produced）, so that plasma discharge can not be normal
Carry out.Therefore, by the repetition test of inventor, determining the pore diameter range of the permeable micropore of first, second water penetration barrier film is
Less than 2 millimeters and more than 1 nanometer, the aperture size of the permeable micropore of the first, second water penetration barrier film is mutual each other
Difference is less than 20%.
The further improvement of above-mentioned technical proposal is：The outside of the source water tank is provided with the housing of encirclement source water tank bottom,
Closing space, the first electrode pair are formed between the housing, source water tank, the first water penetration barrier film and the second water penetration barrier film
Positive electrode and the negative electrode of second electrode pair be located in the closing space, the top of the housing is provided with opening, the opening
Form the first water inlet of the source water tank；The bottom of the housing is provided with the first sewage draining exit.
So, city for water supply water from the first water inlet inject closing space, and under tap water pressure by located at
First, second water penetration barrier film between housing and source water tank enters source water tank.Various pollutants in the water of source are by first, second
The barrier filtering of water penetration barrier film opens the first sewage draining exit and simultaneously keeps appropriate aperture, and start electricity after source water tank fills water
Solution preocess.Water intermediate ion in the water tank of source（Both include original ion being dissolved in the water of source, also include and the ion of water electrolysis is generated
Thing）Optionally appeared on the inside of first, second water penetration barrier film to outside and enter closing space, and it is saturating with first, second
The infiltration water outlet of water-based barrier film, discharged from the first sewage draining exit of bottom, so that the water quality in the water tank of source is continuously available purification.
In addition, in electrolytic process, hydrogen and oxygen are generated between the both sides anodic-cathodic of first, second water penetration barrier film
Escape up, produce certain air supporting flocculation, accelerate water intermediate ion between anode and cathode and first, second water penetration barrier film to analyse
It is agglomerating and precipitate the suspension aggregation such as to go out, deposit buildup is in the bottom of source water tank.Therefore, the bottom of source water tank can be set in certain
Slope taper, the source water tank bottom is provided with the second sewage draining exit, and such flocculate progressively slides to the second blowdown of bottom centre
Discharged after mouthful.Depending on flocculate deposition conditions, can periodically manual unlocking slag-drip opening cock flocculate is discharged.
Preferably, the electrolysis power is that the direct current pulse power source of high level narrow spaces or forward voltage level are more than reversely
The component pulse-changing power of voltage level.Electrolytic efficiency can so be improved.
The further improvement of above-mentioned technical proposal is：It is provided with and protects between first delivery port and reverse osmosis membrane processing unit
Pacify filter, the filter core of the cartridge filter is worked with cross-current flow；The cartridge filter is provided with the 3rd water inlet, second
Delivery port and waste, the 3rd water inlet connect with the first delivery port, and second delivery port and the second water inlet connect
Logical, the waste connects with source water tank；It is useless that first is serially connected between the waste and source water tank of the cartridge filter
Water ratio, first waste water ratio are formed in parallel by the first magnetic valve and first throttle valve.The filter core of cartridge filter in the present invention
It is preferred that milipore filter or microfiltration membranes substitute the microstraining core that tradition uses, rear class reverse osmosis membrane processing unit can not only so be formed
More preferable protection, and avoid the frequent replacing of filter core.Actual test proves that apparatus of the present invention are after specified total water production is reached
Milipore filter is not decreased obviously still in kilter, water-flowing amount.Between the waste and source water tank of the cartridge filter
The first waste water ratio is serially connected with, the magnetic valve of the first waste water ratio is opened so as to cartridge filter before actually water processed
Filter core be also rinsed, the working life of the filter core of cartridge filter can be greatly prolonged.
The further improvement of above-mentioned technical proposal is：Between the concentrated water outlet of the reverse osmosis membrane processing unit and source water tank
The second waste water ratio is serially connected with, second waste water ratio is formed in parallel by second solenoid valve and second throttle.By opening second
The magnetic valve of waste water ratio can utilize the water purification of cartridge filter to export（That is the water outlet of the second delivery port）To reverse osmosis membrane processing
The reverse osmosis membrane surface of unit is rinsed, and removing is attached to film surface deposits.
The further improvement of above-mentioned technical proposal is：It is provided with and protects between first delivery port and reverse osmosis membrane processing unit
Pacify filter, the filter core of the cartridge filter is worked with cross-current flow；The cartridge filter is provided with the 3rd water inlet, second
Delivery port and waste, the 3rd water inlet connect with the first delivery port, and second delivery port and the second water inlet connect
Logical, the waste connects with source water tank；It is useless that first is serially connected between the waste and source water tank of the cartridge filter
Water ratio, first waste water ratio are formed in parallel by the first magnetic valve and first throttle valve.The filter core of cartridge filter in the present invention
It is preferred that milipore filter or microfiltration membranes substitute the microstraining core that tradition uses, rear class reverse osmosis membrane processing unit can not only so be formed
More preferable protection, and avoid the frequent replacing of filter core.Actual test proves that apparatus of the present invention are after specified total water production is reached
Milipore filter is not decreased obviously still in kilter, water-flowing amount.Between the waste and source water tank of the cartridge filter
The first waste water ratio is serially connected with, the magnetic valve of the first waste water ratio is opened so as to cartridge filter before actually water processed
Filter core be also rinsed, the working life of the filter core of cartridge filter can be greatly prolonged.
The further improvement of above-mentioned technical proposal is：Between the concentrated water outlet of the reverse osmosis membrane processing unit and source water tank
The second waste water ratio is serially connected with, second waste water ratio is formed in parallel by second solenoid valve and second throttle.By opening second
The magnetic valve of waste water ratio can utilize the water purification of cartridge filter to export（That is the water outlet of the second delivery port）To reverse osmosis membrane processing
The reverse osmosis membrane surface of unit is rinsed, and removing is attached to film surface deposits.
Brief description of the drawings
The invention will be further described below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation of the embodiment of the present invention one.
Fig. 2 is the structural representation of the embodiment of the present invention two.
Embodiment
Embodiment one
Micro- discharge water purification machine of the present embodiment is as shown in figure 1, including electrolysis cells, reverse osmosis membrane processing unit 9 and finished product
Water tank 10.
Electrolysis cells include the paired electrode of negative and positive, electrolysis power 2 and source water tank 1 for electrode power supply, and 1 sets on the water tank of source
There are the first water inlet 1-1 and the first delivery port 1-2；Paired anodic-cathodic has two pairs, is first electrode pair and the second electricity respectively
It is extremely right, the first water penetration barrier film 5-1 made of non-conducting material is provided between yin, yang electrode 3-1,3-2 of first electrode pair, the
The second water penetration barrier film 5-2, the phase of source water tank 1 made of non-conducting material are provided between yin, yang 4-1,4-2 electrode of two electrode pairs
To side wall on offer first window and the second window respectively, the first water penetration barrier film 5-1, which completely covers, to be laid on first window,
Second water penetration barrier film 5-2, which completely covers, to be laid on the second window；The positive electrode 3-2 and negative electrode 3-1 of first electrode pair are set respectively
In source water tank 1 outwardly and inwardly, the positive electrode 4-2 and negative electrode 4-1 of second electrode pair be respectively arranged on source water tank 1 inside and
It is outside；When in use, the water in source water tank 1 is oozed out by the first water penetration barrier film 5-1 and the second water penetration barrier film 5-2, and
Between first water penetration barrier film 5-1 and the positive electrode 3-2 of first electrode pair and the second water penetration barrier film 5-2 and second electrode pair
Negative electrode 4-1 between be clamped with water membrane respectively.Certainly, water and the first water penetration barrier film 5-1, first electrode pair are permeated
May be point contact or face contact between positive electrode 3-2；Likewise, infiltration water and the second water penetration barrier film 5-2, second electrode
To negative electrode 4-1 between may also be point contact or face contact.
Reverse osmosis membrane processing unit 9 is provided with the second water inlet 9-1, pure water outlet 9-2 and concentrated water outlet 9-3, the first water outlet
Mouth 1-2 connects with the second water inlet 9-1, and the pure water outlet 9-2 of reverse osmosis membrane processing unit 9 connects with finished product water tank 10, reverse osmosis
The concentrated water outlet 9-3 of permeable membrane processing unit 9 connects with source water tank 1；Pipe between first delivery port 1-2 and the second water inlet 9-1
Road is provided with booster pump 6.
When in use, source water carries out electrochemical treatments, inactivation of bacterial and depth degradation removal source water through electrolysis cells first
In organic matter, the major pollutants such as metal ion.Then 9 further physics of osmosis filtration unit is intercepted to filter out in water and remained
Harmful substance, also include filtering out there may be the secondary substance for causing Biological indicators to be deteriorated in the electrolysis course of work, so as to obtain
Required pure water.The concentrated water outlet 9-3 of reverse osmosis membrane processing unit 9 connects with source water tank 1, makes reverse osmosis membrane processing unit 9
Concentrated water return source water tank 1 be further electrolysed deionization, reduce the waste of water resource.
The pore size of the first water penetration barrier film 5-1 permeable micropore and shape are essentially identical in the present embodiment, and second is saturating
The pore size and shape of water-based barrier film 5-2 permeable micropore are also essentially identical.Further, the first water penetration barrier film 5-1 and
The second preferably permeable apertures of water penetration barrier film 5-2 are respectively less than equal to 2 millimeters and more than or equal to 1 nanometer of barrier films, and first, the
Difference is less than 20% to the aperture size of two water penetration barrier film 5-1,5-2 permeable micropore each other between each other.
In order to obtain the first water penetration barrier film 5-1 of the uniform pore diameter of micropore and the second water penetration barrier film 5-2, can use
Known physically or chemically technology is modified to existing milipore filter, microfiltration membranes or NF membrane, such as fenestra Regularization
Shaping, optically catalytic TiO 2, extremely narrow high-voltage pulse are to film pretreatment, etc..In the present embodiment the first water penetration barrier film 5-1 and
Second water penetration barrier film 5-2 preferably uses barrier film made from following method of modifying：
1）By nanometer titanium dioxide titanium solution in the ultraviolet case internal irradiation 10-30 minutes that temperature is 40 DEG C -60 DEG C；
2）Film liquid is formed by the raw material of following mass ratio：
PVDF：20%-30%
Pore-foaming agent：2-5%
Step 1）Nano titanium oxide after irradiation：2%-4%
Surfactant：3%-5%
Solvent：70%-80%；
3）The film liquid configured is passed through into supersonic oscillations 20-40 minutes；
4）Liquid film is spread to knifing machine, liquid film is stood to the 10-30 seconds in atmosphere, is then immersed in solidification liquid and is frozen into
Water-based barrier film；
5）The barrier film soaks 10-40 minutes in concentration is 10% alcohol water blend, is then placed in deionized water and floats
Wash；
6）The barrier film is placed in be applied with the pure water tank of 10kv DC pulse high voltages and handled 1 hour.
The present embodiment can also make following improve：
1）The outside of source water tank 1 is provided with the housing 20 of the bottom of encirclement source water tank 1, housing 20, source water tank 1, the first water penetration
Closing space, the positive electrode 3-2 and second electrode pair of first electrode pair are formed between barrier film 5-1 and the second water penetration barrier film 5-2
Negative electrode 4-1 be located in the closing space, the top of housing 20 is provided with opening 20-1, and opening 20-1 forms source water tank 1
First water inlet 1-1；The bottom of housing 20 is provided with the first sewage draining exit 20-2.
So, closing space is injected for water supply water from the first water inlet 1-1 by city, and by the under tap water pressure
One water penetration barrier film 5-1 and the second water penetration barrier film 5-2 enter source water tank 1.During water processed, close water intaking valve and stop water inlet, open
First sewage draining exit 20-2, apply decomposition voltage into first, second electrode pair, start electrolytic process.Water intermediate ion in source water tank 1
（Both include original ion being dissolved in the water of source, also include the ion product to water electrolysis）From the first water penetration barrier film 5-1
Enter closing space, and oozing with the first water penetration barrier film 5-1 and the second water penetration barrier film 5-2 with the second water penetration barrier film 5-2
Water is appeared, is discharged from the first sewage draining exit 20-2 of bottom, the water quality in source water tank 1 is continuously available purification.
2）In electrolytic process, between the first water penetration barrier film 5-1 and the second water penetration barrier film 5-2 both sides anodic-cathodic
Generation hydrogen and oxygen escape up, and produce certain air supporting flocculation, accelerate anode and cathode and the first water penetration barrier film 5-1 and
The suspension such as water intermediate ion precipitation is assembled agglomerating and precipitated between second water penetration barrier film 5-2, and deposit buildup is in source water tank one
Bottom.Therefore, the bottom that source water tank 1 can be set is in certain slope taper, and is provided with the second sewage draining exit 1- in the bottom of source water tank 1
3, such flocculate progressively slides to the second sewage draining exit 1-3 of bottom centre, depending on flocculate deposition conditions, periodically manual unlocking can arrange
Flocculate is discharged in cinder notch cock.
3）Electrolysis power 2 is more than backward voltage electricity using the direct current pulse power source or forward voltage level of high level narrow spaces
Flat component pulse-changing power.
4）Preferably, for more preferable more generation hydroxyl radical free radical plasma groups, when in use, first water penetration
Plasma discharge is respectively formed in each permeable micropore of barrier film and the second water penetration barrier film.
Embodiment two
Micro- discharge water purification machine of the present embodiment is the improvement on the basis of embodiment one, is existed with the difference of embodiment one
In：As shown in Fig. 2 be provided with cartridge filter 7 between booster pump 6 and reverse osmosis membrane processing unit 9, the filter core of cartridge filter with
Cross-current flow works；Cartridge filter is provided with the 3rd water inlet 7-1, the second delivery port 7-2 and waste 7-3, the 3rd water inlet
Mouth 7-1 and booster pump 6 outlet, the second delivery port 7-2 connect with the second water inlet 9-1, waste 7-3 and source water tank
1 connection；The first waste water ratio is serially connected between the waste 7-3 and source water tank 1 of cartridge filter 7, the first waste water ratio is by first
Magnetic valve 11-1 and first throttle valve 11-2 are formed in parallel.
The present embodiment can also make following improve：1）Concentrated water outlet 9-3 and the source water tank 1 of reverse osmosis membrane processing unit 9 it
Between be serially connected with the second waste water ratio, the second waste water ratio is formed in parallel by second solenoid valve 8-1 and second throttle 8-2.
2）The filter core of cartridge filter 7 is microfiltration membranes or milipore filter.
3）First water penetration barrier film 5-1 and the second water penetration barrier film 5-2 preferred hydrophilics water penetration barrier film.
Micro- discharge water purification machine course of work of the present embodiment is divided into four-stage, and concrete analysis is as follows：
First, fill phase
Now preposition electrolysis cells and rearmounted reverse osmosis membrane processing unit 9 and booster pump 6 not power transmission.City is provided from water
Through the first water inlet by water penetration barrier film 5-1 the second water penetration barrier film 5-2, into the inner chamber of source water tank 1 until reaching given
Water filling position（Source water tank fills）.
2nd, pretreatment stage
Preposition electrolysis cells are started working, while booster pump 6 starts, the first electricity of the first waste water ratio of cartridge filter 7
Magnet valve 4-1 is open-minded, and waterway circulating is：
First delivery port 1-2 water outlets → waste water ratio of 6 → cartridge filter of booster pump 7 → the first bypasses the first magnetic valve 11-1
Between the positive electrode 3-2 and the first water penetration barrier film 5-1 of the latter half concentrate recirculation water inlet of → source water tank 1 → first electrode pair
The gap of gap, the negative electrode 4-1 of second electrode and the second water penetration barrier film 5-2 → top half of source water tank 1.In this cyclic process
In, source water quality is continuously available purification, and various pollutants in water, especially various zwitterions obtain fully degraded, are reverse osmosis
Permeable membrane processing unit 9 creates extremely gravy jobs condition.
In this circulation, the filter core of cartridge filter 7 also obtains (forward direction simultaneously）Rinse.
3rd, the water stage processed
Now water circulation is：
1）Water loop processed：Second delivery port 7-2 of the first delivery port 1-2 water outlets → 6 → cartridge filter of booster pump → anti-
Pure water outlet 9-2 → finished product water tank 10 of the second water inlet 9-1 → reverse osmosis membrane processing unit 9 of permeable membrane processing unit 9；
2）Concentrate recirculation：
The choke valve 11-2 of the waste water ratio of the waste 7-3 of cartridge filter 7 → first → source water tank bottom backflow water inlet；
The concentrated water outlet waste water ratio choke valve 8-2 of 9-3 → second → source water tank bottom of reverse osmosis membrane processing unit flows back into
Water.
In this circulation, from the point of view of water inlet side, the water in source water tank 1 gradually decreases, simultaneously because electrolysis cells are held
Continuous electrolysis deionization, has substantial portion of water intermediate ion to pass through the water penetration barrier film 5-1 between anodic-cathodic, it is empty to be discharged into closing
Between.Therefore although the TDS of the reclaimed water of source water tank 1 has been raised, but not unlimited accumulation.At cartridge filter 7 and reverse osmosis membrane
From the point of view of managing the water inlet side of unit 9, because the bacterium in water, organic matter isocolloid product have been had in source water tank 1 in advance
Effect removes, even if the calcium and magnesium plasma in water can be not easy to form hard scale, it is easy in water processed terminate in film surface temporary deposition
Removed in backwash circulation afterwards.
4th, reverse osmosis membrane processing unit flush cycle
After water processed terminates, the flush cycle of reverse osmosis membrane processing unit 9 is transferred to.The magnetic valve 8-1 of second waste water ratio is connected.
Water circulation route is：The second delivery port 7-2 → counter-infiltration of first delivery port 1-2 water outlets → 6 → cartridge filter of booster pump 7
The electromagnetism of the concentrated water outlet waste water ratio of 9-3 → second of the second water inlet 9-1 → reverse osmosis membrane processing unit 9 of film process unit 9
The bottom concentrate recirculation water inlet of valve 8-1 → source water tank 1.In this circulation, exported using the water purification of cartridge filter 7（I.e. second goes out
The water outlet at the mouth of a river）The reverse osmosis membrane surface of reverse osmosis membrane processing unit 9 is rinsed, removing is attached to film surface deposits.
After the completion of this circulation, fill cycle is transferred to again and pretreatment circulates, is ready for water processed next time.
The present invention is not limited to the concrete technical scheme described in above-described embodiment, and in addition to the implementation, the present invention may be used also
To there is other embodiment.All technical schemes formed using equivalent substitution, it is the protection domain of application claims.
Claims (8)
1. a kind of new micro- discharge water purification machine, including electrolysis cells, reverse osmosis membrane processing unit and finished product water tank；Its feature exists
In：The electrolysis cells include the paired electrode of negative and positive, electrolysis power and source water tank for electrode power supply, the source water tank
It is provided with the first water inlet and the first delivery port；The paired anodic-cathodic has two pairs, is first electrode pair and second respectively
Electrode pair, is provided with the first water penetration barrier film made of non-conducting material between the yin, yang electrode of the first electrode pair, and described
The second water penetration barrier film, first, second water penetration made of non-conducting material are provided between the yin, yang electrode of two electrode pairs
The pore diameter range of the permeable micropore of barrier film is less than 2 millimeters and more than 1 nanometer；The first water penetration barrier film is by first electrode pair
Positive electrode separated with source water tank, the second water penetration barrier film separates the negative electrode of second electrode pair and source water tank, described
First window and the second window are offered in the relative side wall of source water tank respectively, the first water penetration barrier film, which completely covers, is laid in
On one window, the second water penetration barrier film, which completely covers, to be laid on the second window；The positive electrode and negative electricity of the first electrode pair
Pole is respectively arranged on source water tank outwardly and inwardly, and the positive electrode and negative electrode of the second electrode pair are respectively arranged on the interior of source water tank
Portion and outside；The reverse osmosis membrane processing unit is provided with the second water inlet, pure water outlet and concentrated water outlet, first delivery port
Connected with the second water inlet, the pure water outlet of the reverse osmosis membrane processing unit connects with finished product water tank, at the reverse osmosis membrane
The concentrated water outlet of reason unit connects with source water tank；When in use, the sun of the negative electrode of the first electrode pair and second electrode pair
Electrode directly contacts with the water in the water tank of source, the positive electrode of the first electrode pair only with it is saturating by described first in the water tank of source
The infiltration water contact that water-based barrier film oozes out, the negative electrode of the second electrode pair is only with passing through second water penetration in the water tank of source
The infiltration water contact that barrier film oozes out.
2. new micro- discharge water purification machine according to claim 1, it is characterised in that：The outside of the source water tank, which is provided with, to be surrounded
The housing of source water tank bottom, it is empty that closing is formed between the housing, source water tank, the first water penetration barrier film and the second water penetration barrier film
Between, the positive electrode of the first electrode pair and the negative electrode of second electrode pair are located in the closing space, the top of the housing
Provided with opening, described be open forms the first water inlet of the source water tank；The bottom of the housing is provided with the first sewage draining exit.
3. new micro- discharge water purification machine according to claim 1, it is characterised in that：First delivery port and reverse osmosis membrane
Cartridge filter is provided between processing unit, the filter core of the cartridge filter is worked with cross-current flow；The cartridge filter
Provided with the 3rd water inlet, the second delivery port and waste, the 3rd water inlet connects with the first delivery port, and described second goes out
The mouth of a river connects with the second water inlet, and the waste connects with source water tank；The waste and Yuan Shui of the cartridge filter
The first waste water ratio is serially connected between case, first waste water ratio is formed in parallel by the first magnetic valve and first throttle valve.
4. new micro- discharge water purification machine according to claim 3, it is characterised in that：The reverse osmosis membrane processing unit it is dense
The second waste water ratio is serially connected between water out and source water tank, second waste water ratio is in parallel by second solenoid valve and second throttle
Form.
5. new micro- discharge water purification machine according to any one of claim 1-4, it is characterised in that：First water penetration
The pore size and shape of the permeable micropore of barrier film are essentially identical, the pore size of the permeable micropore of the second water penetration barrier film
It is also essentially identical with shape.
6. new micro- discharge water purification machine according to any one of claim 1-4, it is characterised in that：First water penetration
Barrier film and the second water penetration barrier film are hydrophilic water penetration barrier films.
7. new micro- discharge water purification machine according to any one of claim 1-4, it is characterised in that：The bottom of the source water tank
Portion is provided with the second sewage draining exit.
8. new micro- discharge water purification machine according to any one of claim 1-4, it is characterised in that：When in use, it is described
Plasma discharge is respectively formed in each permeable micropore of first water penetration barrier film and the second water penetration barrier film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2015106007812 | 2015-09-20 | ||
| CN201510600781 | 2015-09-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105776680A CN105776680A (en) | 2016-07-20 |
| CN105776680B true CN105776680B (en) | 2018-04-03 |
Family
ID=56396224
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610224093.5A Active CN105776680B (en) | 2015-09-20 | 2016-04-08 | A kind of new micro- discharge water purification machine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105776680B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162285B (en) * | 2017-05-27 | 2020-08-28 | 国兴玉 | Plain water reverse osmosis of water does not have waste water purifier with leading filter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186781A (en) * | 2008-10-17 | 2011-09-14 | 有限会社春天 | Apparatus for producing hydrogen-dissolved drinking water and process for producing the dissolved drinking water |
| CN103932358A (en) * | 2014-04-12 | 2014-07-23 | 大连双迪创新科技研究院有限公司 | Fruit and vegetable cleaning machine |
-
2016
- 2016-04-08 CN CN201610224093.5A patent/CN105776680B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102186781A (en) * | 2008-10-17 | 2011-09-14 | 有限会社春天 | Apparatus for producing hydrogen-dissolved drinking water and process for producing the dissolved drinking water |
| CN103932358A (en) * | 2014-04-12 | 2014-07-23 | 大连双迪创新科技研究院有限公司 | Fruit and vegetable cleaning machine |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105776680A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105858982B (en) | A kind of simple desk type water dispenser | |
| CN205527908U (en) | Continuous drinking water purifier | |
| CN105668873B (en) | A kind of circulating desk type water dispenser | |
| CN105668871B (en) | A kind of micro- discharge water purification machine | |
| CN105668870B (en) | Micro- discharge water purification machine | |
| CN205527904U (en) | Municipality supplies running water deep purification device | |
| CN105692975B (en) | Micro- discharge water purification machine | |
| CN205527887U (en) | Water dispenser | |
| CN105668716B (en) | Water purification machine | |
| CN105776680B (en) | A kind of new micro- discharge water purification machine | |
| CN105668872B (en) | Circulating desk type water dispenser | |
| CN105731608A (en) | Floating sterile drinking water storage device | |
| CN105712445B (en) | For deep purifying city for the pretreatment unit of tap water | |
| CN105692974B (en) | A kind of water purification machine | |
| CN205710018U (en) | Urban roof water storage device | |
| CN105692976B (en) | Simple desk type water dispenser | |
| CN105753227B (en) | Electrolysis water water dispenser | |
| CN105692807A (en) | Water purification kettle | |
| CN205527938U (en) | Fixed no bacterial type drinking water storage device | |
| CN105731607A (en) | Rural roof water storage device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |