CN101475282A - Photocatalysis-plant cooperated water purifying method for pisciculture water - Google Patents
Photocatalysis-plant cooperated water purifying method for pisciculture water Download PDFInfo
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- CN101475282A CN101475282A CNA2008102041301A CN200810204130A CN101475282A CN 101475282 A CN101475282 A CN 101475282A CN A2008102041301 A CNA2008102041301 A CN A2008102041301A CN 200810204130 A CN200810204130 A CN 200810204130A CN 101475282 A CN101475282 A CN 101475282A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a photocatalysis-plant synergy water purifying method for fish-farming water, which comprises the following steps that: 1) sewage in a fish pond is pumped into a filter tank by a diving pump, solid impurities are filtered by sponge foam, and the intercepted solid impurities are discharged by a blowdown valve; 2) clear water filtered by sponge foam falls into a nacreous glass catalytic reaction curtain which is vertically hung on the side wall of the filter tank to contact and react with a photocatalysis material, wherein the nacreous glass catalytic reaction curtain is formed by connecting glass balls in series and in parallel, and the surfaces of the glass balls are burnt and plated with a TiO2 series catalytic material; and 3) the catalyzed water falls into a plant culture tank; and the water flows into the fish pond after pollutants in the water are reduced. The method has the advantages of good natural light transmission, high mass transfer efficiency, no oxygen supplement and nitrogen release power consumption and no blockage, and the practical characteristics of low cost and continuous work. Except for the water pollution treatment for circulating water fish-farming, the method can also be applied to low concentration water treatment of the occasions of environmental protection, civicism, landscape greenbelts and the like.
Description
Technical field
The present invention relates to the water pollution treatment process of cycle water fish-cultivating, refer to adopt the continuity water-purifying process that the also collaborative plant nutrition of organic pollutant absorbs in the light-catalyzed reaction degradation water especially.
Background technology
Because the proteic nutrition of hydrocoles, healthy value are familiar with gradually, the fishery products requirement constantly increases, and pisciculture is developed rapidly.Yet high-density breeding can produce a large amount of organic pollutants, ruins water body, jeopardizes feeding animals life when serious.Simultaneously, sewage discharge also influences peripheral water ecological environment.Especially in the high-density breeding of closed circulation water, water treatment is most important timely and effectively.The water pollution treatment process that present industrial circulating water is breeded fish is to adopt complete water purification facilities equipment and the technology that comprises Microfilter, protein separator, biological bag, oxygenating machine, ultraviolet and ozone sterilization and supply and drain water system etc., long flow path, equipment is many, and power consumption is big, the running cost height.Wherein the biology bag of core technology is by the microorganism nitrification, and organic pollutant in the water progressively is degraded into ammonia nitrogen, nitrite, nitrate, to keep the water quality environment that is fit to the fish normal growth.But exist microorganism responsive to the water quality variation, the flora time for initial establishment is long, the problem of purifying water effect low-response; Stability is also influenced by ambient temperature, and purifying water effect obviously descended when temperature was low; In addition, biodegradation process under the closed cycle water fish-cultivating condition has the accumulation of end products-nitrate, exchanging employing day partly at present mostly, the way of fresh water reduces Nitrate Accumulation solubility, this is consume water resources both, equally also influence extraneous water environment, and the water body of heating winter is also existed the problem of thermal waste.There is the limitation that absorption is saturated easily, work-ing life is short in other as process for purifying water such as activated carbon adsorption, clinoptilolite ion-exchanges.
Photochemical catalytic oxidation (reduction) technology, but because energy consumption is low, purify thoroughly sterilization, non-secondary pollution, be considered to the most potential novel environment friendly technology, development is rapid, and it mainly relies on TiO
2The energy of based semiconductor absorbed lamp (or source of artificial light), the excitation material surface produces has the photohole of high oxidation capacity and the light induced electron of reducing power, again by photohole (electronics) and pollutent contact reacts, making contaminant degradation is the inorganics of environmental sound, light-catalyzed reaction just can be carried out deep reaction at normal temperatures, the thorough mineralising of multiple organic pollutant is removed, particularly shown outstanding ability aspect the removal of the hazardous and noxious substances that is difficult to degrade at biology (comprising some heavy metal).Be successfully applied to that air disinfection is antibacterial, water body algal control and contain the processing of poisonous, the organic wastewater with difficult degradation thereby of algae toxin organism, dyestuff, Organohalogen compounds, sterilant or synthetic, and the advanced treatment of tap water.TiO
2Photocatalytic reaction device has two kinds on suspensoid and fixed bed, TiO in the suspensoid reactor at present
2With the powdered form suspension effect, specific surface area is big, the mass-transfer efficiency height, but, easily condense inactivation with the back separation difficulty, and cause secondary pollution, cause the working cost height; Fixed-bed reactor adopt fixedly TiO of surface
2The inert support interstitital texture of fine catalyst by the irradiation realization light-catalyzed reaction of sunlight or ultraviolet light, has been avoided TiO
2The problem of powdered catalyst Separation and Recovery difficulty, but non-stop run form solid thing obstruction easily but also exist in the reactor, influence the defective of illumination and flow.
Comprehensive related background art is rarely reported at the water body photocatalysis treatment of breeding fish of lower concentration organic contamination characteristic, adopts the process for purifying water of the collaborative plant of photochemical catalysis to yet there are no report.
Summary of the invention
The objective of the invention is, at the deficiencies in the prior art and defective, propose a kind of organic pollutant degradation that utilizes light-catalyzed reaction to rest in the fish and water and become micromolecular inorganic nitrogen and mineralizer, and by placed in-line plant nutrition absorption in the system, make water quality obtain the processing method of continuous purification, and can be applicable to the have stable political situation lower concentration water quality of occasions such as landscape green space of environmental protection, city and handle.
For achieving the above object, the technical solution used in the present invention is: a kind of photochemical catalysis of the water body of breeding fish-plant cooperated process for purifying water, it is characterized in that,
1) by submersible pump the sewage in the fishpond is evacuated to filter vat, filters solid phase impurity by foam sponge, the solid phase impurity of holding back discharges by wash water valve;
2) clear water after foam sponge filters falls into the granulated glass sphere light-catalyzed reaction curtain and the photocatalyst material contact reacts of vertical hanging filter vat sidewall; Granulated glass sphere light-catalyzed reaction curtain burns plating TiO by the surface
2The granulated glass sphere series-parallel connection of photocatalyst material is formed;
3) drop into plant cultivation trough through the water body of photocatalysis treatment; Water pollutant obtains flowing back to the fishpond again after the decrement.
Recycle system principle of work of the present invention is, by submersible pump the sewage in the fishpond extracted out, sends to the lower layer space of filter vat foam sponge, in the overflow process of constantly moisturizing, filters solid phase impurity by foam sponge, improved the transparency of water.The solid phase impurity of holding back after the filtration regularly discharges by wash water valve.Water after foam sponge filters continues to go up and overflows filter vat, and the granulated glass sphere light-catalyzed reaction curtain that hangs along the filter vat sidewall falls, and forms moisture film continuously on the granulated glass sphere surface, and integral body becomes dynamic photochemical catalysis contact reacts; Under the irradiation of solar ray or ultraviolet lamp light, the TiO on granulated glass sphere surface
2Be that photocatalyst material is excited, the high oxidative capacity of generation becomes micromolecular inorganic nitrogen and mineralizer with organic pollutant degradation in the water.Water body through photocatalysis treatment falls, flow to plant cultivation trough, the inorganic mineralizer of small molecules just in time is that the water thing of planting is needed, general plant does not directly absorb macromole attitude organism, middle small molecules, the mineralizing and degrading conversion process that microorganism need be arranged absorbs through plant nutrition, and water pollutant obtains corresponding decrement and flows back to the fishpond, by the continuous circulation of system, realize the eubiosis of fish and plant.
The present invention adopts the collaborative process for purifying water of photochemical catalysis-combinations of plant, the organic pollutant of low solubility and digesting and assimilating in the water capable of being fast degraded, effectively handle " the ternary nitrogen " of the water body of breeding fish, solve the accumulation problem of nitrate, and light-catalyzed reaction has the sterilization effect, can prevent infection such as plant root rot, non-secondary pollution, to eco-friendly, optimized the water pollution treatment technology technology and the route of cycle water fish-cultivating, the superiority of Sustainable development is obvious.The light-catalyzed reaction curtain mode of its centre mounted type granulated glass sphere string, make the water body on granulated glass sphere surface between light and photocatalyst material, be dynamic film like contact reacts all the time, and apparent free-fall velocity upgrades contact, efficient mass transfer, oxygen supply and nitrogen discharge fully, help the raising of light-catalyzed reaction efficient, and exempted the gas transmission energy consumption, the energy efficiency height.In addition, the moisture film light transmission is good, and it is little influenced by the shading of water body impurity and water colour, even if idol has impurity, also in a flash and there is not successional shading influence in mistake, does not more have the anxiety of obstruction.Processing method of the present invention is simple and direct, and applicability is strong, is easy to promote.Compare with background technology, it is responsive to the water quality variation to have overcome the nitrated edman degradation Edman of microorganism, the deficiency that the flora time for initial establishment is long; Existing light-catalyzed reaction method is more practical, and with the no Separation and Recovery operation in back, natural light transmission is good, efficient mass transfer, and the nitrogen power consumption is released in no oxygenating, can not stop up, and has the practical characteristics of low cost, non-stop run.Natural light transmission of the present invention is good, efficient mass transfer, and the nitrogen power consumption is released in no oxygenating, can not stop up, and has the practical characteristics of low cost, non-stop run.Remove the water pollution be used for cycle water fish-cultivating and handle, and can be applicable to the have stable political situation lower concentration water quality of occasions such as landscape green space of environmental protection, city and handle.
Description of drawings
Accompanying drawing is a principle of work synoptic diagram of the present invention.
1 filter vat, 2 foam sponges, 3 granulated glass sphere light-catalyzed reaction curtains, 4 plant cultivation troughs, 5 back up pads, 6 ultraviolet LEDs.
Embodiment
Embodiment 1:
A kind of photochemical catalysis of the water body of breeding fish-plant cooperated process for purifying water, its technical process is as follows:
1) submersible pump is placed in the water body of breeding fish, and pump discharge is connected by the water intaking valve of pipeline with filter vat 1.By submersible pump the sewage in the fishpond is evacuated to filter vat; Sewage in the filter vat filters solid phase impurity by foam sponge 2; The solid phase impurity of holding back after the filtration regularly discharges by wash water valve.
2) the granulated glass sphere surface is burnt and is coated with TiO
2Be photocatalysis thin film, whole pearl is transparence, establishes the hole in the middle of the granulated glass sphere, and by nylon wire series connection bunchiness, vertical hanging filter vat sidewall in parallel forms granulated glass sphere light-catalyzed reaction curtain 3, sagging aligning plant cultivation trough 4.Clear water after foam sponge filters falls into granulated glass sphere light-catalyzed reaction curtain, contacts with granulated glass sphere, forms moisture film continuously on the granulated glass sphere surface, under the irradiation of solar ray or ultraviolet lamp light, and the TiO on granulated glass sphere surface
2Be that photocatalyst material is excited, the high oxidative capacity of generation becomes micromolecular inorganic nitrogen and mineralizer with organic pollutant degradation in the water.Establish back up pad 5 in the granulated glass sphere light-catalyzed reaction curtain, the two-sided photochemical catalysis inner light source that has ultraviolet LED 6 matrixes concurrently of plate.Described ultraviolet lamp is several ultraviolet LEDs, and the distance of photodiode is 2cm, forms the UV-light matrix, lumination of light emitting diode spectrographic centre wavelength or 165nm or 253.7nm or 365nm.
3) drop into plant cultivation trough through the water body of photocatalysis treatment, absorb by plant nutrition; Water pollutant obtains flowing back to the fishpond again after the corresponding decrement.
Start submersible pump, the sewage in the fishpond is pumped to filter vat, filter the solid phase foreign material by foam sponge, the solid phase impurity of holding back after the filtration regularly discharges by wash water valve, filter back clear water contacts with the light-catalyzed reaction curtain, and excites by irradiate light, utilizes solar ray daytime, open ultraviolet lamp night, organic pollutant is degraded to micromolecular inorganic nitrogen and mineralizer in the water, drops into plant cultivation trough then, is absorbed by plant nutrition, purify waste water and flow back to the fishpond, form systemic circulation.
The pure TiO of granulated glass sphere surface-coated
2Film catalyst:
Condition is: be the titanium source with the tetra-n-butyl titanate, nitric acid and methyl ethyl diketone are hydrolysis inhibitor, and deionized water is a hydrolytic reagent, polyoxyethylene glycol and 1,5 pentanediol additive.
Pipette 4 milliliters of tetra-n-butyl titanates with transfer pipet, it is dissolved in to stir in 1 milliliter the methyl ethyl diketone made solution A in 0.5 hour.Other gets 1g polyoxyethylene glycol, 0.25g 1,5 pentanediol, 0.7g water dissolution and make solution B in 32.5 milliliters of ethanol.Solution B slowly is added drop-wise in the solution A and stirred 1 hour, and an amount of concentrated nitric acid adjustment of acidity makes forerunner's colloidal sol.
With the NaOH solution soaking of 2mol/L 5 hours, it was neutral cleaning repeatedly until washing lotion with redistilled water then with granulated glass sphere.It is standby to put into 100 ℃ of oven for drying.
The granulated glass sphere of oven dry is immersed in the colloidal sol for preparing above, leave standstill after 10 minutes and take out, in 60 ℃ of baking ovens dry 10 minutes then, at last, be placed on the interior heat-up rate of retort furnace and rise to 500 ℃ with 10 ℃/minute, be incubated 1 hour, in stove, naturally cool to room temperature at last, promptly obtain the granulated glass sphere surface and cover and be coated with pure TiO
2Film catalyst.
Embodiment 2:
The TiO on described granulated glass sphere surface
2Be that photocatalyst material is, the TiO2 film catalyst of granulated glass sphere surface-coated doping Ag nano particle:
Condition is: be the titanium source with the tetra-n-butyl titanate, nitric acid and methyl ethyl diketone are hydrolysis inhibitor, and deionized water is a hydrolytic reagent, polyoxyethylene glycol and 1,5 pentanediol additive, and Silver Nitrate is silver-colored source.
Pipette 4 milliliters of tetra-n-butyl titanates with transfer pipet, it is dissolved in to stir in 1 milliliter the methyl ethyl diketone made solution A in 0.5 hour.Other gets 0.1g Silver Nitrate, 1g polyoxyethylene glycol, 0.25g 1,5 pentanediol, 0.7g water dissolution and make solution B in 32.5 milliliters of ethanol.Solution B slowly is added drop-wise in the solution A and stirred 1 hour, and an amount of concentrated nitric acid adjustment of acidity makes forerunner's colloidal sol.
Granulated glass sphere with the NaOH solution soaking of 2mol/L 5 hours, is cleaned until washing lotion p hour to neutral with redistilled water then repeatedly.It is standby to put into the 100oC oven for drying.
The granulated glass sphere of oven dry is immersed in the colloidal sol for preparing above, leave standstill after 10 minutes and take out, in 60 ℃ of baking ovens dry 10 minutes then, at last, be placed on the interior heat-up rate of retort furnace and rise to 500 ℃ with 10 ℃/minute, be incubated 1 hour, in stove, naturally cool to room temperature at last, promptly obtain the granulated glass sphere surface and cover the TiO that is coated with doping Ag nano particle
2Film catalyst.
Detect through experimental installation, each round-robin cleaning water reaches 12%, satisfies the water requirement of breeding fish.
Claims (7)
1, a kind of photochemical catalysis of the water body of breeding fish-plant cooperated process for purifying water is characterized in that,
1) by submersible pump the sewage in the fishpond is evacuated to filter vat, filters solid phase impurity by foam sponge, the solid phase impurity of holding back discharges by wash water valve;
2) clear water after foam sponge filters falls into the granulated glass sphere light-catalyzed reaction curtain and the photocatalyst material contact reacts of vertical hanging filter vat sidewall; Granulated glass sphere light-catalyzed reaction curtain burns plating TiO by the surface
2The granulated glass sphere series-parallel connection that is photocatalyst material is formed;
3) drop into plant cultivation trough through the water body of photocatalysis treatment; Water pollutant obtains flowing back to the fishpond again after the decrement.
2, according to the photochemical catalysis-plant cooperated process for purifying water of the described water body of breeding fish of claim 1, it is characterized in that, establish back up pad in the granulated glass sphere light-catalyzed reaction curtain, the two-sided photochemical catalysis inner light source that has the ultraviolet LED matrix concurrently of plate.
3, according to the photochemical catalysis-plant cooperated process for purifying water of claim 1 or the 2 described water bodys of breeding fish, it is characterized in that the TiO on described granulated glass sphere surface
2Be that photocatalyst material is, the granulated glass sphere surface is covered and is coated with pure TiO
2Film catalyst;
Condition is: be the titanium source with the tetra-n-butyl titanate, nitric acid and methyl ethyl diketone are hydrolysis inhibitor, and deionized water is a hydrolytic reagent, polyoxyethylene glycol and 1,5 pentanediol additive;
Pipette 4 milliliters of tetra-n-butyl titanates with transfer pipet, it is dissolved in to stir in 1 milliliter the methyl ethyl diketone made solution A in 0.5 hour; Other gets 1g polyoxyethylene glycol, 0.25g1, and 5 pentanediols, 0.7g water dissolution make solution B in 32.5 milliliters of ethanol; Solution B slowly is added drop-wise in the solution A and stirred 1 hour, and an amount of concentrated nitric acid adjustment of acidity makes forerunner's colloidal sol;
With the NaOH solution soaking of 2mol/L 5 hours, it was neutral cleaning repeatedly until washing lotion ph with redistilled water then with granulated glass sphere, and it is standby to put into 100 ℃ of oven for drying;
The granulated glass sphere of oven dry is immersed in the above-mentioned colloidal sol for preparing, leave standstill after 10 minutes and take out, in 60 ℃ of baking ovens dry 10 minutes then, at last, be placed on the interior heat-up rate of retort furnace and rise to 500 ℃ with 10 ℃/minute, be incubated 1 hour, in stove, naturally cool to room temperature at last, promptly obtain the granulated glass sphere surface and cover and be coated with pure TiO
2Film catalyst.
According to the photochemical catalysis-plant cooperated process for purifying water of claim 1 or the 2 described water bodys of breeding fish, it is characterized in that 4, the TiO2 on described granulated glass sphere surface is that photocatalyst material is, the TiO2 film catalyst that is coated with doping Ag nano particle is covered on the granulated glass sphere surface;
Condition is: be the titanium source with the tetra-n-butyl titanate, nitric acid and methyl ethyl diketone are hydrolysis inhibitor, and deionized water is a hydrolytic reagent, polyoxyethylene glycol and 1,5 pentanediol additive, and Silver Nitrate is silver-colored source;
Pipette 4 milliliters of tetra-n-butyl titanates with transfer pipet, it is dissolved in to stir in 1 milliliter the methyl ethyl diketone made solution A in 0.5 hour; Other gets 0.1g Silver Nitrate, 1g polyoxyethylene glycol, 0.25g 1,5 pentanediol, 0.7g water dissolution and make solution B in 32.5 milliliters of ethanol; Solution B slowly is added drop-wise in the solution A and stirred 1 hour, and an amount of concentrated nitric acid adjustment of acidity makes forerunner's colloidal sol;
With the NaOH solution soaking of 2mol/L 5 hours, it was neutral cleaning repeatedly until washing lotion ph with redistilled water then with granulated glass sphere, and it is standby to put into the 100oC oven for drying;
The granulated glass sphere of oven dry is immersed in the colloidal sol for preparing above, leave standstill after 10 minutes and take out, in 60 ℃ of baking ovens dry 10 minutes then, at last, be placed on the interior heat-up rate of retort furnace and rise to 500 ℃ with 10 ℃/minute, be incubated 1 hour, in stove, naturally cool to room temperature at last, promptly obtain the granulated glass sphere surface and cover the TiO that is coated with doping Ag nano particle
2Film catalyst.
5, according to the photochemical catalysis-combinations of plant process for purifying water of the described water body of breeding fish of claim 2, it is characterized in that, described ultraviolet lamp is several ultraviolet LEDs, the distance of photodiode is 2cm, form the UV-light matrix, lumination of light emitting diode spectrographic centre wavelength or 165nm or 253.7nm or 365nm.
6, according to the photochemical catalysis-combinations of plant process for purifying water of the described water body of breeding fish of claim 3, it is characterized in that, described ultraviolet lamp is several ultraviolet LEDs, the distance of photodiode is 2cm, form the UV-light matrix, lumination of light emitting diode spectrographic centre wavelength or 165nm or 253.7nm or 365nm.
7, according to the photochemical catalysis-combinations of plant process for purifying water of the described water body of breeding fish of claim 4, it is characterized in that, described ultraviolet lamp is several ultraviolet LEDs, the distance of photodiode is 2cm, form the UV-light matrix, lumination of light emitting diode spectrographic centre wavelength or 165nm or 253.7nm or 365nm.
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| CN2008102041301A CN101475282B (en) | 2008-12-05 | 2008-12-05 | Photocatalysis-plant cooperated water purifying method for pisciculture water |
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|---|---|---|---|
| CN2008102041301A CN101475282B (en) | 2008-12-05 | 2008-12-05 | Photocatalysis-plant cooperated water purifying method for pisciculture water |
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| CN101475282A true CN101475282A (en) | 2009-07-08 |
| CN101475282B CN101475282B (en) | 2010-12-01 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257983A (en) * | 2010-12-24 | 2011-11-30 | 戴锐 | Water saving method for fish tank |
| CN102329046A (en) * | 2011-08-03 | 2012-01-25 | 中国科学院水生生物研究所 | Method for processing phosphorus in sediment by combining photocatalytic reduction with submerged plants |
| CN105393973A (en) * | 2014-08-21 | 2016-03-16 | 胡士怀 | Fish and vegetable co-existing water circulation system |
| CN105854868A (en) * | 2016-03-30 | 2016-08-17 | 盐城工学院 | Method for preparing molybdenum doped titanium dioxide film by virtue of sol-gel method |
| CN108293938A (en) * | 2018-03-22 | 2018-07-20 | 禹振军 | A kind of fish and vegetable symbiotic breeding circulatory system |
| CN110203999A (en) * | 2019-06-18 | 2019-09-06 | 黄红锋 | A kind of sunlight fish pond circulating purification system |
| WO2021218630A1 (en) * | 2020-04-26 | 2021-11-04 | Xing Yifan | Heterogeneous catalytic reactor |
-
2008
- 2008-12-05 CN CN2008102041301A patent/CN101475282B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102257983A (en) * | 2010-12-24 | 2011-11-30 | 戴锐 | Water saving method for fish tank |
| CN102329046A (en) * | 2011-08-03 | 2012-01-25 | 中国科学院水生生物研究所 | Method for processing phosphorus in sediment by combining photocatalytic reduction with submerged plants |
| CN102329046B (en) * | 2011-08-03 | 2012-12-12 | 中国科学院水生生物研究所 | Method for processing phosphorus in sediment by combining photocatalytic reduction with submerged plants |
| CN105393973A (en) * | 2014-08-21 | 2016-03-16 | 胡士怀 | Fish and vegetable co-existing water circulation system |
| CN105854868A (en) * | 2016-03-30 | 2016-08-17 | 盐城工学院 | Method for preparing molybdenum doped titanium dioxide film by virtue of sol-gel method |
| US20170282159A1 (en) * | 2016-03-30 | 2017-10-05 | Yancheng Institute Of Technology | Method for Preparing Molybdenum Doped Titanium Dioxide Thin Film by Sol-Gel |
| CN108293938A (en) * | 2018-03-22 | 2018-07-20 | 禹振军 | A kind of fish and vegetable symbiotic breeding circulatory system |
| CN110203999A (en) * | 2019-06-18 | 2019-09-06 | 黄红锋 | A kind of sunlight fish pond circulating purification system |
| WO2021218630A1 (en) * | 2020-04-26 | 2021-11-04 | Xing Yifan | Heterogeneous catalytic reactor |
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