CN103193291A - Purification treatment method for organotin-polluted seawater - Google Patents
Purification treatment method for organotin-polluted seawater Download PDFInfo
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Abstract
The invention discloses a purification treatment method for organotin-polluted seawater. The purification treatment method comprises the following steps of: step 1, filtering: filtering the organotin-polluted seawater by using a filter of 50-100 mu m; step 2, pumping the filtered seawater into an electric ultraviolet catalytic reduction system, wherein the system comprises a photocatalyst and an ultraviolet source, in the system, the seawater is in full contact with a photocatalyst material and is irradiated by ultraviolet light to carry out an ultraviolet photodegradation reaction and a photocatalytic reduction mineralization reaction, a mixture is kept for 60-240 seconds and is then exhausted safely, and the photocatalyst is a metal-oxide photocatalyst with a photocatalytic reduction function. The method provided by the invention has the advantage of safety, reliability, high efficiency, low energy consumption, thorough mineralization of organotin pollutants, no addition of chemical agent, no secondary pollution, no change of physicochemical property of seawater and environment friendliness, and can meet the demands of purifying and quickly restoring the organotin-polluted seawater, especially the seawater polluted by organotin in offshore cultivation farms.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of purifying treatment method of polluted water, specifically, relate to a kind of purifying treatment method of organotin pollution seawater.
Background technology
Since mid-term in 20th century, organo-tin compound (organotin compounds, OTC) can prevent marine attaching organism stained to hull and marine building because of anti-biological stained coating, this coating that is used as poly-marine vessel, offshore platform, to prolong the work-ing life of marine building and boats and ships, reduce fuel consumption, reduce maintenance cost.Wood preservative, sterilant, sterilant etc. and be extensive use of on a large scale.But the Recent study report shows that organotin is very big to the toxic effect of marine fishes, Crustacean, mollusk and marine algae.Marine organisms have very strong accumulation ability to organotin, between 5000-10000 times, therefore, just can cause above-mentioned marine organisms cumulative poison or cause the variation of the reverse property of fearful reproduction under the very low situation of concentration.Organo-tin compound (mainly be three replace organo-tin compounds, as tributyl tin TBT, triphenyltin TPT) causes that the phenomenon of coastal waters product population depression such as oyster and distortion has discovery in the U.S., Canada, Britain and method state.This year, oceanographic survey showed, the Asia is one of serious area of organotin pollution in the world at present, and wherein the oyster in some harbour in Japan and China Taiwan has been found that the phenomenon of a hundred per cent feminisation.According to the nineteen ninety sampling survey national coastal to Japan, sample over half has exceeded residual benchmark, and Japanese government has now forbidden containing the production of organotin antifouling paint.At the numerous harbour, beach of China so that inner waters have all been found organotin pollution in various degree, the She Kou of Shenzhen port and close on the marine site and found serious organotin pollution wherein, the concentration of tributyl tin surpasses nearly 8 times of U.S.'s residue criterion in the seawater, is higher than nearly 80 times of Canadian residue criterion.In a word, organo-tin compound is acknowledged as artificially to be introduced poisoning most of ocean environment up to now and learns one of material, and utmost point difficult degradation, the consequence of its pollution is to the marine organisms toxigenicity, chronic pollution will cause the population depression of most spiral shells, shell, and food qualities such as sea-food are produced serious threat safely.Therefore; control to the ocean organotin pollution in urgent need of strengthening at present; develop the method that counterweight Polluted area seawater is repaired and administered as early as possible; especially develop the method that organotin pollution thing in the coastal waters plant seawater is administered and repaired, with oceanic resources and the human health of protecting us to depend on for existence.
The migration path for transformation of OTC material and degradation method are mainly concentrated on the attached effect of adsorption and desorption to organotin in seawater and the settling at present, biomagnification, biological degradation, and in the mechanism research of Degradation such as some chemical method cracking, but no matter be absorption degradation method [environmental science and technology (M.Carmen Hermosin such as M. toll bar He Mosen, et a1.Environ.Sci.Technol), 1993.27:2606-26l1], biodegradation method [D. bar glug ozonosphere (D.Barug, Chemosphere), 1981,10:1145], or chemical method cracking [Jiang Chengchun, Ma Jun etc., micro-polluted water is handled in potassium permanganate and the coupling of powder charcoal, China's plumbing, 2001,17 (3): 12-15] etc. method, mostly there is length consuming time, adopt initial compounds or the non-aqueous solvent of high density, organotin continues accumulation in organism, can't thoroughly from environment, remove, be difficult to thorough mineralising and become problems such as inorganic tin, so aforesaid method is difficult to be applied to purification and the environment remediation of large-scale pollution seawater.The most significant work is to be finished by [R.J Ma Kuier (Maguire) etc., agricultural food product chemistry (Agric.Food Chem), 1983,91:1060] such as Ma Kuier (Maguire) in the relevant photodegradation.They come tributyl tin in the degradation water with sunlight, find that this compound removes butyl in turn in irradiation process, change inorganic tin at last into, and regrettably degradation speed is very slow, and the tributyl tin transformation period was greater than 89 days.Because ultraviolet penetrativity is poor, photodegradation only occurs in several centimetres of water body top, thereby can not become the main process of tributyl tin degraded, can't use in actual production.In addition, people such as Yang Yu [Yang Yu, Environmental Pollution and Control, 2009,31 (1): 62-64] carried out the degradation mechanism research of laser flash method light to organo-tin compound, the powerful energy that this method proof laser flash sends can be attacked TPhT and go up the phenyl ring that connects, cause its open loop or Sn-C bond rupture, thereby can reach the purpose of thorough mineralizing and degrading TPhT, but because this method need adopt powerful Nd:YAG laser apparatus, and be a kind of for understanding or disclosing organo-tin compound and derivative thereof at the conversion of Atmospheric Liquid Phase and the experimental technique of home to return to approach, the possibility that does not also have large-scale application to repair in the detoxification of organotin pollution seawater.
In sum, at present in the seawater especially quick improvement and the reparation to organotin pollution thing in the coastal waters plant seawater become a difficult problem, still there are many weak points in present method, need the thoroughly sea pollution improvement method of mineralising organotin of development badly, expand the heavily contaminated zone to adjacent marine site so that wider from harbor district for avoiding, it is significant that the initiation oceanic resources fail, pollution jeopardizes people ' s health.
Summary of the invention
The object of the present invention is to provide a kind of brand-new high-level efficiency, the electricity of thorough mineralising organotin pollution thing to help photo catalytic reduction mineralising method, the concrete mechanism of this method is ultraviolet light catalyzing and strong reduction mineralization, has not change seawater physico-chemical property (as temperature, pH value, salinity etc.), safe, reliable, efficient, less energy-consumption, organotin pollution thing mineralising and thoroughly, do not introduce numerous advantages such as adding chemical agent, non-secondary pollution, environment permission.Can satisfy the organotin pollution seawater, especially coastal waters plant etc. is subjected to the purification of seawater of organotin pollution and the demand of quick repairing and treating.
For achieving the above object, the invention provides a kind of purifying treatment method of organotin pollution seawater, this method comprises following concrete steps:
Step 1 is filtered: with the strainer filtration treatment of organotin pollution seawater through 50-100 μ m;
Step 2, seawater after filtering is pumped into electricity help the ultraviolet catalytic restoring system, this electricity helps the ultraviolet catalytic restoring system to comprise photocatalyst and ultraviolet source, in this system, seawater fully contacts with photocatalyst material, again through UV-irradiation, ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising takes place, after stopping 60s-240s, safety dumping;
Described photocatalyst has the photocatalyst of photo catalytic reduction function for the metal oxide type.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described method also comprises filter step just, that is, the organotin pollution seawater crossed through coarse filtration system (being preferably grid) commonly used filter out granule foreign.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described electricity helps the ultraviolet catalytic restoring system also to comprise extra electric field, and this extra electric field is the direct supply electric field, extra electric field voltage hold-in range-0.05V ~-0.35V.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described direct supply is nickel-cadmium cell, lithium ion battery, solar cell.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described ultraviolet source is the low pressure mercury lamp that is lower than the 290nm UV-light, middle pressure ultraviolet lamp, LED lamp for launching predominant wavelength.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described ultraviolet source is for can launch the ultraviolet source that predominant wavelength is the following UV-light of 200nm.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described photocatalyst is TiO
2-NiO-CuO composite type metallic oxide photocatalyst.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described TiO
2In-NiO-CuO composite type metallic oxide the photocatalyst, count TiO in molar ratio
2: NiO:CuO=1-10:30-60:30-69.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, described photocatalyst loads on the base material of seawater corrosion resistance, and this base material is more than in conductive glass, graphite, stainless steel, nickel, the titanium any one.
The purifying treatment method of above-mentioned organotin pollution seawater, wherein, that described base material is is spherical, sheet, netted, fiber or spongy.
Described electricity helps the ultraviolet catalytic restoring system to comprise:
Cavity;
Be disposed on the some grids in the cavity;
Be arranged on the ultraviolet source between adjacent two grids;
Be arranged on the photocatalyst on each grid surface; And
Be arranged on the lead tightness system on the grid, by this lead tightness system, make photocatalyst to be connected with outside constant voltage power supply.
Concrete principle of the present invention is as follows:
Make the ultraviolet sources such as low pressure mercury lamp of emission ultraviolet rays shine pending polluted seawater and the semiconductor light-catalyst that is evenly distributed in the water ballast simultaneously, then the organotin pollution thing in the contaminated seawater (being mainly tributyl tin, triphenyltin etc.) at first is degraded to dibutyl tin, tin diphenyl and monobutyl tin, a phenyltin etc. by ultraviolet irradiation.Simultaneously, the reduction photocatalyst that is evenly distributed in the seawater receives that energy is greater than the ultraviolet light irradiation of its forbidden band energy, electronics on its valence band (e-) is excited and is passed forbidden transition to generate light induced electron (e-) to its conduction band, on valence band, then generate photohole (h+) accordingly, this photohole has stronger oxidation capacity, but it powers up under the effect that helps electric microfield outside, and neutralization reaction takes place rapidly, is consumed by original position; And the light induced electron with strong reducing power (e-) that generates on the conduction band, then can move to catalyst surface rapidly, the reaction of reduction mineralising takes place with the tributyl tin in the seawater, triphenyltin, dibutyl tin, tin diphenyl and monobutyl tin, a phenyltin etc. in the light induced electron with strong reducing power, and product is inorganic tin and water, CO
2And corresponding inorganic salt; The light induced electron of this reduction photocatalyst surface can also form superoxide anion with the dissolved oxygen effect that is adsorbed on photocatalyst surface, also further with the tributyl tin in the seawater, triphenyltin, dibutyl tin, tin diphenyl and monobutyl tin, a phenyltin etc. the reaction of reduction mineralising takes place, final product is inorganic Sn and CO
2And H
2O and corresponding inorganic salt.As everyone knows, inorganic Sn is a kind of natural antiseptic-germicide, and the organotin pollution thing in the seawater can be realized thorough detoxification after in a single day being become inorganic tin by mineralising.
The advantage of method of the present invention is:
1. the present invention's effect of ultraviolet light irradiation and photo catalytic reduction method that has been coupled, the degradation rate of organotin pollution thing is greatly improved, and improves more than 3 times than conventional ultraviolet photolysis speed;
2. the photochemical catalysis strong reducing action has overcome the thoroughly shortcoming of mineralising detoxification (be dibutyl tin and monobutyl machine tin as the tributyl tin product, can't generate inorganic tin, it is thoroughly deviate from) of conventional ultraviolet photolysis technical finesse organotin from environment;
3. have do not change seawater physico-chemical property (as temperature, pH value, salinity etc.), safe, reliable, efficient, mineralising thoroughly, is not introduced numerous advantages such as adding chemical agent, non-secondary pollution, environment permission;
4. purifying treatment equipment volume is little, energy consumption is low, processing efficiency is high, applied widely, can help the number of ultraviolet catalytic reduction reaction system to adjust treatment scale flexibly by increasing and decreasing electricity, the brine disposal ability can reach 500-5000m3/h;
5. can to the killing action of harmful virus, bacterium in the seawater, improve the water quality of discharging seawater in the degraded seawater in the organic pollutant.
Description of drawings
Fig. 1 is the process flow sheet of a kind of organotin pollution method of seawater treatment of the present invention.
The electricity that Fig. 2 uses for a kind of organotin pollution method of seawater treatment of the present invention helps the structural representation of ultraviolet catalytic reduction reaction system.
Fig. 3 is the A-A sectional view of Fig. 2.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
The present invention is achieved through the following technical solutions:
As shown in Figure 1, at first, the organotin pollution seawater falls the particle foreign material through coarse filtration system filtrations such as grids and comprises fish, shellfish and part silt etc., again after the fine filtering system of 50-100 μ m is with solid particulate matters such as further removal miniature organisms, can enter electricity and help ultraviolet catalytic reduction reaction system, warp is with the abundant contact of reduction photocatalyst material and the irradiation of UV-light in this reactive system, ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising take place simultaneously, after stop action time of 60s-240s, mineralising reaction namely takes place thoroughly to reduce in the organotin pollution thing, reaction product is the inorganic tin of thorough detoxification, flow out ultraviolet catalytic reduction reaction system in company with seawater, the seawater that flows out ultraviolet catalytic reduction reaction system can drain back to the ocean safely.The organotin pollution thing is handled the effect of implementing and can be measured by high performance liquid chromatography.
As shown in Figure 2, help the structural representation of ultraviolet catalytic reduction reaction system for electricity used in the present invention.This electricity helps ultraviolet catalytic reduction reaction system to comprise cavity 10, be disposed on some grid 11(in the cavity 10 and can increase or delete grid number in the cavity according to the demand of the actual treatment water yield), being provided with this ultraviolet source of ultraviolet source 12(between per two grids is installed in the cavity), all be set with the photocatalyst 13 of shapes such as the sheet that loads on the various carriers or mesh-like at each grid surface.Also be provided with lead tightness system 131 on the grid 11, by this lead tightness system 131, make photocatalyst be connected with outside constant voltage power supply.Grid 11 in the cavity 10 is folded plate type, handles seawater and can press arrow direction indication tumble flows mistake in reaction cavity, as shown in Figure 3.Pending polluted seawater enters reaction cavity 10 via valve 101 and adapter 102, in cavity 10, contacts with photocatalyst 13, after uv irradiating reacts, discharges via pipeline adaptor 103 and the valve switch 104 of upper end again.
Described ultraviolet source is to comprise that can launch predominant wavelength is the low pressure mercury lamp that is lower than the 290nm UV-light, middle pressure ultraviolet lamp, LED lamp etc., and optimum is the following ultraviolet source of 200nm for wavelength.
It is the direct supply electric field that described electricity helps the extra electric field of photo catalytic reduction system, can provide for various energy-storage battery power supplys, is specially nickel-cadmium cell, lithium ion battery, solar cell etc.Extra electric field voltage hold-in range-0.05V ~-0.35V.
The photocatalyst that described photocatalyst has the photo catalytic reduction function for the metal oxide type, optimum is TiO
2-NiO-CuO composite type metallic oxide photocatalyst; The compositely proportional of this catalyzer is (meter in molar ratio): TiO
2: NiO:CuO=1-10:30-60:30-69.
Described photocatalyst can load on the base material of seawater corrosion resistance, and on the inorganic or organic conductive structured material, shape is not limit as conductive glass, graphite, stainless steel, nickel, titanium etc., can be spherical, sheet, netted, fiber, shape such as spongy.
Embodiment 1
Take from harbour, Wusong, Shanghai surface seawater, the pH value of seawater is 7.45, salinity is 23.1psu, simultaneously, through adopting high-efficient liquid phase chromatogram technique analysis to learn that tributyl tin content is 16.8 μ g/L, after at first via hole diameter is the strainer filtration of 100 μ m, pumps into electricity and help ultraviolet catalytic reduction reaction system, ultraviolet source adopts and can launch the low pressure mercury lamp that predominant wavelength is the 254nm wavelength in this reactive system, and the reduction photocatalyst material is for being the TiO of load base material with the industrially pure titanium net
2(wherein the component proportions of each metal oxide is in molar ratio: TiO for-NiO-CuO composite type metallic oxide
2: NiO:CuO=5:55:40), adopt lithium ion battery as the power supply of extra electric field, the voltage maintenance-0.14V of extra electric field ~-0.20V; Polluted seawater in this reactive system through with reduction fully the contacting and UV-irradiation of photocatalyst material, stop 120s, after sufficient ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising took place, the seawater after the purifying treatment flowed out this reactive system, can drain back to the ocean safely.This organotin pollution thing is handled the effect of implementing and is shown that through the high effective liquid chromatography for measuring result degradation rate of tributyl tin is 99.8%, and the inorganic tin mineralization rate surpasses 95%.The pH value that purifies back discharging seawater is 7.47, and salinity is 22.9psu, does not change substantially.
Embodiment 2
Take from the surface seawater at Xiangshan Bay harbour, Ningbo, the pH value of seawater is 7.32, salinity is 21.6psu, simultaneously, through adopting high-efficient liquid phase chromatogram technique analysis to learn that tributyl tin content is 11.5 μ g/L, after at first via hole diameter is the strainer filtration of 100 μ m, pumps into electricity and help ultraviolet catalytic reduction reaction system, ultraviolet source adopts and can launch the low pressure mercury lamp that predominant wavelength is the 185nm wavelength in this reactive system, and the reduction photocatalyst material is for being the TiO of load base material with the industrially pure titanium net
2(wherein the component proportions of each metal oxide is in molar ratio: TiO for-NiO-CuO composite type metallic oxide
2: NiO:CuO=10:30:60), adopt lithium ion battery as the power supply of extra electric field, the voltage maintenance-0.25V of extra electric field ~-0.27V; Abundant contact and the UV-irradiation of the polluted seawater same reduction of warp photocatalyst material in this reactive system, stop 60s, after sufficient ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising took place, the seawater after the purifying treatment flowed out this reactive system, can drain back to the ocean safely.This organotin pollution thing is handled the effect of implementing and is shown that through the high effective liquid chromatography for measuring result degradation rate of tributyl tin is 99.9%, and the inorganic tin mineralization rate surpasses 99%.The pH value that purifies back discharging seawater is 7.33, and salinity is 21.7psu, does not change substantially.
Embodiment 3
Take from the surface seawater at harbour, Shanghai Yangshan port, the pH value of seawater is 7.55, salinity is 24.1psu, simultaneously, through adopting high-efficient liquid phase chromatogram technique analysis to learn that tributyl tin content is 12.9 μ g/L, after at first via hole diameter is the strainer filtration of 100 μ m, pumps into electricity and help ultraviolet catalytic reduction reaction system, ultraviolet source adopts the low pressure mercury lamp can launch 185nm mixings 254nm wavelength in this reactive system, and the reduction photocatalyst material is to be the TiO of load base material with the industrially pure titanium net
2(wherein the component proportions of each metal oxide is in molar ratio: TiO for-NiO-CuO composite type metallic oxide
2: NiO:CuO=1:55:44, adopt lithium ion battery as the power supply of extra electric field, the voltage maintenance-0.32V of extra electric field ~-0.34V; Polluted seawater in this reactive system through with reduction fully the contacting and UV-irradiation of photocatalyst material, stop 180s, after sufficient ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising took place, the seawater after the purifying treatment flowed out this reactive system, can drain back to the ocean safely.This organotin pollution thing is handled the effect of implementing and is shown that through the high effective liquid chromatography for measuring result degradation rate of tributyl tin is 99.99%, and the inorganic tin mineralization rate surpasses 99.5%.The pH value that purifies back discharging seawater is 7.54, and salinity is 24.2psu, does not change substantially.
Method of the present invention can be used for quick improvement and the reparation of seawater organotin pollution thing, and can carry out disinfection to harmful organisms such as the algae in the polluted seawater, pathogenic micro-organisms simultaneously, and various organic pollutants are had the removal effect.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. the purifying treatment method of an organotin pollution seawater is characterized in that, this method comprises following concrete steps:
Step 1 is filtered: with the strainer filtration treatment of organotin pollution seawater through 50-100 μ m;
Step 2, seawater after filtering is pumped into electricity help the ultraviolet catalytic restoring system, this electricity helps the ultraviolet catalytic restoring system to comprise photocatalyst and ultraviolet source, in this system, seawater fully contacts with photocatalyst material, again through UV-irradiation, ultraviolet photolysis reaction and the reaction of photo catalytic reduction mineralising takes place, after stopping 60s-240s, safety dumping;
Described photocatalyst has the photocatalyst of photo catalytic reduction function for the metal oxide type.
2. the purifying treatment method of organotin pollution seawater as claimed in claim 1 is characterized in that, described method also comprises filter step just,, the organotin pollution seawater is removed granule foreign through coarse filtration system filtration commonly used that is.
3. the purifying treatment method of organotin pollution seawater as claimed in claim 1, it is characterized in that, described electricity helps the ultraviolet catalytic restoring system also to comprise extra electric field, and this extra electric field is the direct supply electric field, extra electric field voltage hold-in range-0.05V ~-0.35V.
4. the purifying treatment method of organotin pollution seawater as claimed in claim 3 is characterized in that, described direct supply is nickel-cadmium cell, lithium ion battery, solar cell.
5. the purifying treatment method of organotin pollution seawater as claimed in claim 1 is characterized in that, described ultraviolet source is the low pressure mercury lamp that is lower than the 290nm UV-light, middle pressure ultraviolet lamp, LED lamp for launching predominant wavelength.
6. the purifying treatment method of organotin pollution seawater as claimed in claim 1 is characterized in that, described photocatalyst is TiO
2-NiO-CuO composite type metallic oxide photocatalyst.
7. the purifying treatment method of organotin pollution seawater as claimed in claim 6 is characterized in that, described TiO
2In-NiO-CuO composite type metallic oxide the photocatalyst, count TiO in molar ratio
2: NiO:CuO=1-10:30-60:30-69.
8. the purifying treatment method of organotin pollution seawater as claimed in claim 1 is characterized in that, described photocatalyst loads on the base material of seawater corrosion resistance, and this base material is more than in conductive glass, graphite, stainless steel, nickel, the titanium any one.
9. the purifying treatment method of organotin pollution seawater as claimed in claim 8 is characterized in that, that described base material is is spherical, sheet, netted, fiber or spongy.
10. the purifying treatment method of organotin pollution seawater as claimed in claim 1 is characterized in that, described electricity helps the ultraviolet catalytic restoring system to comprise:
Cavity (10);
Be disposed on the some grids (11) in the cavity (10);
Be arranged on the ultraviolet source (12) between adjacent two grids (11);
Be arranged on the photocatalyst (13) on each grid surface; And
Be arranged on the lead tightness system (131) on the grid (11), by this lead tightness system (131), make photocatalyst (13) to be connected with outside constant voltage power supply.
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|---|---|---|---|---|
| CN101274808A (en) * | 2008-05-14 | 2008-10-01 | 云南大学 | Treatment process for waste water in Methyl stannum mercaptide production |
| CN101337751A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Processing process for production waste water of tetrabutyltin |
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| CN101274808A (en) * | 2008-05-14 | 2008-10-01 | 云南大学 | Treatment process for waste water in Methyl stannum mercaptide production |
| CN101337751A (en) * | 2008-08-27 | 2009-01-07 | 云南大学 | Processing process for production waste water of tetrabutyltin |
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| CN105498525A (en) * | 2015-11-27 | 2016-04-20 | 大连理工大学 | Catalysis system capable of removing harmful component formaldehyde in air |
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Effective date of registration: 20150414 Address after: 201400 room 1, building 1800, Lane 215, Xinyang Road, Shanghai, Fengxian District Patentee after: SHANGHAI GREENSUN ENVIRONMENTAL PROTECTION TECHNOLOGY CO., LTD. Address before: 1550 No. 201306 Shanghai Pudong New Area Lingang New City Harbor Boulevard Patentee before: Shanghai Maritime University |