CN102173485B - Method for treating ship ballast water by injecting oxygen active particles in transmission pipe - Google Patents
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- CN102173485B CN102173485B CN2010106023051A CN201010602305A CN102173485B CN 102173485 B CN102173485 B CN 102173485B CN 2010106023051 A CN2010106023051 A CN 2010106023051A CN 201010602305 A CN201010602305 A CN 201010602305A CN 102173485 B CN102173485 B CN 102173485B
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Abstract
The invention provides a method for treating ship ballast water by injecting oxygen active particles in a transmission pipe and belongs to the technical fields of plasma physics and marine environmental protection application. The method is characterized in that oxygen is ionized and dissociated in a strong ionization electric field to form oxygen active particles (O2+, O(1D), O(3P) and O3), and the concentration of the oxygen active particles reaches 100 mg/L to 400 mg/L; the oxygen active particles react with the ballast water to generate a HO2- initiator with a reaction rate constant of 2.2*106 L/mol.s, and the concentration of the HO2- initiator reaches 40 mg/L to 300 mg/L; the oxygen active particles react with the ballast water under the action of the HO2- initiator to generate hydroxyl radicals (.OH), and the concentration of the hydroxyl radicals reaches 0.4 mg/L to 160 mg/L; and the efficiency of killing aquatic organisms and pathogens in the ballast water reaches 96% to 100%. The invention has the benefit and advantage of solving the problems of ballast water treatment and providing the simple and high-efficiency ballast water treatment method which does not need catalysts, absorbents or reducers and does not cause any adverse effect on the environment.
Description
Technical field
The invention belongs to plasma physics and marine environmental protection applied technical field, relate to a kind of in conveying pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method.
Background technology
The disaster that external harmful organism invasion spreads through sex intercourse and causes is regarded as four one of threats greatly that the ocean faces by Global Environment Facility's tissue (GEF).The ballast water of boats and ships discharging is to cause the main approach that harmful organism is propagated between geographical sexual isolation water body.About 10,000,000,000 tons of the ballast water that annual global boats and ships carry, the ballast water yield that 100,000 tons of freighters of a load-carrying carry can reach ten thousand tons of 5-6, and average every cubic meter ballast water has 1.1 hundred million of the animals and plants of swimming, bacterium 10
3Hundred million, virus 10
4Hundred million, the biology that every day, carried in ballast water in the whole world has the 3000-4000 kind, and 300,000,000 of survival dinoflagellate cysts are only just arranged in a ballast chamber, and 22500/cm is arranged in the sediment of the bilge
3The phytoplankton spore.Up to the present, confirmed that the living species about 500 kinds is water-borne by ballast for cruising.Compare with the natural marine eco-environment, ballast water for ship is the ecosystem under a kind of particular surroundings, often has extremely strong survivability and competitive power through the biology of ballast water domestication and survival.In a single day they be discharged in the nature marine environment, just possibly produce uncontrollable " avalanche type " breeding, endemic species caused great impact, even cause local species extinction, causes a series of ecocatas-trophes.The fact shows that ballast water for ship is to cause the one of the main reasons that the ocean bio-diversity is destroyed in the global range, also is one of swift and violent important channel of propagating of large tracts of land of causing harmful parasite and pathogen.Invasive species brings massive losses to global economy, and according to incompletely statistics, this loss is annual with nearly 10,000,000,000 dollars speed increase.The external harmful organism invasion scale that ballast water for ship causes is still enlarging, and therefore, the IMO of International Maritime Organization (IMO) seeks actv. ballast water tackling method to whole world urgent appeal.And all there are many problems in existing ballast water treatment equipment and method:
1) power consumption is high " to change the method for ballast water at the boat deep-sea ", and operation, time of run are long;
2) facility that not only adds in the heavy corrosion cabin for the method that guarantees the killing microorganisms superchlorination more can produce carcinogenic organic chloride, and can there be safety problems such as leakage, blast in the liquid chlorine of depositing several tons aboard ship;
3) present adoptable method all exists safety and energy consumption big as change to handle in boat or handle at destination port on the bank, or local government invests a few mouthful maintenance problems such as management are set.Therefore, a kind of method simple, the online improvement ballast water of actv. of exploitation is extremely urgent.
The improvement of ballast water for ship should be followed the requirement of senior (advanced person) oxidation technology (AOT or AOP), solves the problem of environmental pollution the governance process from the source, makes every effort to realize zero pollution, zero waste discharge.For this reason, adopting green strong oxidizer hydroxyl radical free radical (OH) is first-selected method, OH (E
0=2.80V) oxidability with fluorine is suitable, is one of the strongest chemical substance of offensiveness, and dissimilar chemical reactions almost can take place with all biomacromolecule, organic matter and inorganic matters in it.Hydroxyl radical free radical has the extremely strong characteristic of killing the ocean biological invasion, can in the ballast water course of conveying, kill the ocean biological invasion.
The main production method of hydroxyl radical free radical has photocatalytic method (UV+TiO
2), light radiation (UV), Fe
2+(Feton) reaction, UV (ultraviolet light)+O
3(ozone), UV+H
2O
2(hydrogen peroxide), super sonic decompose and synergy etc., have been effectively applied to remove organic in the sewage, noxious pollutant and aspects such as earthing water, drinking water treatment.But the problem that above-mentioned hydroxyl free base generation method exists: concentration and generation that OH is produced in (1) are little, can only among a small circle, experimentize and applied research; Need add a large amount of medicaments and catalyst such as H when (2) processing hydroxyl radical free radical
2O
2, O
3, TiO
2, Fe
2+(molysite) is with H mostly
2O
2, O
3As reactive agent, there is the high and use H of treatment cost
2O
2Security problems; (3) chemical reaction rate constant is lower than 3L/mols, accomplishes chemical time at 20min-90min; (4) need add bulky equipment such as efficient bubble column reaction vessel, rotary packed bed reaction vessel, fluidized bed photo catalysis reaction vessel, impact flow reactor in the application process, so that strengthen biochemical reaction rate and improve treatment effeciency; (5) because ultraviolet irradiation (UV) penetrance ability is poor, need add huge ultraviolet radiation apparatus, be difficult to be applied to administer on the large ship ballast water.
Summary of the invention
The present invention provide a kind of in conveying pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method.This method has been followed internationalization educational circles research forward position " Green Chemistry " principle, adopts natural materials O
2Be raw material, under green environment friendly normal temperature and pressure and catalyst-free condition, utilize the extreme physical means of atmospheric pressure electric field discharge, O
2(8.4eV 12.5eV) generates O to dissociative ionization
2 +, O (
1D), O (
3P), O
3The isoreactivity particle injects ballast water conveying pipe, the O in the oxygen activity particle with the high concentration oxygen active particle that is generated through air and liquid mixer
2 +Generating high initial reaction rate constant with the water reaction is 2.2 * 10
6The hydroperoxyl IONS OF H O of L/mol.s
2 -Initiating agent, the O in the oxygen activity particle
2 +, O
3With initiating agent HO
2 -Carrying out the plasma reaction generation is main active particle group with OH, kills harmful hydrobiont and pathogen in the ballast water, while degradable organic pollutant matter, purifier vessel ship ballast water; This equipment is simple, efficient, without catalyst, absorbent and deoxidation compound, does not produce the side production of any secondary pollution, environment is not produced the ballast water processing of any negative effect.
Technical solution technical scheme that problem adopts of the present invention is:
The oxygen activity particle generator utilizes the extreme physical means of high-frequency and high-voltage power supply highfield discharge, airborne oxygen ionization is generated the O of low discharge high concentration
2 +, O (
1D), O (
3P), O
3On the oxygen activity particle, inject the ballast water conveying pipe or transport trunk line, O in the oxygen activity particle
2 +Generate high concentration (100mg/L～400mg/L), high initial reaction rate constant (2.2 * 10 through ballast water generation plasma chemical reaction in air and liquid mixer and the pipeline
6L/mol.s) HO
2 -Initiating agent, O
2 +, O
3Deng oxygen activity particle and initiating agent HO
2 -Reaction generates high concentration hydroxyl radical free radical OH, and (0.4mg/L～160mg/L), the ballast water that reinjects transports harmful hydrobiont and the pathogen of killing in the trunk line wherein, oxidation, pollution degradation material.
At the ballast water conveying pipe or transport in the trunk line and to inject the oxygen activity particle, generate high concentration HO with the water reaction
2 -The detailed process that initiating agent produces the hydroxyl free based sols then is following:
1. the oxygen activity particle of oxygen activity particle generator is produced
Oxygen activity gas ions generator of the present invention adopts dielectric impedance highfield ionic discharge method O
2Process the oxygen activity particle that concentration reaches 100mg/L～400mg/L.Set up reduced electric field intensity in 0.5mm between discharge electrode and earthing pole～0.01mm discharging gap at 200Td～400Td scope internal ionization discharge electric field; Electronics obtains average energy and reaches 6eV～9eV from electric field, the useful energy (8.4eV～12.5eV) will be deposited on O that wherein most of electron institute has
2On, be enough to oxygen (O
2) dissociate, be ionized into the high concentration active particle, and the difference orientation is synthesized oxygen activity particle [O under the electric pulse field parameter regulation and control
2 +, O (
3P), O (
1D), O
3].Produce oxygen activity particle plasma reaction pattern shown in A among Fig. 5, its plasma reaction formula:
For injecting the ballast water conveying pipe [O is provided
2 +, O (
3P), O (
1D), O
3] the oxygen activity particle concentration reaches 100mg/L～400mg/L.
2. initiating agent HO
2 -Produce
Like O in the oxygen activity particle of A generation among Fig. 5
2 +In the gas-liquid dissolver, react generation HO with water
2 -Initiating agent; H
2O
2With HO
2 -Be in a kind of balanced reaction state, form initiating agent HO
2 -Concentration reach 40mg/L～300mg/L.Its plasma chemical reaction formula:
3. the producing of OH solution in the ballast water conveying pipe
Inject the O of ballast water conveying pipe
2 +, O
3Deng oxygen activity particle and HO
2 -It is main high concentration active particle group with OH that initiating agent carries out the plasma chemical reaction generation.The plasma reaction pattern that forms OH in the ballast water conveying pipe shown in B among Fig. 5, its plasma reaction formula:
Oxygen activity particle O
2 +, O
3At HO
2 -Following and the ballast water reaction generation hydroxyl radical free radical OH of initiating agent effect, its concentration reaches 40mg/L～160mg/L.
The biochemical reaction rate constant of hydrobiont and pathogen is 10 in the deadly ballast water of hydroxyl radical free radical OH
7L/mols～10
10L/mols, lethal time is 1s～10s.Do not adding under any chemical agent condition; In the long ballast water conveying pipe of 4m～20m, inject deadly hydrobiont of oxygen activity particle and pathogen efficient and reach 96%～100%; Thereby kill hydrobiont and pathogen in the ballast water quickly and efficiently, reach the discharge of ballast water standard of national International Maritime Organization (IMO) regulation.
Effect of the present invention and benefit are: concentration height and generation that OH is produced in (1) are big; (2) equipment that adopts this method to develop is simple, efficient, without catalyst, absorbent and deoxidation compound; (3) do not produce the side production of any secondary pollution, environment is not produced any negative effect; (4) in the ballast water course of conveying, accomplish ballast water treatment.The present invention can be widely used in the ballast for cruising water treatment.
Description of drawings
Fig. 1 is in the discharge of ballast water process, and oxygen activity particle injection ballast water transports trunk line and kills harmful hydrobiont of water and pathogen diagram of circuit.
Fig. 2 is in the ballast water loading process, and oxygen activity particle injection ballast water transports trunk line and kills harmful hydrobiont of water and pathogen diagram of circuit.
Fig. 3 is that the discharge of ballast water process transports the diagram of circuit that main total pipeline is killed water evil hydrobiont and pathogen to OH solution injection ballast water.
Fig. 4 is that ballast water injection ballast tank process transports the diagram of circuit that the seawater total pipeline is killed water evil hydrobiont and pathogen to the injection of OH solution.
Fig. 5 is the plasma chemical reaction illustraton of model that produces OH.
Fig. 6 is the structural representation of oxygen activity particle generator.
Among the figure: 1. ballast tank, 2. ballast water, 3. valve, 4. pump, 5. FL/MTR, 6. gas-liquid dissolver; 7. conveying pipe effluxes ballast water after 8. purifying, 9. ocean, 10. oxygen, 11. oxygen activity particle generators, 12. high-frequency and high-voltage power supplies; 13. the oxygen activity particle, 14. are used to produce the ballast water of OH solution, and 15. ballast waters transport total pipeline, 16.OH solution, and 17. purify the back seawater; 18. seawater, 19. filters, 20. are used to produce the seawater of OH solution, 21. earthing poles, 22. cooling liquids or gas access; 23. discharge plate, 24. partitions, 25. dielectric layers, 26. oxygen intakes, 27. shells.
A. be the plasma chemical reaction pattern that the oxygen activity particle produces.
B. be the OH chemical reaction template.
The specific embodiment
Be described in detail specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
Of the present invention a kind of in conveying pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method; Can realize through following four kinds of modes: (1) is in the process of discharge of ballast water; Oxygen activity particle injection ballast water transports trunk line generation hydroxyl radical free radical and carries out the ballast for cruising water treatment, shown in accompanying drawing 1; (2) in the process of loading ballast water, oxygen activity particle injection ballast water transports trunk line generation hydroxyl radical free radical and carries out the ballast for cruising water treatment, shown in accompanying drawing 2; (3) in the process of discharge of ballast water; The oxygen activity particle injects and to transport the bypass line that main line takes out 1/4～1/20 ballast water from ballast water and process hydroxyl radical free radical (OH) solution; Refill ballast water again and transport and carry out the ballast for cruising water treatment in the main line, shown in accompanying drawing 3; (4) in loading the process of ballast water, the oxygen activity particle injects and transports the bypass duct that main line takes out 1/4～1/20 ballast water from ballast water and process OH solution, refills ballast water again and transports and carry out the ballast for cruising water treatment in the main line, shown in accompanying drawing 4.Be described in detail as follows:
High-frequency and high-voltage power supply 12 applies high-frequency high-voltage to oxygen activity particle generator 11, and forming electric field intensity is the highfield ionic discharge of 200～400Td, oxygen 10 ionization, disassociation is generated the [O of low discharge high concentration
2 +, O (
1D), O (
3P), O
3] to wait oxygen activity particle 13, its concentration be 100mg/L～400mg/L; Air and liquid mixer 6 injection ballast waters transport trunk line 15 in the oxygen activity particle 13 then; Accompanying drawing 1 is in the process of discharge of ballast water, to inject oxygen activity particle 13 to transport trunk line 15 to ballast water, and accompanying drawing 2 is in the ballast water process of loading, to inject oxygen activity particle 13 to transport trunk line 15 to ballast water.O in the oxygen activity particle 13
2 +With ballast water 2 plasma chemical reactions taking place generates high concentrations (100mg/L～400mg/L), high initial reaction rate constant (2.2 * 10
6L/mol.s) hydroperoxyl ionic initiator HO
2 -O in the oxygen activity particle 13
2 +, O
3Deng with initiating agent HO
2 -Reaction generates high concentration hydroxyl radical free radical OH, and its concentration is 0.4mg/L～160mg/L, and the biochemical reaction rate constant of hydrobiont and pathogen is 10 in the deadly ballast water of hydroxyl radical free radical OH
7L/mols～10
10L/mols, lethal time is 1s～10s.Do not adding under any chemical agent condition, in the long ballast water conveying pipe of 4m～20m, injecting deadly hydrobiont of oxygen activity particle and pathogen efficient and reach 96%～100%.Oxygen activity particle 13 can also inject from the bypass line 7 of ballast water and process OH solution 16 in addition; Refilling ballast water again transports and carries out the ballast for cruising water treatment in the main line 15; Accompanying drawing 3 is in the process of discharge of ballast water; Inject oxygen activity particle 13 to ballast water conveying pipe 7 OH solution 16; Refill and process ballast water and transport trunk line 15, accompanying drawing 4 is in the ballast water process of loading, to inject oxygen activity particle 13 to ballast water conveying pipe 7 OH solution 16, refills to process ballast water and transport trunk line 15 again.Described ballast water conveying pipe 7 is to transport from ballast water to take out 1/4～1/20 ballast water the main line 15.In the ballast water conveying pipe concentration of oxygen activity particle can be according to ballast water in the biomass of hydrobiont and pathogen adjust.
Gordian technique of the present invention is newly to develop to produce high concentration [O
2 +, O (
1D), O (
3P), O
3] waiting the oxygen activity particle generator 5 of oxygen activity particle 13, its structure is as shown in Figure 6.It is made up of parts such as discharge plate 21, earthing pole 23, dielectric layer 25 and partitions 24.Discharge plate 21 is to be that dielectric layer 25 sintering of (330 μ m) form as thin as a wafer by middle metallizing material and skin, and also available stainless sheet steel is processed into discharge plate 21, and pastes dielectric layer 25 in discharge one side; Earthing pole 23 is to be processed into the cavity plate with titanium or corrosion-resistant steel; And regulate and control the temperature of plasma process reactor at cooling liquid or oxygen intake 26 input cooling system conditioners; On the earthing pole surface, also can spray the thin dielectric layer 25 of smelting one deck, dielectric substance is ultramicrofine pure Al
2O
3Powder.
According to method of the present invention, " 250 tons of/hour ballast for cruising water treatment equipments " big shipping management Co., Ltd in the sea, Dalian of development " is educated imperial number " and is carried out real ship industrial test, and test result is shown in table 1, table 2.
1) Bacteria Detection result in the deadly ballast water of hydroxyl radical free radical
Efflux in the ballast water for ship main line, e. coli concentration is 1.1 * 10
4Individual/mL, enterococcus concentration is 0.87 * 10
4Individual/mL, bacteria total amount is 1.8 * 10
4Individual/mL; The oxygen activity particle injects the ballast water conveying pipe and processes OH solution, and the ballast water that reinjects transports trunk line, and its OH solution concentration is 0.40mg/L.Reach appearance in the main line somewhere, its corresponding lethal time is 6.0s; Handling the back Escherichia coli is 59cfu/100mL, and enterococcus is 31cfu/100mL/mL, and total number of bacteria is 198.00cfu/100mL, fatal rate 100.00%, 24 hour (2 days) and all do not have orthogenesis after (5 days) in 120 hours.
The deadly data of table 1. bacterium in the ballast water treatment cabin
Annotate: total number of bacteria comprises anaerobic bacteria and peculiar bacterium, and according to the IMO requirement, this test only detects Escherichia coli and the enterococcus in the anaerobic bacteria.
2) phytoplankton testing result in the deadly ballast water of hydroxyl radical free radical
The deadly data of table 2. phytoplankton in the ballast water treatment cabin
Effluxing that ballast water for ship transports in the main line greater than 50 μ m phytoplankton content is 3 * 10
2Individual/mL, the oxygen activity particle injects the ballast water conveying pipe and processes OH solution, and the ballast water that reinjects transports trunk line, and its OH solution concentration is 0.40mg/L.The sampling in the main line somewhere, its corresponding lethal time is 6.0s, detects 0/mL of phytoplankton alive after the processing, fatal rate does not all have orthogenesis after 100.00%, 24 hour and 120 hours.Efflux that 10～50 μ m phytoplankton content are 5 * 10 in the ballast water for ship main line
3Individual/mL, the oxygen activity particle injects the ballast water conveying pipe and processes OH solution, and the ballast water that reinjects transports trunk line, and its OH solution concentration is 0.40mg/L.The sampling in the main line somewhere, its corresponding lethal time is 6.0s, detects 6/mL of phytoplankton alive after the processing, fatal rate does not all have orthogenesis after 99.88%, 24 hour and 120 hours.
In sum, efflux in the ballast water for ship main line phytoplankton concentration 3 * 10 of long＞50 μ m of body
2Individual/mL, the phytoplankton concentration 5 * 10 of long 10～50 μ m of body
3Individual/mL, bacterial concentration is 1.8 * 10
4Individual/mL; Inject 0.40mg/L hydroxyl free based sols, lethal time 6.0s; The phytoplankton of handling in the ballast water of back is that 3/mL, total number of bacteria are 198cfu/100mL; Fatal rate reaches 100.00%, and does not all have orthogenesis after 24 hours and 120 hours; Testing result has reached the effluent standard of the G8-D2 of International Maritime Organization (IMO).
Claims (5)
- One kind in water pipe the oxygen activity particle inject Treatment of Ships'Ballast Water method, i.e. oxygen activity particle O 2 +, O ( 1D), O ( 3P) and O 3Inject the ballast water conveying pipe or transport trunk line, be implemented in hydrobiont and the pathogen killed in the ballast water transport process in the ballast water, it is characterized in that:A) oxygen ionization in the dense ionization electric field, disassociation form oxygen activity particle O 2 +, O ( 1D), O ( 3P) and O 3, its concentration reaches 100mg/L～400mg/L;B) oxygen activity particle and ballast water reaction reaction of formation rate constant is 2.2 * 10 6Hydroperoxyl ion (the HO of L/mols 2 -) initiating agent, its concentration reaches 40mg/L～300mg/L;C) the oxygen activity particle is at HO 2 -Following and the ballast water reaction generation hydroxyl radical free radical (OH) of initiating agent effect, its concentration reaches 0.4mg/L～160mg/L;D) do not adding under any chemical agent condition, in the long ballast water conveying pipe of 4m～20m, injecting deadly hydrobiont of oxygen activity particle and pathogen efficient and reach 96%～100%;E) the biochemical reaction rate constant of hydrobiont and pathogen is 10 in the deadly ballast water 7L/mols～10 10L/mols, lethal time is 1s～10s.
- 2. according to claim 1 a kind of in water pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method; It is characterized in that: ballast water is from the process of ballast tank discharging or injection ballast tank, and the oxygen activity particle directly injects ballast water through the gas-liquid dissolver and transports trunk line deadly wherein hydrobiont and pathogen.
- 3. according to claim 1 a kind of in water pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method; It is characterized in that: transport from ballast water and take out 1/4～1/20 ballast water the main line and be divided into 2～20 branch roads; Every road ballast water contacts with the oxygen activity particle through 1 gas-liquid dissolver, processes OH solution.
- 4. according to claim 3 a kind of in water pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method, it is characterized in that: the concentration that each branch road is produced is the OH solution of 40～160mg/L, refills ballast water again and transports in the main line.
- 5. according to claim 1 a kind of in water pipe the oxygen activity particle inject the Treatment of Ships'Ballast Water method, it is characterized in that: the concentration of oxygen activity particle is adjusted according to the biomass of hydrobiont in the ballast water and pathogen in the described discharge of ballast water pipeline.
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|---|---|---|---|
| CN2010106023051A CN102173485B (en) | 2010-12-14 | 2010-12-14 | Method for treating ship ballast water by injecting oxygen active particles in transmission pipe |
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|---|---|---|---|
| CN2010106023051A CN102173485B (en) | 2010-12-14 | 2010-12-14 | Method for treating ship ballast water by injecting oxygen active particles in transmission pipe |
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| CN102173485B true CN102173485B (en) | 2012-07-25 |
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Cited By (1)
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|---|---|---|---|---|
| EP3666736A1 (en) * | 2018-12-14 | 2020-06-17 | ABB Schweiz AG | Ballast water treatment apparatus and method for treatment of ballast water |
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| CN103058349B (en) * | 2013-01-21 | 2013-11-13 | 张钰博 | Advanced oxidation treatment device and method for controlling red tide plankton invasion on offshore culture zone |
| CN103922510B (en) * | 2014-04-27 | 2015-02-04 | 大连海事大学 | Emergency treatment device for prevention and control of invasion of marine non-indigenous organisms in ballast water of entering-ships |
| CN103979661B (en) * | 2014-05-13 | 2015-06-24 | 大连海事大学 | Residual oxidant neutralization device and method used for ballast water discharging process |
| CN107777848A (en) * | 2017-10-17 | 2018-03-09 | 慈溪市卫诚环保科技有限公司 | A kind of waters administering method |
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Cited By (2)
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| EP3666736A1 (en) * | 2018-12-14 | 2020-06-17 | ABB Schweiz AG | Ballast water treatment apparatus and method for treatment of ballast water |
| WO2020120763A1 (en) * | 2018-12-14 | 2020-06-18 | Abb Schweiz Ag | Water treatment apparatus and method for treatment of water |
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| CN102173485A (en) | 2011-09-07 |
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