SG192129A1 - Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flow - Google Patents
Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flow Download PDFInfo
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- SG192129A1 SG192129A1 SG2013056601A SG2013056601A SG192129A1 SG 192129 A1 SG192129 A1 SG 192129A1 SG 2013056601 A SG2013056601 A SG 2013056601A SG 2013056601 A SG2013056601 A SG 2013056601A SG 192129 A1 SG192129 A1 SG 192129A1
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- water stream
- peracetic acid
- hydrogen peroxide
- water
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- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 title claims abstract description 154
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 130
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 40
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 12
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- JFBJUMZWZDHTIF-UHFFFAOYSA-N chlorine chlorite Inorganic materials ClOCl=O JFBJUMZWZDHTIF-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical class ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- 241000238578 Daphnia Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000005791 algae growth Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 102100025854 Acyl-coenzyme A thioesterase 1 Human genes 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 241001494246 Daphnia magna Species 0.000 description 1
- 241000305506 Desmodesmus Species 0.000 description 1
- 101000720368 Homo sapiens Acyl-coenzyme A thioesterase 1 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 102000010292 Peptide Elongation Factor 1 Human genes 0.000 description 1
- 108010077524 Peptide Elongation Factor 1 Proteins 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004680 hydrogen peroxides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63J—AUXILIARIES ON VESSELS
- B63J4/00—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for
- B63J4/002—Arrangements of installations for treating ballast water, waste water, sewage, sludge, or refuse, or for preventing environmental pollution not otherwise provided for for treating ballast water
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B13/00—Conduits for emptying or ballasting; Self-bailing equipment; Scuppers
-
- 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
- C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2103/008—Originating from marine vessels, ships and boats, e.g. bilge water or ballast water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/18—Removal of treatment agents after treatment
Abstract
1 5Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flowAbstract:A device comprising a measuring device for determining the flow rate of a water stream, a measuring device for determining the concentration of hydrogen peroxide in the water stream, a measuring device for determining theconcentration of peracetic acid in the water stream, a metering device for metering a reducing agenT into the10 water stream downstream of the measuring devices for the concentrations, and a control device which, from the flowrate of the water stream, the concentration of hydrogen peroxide in. the water stream and the coneentralion of peracetic acid in the water stream, calculates an amount of15 reducing agent for reducing the content of hydrogen peroxide and peracetic acid to a desired value and actuates the metering device for metering the reducing agent, makespossible reliable reduction of the content of hydrogen peroxide and perapetic acid in a. water stream. The device20 is suitable for reducing the content of hydrogen peroxideand peracetic acid in a water stream which is withdrawn from ballast water tanks of a ship.
Description
Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flow
The invention relates to a device and a method for reducing the content of hydrogen pevoxide and peracetic acid in a water stream, 1n particular in a water stream which is withdrawn from ballast water tanks of a ship.
Peracetic acid is a biocide which has a number of advantages compared with other biccides. Paracetic acid, even at low concentrations of legs than & opm, exhibits a 14 bread biccidal activity againet bacteria, phyteplankton and zooplankton, without registances cccourring. In contrast Lo most other biocides, peracetic acid in dilute agueocus sclutions 1s rapidly degraded by hydrolysis and decomposition to substances which are no longer bioccidally active. In contrast to ozone or chlorine dioxide, peracetic acid can safely be transported and stored in the form of equilibrium peracetic acid. A treatment of water streams with peracetic acid, in contrast to chlorine or hypochlorite, does not lead, or leads only to a small extent, to the formation of halogenated organic compounds and therefore does not lead to an increase in the AOX content | Peracetic acid is therefcre suitable {or the biocidal treatment of water streams which are released into the surroundings in a large amount after the treatment, such as, for example, cooling water streams or ssawage treatment plant discharges and, in particular, ballast water of ships. The treatment of ballast water with peracetic acid in the SEDNAY method is approved by the
International Maritime Organization (IMO) for the removal of phytoplankton and zooplankton.
Although peracetic acid and the hydrogen peroxides that ig present in equilibrium peracetic acid due to the production process rapidly degrade in the treated water, it can be necessary 1n some applications, in particular in the
Zz treatment of ballast water, to remove any residual amounts of peracetic acaid and hydrogen peroxide still present after the treatment before the treated water is released co the surroundings.
For removing chloramines or bromanmines from treated ballast water, WO 02/072478 proposed to add a reducing agent such as sodium thicsulphate cor sodium sulphite in a molar excess to the treated ballast water. In this method, however, after reducing the chloramine oy bromamine, oxygen must further be introduced intc the treated water before in can he released to the surroundings.
WO 2004/054932 proposes to add a solution of sodium thiosulphate to the ballast water and control this metering via the redox potential of the chlorine-containing ballast water ror removing electrolytically generated chlorine from treated ballast water.
WO 2006/058261 and WO 2008/153808 propose to add a solution of sodium sulphite to the ballast water and control this metering via a sulphite analyser, which releases SO, by acid addition and determines this with a sensor, in such a manner that the treated ballast water contains excess sodium sulphite for removing electrolytically generated hypochlorite from treated ballast water.
U8 2010/072144 proposes to add a sclution of sodium sulphite toe the ballast water and control this metering vias measurement of the redox potential in the ballast water after additicn of the godium sulphite sclution in such a manner that the redox potential is in the yrange from 200 fo 500 mV for removing hypochlorite from treated ballast water.
Us 7,776,224 proposes to measure The concentration of hydrogen peroxide in the ballast water and add a veducing agent on the basis of Cle measured value for removing hydrogen peroxide from treated ballast water. It is further proposed toe check after addition of the reducing agent with a hydrogen peroxide densitometer or measurement of the redox potential whether unreacted hydrogen peroxide is praesent.
EF 1 &71 332 proposes to add one of the substances ivon (IT) sulphate, iodide or catalase with the oxidizing agent for a treatment of ballast water with hydrogen peroxide or equilibrium peracetic acid, in order to achieve 14) decomposition of hydrogen peroxide during the ballast water treatment.
However, there iz still a need for a device and a method that allows to reduce the content of hydrogen peroxide and peracetic acid in a water stream ag required and with which i5 the water stream, after removal of hydrogen peroxide and peracetic acid, contains no substances hazardous to water.
The inventors of the present invention have established that the method known from US 2010/072144 for removing hypochlorite is not suitable for removal of hydrogen peroxide from a water stream, since, by measuring the redox potential in the water after addition of a reducing agent, it cannot be reliably established that the water does not contain either unreacted hydrogen peroxide or excess reducing agent, Also, the method known from WO 2004/054832 for removing chlorine is not suitable for removing peracetic acid and hydrogen peroxide from a water stream, since the amount of reducing agent which would be reguired for removing peracetic acid and hydrogen peroxide cannct be calculated in advance from the redox potential of a water stream containing peracetic acid and hydrogen peroxide.
The inventors of the present invention have therefore developed a device and a method by means of which the contents of hydrogen peroxide and peracetic acid can be reliably reduced in a walber stream.
The invention relates to a device for reducing the content of hydrogen peroxide and peracetic acid in a water stream (1), comprising a first measuring device (2) for determining the flow rate of the water stream, a second measuring device (3) for determining the concentration of hydrogen peroxide in the water stream, a third measuring device (4) for determining the concentration of peracetic acid in the water stream, a metering device (5) for metering a reducing agent inte the water stream downstream of the second and third measuring devices and a control device {6} which, from the flow rate of the water stream, the concentration of hydrogen peroxide in the water stream, and the concentration of peracetic acid in the water stream, calculates an amount of reducing agent for reducing the content of hydrogen peroxide and peracetic acid to a desired value and actuates the metering device for metering the reducing agent.
The invention additionally relates to a method for reducing the content cof hydrogen peroxide and peracetic acid in a water stream, comprising metering a liguid reducing agent into the water stream using a device according to the invention. The water stream ls preferably withdrawn from ballast water tanks (10) of a ship.
Fig. 1 shows a device according to the invention in an emiodiment having an additional measuring device (7) for determining the salinity and an arrangement of the second and the third measuring device in a side stream (9),
The device according to the invention comprises a first measuring device (2) for determining the flow rate of the water stream (1). For this purpose, measuring devices which which determine a mass flow rate as well ag measuring devices which determine a volumetric flow rate are both suitable. For the device according to the invention, all measuring devices known from the prior art for determining the flow rate of a water stream may be used such as, for example, mass [low meters, differential pressure measurements at orifice plates and inductive flow meters.
Preferably, a mass {low meter ig used for derermining the flow rate of the water stream in order to determine the 5 flow rate of the water stream reliably seven for watery gtreams having different salt contents.
The device according to the invention additionally comprises a second measuring device (2) for determining the concentration of hydrogen peroxide in the water gtyeam (1).
Suitable measuring devices are all those known from the prior art with which the concentration of hydrogen peroxide may be determined in water and which do not exhibit, or exhibit only to a slight extent, a crosg-gensgitivity to peracetic acid. Suitable measuring devices are, for example, those which determine the concentration of hydrogen peroxide colorimetrically and use a colour reaction specific for hydrogen peroxide such as, for example, the reaction of hydrogen peroxide with titanyl sulphate, forming a scluble titanium{IV) peroxo complex.
Preferably, an amperometric sensor is used for determining the concentraticn of hydrogen peroxide, particularly preferably an amperometric sensor at which an oxidation of hydrogen peroxide proceeds according to the reaction equation
HO, COs + 2 H + 2 en.
Sultable amperometvic sensors for hydrogen peroxide that do not exhibit cross-sensitivity to peracetic acid are commercially available, for sxample from ProMinent™ under the name DULCOTESTY® PEROX. The response time of these sensors can be adapted by the manufacturer by exchanging the membrane which covers the sensor to the rate of change ol the hydrogen peroxide concentration in the water stream
Chat is to be treated.
The device according to the invention further comprises a third measuring device (4) for determining the concentration of peracetic acid in the water stream (1).
Suitable measuring devices are all those known from the prior art with which the concentration of peracetic acid may be determined in water and which do not show, or show cnly to a minor extent, a creoss-sensitivity fo hydrogen peroxide. Suitable measuring devices are, for example, those which determine the concentration of peracetic acid colorimetrically and use a colour reaction specific to peracetic acid, such as, for example, the reaction of peracetic acid with 2, Z-azinobils(3-ethylbenzothiazoline- t-sulphonic acid) diammonium salt (ABTS), forming a soluble dye. Preferably, an amperometric gensor 1s used for determining the concentration of peracetic acid, particularly preferably an amperometric sensor at which a is reduction of peracetic acld proceeds according to the reaction eguation
CH.COOOH + 2 HI" + 2 e .» CH,;COCH + H.O.
Suitable amperometric sensors for peracetic acid which show a sufficiently low cross-sensitivity to hydrogen peroxide are commercially available, for example {from ProMinent® under the name DULCOTESTY PAA. The response time of these gsengors can be adapted by the manufacturer, by exchanging the membrane which covers the sensor, to the rate of change of peracetic acid concentration in the water stream that is to be treated. Amperometric sensors that are likewise suitable are commercially available amperometric sensors for determining the total chlorine content, for example the sensors marketed by ProMinent? under the name DULCOTEST®
CTE-1. Since, due to the rapid reaction of chlorine and hypochlorite with hydrogen peroxide, a water stream containing hydrogen peroxide can contain only small amounts of chlorine and hypochlorite, and the amperometric sensors for determining the total chlorine content also determine peracetic acid with low crosg-sensitivity to hydrogen 3h peroxide, the content of peracetic acid can alsc be reliably determined in the water stream using such sensors.
The use of amperometric sensors for determining the concentrations of hydrogen peroxide and peracetic acid makes possible a gubstantially automated operation of the device according to the invention by staff such as, for example, a ship's crew, that has no training in operating analytical equipment,
Instead of two separate measuring devicez for determining the concentrations of hydrogen peroxide and peracetic acid, it is also possible to use one meaguring device, which determines both the concentration of hydrogen peroxide and the concentration of peracetic acid, in the device according to the invention. One example of such a measuring device is an automated titration with sequential cerimetric determination of the hydrogen peroxide concentration and iodometric determination of the peracetic acid concentration.
The measuring devices for determining the concentrations of hydrogen peroxide and peracetic acid are preferably arranged in a side stream (9) of rhe water stream in order to avoid damage to the measuring devices by solids carried by the water stream. For the game purposes, preferably a filter is arranged in the side stream upstream of the measuring devices.
The device according to the invention additionally comprises a metering device (5) for metering a reducing agent into the water stream (1) downstream of the second and third measuring devices. Suitable metering devices are those for continuous or intermittent metering of a reducing agent, which reducing agent is preferably gaseous ov 20 tiguid, and particularly preferably liguid. Preferably, the metering device comprises a storage vessel (8) and a controllable metering pump (5) for liguld reducing agent, such that a continuous metering of the liguid reducing agent is possible with a variable volumetric flow rate.
Particularly preferably, the metering device comprises a positive-displacement metering pump such as, for example, a diaphragm pump, gear pump or piston pump which makes possible setting a calculated volumetric flow rate for metering liguld reducing agent.
The device according to the invention further compriges a control device (6) which calculates an amount of reducing agent for reducing the content of hydrogen peroxide and peracetic acid to a desired value from the flow rate of the water stream (1), Che concentration of hydrogen peroxide in the water stream and the concentration of peracetic acid in the water stream, and actuates the metering device (5) for metering the reducing agent. The control device can be designed ag a hard-wired controller or as a calculation and control program on a process control computer. The calculation of the amount of reducing agent from the flow rate of the water stream, the concentration of hydrogen peroxide in the watery stream and the concentration of peracetic acid in the water stream can proceed using empirical conversion factors determined by experiments or, preferably, using conversion factors calculated from the stoichiometry of the reduction reaction. For salt-free walter gireams and a reduction using an aguesous sclution of sodium sulphite, the conversion factors can be calculated on the basis of the reaction equations (I) and (II). (I) HyDs + Na 80: - HO + Ha. S50, (II) CH,COO0H + N&;S0; — CH.COOHM + Na.80,
For liguid reducing agents which are metered via a positive-displacement metering pump, the volumetric flow rate to be set at the metering pump can be calculated directly from the calculated amount of reducing agent and the metering pump actuated accordingly.
In a preferred embodiment, the device according to the invention comprises an additional measuring device (7) for determining the salinity in the water stream (1). The expression salinity here designates the dimensionless
S salinity 8 on the Practical Salinity Scale 1978. The salinity can be determined on the basis of density measurements, and preferably on the basis of the electrical conductivity using a conductivity sensor. In this embodiment, the amount of reducing agent is calculated by the control device with the salinity. Preferably, here, the amount of reducing agent calculated for a zalt-free water stream is corrected by a correction factor for the salinity determined by experiments. For salt-containing water streams and a reduction with an aguecus aclution of sodium sulphite, preferably the amount of veducing agent calculated for a sait-free water stream ig increased by a fraction proportional to the salinity. Taking inte account the salinity in metering the reducing agent makes possible reliable reduction cof the content of hydrogen percxide and peracetic acid to below predetermined limits even for a variable salt content of the water stream, without overdosing of reducing agent occurring.
In the method according to the invention for reducing the content of hydrogen peroxide and peracetic acid in a water stream, a liquid reducing agent 1s metersd into the water stream (1) by a device according to the invention. The water stream is preferably a water stream treated by adding equilibrium peracetic acid as bioccide, in particular a cooling water stream, or a sewage Lreatment plant discharge, and most preferably, a water stream which is withdrawn from ballast water tanks (10) of a ship.
In the method according to the invention, preferably, an aguecus solution of sodium sulphite is used ag liguid reducing agent.
The method according to the invention makes possible a reliable reduction of the content of hydrogen peroxide and peracetic acid In a watery stream below predetermined limiting values, wherein, by using godium sulphite as 3h reducing agent, the water stream after the treatment no longer has properties impairing the water quality. This makes it possible to discharge a ballast water breated with equilibrium peracetic acid for destroying phytoplankton and zooplankton into bodies of water guch as, for example, constricted port basins in which the ballast water is diluted only poorly, without impairing the water quality of the body of water.
Fxamples: 18 For the working exemples embodiments, water which had been taken from a drinking water supply network was treated with 80 ppm eguilibrium peracetic acid that contained 14.4% by weight peracetic acid and 13.5% by weight hydrogen peroxide. After the treatment with equilibrium peracetic acid, the water contained 11.9 ppm peracetic acid and 12.3 ppm hydrogen peroxide on a weight basis.
To a gtream of the water that had been treated with equilibrium peracetic acid, an agueocus solution of sodium sulphite was metered continuously in a device according to the invention as per Figure 1. The concentrations of hydrogen peroxide and peracetic acid were determined here using amperometric sensors from ProMinent®. In Example 1, 1.03 times the stoichiometric amount of sodium sulphite, calculated according to reaction eguations {I} and (11) from the concentrations of hydrogen peroxide and peracetic acid and the flow rate of water, was metered. In Example 2, 1.21 times the calculated stoichiometric amount of sodium sulphite was metered.
In Example 1, the water contained 0.1 ppm peracetic acid and 1.0 ppm hydrogen peroxide, on a weight basis, after metering sodium sulphite. In Example 2, the water contained 0.2 ppm peracetic acid and 0.1 ppm hydrogen peroxide, on a welght basis, after the metering of sodium sulphite.
li
For the water trested with equilibrium peracetic acid and the water streams obtained in Examples 1 and 2, the inhibition of algal growth and the acute immobilization of daphnia were determined in accordance with OECD guidelines 20% and 202 for the tegting of chemicals.
The water treated with eguilibrium peracetic acid caused, undiluted, complete inhibition of the algal growth of
Desmodesmus subgpicatus with an ECs: value of 48% for the inhibition of the growth rate and 25% for the inhibition of 19 the vield. In contrast, the water stream obtained in
Example 1 caused, undiluted, only a statistically insignificant inhibition of the growth rate of 5%. The water stream obtalned in Example 2 caused, undiluted, an inhibition of the growth rate of 13%.
The water treated with equilibrium peracetic acid caused, undiluted, complete immobilization of Daphnia magna with an
Eley value of 12%. In contrast, the water gtreams obtained in Examples 1 and 2 caused, even undiluted, no immobilization and displayed no recognizable effect on daphnia.
The examples show that, with the device according to the invention and the method according to the invention, the contents of hvdrogen peroxide and peracetic acid may be reliably reduced in a water stream containing hydrogen peroxide and peracetic acid in such a manner that upon introduction inte bodies of water the watey stream has no narmful effects on water organisms.
List of reference numerals: (1} water stream (2) measuring device for determining the flow rate (3) measuring device for determining the concentration of hydrogen peroxide
(4) measuring device for determining the concentration of peracetic acid (5) metering device for metering a reducing agent (6) control device (7) measuring device for determining salinity (8) storage vessel for liguld reducing agent {9] side gtream (10) ballast water tanks
Claims (10)
- Claims:i. Device for reducing the content of hydrogen peroxide and peracetic acid in a water stream (1), comprising a first measuring device (2! for determining the flow rate of the water stream, a pecond measuring device (3) for determining the concentration of hydrogen peroxide in the water stream, a third measuring device (4; for determining the concentration of peracetic acid in the water stream, a metering device (5) for metering a reducing agent into the water stream downstream of the second and third measuring devices and a control device (6) which, from the flow rate of the water stream, the concentration of hydrogen peroxide in the water streaw, and the concentration of peracetic acid in the water gctream, calculates an amount of reducing agent for reducing the content of hydrogen peroxide and peracetic acid to a desired value and actuates the metering device for metering the reducing agent.
- 2. Device according to Claim I, characterized in that the measuring device for determining the concentration of hydrogen peroxide in the water stream comprises an amperomelyic Sensor.
- 3. Device according to Claim 1 or 2, characterized in that the measuring device for determining the concentration of peracetic acid in the water stream comprises an amperometric sensor.
- 4. Device according to any one of Claims 1 to 3, characterized in that it comprises an additional measuring device (7) for determining the salinity in the water stream and the control device calculates the amount of reducing agent with vhe salinity.
- 5. Device according to Claim 4, characterized in that the measuring device for determining the salinity comprises a conductivity sengor.
- &. Device according to any one of Claims 1 to 5, characterized in that the metering device for metering a reducing agent comprises a storage vessel (8) and a controllable metering pump (5) for liguid reducing agent.
- 7. Device according to any one of Claims 1 to 6, characterized in that the second and third measuring devices are arranged 1n a side stream (9) of the water stream.
- 8. Method for reducing the content of hydrogen peroxide and peracetic acid in a watery gtream, comprising metering a liguid reducing agent into the water stream using a device according to any one of Claims 1 to 7.
- 8. Method according to Claim 8, characterized in that the water stream 1s withdrawn from ballast water tanks (10) of a ship.
- 10. Method according to Claim 8 or 9, characterized in that the liquid reducing agent is an aqueous solution of sodium sulphite.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102011003187A DE102011003187A1 (en) | 2011-01-26 | 2011-01-26 | Apparatus and method for reducing the content of hydrogen peroxide and peracetic acid in a water stream |
| PCT/EP2012/050743 WO2012101026A1 (en) | 2011-01-26 | 2012-01-19 | Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flow |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SG192129A1 true SG192129A1 (en) | 2013-08-30 |
Family
ID=45554650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SG2013056601A SG192129A1 (en) | 2011-01-26 | 2012-01-19 | Device and method for reducing the hydrogen peroxide and peracetic acid content in a water flow |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US20130327718A1 (en) |
| EP (1) | EP2668138B1 (en) |
| JP (1) | JP5460936B2 (en) |
| KR (2) | KR20140014148A (en) |
| CN (1) | CN103370282B (en) |
| AP (1) | AP3841A (en) |
| AU (1) | AU2012210701B2 (en) |
| CY (1) | CY1117473T1 (en) |
| DE (1) | DE102011003187A1 (en) |
| DK (1) | DK2668138T3 (en) |
| HK (1) | HK1190696A1 (en) |
| RU (1) | RU2579383C2 (en) |
| SG (1) | SG192129A1 (en) |
| WO (1) | WO2012101026A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013200541B4 (en) * | 2013-01-16 | 2021-01-14 | Robert Bosch Gmbh | Method and device for pressure indexing in a dosing system |
| JP6379777B2 (en) * | 2014-07-15 | 2018-08-29 | 栗田工業株式会社 | Method for treating hydrogen peroxide-containing water |
| US11192809B2 (en) | 2017-11-14 | 2021-12-07 | Biosafe Systems Llc | Chiller water sampling device |
| DE102018113300A1 (en) * | 2018-06-05 | 2019-12-05 | Krones Ag | Method and measuring device for determining a peracetic acid concentration in a peracetic acid and hydrogen peroxide-containing sterilizing medium |
| US11953480B2 (en) * | 2018-06-29 | 2024-04-09 | Hach Company | Aqueous peracetic acid detection |
| JP7178833B2 (en) * | 2018-09-03 | 2022-11-28 | オルガノ株式会社 | Hydrogen peroxide-containing water treatment equipment |
| NO346187B1 (en) * | 2020-07-01 | 2022-04-11 | Niva Norwegian Institute For Water Res | Method of neutralizing hydrogen peroxide in wastewater from aquaculture delousing treatment |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6558529B1 (en) * | 2000-02-07 | 2003-05-06 | Steris Inc. | Electrochemical sensor for the specific detection of peroxyacetic acid in aqueous solutions using pulse amperometric methods |
| DE60128725T2 (en) | 2000-11-06 | 2008-01-24 | Larry Berckeley Russell | BALLAST WATER TREATMENT FOR REGULATING EXOTIC SPECIES |
| US7189314B1 (en) * | 2002-09-06 | 2007-03-13 | Sensicore, Inc. | Method and apparatus for quantitative analysis |
| GR1004273B (en) | 2002-12-18 | 2003-06-23 | Μαρκος Αναστασιου Νινολακης | Electrochemical method of sterilising seawater ballast in ships. |
| FR2869309B1 (en) * | 2004-04-22 | 2007-03-30 | Sidel Sas | PROCESS FOR PRODUCING QUALITY WATER FROM AN EFFLUENT CONTAINING A MIXTURE OF PEROXYGENIC OXIDIZING REAGENTS AND APPLICATION TO A DECONTAMINATION INSTALLATION OF OBJECTS |
| WO2006017063A2 (en) * | 2004-07-07 | 2006-02-16 | Disney Enterprises, Inc. | Process control oxidation |
| JP5135600B2 (en) | 2004-07-30 | 2013-02-06 | 株式会社片山化学工業研究所 | Ship ballast water treatment method |
| US7244348B2 (en) * | 2004-11-29 | 2007-07-17 | Severn Trent De Nora, Llc | System and method for treatment of ballast water |
| US8147673B2 (en) | 2005-01-18 | 2012-04-03 | Severn Trent De Nora, Llc | System and process for treatment and de-halogenation of ballast water |
| WO2006132157A1 (en) | 2005-06-10 | 2006-12-14 | Jfe Engineering Corporation | Ballast water treating apparatus and method of treating |
| US20100072144A1 (en) | 2006-09-27 | 2010-03-25 | Tsugiyoshi Osakabe | Method of treating ballast water of ship |
| JP4816671B2 (en) * | 2008-04-02 | 2011-11-16 | Ｊｆｅエンジニアリング株式会社 | Ballast water treatment method and apparatus |
| JP4816681B2 (en) * | 2008-05-27 | 2011-11-16 | Ｊｆｅエンジニアリング株式会社 | Ballast water treatment method and apparatus |
| KR100883444B1 (en) * | 2008-07-24 | 2009-02-17 | (주) 테크윈 | Apparatus and method for ballast water management |
-
2011
- 2011-01-26 DE DE102011003187A patent/DE102011003187A1/en not_active Withdrawn
-
2012
- 2012-01-19 DK DK12701481.9T patent/DK2668138T3/en active
- 2012-01-19 CN CN201280006803.7A patent/CN103370282B/en not_active Expired - Fee Related
- 2012-01-19 KR KR1020137022333A patent/KR20140014148A/en active IP Right Grant
- 2012-01-19 JP JP2013550830A patent/JP5460936B2/en not_active Expired - Fee Related
- 2012-01-19 WO PCT/EP2012/050743 patent/WO2012101026A1/en active Application Filing
- 2012-01-19 AU AU2012210701A patent/AU2012210701B2/en not_active Ceased
- 2012-01-19 US US13/981,814 patent/US20130327718A1/en not_active Abandoned
- 2012-01-19 AP AP2013007068A patent/AP3841A/en active
- 2012-01-19 RU RU2013139237/05A patent/RU2579383C2/en not_active IP Right Cessation
- 2012-01-19 KR KR1020167007617A patent/KR20160036673A/en not_active Application Discontinuation
- 2012-01-19 EP EP20120701481 patent/EP2668138B1/en not_active Not-in-force
- 2012-01-19 SG SG2013056601A patent/SG192129A1/en unknown
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2014
- 2014-04-21 HK HK14103766.0A patent/HK1190696A1/en not_active IP Right Cessation
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- 2015-07-21 CY CY20151100641T patent/CY1117473T1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN103370282B (en) | 2014-10-29 |
| US20130327718A1 (en) | 2013-12-12 |
| HK1190696A1 (en) | 2014-07-11 |
| AU2012210701B2 (en) | 2016-06-09 |
| KR20140014148A (en) | 2014-02-05 |
| CY1117473T1 (en) | 2017-04-26 |
| RU2013139237A (en) | 2015-04-10 |
| EP2668138A1 (en) | 2013-12-04 |
| DE102011003187A1 (en) | 2012-07-26 |
| KR20160036673A (en) | 2016-04-04 |
| JP2014506528A (en) | 2014-03-17 |
| AU2012210701A1 (en) | 2013-07-25 |
| CN103370282A (en) | 2013-10-23 |
| AP3841A (en) | 2016-09-30 |
| RU2579383C2 (en) | 2016-04-10 |
| AP2013007068A0 (en) | 2013-08-31 |
| WO2012101026A1 (en) | 2012-08-02 |
| DK2668138T3 (en) | 2015-07-27 |
| EP2668138B1 (en) | 2015-04-22 |
| JP5460936B2 (en) | 2014-04-02 |
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