WO2011067721A2 - Traitement de l'eau - Google Patents

Traitement de l'eau Download PDF

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Publication number
WO2011067721A2
WO2011067721A2 PCT/IB2010/055523 IB2010055523W WO2011067721A2 WO 2011067721 A2 WO2011067721 A2 WO 2011067721A2 IB 2010055523 W IB2010055523 W IB 2010055523W WO 2011067721 A2 WO2011067721 A2 WO 2011067721A2
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WO
WIPO (PCT)
Prior art keywords
water
treatment composition
mass
acid
water treatment
Prior art date
Application number
PCT/IB2010/055523
Other languages
English (en)
Other versions
WO2011067721A3 (fr
Inventor
Bethseus Edwin Du Toit
Original Assignee
Bethseus Edwin Du Toit
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bethseus Edwin Du Toit filed Critical Bethseus Edwin Du Toit
Publication of WO2011067721A2 publication Critical patent/WO2011067721A2/fr
Publication of WO2011067721A3 publication Critical patent/WO2011067721A3/fr

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Classifications

    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/02—Sulfur; Selenium; Tellurium; Compounds thereof
    • 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
    • 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

Definitions

  • THIS INVENTION relates to the treatment of water.
  • the invention relates to a method of treating water and to a water treatment composition.
  • a dry water treatment composition which is free of chlorine and other halogen-based ingredients, and which is not affected by photo-decomposition, temperature and aeration during use, would be desirable. Such a water treatment composition would be easy to doze, detect, monitor and control. Preferably, such a water treatment composition should be usable as a residual disinfectant which can be used in conjunction with existing ultraviolet or ozone disinfectant systems and must act as a bio fouling reduction agent.
  • a method of treating water including adding a water treatment composition which is a solids admixture which includes at least one water soluble oxidant, at least one water soluble organic acid, a flocculent and water soluble bioflavonoids which are active against gram-positive and gram-negative bacteria, to water to be disinfected in a concentration sufficient to disinfect the water for human consumption.
  • a water treatment composition which is a solids admixture which includes at least one water soluble oxidant, at least one water soluble organic acid, a flocculent and water soluble bioflavonoids which are active against gram-positive and gram-negative bacteria
  • a water treatment composition which is a solids admixture which includes at least one water soluble oxidant, at least one water soluble organic acid, a flocculent and water soluble bioflavonoids which are active against gram-positive and gram-negative bacteria.
  • the water treatment composition is thus in dry form, e.g. in the form of a free-flowing powder, a tablet or a capsule.
  • the water treatment composition is ideally suitable for sanitising water on a small scale, e.g. for individual use of hikers or campers, for the military, for small human settlements, rural areas, and the like.
  • the water treatment composition can however also be used for sanitizing water on a large scale, e.g. for bulk use in municipal and other distributed drinking water systems, or to provide bulk water supply with a residual disinfectant capability throughout the reservoir and piping system.
  • the at least one water soluble oxidant may include one or more persulfate salts.
  • the water soluble oxidant includes potassium monopersulfate and sodium persulfate.
  • the potassium monopersulfate is in the form of potassium monopersulfate triple salt.
  • Potassium monopersulfate is the potassium salt of peroxymonosulfuric acid and is a component of a triple salt with the empirical formula K 5 H 5 S 4 Oi8 (2KHSO 5 KHSO 4 K 2 SO 4 ).
  • Potassium monopersulfate triple salt is available from Evonik under the trade name Caroat, from DuPont under the trade name Oxone, and from Shangyu Jiehua Chemical Co. Ltd.
  • Na2S2Os Sodium persulfate
  • the at least one water soluble organic acid may be a fruit acid, e.g. ascorbic acid.
  • the water treatment composition includes a mixture of ascorbic acid, citric acid and malic acid.
  • the acid or acids are food grade acids and are not neutralised.
  • the water soluble bioflavonoids typically include phenolic or polyphenolic substances.
  • the bioflavonoids thus typically include flavonones, flavones and flavonols.
  • the bioflavonoids may include water soluble flavonone glycosides, such as naringin, hesperidin and neohesperidin, as major components of the bioflavonoids.
  • Minor flavonone components may include didymin, neoeriocitrin and poncirin, e.g. as extracted from citrus fruits, preferably bitter oranges.
  • the bioflavonoids may also include one or more of anthocyanidins, proanthocyanidins, procyanidolic oligomers, catechens, biflavans, and rutinosides as minor components.
  • the bioflavonoids include hydroxylated phenols, quinones, coumarins and hydroxycinnamic acids.
  • the flocculent may be a cationic flocculent safe for human consumption, at least at low concentrations, e.g. a cationic polyacrylamide flocculent.
  • the water treatment composition may include potassium monopersulfate triple salt in a concentration of between about 40% and about 65% by mass, preferably between about 55% and about 60% by mass, e.g. about 59.5% by mass.
  • the water treatment composition may include sodium persulfate in a concentration of between about 25% and about 45% by mass, preferably between about 35% and about 40% by mass, e.g. about 39% by mass.
  • the water treatment composition may include water soluble bioflavonoids in a concentration of between about 0.005% and about 0.5% by mass, preferably between about 0.005% and about 0.015% by mass, e.g. about 0.01 % by mass.
  • the water treatment composition may include fruit acids in a concentration of between about 0.5% and about 2% by mass, preferably between about 1 % and about 1 .5% by mass, e.g. about 1 .44% by mass.
  • the water treatment composition may include ascorbic acid and citric acid in a combined concentration in the water treatment composition of between about 1 % and about 2% by mass, preferably between about 1 .3% by mass and about 1 .5% by mass, e.g. about 1 .42% by mass.
  • the water treatment composition may include ascorbic acid and malic acid in a combined concentration in the water treatment composition of between about 1 % by mass and about 2% by mass, preferably between about 1 .2% by mass and about 1 .45% by mass, e.g. about 1 .42% by mass.
  • the water treatment composition may include a cationic polyacrylamide flocculent in a concentration of between about 0.002% by mass and about 0.10% by mass, preferably between about 0.03% by mass and about 0.07% by mass, e.g. about 0.05% by mass.
  • the method may include adding the water treatment composition to water in a ratio of between 10mg/t and 300mg/t.
  • a dosage of about 50mg/l should be sufficient, whereas the dosage can be increased to as much as 140mg/l for more severely contaminated water.
  • a dosage of as little as 10mg/l can be used for application of the water treatment composition as residual disinfectant in large water systems, while the required dosage in bulk treatment systems (municipal) can be as much as 300mg/l.
  • a water treatment composition in accordance with the invention was formulated as follows:
  • Citrox BC Bioflavonoids proprietary blend 0.01 % by mass
  • Citrox BC bioflavonoids blend is obtainable from Citrox Limited of Unit 9, River Court, Brighouse Road, Riverside Park, Middlesbrough, TS2 1 RT, United Kingdom. The effectiveness of the Citrox BC bioflavonoids blend was tested to
  • the water treatment composition is useful to disinfect drinking water contaminated with pathogens, Cholera, and other harmful substances causing e.g. diarrhoea.
  • the water treatment composition is a free-flowing granular water soluble composition containing no chlorine or any other halogen-based product. Accordingly, the water treatment composition does not affect the thyroid gland as iodine does. It also does not create THM's (Trihalomethanes), which are carcinogenic byproducts of chlorine. It also does not create DBPs (disinfection by-products), which are formed when chlorine reacts negatively with natural organic compounds.
  • THM's Trihalomethanes
  • DBPs disinfection by-products
  • This water treatment composition contains natural anti-microbial substances in the form of bioflavonoid complexes active against gram-positive and gram-negative bacteria.
  • the inorganic salts act as a powerful oxidiser and disinfectant, making the water treatment composition ideally suitable for conditioning or treatment of drinking water.
  • the water treatment composition is capable of removing biofilm from water systems and is also capable of preventing biofilms from forming in water systems.
  • Microbiological deposits are often associated with the deposition of inorganic matter in low velocity areas of the distribution system, such as reservoirs. Ingress of mud may occur where reservoirs are not covered, or where filtration systems are not used in the treatment plant. Where mud or inorganic material deposition occurs, bacterial growth is often present. In situations where biological deposits and/or mud deposits are present together with water, containing positive dissolved oxygen content, corrosion of pipe work and metal fittings is inevitable.
  • the water treatment composition of the invention has been shown to be the disinfectant of choice for water supplies known to have a fouled pipeline system, or where iron and manganese cannot be fully eliminated at a treatment plant.
  • Some of the most common pathogens such as E. coli, Legionella, Salmonella sp., Pseudomonas aeruginosa, Staphylococcus aureus and Vibrio cholera have no tolerance against the water treatment composition as exemplified.
  • the water treatment composition is superior to other conventional disinfectant products in the destruction of spores, bacteria, viruses, fungi and other pathogen organisms, even Cryptosporidium and giardia, and also destroys phenols.
  • the water treatment composition is not affected by photodecomposition, temperature and aeration and is therefore suitable for use in uncovered reservoirs or poorly designed reservoirs subject to water turbulence, as reserve residual concentrations of the water treatment composition will not be affected.
  • Water treated with the water treatment composition is free from taste, taint and odour. Furthermore, the water treatment composition is easy to dose, detect, monitor and control, with the primary products from the reduction of the water treatment composition during use being oxygen and water, rendering the water treatment composition environmentally friendly without adverse breakdown or byproducts.
  • the potassium monopersulfate in the water treatment composition is a strong oxidising agent capable of oxidising organic and inorganic matter in water. Its solubility in water ranges from approximately 250g/t at 20°C to 330g/t at 70°C but it has a limited residual disinfectant value.
  • Sodium persulfate is also a strong oxidising agent. It is almost non- hydroscopic and can thus be stored for long periods of time. It is easy and safe to handle, is not combustible but releases oxygen easily. It is also capable of oxidising organic and inorganic matter in water. Sodium persulfate has a solubility in water which ranges from about 515g/t at 10°C to 680g/t at 60°C. It has a good residual disinfectant value and in commercially available products does not contain significant concentrations of impurities.
  • Bioflavonoids are also collectively known as Vitamin P and citrin. They are most commonly known for their antioxidant activity. Bioflavonoids are the most common group of polyphenolic compounds in the human diet and are found ubiquitously in plants such as berries, tea, beer, grapes, olive oil, cocoa, coffee, walnuts, peanuts and other fruits and vegetables. Bioflavonoids show anti-allergic, antiinflammatory, anti-microbial and anti-cancer activity. Over 5,000 naturally occurring bioflavonoids have been characterised from various plants and they have been classified according to their chemical structure.
  • the bioflavonoid mixture as used in the water treatment composition contains both large and small polyphenolic molecules. Formulations containing either all-large or all-small molecules are not so effective when tested against EN1276:1997. In addition, the larger bioflavonoid molecules have sugar molecules associates therewith, which have inherent properties of facilitating overall water solubility of the water treatment composition. A wide spectrum kill of both gram-positive and gram-negative bacteria has been demonstrated with mixed sized polyphenolic molecules.
  • the blend of bioflavonoids used in the water treatment composition is safe for human consumption.
  • Retroscreen Virology Limited carried out a comprehensive human cell toxicity evaluation for a number of bioflavonoids.
  • the report also confirmed that it is non-toxic to humans.
  • a major advantage of many plant polyphenolic derivatives is their low toxic potential.
  • the average western daily diet contains approximately 1 g of mixed bioflavonoids. Pharmacologically active concentrations used in the treatment of water are thus not likely to be harmful to human hosts.
  • caffeic acid belongs to a wide group of phenolpropane-derived compounds, which are in the highest oxidation state, and have been shown to be effective against fungi, bacteria and viruses.
  • Hydroxylated phenols have been shown to be toxic to micro-organisms.
  • the sites and numbers of hydroxyl groups on the phenol group are thought to be related to their relative toxicity to micro-organisms, with evidence that increased hydroxylation results in increased toxicity.
  • Some authors have found that more highly oxidised phenols are inhibitory.
  • the mechanisms thought to be responsible for phenolic toxicity to micro-organisms include enzyme inhibition by the oxidised compounds, possible through reaction with sulfhydryl groups or through more non-specific interactions with proteins.
  • Quinones are aromatic rings with two ketone substitutions, and their range of anti-microbial effects is great.
  • the probable targets in the microbial cell include surface-exposed adhesions, cell wall polypeptides and membrane-bound enzymes.
  • Flavones are phenolic structures containing a 3-hydroxyl group and a carbonyl group. Flavonoids are also hydroxylated phenolic substances but occur as a C6-C3 unit linked to an aromatic ring. These molecules are synthesised by plants in response to microbial infection, and in vitro they are effective anti-microbial substances against a wide array of micro-organisms. Their activity is due to their ability to complex with extracellular and soluble proteins, and to complex with bacterial cell walls as outlined above for quinones. It is also known that more lipophilic flavonoids disrupt microbial membranes.
  • Flavonoid compounds show marked inhibitory effects against multiple viruses. It has been proposed that small structural differences in the compounds quercetin, naringin, hesperitin and catechin are critical to their activities.
  • Proanthocyanidins which are derived from flavonoids monomers, have an anti-microbial action which does not only include complexing with proteins through hydrogen bonding, hydrophobic effects and covalent bond formation, but which may also be related to inactive microbial adhesions, enzymes and cell envelope transport proteins, much in the same way as has been reported for quinones.
  • the food grade acids used in the water treatment composition are used as disinfectants, preservatives and to neutralise the bitter taste associated with bioflavonoids.
  • Malic acid also boosts immunity, reduces the risk of poisoning from build-up of toxic metals in the human body, and has anti-septic properties.
  • Citric acid softens water and controls taste.
  • ascorbic acid neutralises taste and is believed to provide some health benefits to individuals' drinking water containing ascorbic acid.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Abstract

Cette invention concerne un procédé de traitement de l'eau consistant à ajouter à l'eau à désinfecter une composition de traitement de l'eau qui est constituée d'un mélange de solides comprenant au moins un oxydant hydrosoluble, au moins un acide organique hydrosoluble, un agent floculant et des bioflavonoïdes hydrosolubles qui sont actifs contre les bactéries à Gram positif et à Gram négatif. La composition est ajoutée à l'eau en une concentration suffisante pour la désinfecter et la rendre consommable par l'homme.
PCT/IB2010/055523 2009-12-01 2010-12-01 Traitement de l'eau WO2011067721A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA200908517 2009-12-01
ZA2009/08517 2009-12-01

Publications (2)

Publication Number Publication Date
WO2011067721A2 true WO2011067721A2 (fr) 2011-06-09
WO2011067721A3 WO2011067721A3 (fr) 2011-08-04

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ID=43925277

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PCT/IB2010/055523 WO2011067721A2 (fr) 2009-12-01 2010-12-01 Traitement de l'eau

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011154551A3 (fr) * 2010-06-11 2012-03-15 Solvent Solutions Limited Traitement des eaux d'égout
EP2828208A4 (fr) * 2012-03-22 2015-12-09 Peroxychem Llc Activation de persulfates au moyen d'acide organique
CN105536662A (zh) * 2015-12-30 2016-05-04 西安科技大学 一种微胶囊的制备方法
CN108033526A (zh) * 2017-12-12 2018-05-15 东华理工大学 一种耐高温复合水处理剂及其制备方法
CN110946147A (zh) * 2019-12-18 2020-04-03 连云港永荣生物科技有限公司 一种安全环保的污水消毒粉及其制备方法和应用
WO2020079449A1 (fr) * 2018-10-18 2020-04-23 Citrox Biosciences Limited Compositions à base de bioflavonoïdes et leur utilisation pour la purification d'eau et la conservation d'aliments
CN111410289A (zh) * 2020-05-20 2020-07-14 中山大学 一种对含有机污染物水体的处理方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5843375A (en) * 1995-06-07 1998-12-01 Proguard, Inc. Method for decontamination of a liquid of gaseous environment
AU776573B2 (en) * 1999-08-17 2004-09-16 Ipsilon Pools (Proprietary) Limited A biocidal composition and a method of treating water
WO2002022509A1 (fr) * 2000-09-13 2002-03-21 Shawn Alan Stewart Procede de purification ou de decontamination d'un corps liquide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011154551A3 (fr) * 2010-06-11 2012-03-15 Solvent Solutions Limited Traitement des eaux d'égout
EP2828208A4 (fr) * 2012-03-22 2015-12-09 Peroxychem Llc Activation de persulfates au moyen d'acide organique
US9821353B2 (en) 2012-03-22 2017-11-21 Peroxychem Llc Organic acid activation of persulfates
CN105536662A (zh) * 2015-12-30 2016-05-04 西安科技大学 一种微胶囊的制备方法
CN105536662B (zh) * 2015-12-30 2017-12-12 西安科技大学 一种微胶囊的制备方法
CN108033526A (zh) * 2017-12-12 2018-05-15 东华理工大学 一种耐高温复合水处理剂及其制备方法
WO2020079449A1 (fr) * 2018-10-18 2020-04-23 Citrox Biosciences Limited Compositions à base de bioflavonoïdes et leur utilisation pour la purification d'eau et la conservation d'aliments
GB2592330A (en) * 2018-10-18 2021-08-25 Citrox Biosciences Ltd Bioflavonoid compositions and their use for water purification and food preservation
GB2592330B (en) * 2018-10-18 2022-12-21 Citrox Biosciences Ltd Bioflavonoid compositions and their use for water purification and food preservation
US11980185B2 (en) 2018-10-18 2024-05-14 Citrox Biosciences Limited Bioflavonoid compositions and their use for water purification and food preservation
CN110946147A (zh) * 2019-12-18 2020-04-03 连云港永荣生物科技有限公司 一种安全环保的污水消毒粉及其制备方法和应用
CN111410289A (zh) * 2020-05-20 2020-07-14 中山大学 一种对含有机污染物水体的处理方法

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