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WO2012132892A1 - Agent antitartre pour membrane d'osmose inverse et procédé pour prévenir la formation de tartre - Google Patents

Agent antitartre pour membrane d'osmose inverse et procédé pour prévenir la formation de tartre Download PDF

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Publication number
WO2012132892A1
WO2012132892A1 PCT/JP2012/056500 JP2012056500W WO2012132892A1 WO 2012132892 A1 WO2012132892 A1 WO 2012132892A1 JP 2012056500 W JP2012056500 W JP 2012056500W WO 2012132892 A1 WO2012132892 A1 WO 2012132892A1
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Prior art keywords
scale
meth
acid
water
reverse osmosis
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Ceased
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English (en)
Japanese (ja)
Inventor
育子 西田
賢二 木幡
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Kurita Water Industries Ltd
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Kurita Water Industries Ltd
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Priority to CN2012800154808A priority Critical patent/CN103476714A/zh
Priority to JP2012515836A priority patent/JPWO2012132892A1/ja
Publication of WO2012132892A1 publication Critical patent/WO2012132892A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/08—Prevention of membrane fouling or of concentration polarisation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
    • B01D2321/16—Use of chemical agents
    • B01D2321/168—Use of other chemical agents
    • 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
    • C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention

Definitions

  • the present invention relates to a scale inhibitor for reverse osmosis membranes and a scale prevention method. More specifically, the present invention relates to a scale inhibitor and a scale prevention method for preventing adhesion of calcium phosphate scale generated in film treatment.
  • the scale generated in the heat exchange section causes heat transfer inhibition
  • the scale attached to the pipe causes a decrease in flow rate
  • the scale attached to the film causes a decrease in flux.
  • the generated scale is peeled off, it circulates in the system and causes the pump, the piping and the heat exchanging section to be blocked. Further, along with the blockage, the scaling in the pipe and the heat exchanging section is promoted.
  • a similar phenomenon can occur in the reduction well of a geothermal power plant.
  • Scale species generated in these aqueous systems include calcium phosphate, calcium carbonate, calcium sulfate, calcium sulfite, calcium silicate, magnesium silicate, magnesium hydroxide, zinc phosphate, zinc hydroxide, and basic zinc carbonate.
  • inorganic polyphosphoric acids such as sodium hexametaphosphate and sodium tripolyphosphate
  • phosphonic acids such as hydroxyethylidene diphosphonic acid and phosphonobutanetricarboxylic acid
  • maleic acid acrylic acid and itaconic acid
  • vinyl monomers having sulfonic acid groups such as vinyl sulfonic acid, allyl sulfonic acid and 3-allyloxy-2-hydroxypropane sulfonic acid, and nonionic vinyl monomers such as acrylamide are included
  • Copolymers combined according to water quality are used as scale inhibitors.
  • examples of the scale species generated in the reverse osmosis membrane (RO membrane) treatment include calcium phosphate, calcium carbonate, calcium sulfate, barium sulfate, strontium sulfate, and magnesium hydroxide.
  • the scale inhibitor generally has a relatively low molecular weight and a high scale prevention effect. Therefore, inorganic polyphosphates such as sodium hexametaphosphate and sodium tripolyphosphate, aminomethylphosphonic acid, hydroxyethylidene diphosphonic acid and phosphonobu Materials containing phosphorus such as phosphonic acids such as tantricarboxylic acid are used.
  • Patent Document 1 a terpolymer composed of monomers such as polyether polyaminomethylene phosphonate and acrylic acid is combined with hydroxyphosphonoacetic acid
  • Patent Document 3 A method using ⁇ -polyaspartic acid has also been proposed (see Patent Document 3).
  • a copolymer obtained by polymerizing monomers such as acrylic acid and sulfonic acid is used as a scale inhibitor (see Patent Documents 4 to 6).
  • the copolymer used in the scale inhibitors described in Patent Documents 4 to 6 is also free of phosphorus.
  • all these conventional scale inhibitors are premised on use in boilers and cooling water systems. It is difficult to say that it is suitable for RO membrane treatment.
  • scales generated in cooling water, evaporative concentration, boilers, etc. adhere to the surface of a heat exchanger or the like with a certain thickness, thereby causing heat transfer inhibition or affecting the stabilization of equipment.
  • the scale attached to the surface acts as an anticorrosion coating, and therefore some scale generation is allowed.
  • a scale inhibitor such as a cooling water system is required to have the ability to suppress the generated scale growth, and can be applied as long as it has a certain precipitation suppressing effect and gelation resistance.
  • the range of physical properties (molecular weight, composition, etc.) applicable as a scale inhibitor is wide.
  • RO membrane treatment has a small water flow path, and when fine precipitates such as scales and coexisting ions and scale inhibitor gels are formed, the membrane surface is clogged, affecting membrane treatment performance. .
  • the scale inhibitor for RO membrane treatment is required not to generate fine precipitates, and even if it is a material that can be applied in cooling water, evaporative concentration, etc., further limited physical property conditions are required. It is necessary to have.
  • the temperature at the location where scale should be prevented is lower, the residence time of water is shorter, and generally the concentration of the scale inhibitor added is lower than in the cooling water system.
  • the temperature at the place where scale should be prevented is about 10 to 40 ° C. in the RO membrane treatment, whereas it is 50 to 90 ° C. in the cooling water system or the like.
  • the residence time of water is about 15 minutes for the RO membrane treatment, whereas it is about 20 to 100 hours for the cooling water system.
  • the concentration of the scale inhibitor added is about 1 to 10 mg / L for the RO membrane treatment, whereas it is about 5 to 50 mg / L for the cooling water system.
  • the scale inhibitor for RO membrane treatment is different from the scale inhibitor used in other systems such as cooling water system, the processing conditions and required characteristics are different, the scale inhibitor such as cooling water system is treated with RO membrane treatment. Even if it is used, the same effect cannot be obtained.
  • the present invention is for a reverse osmosis membrane that can suppress the precipitation of calcium phosphate scale generated in the osmosis membrane treatment without increasing the phosphorus concentration in the waste water, and does not produce a fine precipitate such as a gelled product.
  • the main object is to provide a scale inhibitor and a scale prevention method.
  • the scale inhibitor for reverse osmosis membrane according to the present invention is a scale inhibitor that suppresses the precipitation of calcium phosphate scale in the reverse osmosis membrane treatment.
  • the main component is a unit derived from (meth) acrylic acid and 2- (meta) )
  • a structural unit derived from acrylamido-2-methylpropanesulfonic acid, the unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid is 10 to 40 mol%, and the mass average molecular weight is
  • the water-soluble copolymer is 1 ⁇ 10 4 to 5 ⁇ 10 4 .
  • the calcium phosphate scale is mainly composed of a water-soluble copolymer having a main constituent unit of a phosphorus-free monomer such as (meth) acrylic acid and 2- (meth) acrylamide-2-methylpropanesulfonic acid. It has a high prevention effect and does not increase the phosphorus concentration in the wastewater. Further, since the water-soluble copolymer has a mass average molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4, it is difficult to produce precipitates such as gelled products. In this scale inhibitor, the water-soluble polymer can be a copolymer of non-phosphorus-containing monomers, that is, not containing phosphorus.
  • the reverse osmosis membrane scale prevention method comprises a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid.
  • a scale mainly composed of a water-soluble copolymer having a unit derived from (meth) acrylamide-2-methylpropanesulfonic acid of 10 to 40 mol% and a mass average molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4
  • An inhibitor is added to the reverse osmosis membrane treated water system.
  • a water-soluble copolymer having a molecular weight within a specific range and containing as a main constituent unit a phosphorus-free monomer such as (meth) acrylic acid or 2- (meth) acrylamido-2-methylpropanesulfonic acid. Since the scale inhibitor mainly composed of is used, there is no increase in the phosphorus concentration in the waste water and no precipitation of gelled products, and the effect of suppressing the precipitation of calcium phosphate scale is high.
  • the “mass average molecular weight” in the present invention is a value measured by gel permeation chromatography using sodium polyacrylate as a standard substance.
  • the main component of the scale inhibitor is a water-soluble copolymer having a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid. Therefore, precipitation of calcium phosphate scale generated in the reverse osmosis membrane treatment can be suppressed without increasing the phosphorus concentration in the waste water, and fine precipitates such as gelled products are not generated.
  • the scale inhibitor of the present embodiment suppresses the precipitation of calcium phosphate scale that occurs in the reverse osmosis membrane treatment and prevents the scale from adhering to the RO membrane or the like, and its main component is (meth) acrylic acid. And a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid.
  • the water-soluble copolymer that is the main component of the scale inhibitor of the present embodiment is a copolymer of (meth) acrylic acid and 2- (meth) acrylamido-2-methylpropanesulfonic acid or These are copolymers of these with other monomers.
  • (meth) acrylic acid means methacrylic acid, acrylic acid or a salt thereof, and these monomers may be used alone or in combination of two or more.
  • 2- (Meth) acrylamide-2-methylpropanesulfonic acid means 2-methacrylamide-2-methylpropanesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid, one or both of which Can be used.
  • maleic acid and epoxy succinic acid can be used as the carboxylic acid.
  • the monoethylenically unsaturated hydrocarbon is not particularly limited, and may have a linear, branched or cyclic structure, but preferably has 3 to 8 carbon atoms.
  • isobutylene or styrene is used. can do.
  • the alkyl ester of monoethylenically unsaturated acid preferably has 1 to 8 carbon atoms.
  • methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl acrylate, N-butyl acrylate, 2-ethylhexyl acrylate is used. be able to.
  • the vinyl ester of monoethylenically unsaturated acid preferably has 1 to 8 carbon atoms, and for example, vinyl acetate and vinyl propionate can be used.
  • the substituted acrylamide is preferably one in which acrylamide is substituted with hydrogen and / or an alkyl group having 1 to 4 carbon atoms.
  • acrylamide, propylacrylamide, N-isopropylacrylamide, dimethylacrylamide, diethylacrylamide and the like can be used. it can. These monomers may be used alone or in combination.
  • the water-soluble copolymer that is the main component of the scale inhibitor of the present embodiment includes a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid. It is sufficient if it has a low phosphorus content, but is obtained by copolymerizing only (meth) acrylic acid and 2- (meth) acrylamido-2-methylpropanesulfonic acid without using other monomers. Water-soluble copolymers are particularly preferred.
  • the water-soluble copolymer that is the main component of the scale inhibitor of the present embodiment has 10 to 40 mol% of sulfonic acid units, that is, structural units derived from 2- (meth) acrylamide-2-methylpropanesulfonic acid. is there.
  • sulfonic acid units that is, structural units derived from 2- (meth) acrylamide-2-methylpropanesulfonic acid. is there.
  • the strong electrolyte (sulfonic acid group) decreases, so that gelation easily occurs and the scale-preventing effect of calcium phosphate also decreases.
  • the water-soluble copolymer that is the main component of the scale inhibitor of the present embodiment has a molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4 .
  • the molecular weight defined here is a mass average molecular weight measured by gel permeation chromatography using sodium polyacrylate as a standard substance, and the same applies to the following description.
  • the gelation resistance can be improved by reducing the molecular weight.
  • a water-soluble copolymer having a small molecular weight has a weak calcium phosphate adsorption ability and is inferior in calcium phosphate scale prevention effect.
  • a water-soluble polymer having a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid has a molecular weight of 1 When it is less than 10 4, the effect of suppressing the precipitation of calcium phosphate scale is not sufficiently obtained.
  • the molecular weight of the water-soluble polymer is preferably 1.1 ⁇ 10 4 or more.
  • the molecular weight of the water-soluble polymer exceeds 5 ⁇ 10 4 , gelation is likely to occur due to binding with cations, and gelation occurs and fine precipitates are generated even in an environment where the concentration of cations is low. Lowers the flux (permeation flow rate).
  • the production method of the water-soluble polymer described above is not particularly limited, and various polymerization methods such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization can be applied. From the viewpoint of ease of solution, solution polymerization is desirable.
  • Solution polymerization is performed in an organic solvent system or an aqueous system.
  • an organic solvent such as toluene or xylene
  • the polymerization initiator can be selected from known peroxides. Examples include dibenzoyl peroxide, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl peroxide. Only one type of polymerization initiator may be used, or two or more types may be used.
  • the organic solvent-based polymerization can be carried out either batchwise or continuously.
  • the polymerization conditions are, for example, a heating temperature of 100 to 200 ° C. and a polymerization time of 2 to 6 hours. After the polymerization, the mixture is allowed to cool to obtain a water-soluble copolymer.
  • the organic solvent polymerization conditions are not particularly limited, and the type, polymerization time, temperature, and the like of the organic solvent to be used can be appropriately changed.
  • aqueous polymerization method in which the polymerization is carried out in an aqueous system, an aqueous solution or dispersion of the monomer is prepared and the monomer is polymerized.
  • the pH of the aqueous monomer solution or aqueous dispersion is adjusted as necessary, the reaction atmosphere is replaced with an inert gas, and then heated to 50 to 100 ° C. in the presence of a water-soluble polymerization initiator.
  • the water-soluble polymerization initiator is not particularly limited.
  • 2,2-azobis (2-amidinopropane) dihydrochloride azobis-N, N′-dimethyleneisobutylamidine dihydrochloride
  • 4,4′-azobis Azo compounds such as 4-cyanovaleric acid
  • persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate
  • peroxides such as hydrogen peroxide and sodium periodate.
  • water-soluble polymerization initiators may be used alone or in combination of two or more.
  • the aqueous polymerization is completed, for example, in a polymerization time of 2 to 6 hours, and allowed to cool, whereby an aqueous solution or dispersion of the polymer can be obtained.
  • Aqueous polymerization can also be performed in the state which added additives, such as a dispersing agent and surfactant, to aqueous solution or an aqueous dispersion.
  • the scale inhibitor of the present embodiment includes a slime control agent, an enzyme, a bactericide, a colorant, a fragrance, a water-soluble organic solvent, and a range that does not impair the object of the present invention.
  • An antifoaming agent etc. may be mix
  • examples of the slime control agent include quaternary ammonium salts such as alkyldimethylbenzylammonium chloride, chloromethyltrithiazoline, chloromethylisothiazoline, methylisothiazoline, ethylaminoisopropylaminomethylthiatriazine, hypochlorous acid, hypochlorous acid, and hypochlorous acid. Bromic acid, a mixture of hypochlorous acid and sulfamic acid, and the like can be used.
  • the scale inhibitor of the present embodiment has a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid, Since the main component is a water-soluble copolymer having a unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid of 10 to 40 mol%, the effect of suppressing precipitation of calcium phosphate scale is excellent.
  • this water-soluble copolymer does not contain phosphorus or contains only a small amount of phosphorus, it hardly affects the phosphorus concentration in the waste water. Furthermore, since the water-soluble copolymer that is the main component of the scale inhibitor of the present embodiment has a molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4, it is difficult to generate fine precipitates such as gelled products. For this reason, the scale inhibitor of this embodiment is suitable for reverse osmosis membrane treatment. In addition, there is no restriction
  • the scale prevention method of the present embodiment is a method for suppressing the precipitation of calcium phosphate scale in the reverse osmosis membrane treatment using the scale inhibitor of the first embodiment described above. That is, the scale prevention method of the present embodiment has a unit derived from (meth) acrylic acid and a structural unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid.
  • Scale inhibitor comprising a water-soluble copolymer having a unit derived from acrylamido-2-methylpropanesulfonic acid of 10 to 40 mol% and a weight average molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4 as a main component Is added to the reverse osmosis membrane treated water system.
  • the addition method of the scale inhibitor is not particularly limited, and may be added at a place where scale adhesion is to be prevented or just before the place. Further, the addition amount is not particularly limited and can be appropriately selected according to the water quality of the aqueous system. However, the concentration of the water-soluble copolymer described above is 0.01 to 100 mg / L. In particular, from the viewpoint of prevention of film surface clogging, it is more preferable to add to 0.1 to 10 mg / L.
  • the scale prevention method of this embodiment can also use together the scale inhibitor of 1st Embodiment mentioned above and another scale inhibitor.
  • the scale inhibitor to be used in combination include polymaleic acid, polyacrylic acid, a copolymer of maleic acid and acrylic acid, a copolymer of maleic acid and isobutylene, a copolymer of maleic acid and sulfonic acid, and other maleic acid.
  • examples thereof include a copolymer, a copolymer of acrylic acid and sulfonic acid, a copolymer of acrylic acid and nonionic group-containing monomer, and a copolymer (terpolymer) of acrylic acid, sulfonic acid and nonionic group-containing monomer.
  • sulfonic acid examples include sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid, 2-acrylamide.
  • sulfonic acid such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, isoprene sulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid, 2-acrylamide.
  • These sulfonic acids may be used alone or in
  • Nonionic group-containing monomers include, for example, alkyl amides having 1 to 5 carbon atoms, hydroxyethyl methacrylate, (poly) ethylene / propylene oxide mono (meth) acrylates having 1 to 30 addition moles, and addition moles. Examples thereof include 1 to 30 monovinyl ether ethylene / propylene oxide. These nonionic group containing monomers may use only 1 type, and may use 2 or more types.
  • the maleic acid polymer (homopolymer and / or copolymer) is not particularly limited, but preferably contains 50 to 100 mol% of maleic acid units.
  • the other monomer to be copolymerized with maleic acid may be a nonionic monomer.
  • Nonionic monomers include, for example, monoethylenically unsaturated hydrocarbons, alkyl esters of monoethylenically unsaturated acids, vinyl esters of monoethylenically unsaturated acids, substituted acrylamides, etc.
  • 1 to The two can be copolymerized with maleic acid.
  • the monoethylenically unsaturated hydrocarbon is preferably a linear, branched or cyclic one having 3 to 8 carbon atoms, such as isobutylene or styrene.
  • the alkyl ester of monoethylenically unsaturated acid preferably has 1 to 8 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl acrylate, N-butyl acrylate, 2-ethylhexyl acrylate, etc. It is.
  • the vinyl ester of a monoethylenically unsaturated acid preferably has 1 to 8 carbon atoms, and examples thereof include vinyl acetate and vinyl propionate.
  • the substituted acrylamide is preferably one substituted with hydrogen and / or an alkyl group having 1 to 4 carbon atoms, and examples thereof include acrylamide, propylacrylamide, N-isopropylacrylamide, dimethylacrylamide and diethylacrylamide.
  • the molecular weight is in a specific range, the unit derived from (meth) acrylic acid, and the structural unit derived from a specific amount of 2- (meth) acrylamido-2-methylpropanesulfonic acid.
  • Suppressing the precipitation of calcium phosphate scale produced in reverse osmosis membrane treatment without affecting the phosphorus concentration in the wastewater because it uses a scale inhibitor mainly composed of a water-soluble copolymer containing In addition, fine precipitates such as gelled products are not generated.
  • the scale prevention method of this embodiment can suppress the precipitation of scale stably only by adding a small amount of a scale inhibitor to the aqueous system.
  • the water quality condition and operation condition of the water system to which the scale prevention method of this embodiment is applied are not particularly limited.
  • the configuration and effects other than those described above in the scale prevention method of the present embodiment are the same as those of the first embodiment described above.
  • ⁇ Flat membrane test> First, in order to measure the initial performance of the membrane, a 500 mg / L NaCl aqueous solution was passed through a polyamide reverse osmosis membrane (ES20 manufactured by Nitto Denko Corporation) at an operating pressure of 0.75 MPa and a recovery rate of 50%. (Flux) was measured for a predetermined time.
  • ES20 polyamide reverse osmosis membrane manufactured by Nitto Denko Corporation
  • an aqueous solution containing calcium chloride 500 mg CaCO 3 / L, Examples 1 to 3 and Comparative Examples 1 to 8 scale inhibitors (polymers): 1 mg / L, disodium hydrogen phosphate: 30 mg CaCO 3 / L
  • the pH was adjusted to 7.0 with a small amount of aqueous sodium hydroxide and sulfuric acid to prepare a test solution.
  • Each test solution was passed through a polyamide reverse osmosis membrane (ES20 manufactured by Nitto Denko Corporation) at an operating pressure of 0.75 MPa and a recovery rate of 50%, and flux was measured for a predetermined time.
  • FIGS. 1 and 2 are graphs showing changes with time in the ratio (flux ratio) to the flux measured with the test solution, where the flux in a 500 mg / L NaCl aqueous solution is 1.
  • FIG. Moreover, the blank (Blank) shown in FIG.1 and FIG.2 is a flux ratio when a chemical
  • Example 1 when the flux reduction rates of Examples 1 to 3 are compared, it is found that Example 1 ⁇ Example 2 ⁇ Example 3 in order, and Example 1 can most effectively suppress the flux reduction.
  • the scale inhibitor of Example 1 using a water-soluble copolymer having a unit derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid in the range of 15 to 25 mol% has reduced flux. was significantly suppressed.
  • the scale inhibitors of Comparative Examples 1 and 2 had the same composition of the scale inhibitor and monomer (AA / AMPS) of Example 1, but the flux was reduced. This is because the scale inhibitor of Comparative Example 1 had a molecular weight of the water-soluble copolymer of less than 1 ⁇ 10 4 , so the effect of suppressing the precipitation of scale was low, and the scale inhibitor of Comparative Example 2 was water-soluble. Since the molecular weight of the copolymer exceeded 5 ⁇ 10 4 , it is considered that a gelled product was generated. In particular, in the scale inhibitor of Comparative Example 2, it is considered that the film was clogged by the generated fine precipitate, and the flux decrease was faster than that of Blank.
  • the scale inhibitors of Comparative Examples 3 and 4 have a molecular weight of 1 ⁇ 10 4 to 5 ⁇ 10 4 of the water-soluble copolymer, but are units derived from 2- (meth) acrylamido-2-methylpropanesulfonic acid. Was less than 10 mol% or more than 40 mol%, the flux decreased.

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Abstract

Cette invention concerne un agent antitartre pour membranes d'osmose inverse et un procédé pour prévenir la formation de tartre qui peut empêcher l'attachement de tartre de type phosphate de calcium survenant dans le traitement par membrane d'osmose inverse sans augmenter la concentration de phosphore dans l'eau déchargée et qui n'entraîne pas la formation d'une fine boue telle que des matériaux gélatinisés. Selon l'invention, un agent antitartre ayant un motif dérivé d'un (méth)acrylate et un motif structural dérivé d'un acide 2-(méth)acrylamide-2-méthylpropane-sulfonique est ajouté à un système de traitement par membrane d'osmose inverse. Le motif dérivé de l'acide 2-(méth)acrylamide-2-méthylpropane-sulfonique représente 10 à 40 % en mol, et le composant principal de l'agent antitartre est un copolymère hydrosoluble ayant un poids moléculaire moyen en poids de 1 à 5 × 104.
PCT/JP2012/056500 2011-03-30 2012-03-14 Agent antitartre pour membrane d'osmose inverse et procédé pour prévenir la formation de tartre Ceased WO2012132892A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2012800154808A CN103476714A (zh) 2011-03-30 2012-03-14 反渗透膜用阻垢剂以及阻垢方法
JP2012515836A JPWO2012132892A1 (ja) 2011-03-30 2012-03-14 逆浸透膜用スケール防止剤及びスケール防止方法

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014079719A (ja) * 2012-10-18 2014-05-08 Japan Organo Co Ltd スケール洗浄液組成物およびスケール洗浄方法
WO2014157139A1 (fr) * 2013-03-29 2014-10-02 栗田工業株式会社 Procédé d'inhibition de la formation de tartes et inhibiteur de formation de tartes d'hydroxyde de magnésium pour une membrane d'osmose inverse
WO2015136992A1 (fr) * 2014-03-14 2015-09-17 栗田工業株式会社 Procédé de recyclage d'effluent eau de refroidissement et appareil de recyclage
CN105169955A (zh) * 2015-09-24 2015-12-23 威海翔宇环保科技股份有限公司 一种适合反渗透膜中水回用阻垢剂及其制备方法
WO2016047267A1 (fr) * 2014-09-22 2016-03-31 東亞合成株式会社 Copolymère à base d'acide acrylique ainsi que procédé de fabrication de celui-ci, et agent de traitement de l'eau
JP2018149462A (ja) * 2017-03-09 2018-09-27 アクアス株式会社 スケール除去剤、および、スケール除去方法
CN114195277A (zh) * 2021-11-11 2022-03-18 德蓝(海南)未来之水有限公司 一种低磷灰水分散剂及其制备方法
CN114213571A (zh) * 2021-12-17 2022-03-22 科威天使环保科技集团股份有限公司 一种三元共聚物阻垢剂的制备方法

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JP6779706B2 (ja) * 2016-08-23 2020-11-04 オルガノ株式会社 逆浸透膜を用いる水処理方法
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59162999A (ja) * 1983-03-07 1984-09-13 カルゴン・コ−ポレ−シヨン カルボン酸／スルホン酸ポリマ−類を含有する相乗効果的なスケ−ルおよび腐食抑制混合剤
JPS63107800A (ja) * 1986-10-23 1988-05-12 Kurita Water Ind Ltd 水系用スケ−ル防止剤
JP2001224933A (ja) * 2000-02-18 2001-08-21 Hakuto Co Ltd 逆浸透膜表面のスケール抑制方法
WO2010028196A1 (fr) * 2008-09-04 2010-03-11 Nalco Company Procédé destiné à inhiber la formation et le dépôt de calamine sur des systèmes membranaires par le biais de l'utilisation d'un copolymère aa ‑ amps

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101652326B (zh) * 2007-01-24 2012-07-04 栗田工业株式会社 逆渗透膜处理方法
CN101948189B (zh) * 2010-09-02 2012-05-23 蓝星环境工程有限公司 一种无磷反渗透膜阻垢剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59162999A (ja) * 1983-03-07 1984-09-13 カルゴン・コ−ポレ−シヨン カルボン酸／スルホン酸ポリマ−類を含有する相乗効果的なスケ−ルおよび腐食抑制混合剤
JPS63107800A (ja) * 1986-10-23 1988-05-12 Kurita Water Ind Ltd 水系用スケ−ル防止剤
JP2001224933A (ja) * 2000-02-18 2001-08-21 Hakuto Co Ltd 逆浸透膜表面のスケール抑制方法
WO2010028196A1 (fr) * 2008-09-04 2010-03-11 Nalco Company Procédé destiné à inhiber la formation et le dépôt de calamine sur des systèmes membranaires par le biais de l'utilisation d'un copolymère aa ‑ amps

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014079719A (ja) * 2012-10-18 2014-05-08 Japan Organo Co Ltd スケール洗浄液組成物およびスケール洗浄方法
WO2014157139A1 (fr) * 2013-03-29 2014-10-02 栗田工業株式会社 Procédé d'inhibition de la formation de tartes et inhibiteur de formation de tartes d'hydroxyde de magnésium pour une membrane d'osmose inverse
JP2014195754A (ja) * 2013-03-29 2014-10-16 栗田工業株式会社 スケール防止方法及び逆浸透膜用水酸化マグネシウムスケール防止剤
WO2015136992A1 (fr) * 2014-03-14 2015-09-17 栗田工業株式会社 Procédé de recyclage d'effluent eau de refroidissement et appareil de recyclage
CN106574021A (zh) * 2014-09-22 2017-04-19 东亚合成株式会社 丙烯酸系共聚物及其制造方法以及水处理剂
WO2016047267A1 (fr) * 2014-09-22 2016-03-31 東亞合成株式会社 Copolymère à base d'acide acrylique ainsi que procédé de fabrication de celui-ci, et agent de traitement de l'eau
JPWO2016047267A1 (ja) * 2014-09-22 2017-06-29 東亞合成株式会社 アクリル酸系共重合体及びその製造方法並びに水処理剤
JP2019031689A (ja) * 2014-09-22 2019-02-28 東亞合成株式会社 アクリル酸系共重合体及びその製造方法並びに水処理剤
CN106574021B (zh) * 2014-09-22 2019-05-14 东亚合成株式会社 丙烯酸系共聚物及其制造方法以及水处理剂
CN105169955A (zh) * 2015-09-24 2015-12-23 威海翔宇环保科技股份有限公司 一种适合反渗透膜中水回用阻垢剂及其制备方法
JP2018149462A (ja) * 2017-03-09 2018-09-27 アクアス株式会社 スケール除去剤、および、スケール除去方法
CN114195277A (zh) * 2021-11-11 2022-03-18 德蓝(海南)未来之水有限公司 一种低磷灰水分散剂及其制备方法
CN114213571A (zh) * 2021-12-17 2022-03-22 科威天使环保科技集团股份有限公司 一种三元共聚物阻垢剂的制备方法

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