CN102397753B - Anti-scaling agent of reverse osmosis membrane, and application thereof - Google Patents
Anti-scaling agent of reverse osmosis membrane, and application thereof Download PDFInfo
- Publication number
- CN102397753B CN102397753B CN201010276448.8A CN201010276448A CN102397753B CN 102397753 B CN102397753 B CN 102397753B CN 201010276448 A CN201010276448 A CN 201010276448A CN 102397753 B CN102397753 B CN 102397753B
- Authority
- CN
- China
- Prior art keywords
- acid
- copolymer
- water
- methylenephosphonic acids
- membrane
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
Abstract
The invention relates to a composite anti-scaling agent of a reverse osmosis membrane, and an application thereof. The composite anti-scaling agent comprises a component a and a component b, wherein the component a comprises at least one selected from methylene phosphonic carboxylic acid, the general formula of the component a is RCH(COOH)N(CH2PO3H2)2, the RCH(COOH)N is selected from an amino acid, the component b comprises at least one material selected from an organic phosphonic acid polymer and/or an organic carboxylic acid polymer. With adopting the composite anti-scaling agent of the present invention to carry out water treatment for a reverse osmosis system, the problems of CaCO3 deposition and CaSO4 deposition on the reverse osmosis membrane can be solved, the membrane pollution due to the CaCO3 deposition and the CaSO4 deposition can be eliminated, the work efficiency of the reverse osmosis system can be improved, the service lives of the reverse osmosis membrane and the reverse osmosis equipment can be prolonged, and the reverse osmosis cost can be reduced.
Description
Technical field
The present invention relates to a kind of composite scale inhibitor and application thereof, relate in particular to a kind of reverse osmosis membrane composite scale inhibitor and the application in counter-infiltration water treatment process thereof.
Background technology
Nineteen fifty-three, the Reid of Univ Florida USA etc. proposes Reverse-osmosis Seawater Desalination Technology the earliest.Nineteen sixty, the Loeb of California, USA university and Sourirajan develop first can be practical reverse osmosis membrane.Hereafter, the exploitation of reverse osmosis membrane starts to grow up gradually.Membrane material develops into the crosslinked aromatic polyamide composite film that adopts surface aggregate technology to make from single cellulose acetate anisotropic membrane.Operating pressure also expands to high pressure (desalinization) film, middle pressure (cellulose acetate) film, low pressure (compound) film and ultralow pressure (compound) film.The form of membrane module also presents diversified trend in recent years.Except traditional doughnut formula, rolling, tubular type and plate and frame, develop again revolution flat diaphragm type, dipping flat diaphragm type etc.In Treatment of Industrial Water, applying maximum is rolled film, and it has occupied most terrestrial water desalinations and increasing desalinization market.In addition, hollow-fibre membrane also occupies very high share in desalinization application.Now, the ability of whole world reverse osmosis membrane water treatment device has reached every day more than ten million ton.
China develops reverse osmosis membrane since middle 1960s, is separated by not farly with external start-up time, but due to raw material and basic industries condition restriction, development speed is slower.In recent years, along with the raising of China's expanding economy and overall national strength, the China that is applied in of reverse osmosis membrane has obtained very fast development, and application constantly expands.At present, domestic reverse osmosis process is mainly used in the pure water in the fields such as electronics, electric power, food, beverage and chemical industry and ultra-pure water preparation, a small amount of for brackish water desalination.
The advantage such as reverse osmosis membrane separation technology has without phase transformation, modularization, flow process is simple, easy to operate, floor space is little, reduced investment, power consumption are low still has wide application space in Treatment of Industrial Water.
In the actual application of reverse osmosis membrane separation technology, membrane pollution problem is the deciding factor that affects this engineering reliability.In membrane filtration processes, the absorption in film surface or fenestra owing to there is physics chemical action or mechanism with film of the large molecule of particulate in water, colloidal particle or solute, deposition, cause membrane aperture to diminish or stop up, the phenomenon that makes film produce the irreversible change that sees through flow and stalling characteristic is called film and pollutes.
The pollution of reverse osmosis membrane can be divided into suspended particulate and colloid pollution, inorganic sediments pollution, Organic Pollution and biological pollution 4 classes substantially.According to counter-infiltration system to enter water water quality different, main pollution type on reverse osmosis membrane is also different, suspended particulate, colloid, organic matter and microorganism etc. can be removed by pretreatment, but the sharply increase due to the various ion concentrations of reverse osmosis concentrated water side, when difficulty soluble salt is constantly concentrated in counter-infiltration system, when the product of its component ion concentration power surpasses its solubility product, will on reverse osmosis membrane surface, constantly deposit and fouling, form inorganic sediments and pollute.When water source is bitter, CaSO
4, CaCO
3, SiO
2it is the main difficulty soluble salt that produces dirty class.When middle water reuse, owing to containing a large amount of PO in middle water
4 3-, Zn
2+, easily form Ca
3(PO
4)
2precipitate with zinc salt.When counter-infiltration moisturizing be surface water, underground water mix with recycled water complicated water source time, reverse osmosis membrane is not only vulnerable to the pollution of above inorganic sediments, is also easily subject to flocculant residual Al in early stage
3+, Fe
3+the pollution of formed metal oxide, metal oxide is irreversible often to the injury of reverse osmosis membrane, and therefore harm is very large.The method of conventional control fouling comprises acid adding, add antisludging agent and acid and antisludging agent mixes and adds.Influent quality and the compatibility of film to acid and antisludging agent are depended in the selection of method, also will consider cost simultaneously.
US Patent No. 4,713,195 disclose a kind of composite scale inhibitor, the organic phosphonate of its maleic acid that comprises about 10-25 % by weight (acid anhydride) homopolymers, about 65-75 % by weight and styrene-maleic acid (acid anhydride) copolymer of about 5-25 % by weight sulfonation.This antisludging agent can be used for sea water distillation plant, reverse osmosis unit etc. and suppresses dirty formation.Its shortcoming is that this composite scale inhibitor dosage is large.
CN101423299A discloses a kind of reverse osmosis membrane antisludging agent, contains polymer class antisludging agent in this antisludging agent, and is selected from the component of phosphine carboxyl acids antisludging agent, organic phosphine acids antisludging agent, auxiliary agent.Its shortcoming is that scale inhibitor dosing amount is large.
CN101497481A discloses the antisludging agent that a kind of reverse osmosis membrane is used, formula comprises organic multicomponent phosphinic acid compounds, phosphine carboxylic acid, acrylic acid bipolymer and poly compound and water, organic multicomponent phosphinic acid compounds 1.0-6.0%, phosphine carboxylic acid 2-12%, acrylic acid bipolymer 10-40%, poly compound 0.2-2%, all the other are water.Its shortcoming is the tolerance of calcium alkali low, is not suitable for high hard high-alkali water quality.
Summary of the invention
Inventor studies discovery: the composite scale inhibitor being comprised of at least one methylene phosphonic carboxylic acid and at least one organic phospho acid and/or organic carboxyl acid base polymer can solve CaCO on reverse osmosis membrane for counter-infiltration system
3, CaSO
4deposition problems.
The object of the present invention is to provide a kind of reverse osmosis membrane composite scale inhibitor.
Another object of the present invention is composite scale inhibitor provided by the invention to be applied in counter-infiltration water treatment process, is particularly suitable for needing emphasis to solve CaCO
3, CaSO
4the reverse osmosis water treatment system of the deposition harm that brings.
For achieving the above object, the invention provides a kind of reverse osmosis membrane composite scale inhibitor, by component a and components b, formed, wherein a is at least one methylene phosphonic carboxylic acid, its general formula is: RCH (COOH) N (CH
2pO
3h
2)
2, RCH in formula (COOH) N is from amino acid; Components b is at least one is selected from the material of organic phospho acid and/or organic carboxyl acid base polymer.
Organic phospho acid of the present invention and organic carboxyl acid base polymer are selectable components, but will at least select a kind of material as b component.When methylene phosphonic carboxylic acid and organic phospho acid are composite, can further strengthen hindering CaCO
3dirt performance, and reduce the consumption of antisludging agent; Organic carboxyl acid base polymer resistance CaSO
4dirt excellent performance, can have good resistance CaCO concurrently together with methylene phosphonic carboxylic acid is composite with organic carboxyl acid base polymer
3dirt and resistance CaSO
4dirt performance.Preferred version is: components b of the present invention is at least one is selected from the material of organic phospho acid and at least one is selected from the material of organic carboxyl acid base polymer.
Methylene phosphonic carboxylic acid of the present invention is selected from glycine two methylenephosphonic acids, glutamic acid two methylenephosphonic acids, alanine two methylenephosphonic acids, valine two methylenephosphonic acids, leucine two methylenephosphonic acids, isoleucine two methylenephosphonic acids, serine two methylenephosphonic acids, threonine two methylenephosphonic acids, cysteine two methylenephosphonic acids, methionine two methylenephosphonic acids, aspartic acid two methylenephosphonic acids, phenylalanine two methylenephosphonic acids and tyrosine two methylenephosphonic acids.Preferably from glycine two methylenephosphonic acids and glutamic acid two methylenephosphonic acids.
Organic phospho acid of the present invention is selected from HEDP, ATMP, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and diethylene triamine pentamethylene phosphonic.
Organic carboxyl acid base polymer of the present invention is selected from organic carboxyl acid class homopolymers, organic carboxyl acid class bipolymer and terpolymer.
Organic carboxyl acid base polymer of the present invention is selected from polyacrylic acid, HPMA, poly-aspartic-acid, poly-epoxy succinic acid, acrylic acid/hydroxypropyl acrylate copolymer, acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer, maleic acid/Styrene Sulfonic Acid Copolymer, maleic anhydride/Styrene Sulfonic Acid Copolymer, acrylic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, maleic acid/allyl sulphonic acid copolymer, maleic anhydride/allyl sulphonic acid copolymer, acrylic acid/allyl sulphonic acid copolymer, acrylic acid/vinyl sulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid copolymer, acrylic acid/maleic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer and acrylic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer.Organic carboxyl acid base polymer is preferably from acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer, acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer and acrylic acid/Styrene Sulfonic Acid Copolymer.Wherein said acrylate is preferably from acrylic acid C
1-8ester, more preferably from methyl acrylate, ethyl acrylate, hydroxypropyl acrylate.
It is benchmark that the concentration of each component of the present invention be take the water yield of processing in counter-infiltration system, and the valid density of methylene phosphonic carboxylic acid in counter-infiltration system (take active matter content) is 1～6mg/L water.
The valid density of organic phospho acid of the present invention (if any) in counter-infiltration system (take active matter content) is 1～6mg/L water.
The valid density of organic carboxyl acid base polymer of the present invention (if any) in reverse osmosis membrane (take active matter content) is 1～6mg/L water.
While preparing composite scale inhibitor of the present invention, the reinforced order of each component is unimportant, and at least one methylene phosphonic carboxylic acid mixes and is made into a kind of liquid medicine in predetermined ratio with at least one organic phospho acid and/or organic carboxyl acid base polymer.
The present invention also provides a kind of method of scale inhibition for reverse osmosis membrane, and its feature is that antisludging agent can add in any position of counter-infiltration system to add composite scale inhibitor of the present invention in counter-infiltration system, as added in reverse osmosis membrane water inlet.
When composite scale inhibitor provided by the invention is used for counter-infiltration system water treatment, can solve CaCO on reverse osmosis membrane
3, CaSO
4deposition problems, effectively eliminate CaCO
3, CaSO
4the film bringing pollutes, and improves the operating efficiency of counter-infiltration system, extends the service life of reverse osmosis membrane and reverse osmosis equipment, reduces the cost of counter-infiltration.Reverse osmosis compound scale inhibitor of the present invention is high to calcium alkali tolerance, is specially adapted to take the hard high buck of height and penetrates the counter-infiltration system of water as reverse osmosis.
The specific embodiment
The following examples will contribute to illustrate the present invention, but not limit to its scope.
Test raw water quality is in Table 1.
Table 1 test raw water quality
| Title | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | pH | Electrical conductivity | SiO 2 |
| High hardness water | 260 | 334 | 497 | 141 | 390 | 8.8 | 1871 | 89 |
Note: pHWu unit, electrical conductivity is μ s/cm, its counit is mg/L, Ca
2+, total alkalinity, total hardness be all with CaCO
3meter, lower same.
In following embodiment, the Reliable Evaluating Methods of Their Performance of antisludging agent for osmosis-reverse membrane is as follows:
Resistance calcium carbonate scale performance is got the former water of test, and by the Ca in former water
2+, HCO
3 -mend 800mg/L (with CaCO
3meter) form test water, add certain density (in valid density) antisludging agent for osmosis-reverse membrane, in 60 ± 1 ℃ of waters bath with thermostatic control, insulation 10h, remains Ca in cooling rear sample analysis water
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Ca
2+concentration
C
0: the Ca of blank sample
2+concentration
C
1: the Ca in former water
2+concentration
Resistance calcium sulfate scale performance is got the former water of test, and by the Ca in former water
2+, SO
4 2-mend 6000mg/L (with CaCO
3meter) form test water, add certain density (in valid density) antisludging agent for osmosis-reverse membrane, in 70 ± 1 ℃ of waters bath with thermostatic control, insulation 10h, remains Ca in cooling rear sample analysis water
2+concentration, make blank sample simultaneously, and calculate scale inhibition performance.
Scale inhibition performance computing formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Ca
2+concentration
C
0: the Ca of blank sample
2+concentration
C
1: the Ca in former water
2+concentration
Analytical method Ca
2+method for measurement of concentration is with reference to Ca in < < boiler feed water and cooling water analytical method > > GB6905.3-86
2+the assay method of concentration, SO
4 2-method for measurement of concentration is with reference to SO in the cooling water analysis of < < China Petrochemical Industry and test method > > Q/SH 3155.S08.007-2006
4 2-the assay method of concentration.
Embodiment 1
Get effective content and be 30% glycine two methylenephosphonic acid 16.7g; Effective content is 50% 2-phosphonate group-1, and 2,4-butane tricarboxylate 4g, is dissolved in 29.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of glycine two methylenephosphonic acids is 5mg/L, 2-phosphonate group-1, and 2,4-butane tricarboxylate's the valid density that adds is 2mg/L.
Embodiment 2
Get effective content and be 30% glutamic acid two methylenephosphonic acid 10g; Effective content is 50% HEDP 6g, is dissolved in 34g water, is made into antisludging agent for osmosis-reverse membrane.Add anti-this permeable membrane and use antisludging agent in test water, adding concentration is 50mg/L, and the valid density that adds of its Glutamic Acid diformazan fork phosphonic acids is 3mg/L, and the valid density that adds of HEDP is 3mg/L.
Embodiment 3
Get effective content and be 30% leucine two methylenephosphonic acid 6.7g; Effective content is 50% ATMP 10g, is dissolved in 33.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of leucine two methylenephosphonic acids is 2mg/L, and the valid density that adds of ATMP is 5mg/L.
Embodiment 4
Get effective content and be 30% glutamic acid two methylenephosphonic acid 16.7g; Limiting Viscosity is 0.075dLg
-1solid content is acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer (mass ratio of acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid is 2: 1: 1) 6.7g of 30%, be dissolved in 26.6g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, the valid density that adds of its Glutamic Acid diformazan fork phosphonic acids is 5mg/L, and the valid density that adds of acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer is 2mg/L.
Embodiment 5
Get effective content and be 30% isoleucine two methylenephosphonic acid 10g; Limiting Viscosity is 0.074dLg
-1, acrylic acid/Styrene Sulfonic Acid Copolymer that solid content is 30% (mass ratio of acrylic acid/styrene sulfonic acid is 2: 1) 10g, is dissolved in 30g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of isoleucine two methylenephosphonic acids is 3mg/L, and the valid density that adds of acrylic acid/Styrene Sulfonic Acid Copolymer is 3mg/L.
Embodiment 6
Get effective content and be 30% glycine two methylenephosphonic acid 6.7g; Limiting Viscosity is 0.075dLg
-1, the polyacrylic acid 16.7g that solid content is 30%, is dissolved in 26.6g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of glycine two methylenephosphonic acids is 2mg/L, and the polyacrylic valid density that adds is 5mg/L.
Embodiment 7
Get effective content and be 30% cysteine two methylenephosphonic acid 10g; Effective content is 50% 2-phosphonate group-1,2,4-butane tricarboxylate 6g, and the diethylene triamine pentamethylene phosphonic 6g that effective content is 50%, is dissolved in 28g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of cysteine two methylenephosphonic acids is 3mg/L, 2-phosphonate group-1,2,4-butane tricarboxylate's the valid density that adds is 3mg/L, and the valid density that adds of diethylene triamine pentamethylene phosphonic is 3mg/L.
Embodiment 8
Get effective content and be 30% serine two methylenephosphonic acid 16.7g; Effective content is 50% diethylene triamine pentamethylene phosphonic 6g; Effective content is 50% ATMP 6g; Be dissolved in 21.3g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of serine two methylenephosphonic acids is 5mg/L, and the valid density that adds of diethylene triamine pentamethylene phosphonic is 3mg/L, and the valid density that adds of ATMP is 3mg/L.
Embodiment 9
Get effective content and be 30% glutamic acid two methylenephosphonic acid 6.7g; Effective content is 50% 2-phosphonate group-1,2,4-butane tricarboxylate 6g; Effective content is 50% HEDP 6g; Be dissolved in 31.3g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and the valid density that adds of its Glutamic Acid diformazan fork phosphonic acids is 2mg/L, 2-phosphonate group-1,2,4-butane tricarboxylate's the valid density that adds is 3mg/L, and the valid density that adds of HEDP is 3mg/L.
Embodiment 10
Get effective content and be 30% methionine two methylenephosphonic acid 10g; Limiting Viscosity is 0.075dLg
-1, the HPMA 10g that solid content is 30%; Limiting Viscosity is 0.073dLg
-1, acrylic acid/allyl sulphonic acid copolymer that solid content is 30% (mass ratio of acrylic acid/allyl sulphonic acid is 2: 1) 10g, is dissolved in 20g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of methionine two methylenephosphonic acids is 3mg/L, and the valid density that adds of HPMA is 3mg/L, and the valid density that adds of acrylic acid/allyl sulphonic acid copolymer is 3mg/L.
Embodiment 11
Get effective content and be 30% alanine two methylenephosphonic acid 16.7g; Limiting Viscosity is 0.075dLg
-1, acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer that solid content is 30% (mass ratio of acrylic acid/hydroxypropyl acrylate/methyl acrylate is 2: 1: 1) 10g; Limiting Viscosity is 0.075dLg
-1, the poly-aspartic-acid 10g that solid content is 30%, is dissolved in 13.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of alanine two methylenephosphonic acids is 5mg/L, the valid density that adds of acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer is 3mg/L, and the valid density that adds of poly-aspartic-acid is 3mg/L.
Embodiment 12
Get effective content and be 30% valine two methylenephosphonic acid 6.7g; Limiting Viscosity is 0.071dLg
-1, the poly-epoxy succinic acid 10g that solid content is 30%; Limiting Viscosity is 0.075dLg
-1, acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer that solid content is 30% (mass ratio of acrylic acid/hydroxypropyl acrylate/methyl acrylate is 2: 1: 1) 10g, is dissolved in 23.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of valine two methylenephosphonic acids is 2mg/L, the valid density that adds of poly-epoxy succinic acid is 3mg/L, and the valid density that adds of acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer is 3mg/L.
Embodiment 13
Get effective content and be 30% glycine two methylenephosphonic acid 10g; Effective content is 50% 2-phosphonate group-1,2,4-butane tricarboxylate 6g; Limiting Viscosity is 0.075dLg
-1, the polyacrylic acid 10g that solid content is 30%, is dissolved in 24g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of glycine two methylenephosphonic acids is 3mg/L, 2-phosphonate group-1,2,4-butane tricarboxylate's the valid density that adds is 3mg/L, and the polyacrylic valid density that adds is 3mg/L.
Embodiment 14
Get effective content and be 30% glutamic acid two methylenephosphonic acid 16.7g; Effective content is 50% HEDP 6g; Limiting Viscosity is 0.074dLg
-1solid content is acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer (mass ratio of acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid is 2: 1: 1) 10g of 30%, be dissolved in 17.3g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, the valid density that adds of its Glutamic Acid diformazan fork phosphonic acids is 5mg/L, the valid density that adds of HEDP is 3mg/L, and the valid density that adds of acrylic acid/acrylamide/2-methyl-2 '-acrylamido propane sulfonic acid copolymer is 3mg/L.
Embodiment 15
Get effective content and be 30% threonine two methylenephosphonic acid 10g; Effective content is 50% ATMP 10g; Limiting Viscosity is 0.073dLg
-1solid content is acrylic acid/maleic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer (mass ratio of acrylic acid/maleic acid/2-methyl-2 '-acrylamido propane sulfonic acid is 2: 1: 1) 10g of 30%, be dissolved in 20g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of threonine two methylenephosphonic acids is 3mg/L, the valid density that adds of ATMP is 5mg/L, and the valid density that adds of acrylic acid/maleic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer is 3mg/L.
Embodiment 16
Get effective content and be 30% phenylalanine two methylenephosphonic acid 10g; Effective content is 50% 2-phosphonate group-1,2,4-butane tricarboxylate 6g; Limiting Viscosity is 0.075dLg
-1, the HPMA 16.7g that solid content is 30%, is dissolved in 17.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of phenylalanine two methylenephosphonic acids is 3mg/L, 2-phosphonate group-1,2,4-butane tricarboxylate's the valid density that adds is 3mg/L, and the valid density that adds of HPMA is 5mg/L.
Embodiment 17
Get effective content and be 30% glutamic acid two methylenephosphonic acid 6.7g; Effective content is 50% ATMP 6g; Limiting Viscosity is 0.073dLg
-1, acrylic acid/vinyl sulfonic acid copolymer that solid content is 30% (mass ratio of acrylic acid/vinyl sulfonic acid is 2: 1) 10g, is dissolved in 27.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, the valid density that adds of its Glutamic Acid diformazan fork phosphonic acids is 2mg/L, and the valid density that adds of ATMP is 3mg/L, and the valid density that adds of acrylic acid/vinyl sulfonic acid copolymer is 3mg/L.
Embodiment 18
Get effective content and be 30% cysteine two methylenephosphonic acid 10g; Effective content is 50% hydroxyethylidene diphosphonic acid guanidine-acetic acid 4g; Limiting Viscosity is 0.075dLg
-1, maleic anhydride/Styrene Sulfonic Acid Copolymer that solid content is 30% (mass ratio of maleic anhydride/styrene sulfonic acid is 2: 1) 10g, is dissolved in 26g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of cysteine two methylenephosphonic acids is 3mg/L, the valid density that adds of hydroxyethylidene diphosphonic acid guanidine-acetic acid is 2mg/L, and the valid density that adds of maleic anhydride/Styrene Sulfonic Acid Copolymer is 3mg/L.
Embodiment 19
Get effective content and be 30% glycine two methylenephosphonic acid 10g; Effective content is 50% ethylene diamine tetra methylene phosphonic acid 6g; Limiting Viscosity is 0.073dLg
-1, the poly-aspartic-acid 6.7g that solid content is 30%, is dissolved in 27.3g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of glycine two methylenephosphonic acids is 3mg/L, and the valid density that adds of ethylene diamine tetra methylene phosphonic acid is 3mg/L, and the valid density that adds of poly-aspartic-acid is 2mg/L.
Comparative example 1
Get effective content and be 30% glycine two methylenephosphonic acid 20g, be dissolved in 30g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of glycine two methylenephosphonic acids is 6mg/L.
Comparative example 2
Get effective content and be 50% 2-phosphonate group-1,2,4-butane tricarboxylate 12g, is dissolved in 38g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, 2-phosphonate group-1 wherein, and 2,4-butane tricarboxylate's the valid density that adds is 6mg/L.
Comparative example 3
Getting Limiting Viscosity is 0.075dLg
-1, the polyacrylic acid 20g that solid content is 30%, is dissolved in 30g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the polyacrylic valid density that adds is 6mg/L.
Comparative example 4
Getting Limiting Viscosity is 0.075dLg
-1solid content is acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer (mass ratio of acrylic acid/hydroxypropyl acrylate/methyl acrylate is 2: 1: 1) 10g of 30%, effective content is 50% HEDP 6g, is dissolved in 34g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, and wherein the valid density that adds of acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer is 3mg/L, and the valid density that adds of HEDP is 3mg/L.
Comparative example 5
Getting Limiting Viscosity is 0.074dLg
-1solid content is maleic anhydride/Styrene Sulfonic Acid Copolymer (mass ratio of maleic anhydride/styrene sulfonic acid is 2: 1) 10g of 30%, effective content is 50% ATMP 6g, effective content is 50% ethylene diamine tetra methylene phosphonic acid 6g, be dissolved in 28g water, be made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of maleic anhydride/Styrene Sulfonic Acid Copolymer is 3mg/L, and the valid density that adds of ATMP is 3mg/L, and the valid density that adds of ethylene diamine tetra methylene phosphonic acid is 3mg/L.
Comparative example 6
Getting Limiting Viscosity is 0.074dLg
-1, acrylic acid/2-methyl-2 that solid content is 30% '-acrylamido propane sulfonic acid copolymer (mass ratio of acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid is 2: 1) 10g, Limiting Viscosity is 0.072dLg
-1, maleic acid/Styrene Sulfonic Acid Copolymer that solid content is 30% (mass ratio be 2: 1) 10g, the hydroxyethylidene diphosphonic acid guanidine-acetic acid 6g that effective content is 50%, is dissolved in 24g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, wherein the valid density that adds of acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid copolymer is 3mg/L, the valid density that adds of maleic acid/Styrene Sulfonic Acid Copolymer is 3mg/L, and the valid density that adds of hydroxyethylidene diphosphonic acid guanidine-acetic acid is 3mg/L.
Comparative example 7
Get effective content and be 50% 2-phosphonate group-1,2,4-butane tricarboxylate 12g; Limiting Viscosity is 0.078dLg
-1, maleic acid/Styrene Sulfonic Acid Copolymer that solid content is 30% (mass ratio of maleic acid/styrene sulfonic acid is 2: 1) 20g, Limiting Viscosity is 0.070dLg
-1, the HPMA 20g that solid content is 30%, is dissolved in 8g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 60mg/L, 2-phosphonate group-1 wherein, 2,4-butane tricarboxylate's the valid density that adds is 6mg/L, the valid density that adds of maleic acid/Styrene Sulfonic Acid Copolymer is 6mg/L, and the valid density that adds of HPMA is 6mg/L.
Comparative example 8
Get effective content and be 50% 2-phosphonate group-1,2,4-butane tricarboxylate 10g; Limiting Viscosity is 0.072dLg
-1, the poly-epoxy succinic acid 60g that solid content is 30%, is dissolved in 10g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 80mg/L, 2-phosphonate group-1 wherein, and 2,4-butane tricarboxylate's the valid density that adds is 5mg/L, the valid density that adds of poly-epoxy succinic acid is 18mg/L.
Comparative example 9
Get effective content and be 50% 2-phosphonate group-1,2,4-butane tricarboxylate 7g; Effective content is 50% ATMP 3g, and Limiting Viscosity is 0.073dLg
-1, acrylic acid/hydroxypropyl acrylate polymer that solid content is 30% (mass ratio of acrylic acid/hydroxypropyl acrylate is 2: 1) 30g, Limiting Viscosity is 0.070dLg
-1, the HPMA that solid content is 30% is dissolved in 2g water, is dissolved in 8g water, is made into antisludging agent for osmosis-reverse membrane.Add this antisludging agent for osmosis-reverse membrane in test water, adding concentration is 50mg/L, 2-phosphonate group-1 wherein, 2,4-butane tricarboxylate's the valid density that adds is 3.5mg/L, the valid density that adds of ATMP is 1.5mg/L, and the valid density that adds of acrylic acid/hydroxypropyl acrylate polymer is 9mg/L, and the valid density that adds of HPMA is 0.6mg/L.
The scale-inhibiting properties of embodiment and comparative example is in Table 2.
The scale-inhibiting properties of table 2 embodiment and comparative example
| Resistance CaCO 3Dirt rate, % | Resistance CaSO 4Dirt rate, % | |
| Embodiment 1 | 92.4 | 47.8 |
| Embodiment 2 | 92.3 | 46.1 |
| Embodiment 3 | 91.9 | 45.1 |
| Embodiment 4 | 91.4 | 81.8 |
| Embodiment 5 | 91.5 | 83.7 |
| Embodiment 6 | 92.0 | 90.8 |
| Embodiment 7 | 92.1 | 52.7 |
| Embodiment 8 | 92.2 | 53.6 |
| Embodiment 9 | 92.6 | 51.7 |
| Embodiment 10 | 91.8 | 93.0 |
| Embodiment 11 | 92.4 | 93.3 |
| Embodiment 12 | 91.8 | 90.8 |
| Embodiment 13 | 92.5 | 93.2 |
| Embodiment 14 | 92.7 | 93.2 |
| Embodiment 15 | 92.5 | 91.9 |
| Embodiment 16 | 92.2 | 93.6 |
| Embodiment 17 | 92.1 | 92.4 |
| Embodiment 18 | 92.4 | 91.7 |
| Embodiment 19 | 92.1 | 90.4 |
| Comparative example 1 | 90.7 | 40.2 |
| Comparative example 2 | 90.1 | 38.2 |
| Comparative example 3 | 84.9 | 90.1 |
| Comparative example 4 | 85.4 | 82.4 |
| Comparative example 5 | 85.8 | 86.8 |
| Comparative example 6 | 84.1 | 90.5 |
| Comparative example 7 | 84.1 | 90.1 |
| Comparative example 8 | 87.8 | 46.1 |
| Comparative example 9 | 85.6 | 91.2 |
Above embodiment and comparative example explanation, reverse osmosis membrane of the present invention has excellent resistance CaCO with composite scale inhibitor
3, CaSO
4performance.Can effectively eliminate CaCO
3, CaSO
4the film that deposits and bring pollutes.
Claims (8)
1. a reverse osmosis membrane composite scale inhibitor, is comprised of component a and components b, and wherein a is at least one methylene phosphonic carboxylic acid, and its general formula is: RCH (COOH) N (CH
2pO
3h
2)
2, RCH in formula (COOH) N is from amino acid, components b is at least one material that is selected from organic phospho acid and at least one organic carboxyl acid base polymer, and organic carboxyl acid base polymer is selected from polyacrylic acid, HPMA, acrylic acid/hydroxypropyl acrylate copolymer, acrylic acid/hydroxypropyl acrylate/methyl acrylate copolymer, maleic acid/Styrene Sulfonic Acid Copolymer, maleic anhydride/Styrene Sulfonic Acid Copolymer, acrylic acid/Styrene Sulfonic Acid Copolymer, acrylate/Styrene Sulfonic Acid Copolymer, maleic acid/allyl sulphonic acid copolymer, maleic anhydride/allyl sulphonic acid copolymer, acrylic acid/allyl sulphonic acid copolymer, acrylic acid/vinyl sulfonic acid copolymer, acrylic acid/2-methyl-2'-acrylamido propane sulfonic acid copolymer, acrylic acid/acrylamide/2-methyl-2'-acrylamido propane sulfonic acid copolymer, acrylic acid/esters/2-methyl-2'-acrylamido propane sulfonic acid copolymer, acrylic acid/maleic acid/2-methyl-2'-acrylamido propane sulfonic acid copolymer and acrylic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2'-acrylamido propane sulfonic acid copolymer.
2. composite scale inhibitor according to claim 1, is characterized in that described methylene phosphonic carboxylic acid is selected from glycine two methylenephosphonic acids, glutamic acid two methylenephosphonic acids, alanine two methylenephosphonic acids, valine two methylenephosphonic acids, leucine two methylenephosphonic acids, isoleucine two methylenephosphonic acids, serine two methylenephosphonic acids, threonine two methylenephosphonic acids, cysteine two methylenephosphonic acids, methionine two methylenephosphonic acids, aspartic acid two methylenephosphonic acids, phenylalanine two methylenephosphonic acids and tyrosine two methylenephosphonic acids.
3. composite scale inhibitor according to claim 2, is characterized in that described methylene phosphonic carboxylic acid is selected from glycine two methylenephosphonic acids and glutamic acid two methylenephosphonic acids.
4. according to the composite scale inhibitor described in claim 1-3 any one, it is characterized in that described organic phospho acid is selected from HEDP, ATMP, 2-phosphonate group-1,2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid and diethylene triamine pentamethylene phosphonic.
5. according to the composite scale inhibitor described in claim 1-3 any one, it is characterized in that the valid density of methylene phosphonic carboxylic acid is counted 1～6mg/L water with active matter content.
6. according to the composite scale inhibitor described in claim 1-3 any one, it is characterized in that the valid density of organic phospho acid is counted 1～6mg/L water with active matter content.
7. according to the composite scale inhibitor described in claim 1-3 any one, it is characterized in that the valid density of organic carboxyl acid base polymer is counted 1～6mg/L water with active matter content.
8. a method of scale inhibition for reverse osmosis membrane, is characterized in that adding the composite scale inhibitor described in claim 1-7 any one in counter-infiltration system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276448.8A CN102397753B (en) | 2010-09-09 | 2010-09-09 | Anti-scaling agent of reverse osmosis membrane, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010276448.8A CN102397753B (en) | 2010-09-09 | 2010-09-09 | Anti-scaling agent of reverse osmosis membrane, and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102397753A CN102397753A (en) | 2012-04-04 |
| CN102397753B true CN102397753B (en) | 2014-01-29 |
Family
ID=45880637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010276448.8A Active CN102397753B (en) | 2010-09-09 | 2010-09-09 | Anti-scaling agent of reverse osmosis membrane, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102397753B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701466A (en) * | 2012-06-15 | 2012-10-03 | 马登山 | Circulating water scale inhibitor |
| CN105597550A (en) * | 2015-12-18 | 2016-05-25 | 潍坊源洁环保科技有限公司 | Reverse osmosis membrane composite anti-scaling bactericide |
| CN110090559A (en) * | 2019-03-05 | 2019-08-06 | 枣庄河源水处理科技有限公司 | A kind of reverse osmosis antisludging agent for sulfate scale |
| CN113908700A (en) * | 2021-11-29 | 2022-01-11 | 湖南沁森高科新材料有限公司 | Reverse osmosis membrane scale inhibitor and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423299A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Reverse osmosis membrane scale inhibitor and preparation and use method thereof |
-
2010
- 2010-09-09 CN CN201010276448.8A patent/CN102397753B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423299A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Reverse osmosis membrane scale inhibitor and preparation and use method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张军等.新型缓蚀阻垢剂GDMP的研制.《南京建筑工程学院学报》.2000,(第1期), |
| 新型缓蚀阻垢剂GDMP的研制;张军等;《南京建筑工程学院学报》;20000131(第1期);第48页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102397753A (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qiu et al. | Removal of heavy metal ions from aqueous solution by ultrafiltration assisted with copolymer of maleic acid and acrylic acid | |
| CN102399018B (en) | Reverse osmosis membrane scale inhibitor and application thereof | |
| CN101622199B (en) | Method of inhibiting scale formation and deposition in desalination systems | |
| CN102285705B (en) | Method for cleaning reverse osmosis system | |
| CN103265696B (en) | Dendrimer with pentaerythritol core terminal and phosphonic acid terminal group, preparation method and uses thereof | |
| CN102397753B (en) | Anti-scaling agent of reverse osmosis membrane, and application thereof | |
| CN102397754B (en) | Reverse osmosis membrane scale inhibitor and application thereof | |
| CN103394289B (en) | A kind of reverse osmosis membrane antisludging agent and application thereof | |
| CN103874663B (en) | With the polymeric blends of making coatings inhibitor in Aquo System | |
| JP2012501833A (en) | Method for inhibiting scale formation and deposition in membrane systems using AA-AMPS copolymers | |
| AU2014208195A1 (en) | Coagulation processing method, coagulation processing unit, and water processing apparatus | |
| Kazner et al. | Forward osmosis for the treatment of reverse osmosis concentrate from water reclamation: process performance and fouling control | |
| CN102397755B (en) | Reverse osmosis membrane scale inhibitor and use thereof | |
| CN105032191A (en) | Special scale inhibitor for seawater and brackish water desalination reverse osmosis membrane and preparation method thereof | |
| Yu et al. | Nanofiltration membrane fouling and control caused by residual aluminum in feed water | |
| CN108816052A (en) | A kind of reverse osmosis research of non-phosphorus scale inhibitor and preparation method thereof | |
| AU2011253329B2 (en) | A composition containing an AA - AMPS copolymer and PMA, and uses thereof | |
| CN102399017A (en) | Reverse osmosis membrane scale inhibitor and application thereof | |
| CN105753195A (en) | Membrane antisludging agent and method for seawater desalination | |
| CN102399019A (en) | Reverse osmosis membrane scale inhibitor and application | |
| CN107758882B (en) | Concentrated scale inhibition and dispersion agent for high sulfate and carbonate and preparation method thereof | |
| WO2005082793A1 (en) | Desalination scale inhibitors | |
| CN105413476A (en) | Antisludging agent special for reverse osmosis membrane for seawater desalination | |
| WO2021235079A1 (en) | Antifouling agent for separation membranes and method for preventing fouling | |
| Noshadi et al. | Determining the optimal ZLD method for Ca and SiO2 removal from RO systems effluent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |