CN118874227B - Ultrafiltration membrane cleaning agent and preparation method thereof - Google Patents
Ultrafiltration membrane cleaning agent and preparation method thereof Download PDFInfo
- Publication number
- CN118874227B CN118874227B CN202411371732.1A CN202411371732A CN118874227B CN 118874227 B CN118874227 B CN 118874227B CN 202411371732 A CN202411371732 A CN 202411371732A CN 118874227 B CN118874227 B CN 118874227B
- Authority
- CN
- China
- Prior art keywords
- ultrafiltration membrane
- cleaning agent
- parts
- membrane cleaning
- component
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 98
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 88
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- 239000002738 chelating agent Substances 0.000 claims abstract description 26
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 30
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- -1 octadecyl dihydroxyethyl Chemical group 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000230 xanthan gum Substances 0.000 claims description 13
- 229920001285 xanthan gum Polymers 0.000 claims description 13
- 235000010493 xanthan gum Nutrition 0.000 claims description 13
- 229940082509 xanthan gum Drugs 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 11
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 7
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 claims description 6
- 239000004302 potassium sorbate Substances 0.000 claims description 6
- 229940069338 potassium sorbate Drugs 0.000 claims description 6
- 235000010241 potassium sorbate Nutrition 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical group [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 30
- 239000003344 environmental pollutant Substances 0.000 abstract description 17
- 231100000719 pollutant Toxicity 0.000 abstract description 17
- 244000005700 microbiome Species 0.000 abstract description 12
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 18
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000004907 flux Effects 0.000 description 10
- 239000006260 foam Substances 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 7
- 229960003330 pentetic acid Drugs 0.000 description 7
- 230000002195 synergetic effect Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 238000005202 decontamination Methods 0.000 description 4
- 230000003588 decontaminative effect Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000005501 phase interface Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000002289 effect on microbe Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
- B01D65/06—Membrane cleaning or sterilisation ; Membrane regeneration with special washing compositions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of semipermeable membrane cleaning, and particularly relates to an ultrafiltration membrane cleaning agent and a preparation method thereof. The ultrafiltration membrane cleaning agent comprises, by weight, 10-30 parts of a surfactant, 5-10 parts of a chelating agent, 5-10 parts of a water softener, 80-99 parts of deionized water and a pH regulator, and 5-12 parts of an oxidizing agent, 10-30 parts of silver nitrate, 5-10 parts of a stabilizer and 80-99 parts of deionized water, wherein the weight ratio of the pH regulator to the chelating agent is (1.1-1.5): 1. The ultrafiltration membrane cleaning agent can remove various pollutants, especially microorganisms, has small damage to the ultrafiltration membrane, low use cost and small environmental pollution, and the preparation method of the ultrafiltration membrane cleaning agent can ensure stable quality of the cleaning agent, is simple and convenient to operate, and is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of semipermeable membrane cleaning, and particularly relates to an ultrafiltration membrane cleaning agent and a preparation method thereof.
Background
The ultrafiltration membrane is a microporous membrane with the aperture of 1-100 nanometers, is widely applied to the fields of water treatment, food, biological pharmacy and the like as an important separation technology, and has the main function of separating pollutants such as polysaccharides, lipids, indissolvable salts, microorganisms and the like in the mixed solution to be treated from water through a microporous structure on the surface of the membrane. However, during use, these contaminants are easily deposited on the ultrafiltration membrane surface, resulting in clogging of the pore channels, resulting in a decrease in membrane flux and deterioration of separation performance. Therefore, regular cleaning of ultrafiltration membranes is critical to maintaining efficient operation thereof.
Currently, common ultrafiltration membrane cleaning methods include physical cleaning and chemical cleaning. The physical cleaning mainly removes pollutants on the surface of the membrane by rinsing with clear water or rinsing with air and water, but has limited effect, and is difficult to thoroughly remove stubborn pollutants, especially microorganisms. The chemical cleaning is to react with the pollutant by using chemical reagent, so as to achieve the purpose of dissolving and stripping the pollutant. Common chemical cleaners include acidic cleaners, alkaline cleaners, chelating agents, and the like. However, the existing chemical cleaning agent has some defects, such as poor cleaning effect on microorganisms, certain corrosiveness on ultrafiltration membranes, high use cost and the like.
Chinese patent CN115591408A discloses an ultrafiltration membrane alkaline cleaner and a preparation method thereof, wherein the ultrafiltration membrane alkaline cleaner is mainly prepared from, by mass, 15-25 parts of sodium dodecyl benzene sulfonate, 10-25 parts of sodium hexametaphosphate, 5-15 parts of EDTA-4 sodium, 8-10 parts of carboxymethyl cellulose, 5-12 parts of sodium tripolyphosphate and 25-35 parts of deionized water.
The ultrafiltration membrane alkaline cleaning agent has the following defects that the ultrafiltration membrane alkaline cleaning agent comprises 8-10 parts by mass of carboxymethyl cellulose, and the adding amount of the carboxymethyl cellulose is large. The carboxymethyl cellulose is used as a thickening agent, so that the viscosity of the alkaline cleaning agent of the ultrafiltration membrane can be increased, the alkaline cleaning agent of the ultrafiltration membrane is uniformly distributed on the surface of the ultrafiltration membrane, the generation of large-volume foam is reduced, the cleaning effect is improved, but the higher viscosity also enables the surfactant to be more easily remained on the surface of the ultrafiltration membrane, so that microorganisms are more easily attached, and in addition, the phosphate consumption of the patent is higher, and the factors can further promote the propagation of microorganisms and further corrode the ultrafiltration membrane.
Chinese patent CN103768955A discloses an ultrafiltration membrane cleaning agent which comprises, by weight, 7-12 parts of sodium dodecyl benzene sulfonate, 5-8 parts of fatty alcohol polyoxyethylene ether sodium sulfonate, 2-6 parts of carboxymethyl cellulose, 3-9 parts of sodium citrate, 1-4 parts of sodium carbonate, 2-8 parts of sodium hydroxide, 0.1-0.6 part of pectase, 1-7 parts of aliphatic polyoxyethylene ether and 0.5-1.9 parts of potassium silicate.
The patent has the following defects that sodium dodecyl benzene sulfonate, sodium fatty alcohol polyoxyethylene ether sulfonate and fatty polyoxyethylene ether are all surfactants, other components cannot chelate heavy metal ions, the heavy metal ion removing effect is poor, on the one hand, heavy metal ions remained on the surface of an ultrafiltration membrane are combined with the active center of pectase to inactivate the pectase, the effect of inhibiting microbial reproduction is affected, in addition, the pectase has relatively harsh storage conditions, and the pectase activity is damaged when the temperature and the humidity are higher or the storage time is long.
In order to solve the problems in the prior art, it is important to develop a novel ultrafiltration membrane cleaning agent and a preparation method thereof.
Disclosure of Invention
The invention aims to provide an ultrafiltration membrane cleaning agent which has high-efficiency cleaning capability, can effectively remove various pollutants, especially microorganisms, has small damage to an ultrafiltration membrane, has low use cost and small environmental pollution, and simultaneously provides a preparation method of the ultrafiltration membrane cleaning agent, which can ensure stable quality of the cleaning agent, is simple and convenient to operate and is suitable for large-scale production and application.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the ultrafiltration membrane cleaning agent comprises, by weight, 10-30 parts of a surfactant, 5-10 parts of a chelating agent, 5-10 parts of a water softener, 80-99 parts of deionized water and a pH regulator, and 5-12 parts of an oxidizing agent, 10-30 parts of silver nitrate, 5-10 parts of a stabilizer and 80-99 parts of deionized water, wherein the weight ratio of the pH regulator to the chelating agent is (1.1-1.5): 1.
Wherein:
the surfactant is prepared by compounding octadecyl dihydroxyethyl amine oxide, xanthan gum, sodium dodecyl sulfate and N, N-dimethylacetamide according to the weight ratio of (5-12): (1-3): (1) (2-7).
Octadecyl dihydroxyethyl amine oxide is a nonionic surfactant with excellent detergency and can adjust the fineness and stability of foam, sodium dodecyl sulfate is an anionic surfactant with stronger foaming, emulsifying and dispersing properties, and N, N-dimethylacetamide is a nonionic solvent with good solubility and permeability. Through the preferable proportion compounding, the emulsifying property, the dispersing property and the permeability of the surfactant can be improved, and the effects of reducing the residual of the surfactant and improving the decontamination efficiency can be achieved.
The chelating agent is ethylenediamine tetraacetic acid or diethylenetriamine pentaacetic acid.
The water softener is sodium phosphate or sodium silicate.
The pH regulator is sodium hydroxide or sodium bicarbonate.
The oxidant is hydrogen peroxide. Compared with strong oxidants such as potassium permanganate, the hydrogen peroxide has moderate oxidizing capability, can prevent silver nitrate from being oxidized during long-term storage, can assist silver nitrate in removing microorganisms, and simultaneously reduces damage to an ultrafiltration membrane due to moderate oxidizing property.
The stabilizer is prepared by compounding hydroxyethylidene diphosphonic acid and potassium sorbate according to the weight ratio of (2-6): 1.
The hydroxyethylidene diphosphonic acid can be used as a peroxide stabilizer, and the combination of the hydroxyethylidene diphosphonic acid and potassium sorbate can obviously improve the chemical stability of the ultrafiltration membrane cleaning agent and prevent the ultrafiltration membrane cleaning agent from going bad in the storage and use processes, thereby ensuring the cleaning effect and prolonging the service life of the cleaning agent.
The preparation method of the ultrafiltration membrane cleaning agent comprises the following steps:
a) Stirring a surfactant, a chelating agent, a water softener and deionized water, and adding a pH regulator to regulate the pH value to obtain a component A;
b) Fully mixing an oxidant, silver nitrate, a stabilizer and deionized water, and uniformly stirring under the heating condition to obtain a component B;
c) When in use, the component A and the component B are compounded to prepare the ultrafiltration membrane cleaning agent.
Wherein:
in the step a), the stirring temperature is 40-80 ℃, the stirring time is 40-60min, the stirring speed is 100-300rpm, and the pH value is 7.5-9.
In the step b), the heating temperature is 50-70 ℃ and the stirring speed is 100-300rpm.
In the step c), the component A and the component B are compounded according to the weight ratio of (1-2.2): 1.
The beneficial effects of the invention are as follows:
1. different components are stored separately, so that the stability of the ultrafiltration membrane cleaning agent in long-term storage is improved:
If the component A and the component B are mixed together and stored for a long time, the empty orbitals of the outer layer of silver ions in the silver nitrate can form insoluble coordination complexes with lone pair electrons on the chelating agent or the surfactant, and the complexes can be attached to the inner wall of the storage container, so that the uniformity and the subsequent use of the ultrafiltration membrane cleaning agent are affected. Therefore, the surfactant, the chelating agent and other raw materials are respectively prepared into the component A, while the silver nitrate is separated from the component A, and the oxidant, the stabilizer and other raw materials are added to prepare the component B, so that deliquescence, oxidation or deterioration of the silver nitrate during long-term storage can be effectively prevented.
2. The component A and the component B are matched for use, so that most kinds of pollutants can be removed, and the cleaning effect is more thorough:
Chelating agents are mainly used for removing inorganic salt contaminants, which are capable of chelating metal ions, thereby forming poorly soluble complexes and further removing inorganic salt contaminants. The oxidant and the silver nitrate are focused on removing microorganisms, and can destroy the cell structure of the microorganisms, so that the sterilizing effect is achieved. The surfactant mainly removes grease pollutants, has remarkable emulsifying effect on the grease, can emulsify the grease pollutants into tiny liquid drops so as to facilitate cleaning and removal, and also has the effect of improving the wettability of the ultrafiltration membrane cleaning agent, and can enhance the contact effect between the ultrafiltration membrane cleaning agent and the pollutants on the surface of the membrane, so that the ultrafiltration membrane cleaning agent can more effectively permeate into tiny pores and folds on the surface of the membrane, fully contact and react with the pollutants, and the cleaning effect is improved. The combination of chelating agent, oxidizing agent, silver nitrate and surfactant can completely remove different types of pollutants.
3. The xanthan gum is compounded with octadecyl dihydroxyethyl amine oxide, sodium dodecyl sulfate and N, N-dimethylacetamide according to a certain proportion, so that the synergistic effect of the xanthan gum on each component in the surfactant is effectively exerted:
Sodium dodecyl sulfate is a strong foaming agent, can generate a large amount of foam, and octadecyl dihydroxyethyl amine oxide can adjust the fineness and stability of the foam, and N, N-dimethylacetamide is used as a nonionic solvent, so that the fluidity of a system can be improved, uniform mixing among components is facilitated, and finally stable and fine foam is formed. The foam is stable and is not easy to break, so that the foam can stay on the surface of the ultrafiltration membrane for a longer time, and the fine foam has larger specific surface area, so that the foam can permeate micro pores on the surface of the ultrafiltration membrane, and surface pollutants can be effectively and comprehensively removed.
The polymer chain of xanthan gum can intertwine with octadecyl dihydroxyethyl amine oxide and sodium dodecyl sulfate in water to form a three-dimensional network structure. The network structure can wrap the greasy dirt particles, is convenient for cleaning the follow-up greasy dirt and the three-dimensional network structure, reduces the surfactant residue on the surface of the ultrafiltration membrane, and further reduces the membrane damage.
Meanwhile, hydrophilic groups such as hydroxyl groups and carboxyl groups on xanthan gum molecules, hydrophilic parts of octadecyl dihydroxyethyl amine oxide and sodium dodecyl sulfate and water molecules form a hydrogen bond network structure, so that surfactant molecules are more orderly and more tightly arranged on the surfaces of oil stain particles to form an interfacial film, the ordered arrangement not only enhances the stability of the interfacial film, but also enables the interfacial film to be more uniform and continuous, thereby more effectively reducing the surface tension between water and oil stains and improving the decontamination effect, and the hydrogen bond network structure also has a guiding effect, so that the oil stain particles and the surfactant molecules are more likely to collide, and the movement speed of the oil stain particles and the surfactant molecules is reduced due to the thickening effect of the xanthan gum, so that the relative distance between the oil stain particles and the surfactant molecules is further shortened. This shortening of the distance increases the chance of collisions between them, thereby improving decontamination efficiency.
4. The sodium dodecyl sulfate and chelating agent ethylenediamine tetraacetic acid (EDTA) or diethylenetriamine pentaacetic acid (DTPA) are compounded, so that the properties and the synergistic effect of the sodium dodecyl sulfate and the chelating agent ethylenediamine tetraacetic acid (EDTA) can be effectively exerted:
The carboxyl of EDTA (or DTPA) can be partially dissociated into carboxylate ions in the A component, and the carboxylate ions and sulfate ions of sodium dodecyl sulfate in the A component form reversible ion pairs, so that the arrangement mode of sodium dodecyl sulfate molecules on an oil-water phase interface is changed. Specifically, EDTA molecules (or DTPA molecules) serve as anchor points, so that sodium dodecyl sulfate molecules are more tightly connected together, and a more ordered, more compact and more stable alignment layer is formed on an oil-water phase interface. On one hand, the arrangement reduces collision and combination among oil drops, prevents surfactant molecules from desorbing from an oil-water phase interface, improves the stability of emulsion, facilitates subsequent cleaning and decontamination, and prevents surfactant from remaining on the surface of an ultrafiltration membrane. On the other hand, the closely arranged molecular layers can effectively reduce the surface energy of the ultrafiltration membrane surface and promote the wetting process.
5. The chelating agent and the silver nitrate are matched for use, so that the synergistic effect of the chelating agent and the silver nitrate can be exerted, wherein the upper empty orbit of the outer orbit of the silver ion can form a coordination complex with the lone pair electrons on the chelating agent, and the silver ion is prevented from losing activity due to hydrolysis. In addition, by combining with the chelating agent, silver ions are fixed in the coordination complex, so that the possibility of directly exposing the coordination complex to the environment is reduced, the toxicity of the coordination complex is reduced, and the environment friendliness is better.
6. The invention comprehensively uses multiple components, can effectively remove most pollutants, does not use strong oxidant, and the components in the ultrafiltration membrane cleaning agent are not easy to remain on the surface of the ultrafiltration membrane, thus reducing membrane damage.
Detailed Description
The present invention is specifically described and illustrated below with reference to examples.
Example 1
Firstly, preparing 20kg of surfactant by compounding octadecyl dihydroxyethyl amine oxide, xanthan gum, sodium dodecyl sulfate and N, N-dimethylacetamide according to the weight ratio of 7:2:1:2, then adding 20kg of surfactant, 5kg of ethylenediamine tetraacetic acid, 5kg of sodium phosphate and 90kg of deionized water into a first reaction kettle, opening a hot water jacket of the first reaction kettle, starting stirring, setting the stirring rotation speed to be 100rpm, stirring uniformly at the temperature of 60 ℃, then adding 7.5kg of sodium hydroxide, and regulating the pH to be 9 to prepare the component A.
Firstly, preparing a stabilizer by compounding hydroxyethylidene diphosphonic acid and potassium sorbate according to the weight ratio of 2:1, then adding 5kg of hydrogen peroxide, 10kg of silver nitrate, 5kg of stabilizer and 90kg of deionized water into a second reaction kettle, opening a hot water jacket of the second reaction kettle, starting stirring, setting the stirring rotating speed to be 100rpm, and uniformly stirring at 70 ℃ to prepare the component B.
The A, B components are labeled and are required to be stored in a dry and light-proof place respectively, and the A, B components are compounded into the ultrafiltration membrane cleaning agent according to the mass ratio of 1:1 only when in use.
Example 2
Firstly, preparing 10kg of surfactant by compounding octadecyl dihydroxyethyl amine oxide, xanthan gum, sodium dodecyl sulfate and N, N-dimethylacetamide according to the weight ratio of 5:1:1:5, then adding 10kg of surfactant, 10kg of diethylenetriamine pentaacetic acid, 10kg of sodium silicate and 80kg of deionized water into a first reaction kettle, mixing, opening a hot water jacket of the first reaction kettle, starting stirring, setting the stirring speed to be 200rpm, uniformly stirring at the temperature of 80 ℃, adding 13kg of sodium bicarbonate, and adjusting the pH to be 8 to prepare the component A.
Firstly, preparing a stabilizer by compounding hydroxyl ethylidene diphosphonic acid and potassium sorbate according to the weight ratio of 6:1, then adding 12kg of hydrogen peroxide, 30kg of silver nitrate, 10kg of stabilizer and 80kg of deionized water into a second reaction kettle, opening a hot water jacket of the second reaction kettle, starting stirring, setting the stirring rotating speed to be 200rpm, and uniformly stirring at 60 ℃ to prepare the component B.
The A, B components are labeled and are required to be stored in a dry and light-proof place respectively, and the A, B components are compounded into the ultrafiltration membrane cleaning agent according to the mass ratio of 1.6:1 only when in use.
Example 3
Firstly, preparing 30kg of surfactant by compounding octadecyl dihydroxyethyl amine oxide, xanthan gum, sodium dodecyl sulfate and N, N-dimethylacetamide according to the weight ratio of 12:3:2:7, then adding 30kg of surfactant, 8kg of diethylenetriamine pentaacetic acid, 8kg of sodium phosphate and 99kg of deionized water into a first reaction kettle, mixing, opening a hot water jacket of the first reaction kettle, starting stirring, setting the stirring speed to 300rpm, uniformly stirring at the temperature of 40 ℃, adding 8.8kg of sodium hydroxide, and adjusting the pH to 7.5 to obtain the component A.
Firstly, preparing a stabilizer by compounding hydroxyethylidene diphosphonic acid and potassium sorbate according to the weight ratio of 4:1, then adding 9kg of hydrogen peroxide, 25kg of silver nitrate, 8kg of stabilizer and 99kg of deionized water into a second reaction kettle, opening a hot water jacket of the second reaction kettle, starting stirring, setting the stirring rotating speed to 300rpm, and uniformly stirring at 50 ℃ to prepare the component B.
The A, B components are labeled and are required to be stored in a dry and light-proof place respectively, and the A, B components are compounded into the ultrafiltration membrane cleaning agent according to the mass ratio of 2.2:1 only when in use.
Comparative example 1
The procedure of example 1 was repeated except that sodium lauryl sulfate was not added to the surfactant.
Comparative example 2
The procedure of example 1 was followed except that no xanthan gum was added to the surfactant.
Comparative example 3
The chelating agent was not added to the A component, and the rest of the procedure was the same as in example 1.
Comparative example 4
The oxidant is compounded by potassium permanganate and 55wt% hydrochloric acid according to the weight ratio of 1:1, and is used for replacing hydrogen peroxide, and the rest steps are the same as those of the example 1.
Comparative example 5
The A, B components are compounded into an ultrafiltration membrane cleaning agent according to the mass ratio of 1:1, the ultrafiltration membrane cleaning agent is labeled, the ultrafiltration membrane cleaning agent is stored in a dry and light-proof place for 4 months, and the rest steps are the same as those of the example 1.
The effect of using the ultrafiltration membrane cleaning agents prepared in examples and comparative examples was evaluated:
(1) A conventional ultrafiltration membrane filter device which is used for 80 days is selected, and the ultrafiltration membrane filter device is mainly used for the post-treatment of wastewater in the production process of chromate dye, wherein the wastewater contains chromium and other heavy metal ions, organic waste solvent, acidic substances, suspended particles, microorganisms and other impurities. The ultrafiltration membrane filtering device comprises an ultrafiltration membrane component, a pressure system, a circulating system, a cleaning system and the like, wherein the ultrafiltration membrane component comprises primary ultrafiltration membranes, secondary ultrafiltration membranes, tertiary ultrafiltration membranes and quaternary ultrafiltration membranes, and the pure water flux performance index of the primary ultrafiltration membrane is 553L/(m 2. H). Firstly, the transmembrane pressure difference and pure water flux of the first-stage ultrafiltration membrane before cleaning (namely after normal use) are recorded, the transmembrane pressure difference of the second-stage ultrafiltration membrane after cleaning is required to be less than or equal to 0.15MPa, the pure water flux is required to be more than or equal to 530L/(m 2.h), and specific data are shown in Table 1.
And finally taking out the first-stage ultrafiltration membrane, cutting the first-stage ultrafiltration membrane into 8 pieces of samples with the same size, respectively using the ultrafiltration membrane cleaning agents described in the examples 1-3 and the comparative examples 1-5 with the same weight as the cleaning agents, respectively soaking the samples in 8 parts of the cleaning agents in an upright mode, circulating the cleaning agents on the inner side and the outer side of the samples for 20min, taking out the samples, flushing the samples by using clear water, removing residual cleaning agents, and respectively testing the transmembrane pressure difference (MPa) and the pure water flux (L/(m 2 & h)) after cleaning, wherein the specific data are shown in the table 1.
(2) Before cleaning with cleaning liquid, the culture dish is first scraped slightly at 5 positions of each sample with sterile cotton swab, diluted with agar aqua in sterile diluting bottle to obtain diluted liquid, and then spread onto the culture dish, and the culture dish is then incubated at 30 deg.c for 72 hr, taken out, observed and recorded.
After washing with the washing liquid, the same 5 positions of each sample were gently scraped with a sterile cotton swab, the culturing step was the same as in step (2), the colony count on the petri dish was observed and recorded, and the microorganism removal rate (%) was determined, and specific data are shown in table 1.
The comparative example 1 is a synergistic system in which sodium dodecyl sulfate and a chelating agent cannot be formed without adding sodium dodecyl sulfate, the comparative example 2 is a synergistic system in which no xanthan gum is added, i.e., no surfactant is formed, the comparative example 3 is a synergistic system in which sodium dodecyl sulfate and a chelating agent cannot be formed and no synergistic effect of a chelating agent and silver nitrate cannot be produced, the comparative example 4 uses a strong oxidizing agent instead of hydrogen peroxide with moderate oxidizing property, and the comparative example 5 is a uniform mixing and storage of A, B components, i.e., the silver nitrate, the surfactant and the chelating agent are not separated for a long time.
According to the data in Table 1, the transmembrane pressure difference of the ultrafiltration membrane of the subsequent stage in examples 1-3 is less than or equal to 0.10MPa, the pure water flux is more than or equal to 547L/(m 2 & h), which shows that the ultrafiltration membrane cleaning agent has good cleaning effect, can remove most pollutants, especially the removal rate of microorganisms is more than 92 percent, and compared with the original pure water flux performance index of the ultrafiltration membrane of the first stage, the pure water flux after cleaning has little change, which shows that the membrane structure is basically not damaged after cleaning, the transmembrane pressure difference and the pure water flux parameter of the ultrafiltration membrane basically meet the cleaning requirement, and the ultrafiltration membrane can still be used continuously.
The ultrafiltration membrane cleaning agent prepared in the comparative examples 1-5 has the advantages that after cleaning, the transmembrane pressure difference of the ultrafiltration membrane is still larger, the pure water flux is smaller, the cleaning effect is poor, some pollutants are not removed, and the damage to the ultrafiltration membrane during cleaning is larger, so that the pore channel structure of the ultrafiltration membrane is damaged.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411371732.1A CN118874227B (en) | 2024-09-29 | 2024-09-29 | Ultrafiltration membrane cleaning agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411371732.1A CN118874227B (en) | 2024-09-29 | 2024-09-29 | Ultrafiltration membrane cleaning agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118874227A CN118874227A (en) | 2024-11-01 |
| CN118874227B true CN118874227B (en) | 2025-02-11 |
Family
ID=93221489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411371732.1A Active CN118874227B (en) | 2024-09-29 | 2024-09-29 | Ultrafiltration membrane cleaning agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118874227B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162366A (en) * | 2014-07-31 | 2014-11-26 | 宿迁嵘锦信息科技有限公司 | Cleaning agent for filtering membranes |
| CN108939926A (en) * | 2018-09-03 | 2018-12-07 | 成都水医生化学品科技有限责任公司 | Cleaning agents of membrane and its preparation and application |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8933009B2 (en) * | 2013-03-12 | 2015-01-13 | Ecolab Usa Inc. | Surfactant blends for cleaning filtration membranes |
| CN109289539B (en) * | 2018-09-18 | 2021-07-20 | 中国海洋石油集团有限公司 | Nanofiltration membrane cleaning agent for brine refining and preparation method thereof |
| CN111286561B (en) * | 2020-02-20 | 2021-09-07 | 中国科学院过程工程研究所 | A cleaning system and method for decolorizing membrane in a membrane sugar production system |
-
2024
- 2024-09-29 CN CN202411371732.1A patent/CN118874227B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104162366A (en) * | 2014-07-31 | 2014-11-26 | 宿迁嵘锦信息科技有限公司 | Cleaning agent for filtering membranes |
| CN108939926A (en) * | 2018-09-03 | 2018-12-07 | 成都水医生化学品科技有限责任公司 | Cleaning agents of membrane and its preparation and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118874227A (en) | 2024-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100404657C (en) | Cleaning agent for ceramic film and its preparation method | |
| CN106237864B (en) | A kind of reverse osmosis membrane cleaning agent and its application method | |
| CN106110895A (en) | Embrane method is poly-drives ultrafilter membrane cleaning method during oil extraction waste water processes | |
| CN106957089A (en) | A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater | |
| CN101641147A (en) | Washing agent for separation membrane, process for producing the same and method of washing | |
| KR102714256B1 (en) | Cleaning agent for fouled reverse osmosis membrane and cleaning method using the same | |
| CN111437728A (en) | Reverse osmosis special-purpose pickling cleaning agent and preparation method thereof | |
| CN110106027A (en) | A kind of reverse osmosis membrane dirt detergent and preparation method thereof and application method | |
| CN106943879A (en) | A kind of cleaning agent of the organic dirt of reverse osmosis membrane | |
| JP2663141B2 (en) | Detergent for ion exchange membrane | |
| CN113881515B (en) | Cleaning agent and cleaning method for nanofiltration membrane or reverse osmosis membrane | |
| CN118874227B (en) | Ultrafiltration membrane cleaning agent and preparation method thereof | |
| CN213668728U (en) | Membrane pollution strengthening cleaning system based on gas-liquid two-phase flow | |
| JP7597521B2 (en) | How to remove biofilm | |
| CN113786735B (en) | Ceramic membrane cleaning agent and preparation and cleaning methods thereof | |
| CN111589305A (en) | Sulfur scale removal DTRO membrane cleaning agent and preparation method and use method thereof | |
| CN111440679A (en) | Cleaning agent for cleaning high sulfate scale and preparation method and application thereof | |
| CN107754612A (en) | A kind of cleaning agent of reverse-osmosis membrane element cleaning to for concentrating tea and preparation method thereof | |
| CN118594265B (en) | Ceramic membrane cleaning method and application thereof | |
| CN103341326B (en) | Cleaning agent of oxidized film and its preparation method and use | |
| CN107441944A (en) | A kind of Treated sewage reusing counter-infiltration system scavenger specially and its production and use | |
| CN108479410A (en) | A kind of starch wastewater treatment cleaning agents of membrane and preparation method thereof | |
| CN112760664A (en) | Alkalescent degreasing and paraffin removal integrated agent and preparation method thereof | |
| CN119842447A (en) | Diaphragm bag pickling agent and preparation method and application thereof | |
| CN110408475A (en) | A kind of cleaning combination of the membranous system for the dirt containing polyacrylamide, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |