CN113617230B - Membrane cleaning agent composition and preparation method and application thereof - Google Patents
Membrane cleaning agent composition and preparation method and application thereof Download PDFInfo
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- CN113617230B CN113617230B CN202110856882.1A CN202110856882A CN113617230B CN 113617230 B CN113617230 B CN 113617230B CN 202110856882 A CN202110856882 A CN 202110856882A CN 113617230 B CN113617230 B CN 113617230B
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- 239000012528 membrane Substances 0.000 title claims abstract description 189
- 239000000203 mixture Substances 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012459 cleaning agent Substances 0.000 title description 84
- 238000004140 cleaning Methods 0.000 claims abstract description 184
- 102000004190 Enzymes Human genes 0.000 claims abstract description 155
- 108090000790 Enzymes Proteins 0.000 claims abstract description 155
- 230000000694 effects Effects 0.000 claims abstract description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002994 raw material Substances 0.000 claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 239000013543 active substance Substances 0.000 claims abstract description 50
- 239000003814 drug Substances 0.000 claims abstract description 42
- 239000002738 chelating agent Substances 0.000 claims abstract description 34
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 102000004882 Lipase Human genes 0.000 claims description 44
- 108090001060 Lipase Proteins 0.000 claims description 44
- 239000004367 Lipase Substances 0.000 claims description 44
- 235000019421 lipase Nutrition 0.000 claims description 44
- 108091005804 Peptidases Proteins 0.000 claims description 43
- 239000004365 Protease Substances 0.000 claims description 43
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000001509 sodium citrate Substances 0.000 claims description 29
- 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 claims description 29
- 229920002873 Polyethylenimine Polymers 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 23
- 238000001223 reverse osmosis Methods 0.000 claims description 22
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 21
- 241001122767 Theaceae Species 0.000 claims description 21
- 239000001397 quillaja saponaria molina bark Substances 0.000 claims description 21
- 229930182490 saponin Natural products 0.000 claims description 21
- 150000007949 saponins Chemical class 0.000 claims description 21
- 239000008194 pharmaceutical composition Substances 0.000 claims description 20
- 239000002518 antifoaming agent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 16
- 108010064470 polyaspartate Proteins 0.000 claims description 16
- -1 polyoxypropylene Polymers 0.000 claims description 15
- USIPWJRLUGPSJM-UHFFFAOYSA-K trisodium 2-(2-aminoethylamino)ethanol triacetate Chemical compound [Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCNCCO USIPWJRLUGPSJM-UHFFFAOYSA-K 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000013530 defoamer Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000003921 oil Substances 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 10
- 244000005700 microbiome Species 0.000 abstract description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 9
- 231100000719 pollutant Toxicity 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000009285 membrane fouling Methods 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 229940088598 enzyme Drugs 0.000 description 141
- 230000000052 comparative effect Effects 0.000 description 77
- 235000019419 proteases Nutrition 0.000 description 41
- 230000000670 limiting effect Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000003945 anionic surfactant Substances 0.000 description 10
- 238000011010 flushing procedure Methods 0.000 description 10
- 239000004382 Amylase Substances 0.000 description 9
- 102000013142 Amylases Human genes 0.000 description 9
- 108010065511 Amylases Proteins 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 235000019418 amylase Nutrition 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 239000002736 nonionic surfactant Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 108010059892 Cellulase Proteins 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 229940106157 cellulase Drugs 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- WHNXAQZPEBNFBC-UHFFFAOYSA-K trisodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O WHNXAQZPEBNFBC-UHFFFAOYSA-K 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229940079919 digestives enzyme preparation Drugs 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 235000019626 lipase activity Nutrition 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- 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 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 235000019830 sodium polyphosphate Nutrition 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment 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
-
- 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
- B01D2321/162—Use of acids
-
- 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
- B01D2321/164—Use of bases
-
- 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
- B01D2321/166—Use of enzymatic agents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Abstract
The invention provides a membrane cleaning medicament composition, a preparation method and application thereof, and relates to the technical field of membrane cleaning. The membrane cleaning medicament composition is mainly prepared from chelating agent, alkali, complex enzyme, enzyme activity maintaining agent, active agent, water and other raw materials, wherein the enzyme activity maintaining agent of a specific type and the complex enzyme have a synergistic effect, and the addition of the enzyme activity maintaining agent is beneficial to maintaining the activity of the complex enzyme and promoting the improvement of the cleaning effect of the membrane cleaning medicament composition; through the cooperation of the raw materials, the membrane cleaning medicament composition has excellent cleaning performance, has good cleaning effect on various composite pollutants such as microorganisms, organic matters, oils and the like, can effectively recover the flux of membrane elements, prolongs the cleaning period of membrane fouling, and is environment-friendly and small in pollution. The invention also provides a preparation method and application of the membrane cleaning medicament composition.
Description
Technical Field
The invention relates to the technical field of membrane cleaning, in particular to a membrane cleaning medicament composition, a preparation method and application thereof.
Background
The membrane is a material with unique selective permeability, can effectively separate each component in fluid under external driving pressure, and has been widely applied to the fields of sea water desalination, zero discharge of waste water, garbage leachate treatment, reclaimed water recycling, chemical wastewater treatment, material separation, purification, concentration and the like.
In the operation process of the membrane system, various inorganic matters, microorganisms, organic matters and oils in raw water are concentrated and enriched on the surface of the membrane, and dirt is blocked on the surface of the membrane and even on membrane holes, so that the water yield is reduced, the pressure difference is increased, the desalination rate is reduced, the water quality of produced water is poor, the service life of the membrane is seriously influenced, and the use and development of the membrane technology are restricted, therefore, the efficient and reliable membrane cleaning agent and the cleaning mode are the final guarantee of the stable operation of the membrane system.
Currently, membrane cleaning agents existing in the market are often only aimed at certain pollutants (such as oils or organic matters), and have narrow application scenes. For complex component combined pollution caused by oil, microorganism and organic matters, the cleaning agent is difficult to clean, a plurality of different types of cleaning agents are often required to be matched, the consumption of the cleaning agents is large, the cleaning time is long, and the membrane flux recovery is poor.
In view of the above, the present invention has been made to solve at least one of the above-mentioned technical problems.
Disclosure of Invention
The first objective of the present invention is to provide a membrane cleaning agent composition, which is capable of alleviating the technical problems of narrow application scenario of the existing membrane cleaning agent and poor cleaning effect on combined pollution caused by oils, microorganisms and organic matters.
A second object of the present invention is to provide a method for producing the above membrane cleaning pharmaceutical composition.
A third object of the present invention is to provide the use of the above membrane cleaning pharmaceutical composition.
In order to achieve the above object, the following technical solutions are specifically proposed:
The invention provides a membrane cleaning medicament composition, which comprises the following raw materials in percentage by mass:
15-30% of chelating agent, 15-21% of alkali, 0.1-5% of complex enzyme, 2-5% of enzyme activity maintaining agent, 1-5% of active agent and the balance of water to 100%;
Wherein the complex enzyme comprises a combination of at least two of a cellulase, an amylase, a lipase and a protease; the enzyme activity maintaining agent comprises a combination of at least two of sodium citrate, ethoxylated polyethyleneimine and polyacrylate.
Furthermore, on the basis of the technical scheme, the membrane cleaning medicament composition comprises the following raw materials in percentage by mass:
18-25% of chelating agent, 18-20% of alkali, 0.5-4% of complex enzyme, 2.5-4.0% of enzyme activity maintaining agent, 2-5% of active agent and the balance of water to 100%.
Further, on the basis of the technical scheme, the chelating agent comprises any one or a combination of at least two of phosphates, aminocarboxylic acids or organic phosphonic acids;
Preferably, the phosphate comprises any one or a combination of at least two of sodium tripolyphosphate, sodium polyphosphate, sodium pyrophosphate or sodium hexametaphosphate;
Preferably, the amino carboxylic acid comprises any one or a combination of at least two of ethylenediamine tetraacetic acid, N-tetraacetic acid, nitrilotriacetic acid, polyaspartic acid, hydroxyethyl ethylenediamine trisodium acetate or dihydroxyethyl glycine;
Preferably, the organic phosphonic acid comprises any one or a combination of at least two of amino trimethylene phosphonic acid, amino trimethylene phosphonic acid or ethylenediamine tetramethylphosphonic acid;
preferably, the chelating agent comprises trisodium hydroxyethyl ethylenediamine triacetate and polyaspartic acid;
Preferably, the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is (10-25): (2-15).
Further, on the basis of the above technical solution of the present invention, the alkali includes any one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate, and preferably includes sodium hydroxide.
Furthermore, on the basis of the technical scheme, the complex enzyme comprises lipase and protease;
Preferably, the mass ratio of the lipase to the protease is (0.1-2): (0.1-4).
Further, on the basis of the technical scheme, the enzyme activity maintaining agent comprises sodium citrate and ethoxylated polyethyleneimine;
preferably, the mass ratio of the sodium citrate to the ethoxylated polyethyleneimine is (2.5-4): (0.1-4).
Further, on the basis of the above technical solution of the present invention, the active agent includes an anionic surfactant and a nonionic surfactant;
preferably, the anionic surfactant comprises sodium dodecyl sulfonate and/or lauric acid;
preferably, the nonionic surfactant comprises any one or a combination of at least two of tea saponin, fatty alcohol polyoxyethylene ether sodium sulfate or nonylphenol polyoxyethylene ether;
Preferably, the active agent comprises tea saponin and sodium dodecyl sulfate;
preferably, the mass ratio of the tea saponin to the sodium dodecyl sulfate is (2-5): (2-5);
Preferably, the raw materials of the film cleaning medicament composition further comprise an antifoaming agent, and the mass fraction of the antifoaming agent is 0.1-1%;
Preferably, the defoamer comprises polyoxyethylene polyoxypropylene pentaerythritol ether and/or polyoxypropylene polyoxyethylene glycerol ether.
The invention also provides a preparation method of the membrane cleaning medicament composition, which comprises the following steps:
and mixing the raw materials in the formula amount to obtain the membrane cleaning medicament composition.
Furthermore, on the basis of the technical scheme, the preparation method of the membrane cleaning medicament composition comprises the following steps of:
mixing a formula amount of alkali and water, and heating to obtain a mixture A;
mixing the mixture A with a chelating agent, an active agent and a formula amount to obtain a mixture B;
And mixing the mixture B with a formula amount of enzyme activity maintaining agent and complex enzyme to obtain the membrane cleaning medicament composition.
The invention also provides application of the membrane cleaning medicament composition or the membrane cleaning medicament composition prepared by the preparation method in the field of membrane system cleaning;
Preferably, the membrane system comprises a nanofiltration membrane system or a reverse osmosis membrane system.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a membrane cleaning medicament composition, which is mainly prepared from chelating agent, alkali, complex enzyme, enzyme activity maintaining agent, active agent, water and other raw materials, wherein the enzyme activity maintaining agent of a specific type and the complex enzyme have a synergistic effect, and the addition of the enzyme activity maintaining agent is beneficial to maintaining the activity of the complex enzyme and promoting the improvement of the cleaning effect of the membrane cleaning medicament composition; through the cooperation of the raw materials, the membrane cleaning agent composition has excellent cleaning performance and good cleaning effect on various composite pollutants such as microorganisms, organic matters, oils and the like, and the membrane element is cleaned by adopting the membrane cleaning agent composition, so that the flux of the membrane element can be effectively recovered, and the cleaning period of membrane fouling is prolonged;
in addition, the membrane cleaning agent composition is environment-friendly and has little pollution.
(2) The invention provides a preparation method of the membrane cleaning medicament composition, which is simple to operate, stable in process and suitable for industrial mass production.
(3) The invention provides application of the membrane cleaning medicament composition, and has good application prospect in the field of membrane system cleaning in view of the advantages of the membrane cleaning medicament composition.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
According to a first aspect of the present invention, there is provided a membrane cleaning pharmaceutical composition comprising the following raw materials in mass percent:
15-30% of chelating agent, 15-21% of alkali, 0.1-5% of complex enzyme, 2-5% of enzyme activity maintaining agent, 1-5% of active agent and the balance of water to 100%;
Wherein the complex enzyme comprises a combination of at least two of cellulase, amylase, lipase and protease; the enzyme activity maintaining agent comprises a combination of at least two of sodium citrate, ethoxylated polyethyleneimine and polyacrylate.
Specifically, the chelating agent is mainly used for chelating various metal ions in pollutants to form salt which is easy to dissolve in water, and meanwhile, dirt deposition is prevented, so that the optimal cleaning effect is achieved. The chelating agent is typically, but not limited to, 15%, 16%, 18%, 20%, 22%, 24%, 25%, 26%, 28% or 30% by mass.
The alkali mainly reacts with organic matters in the pollutants to transfer the pollutants from the organic phase into the water phase, so that the cleaning is facilitated. The base is typically, but not limited to, 15%, 16%, 17%, 18%, 19%, 20% or 21% by mass.
The complex enzyme comprises at least two enzymes selected from cellulase, amylase, lipase and protease, and has the main effects of decomposing oils, microorganisms, celluloses and starch substances in pollutants, so that the cleaning is more thorough, and the cleaning period is prolonged. Typical but non-limiting percentages by mass are 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%; the enzyme activity-maintaining agent is typically, but not limited to, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8% or 5% by mass.
The inventor creatively discovers in a large number of experimental processes that as the complex enzyme is compounded by adopting different types of enzymes, certain interaction can exist between the different types of enzymes to reduce the enzyme activity, and the addition of the enzyme activity maintaining agent of a specific type can weaken the interaction between the different types of enzymes to improve the activity of the complex enzyme.
The enzyme activity maintaining agent comprises a combination of at least two of sodium citrate, ethoxylated polyethyleneimine and polyacrylate. That is, the enzyme activity-maintaining agent may include a combination of sodium citrate and ethoxylated polyethyleneimine, may include a combination of sodium citrate and polyacrylate, may include a combination of ethoxylated poly and polyacrylate, or may include a combination of sodium citrate, ethoxylated polyethyleneimine, and polyacrylate. The enzyme activity-maintaining agent is typically, but not limited to, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.8%, 4%, 4.2%, 4.5%, 4.8% or 5% by mass.
The active agent is mainly used for emulsifying and compatibilizing oils, proteins and the like in pollutants. Typical, but non-limiting, mass percentages of active agents are 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
The invention provides a membrane cleaning medicament composition, which is mainly prepared from chelating agent, alkali, complex enzyme, enzyme activity maintaining agent, active agent, water and other raw materials, wherein the enzyme activity maintaining agent of a specific type and the complex enzyme have a synergistic effect, and the addition of the enzyme activity maintaining agent is beneficial to maintaining the activity of the complex enzyme and promoting the improvement of the cleaning effect of the membrane cleaning medicament composition; through the cooperation of the raw materials, the membrane cleaning agent composition has excellent cleaning performance and good cleaning effect on various composite pollutants such as microorganisms, organic matters, oils and the like, and the membrane element is cleaned by adopting the membrane cleaning agent composition, so that the flux of the membrane element can be effectively recovered, and the cleaning period of membrane fouling is prolonged;
in addition, the membrane cleaning agent composition is environment-friendly and has little pollution.
In the present invention, "comprising" means that it may include other components, such as an antifoaming agent, in addition to the components, which impart different properties to the film cleaning agent composition. In addition, the "including" of the present invention may be replaced by "being" or "being made of … …" which are closed.
In addition, it should be noted that the balance of water is up to 100%, meaning that the balance of water excluding the chelating agent, the base, the complex enzyme, the enzyme activity maintaining agent, the active agent, and optionally other raw materials in the raw materials of the membrane cleaning agent composition of the present invention is 100% by mass of the sum of the water and the chelating agent, the base, the complex enzyme, the enzyme activity maintaining agent, the active agent, and optionally other raw materials.
As an alternative embodiment of the present invention, the membrane cleaning pharmaceutical composition comprises the following raw materials in mass percent:
18-25% of chelating agent, 18-20% of alkali, 0.5-4% of complex enzyme, 2.5-4.0% of enzyme activity maintaining agent, 2-5% of active agent and the balance of water to 100%.
Through further limiting the mass fraction of each raw material, the cleaning effect is better, and the cleaning cost is lowest.
As an alternative embodiment of the present invention, the chelating agent comprises any one or a combination of at least two of phosphates, aminocarboxylic acids or organophosphonic acids;
preferably, the phosphate comprises any one or a combination of at least two of sodium tripolyphosphate, sodium polyphosphate, sodium pyrophosphate or sodium hexametaphosphate;
Preferably, the aminocarboxylic acid comprises any one or a combination of at least two of ethylenediamine tetraacetic acid, N-tetraacetic acid, nitrilotriacetic acid, polyaspartic acid, hydroxyethyl ethylenediamine trisodium triacetate or dihydroxyethyl glycine;
preferably, the organic phosphonic acid comprises any one or a combination of at least two of aminotrimethylene phosphonic acid, aminotrimethylene phosphonic acid or ethylenediamine tetramethylphosphonic acid;
As a preferred embodiment of the present invention, the chelating agent includes trisodium hydroxyethyl ethylenediamine triacetate and polyaspartic acid.
Preferably, the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is (10-25): (2-15), more preferably (12-15): (5-10), more preferably 13.5:8. typical, but non-limiting, mass ratios of trisodium hydroxyethyl ethylenediamine triacetate and polyaspartic acid are 10：2、10：4、10：5、10：8、10：10、10：12、10：15、13.5：2、13.5：4、13.5：5、13.5：8、13.5：10、13.5：12、13.5：15、15：2、15：4、15：5、15：8、15：10、15：12、15：15、20：2、20：4、20：5、20：8、20：10、20：12、20：15、25：2、25：4、25：5、25：8、25：10、25：12 or 25:15.
Through the specific limitation of the types and the dosage proportion of the chelating agent, the chelating agent can achieve better use effect and does not waste medicament.
As an alternative embodiment of the present invention, the base comprises any one of sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate, preferably sodium hydroxide.
The ideal cleaning effect can be achieved by adopting sodium hydroxide, and the sodium hydroxide is used as a common industrial raw material, and has wide sources and low price.
As an alternative embodiment of the invention, the cellulase activity is 5-20 mu/g. Typical but non-limiting activities are 5, 8, 10, 12, 15, 18 or 20 thousand u/g.
As an alternative embodiment of the invention, the amylase activity is 5-20 mu/g. Typical but non-limiting activities are 5, 8, 10, 12, 15, 18 or 20 thousand u/g.
As an alternative embodiment of the present invention, the lipase activity is 5-20 mu/g. Typical but non-limiting activities are 5, 8, 10, 12, 15, 18 or 20 thousand u/g.
As an alternative embodiment of the present invention, the protease activity is 20-40 mu/g. Typical but non-limiting activities are 20, 22, 25, 28, 30, 32, 35, 38 or 40 thousand u/g.
As a preferred embodiment of the present invention, the complex enzyme includes lipase and protease.
Preferably, the mass ratio of lipase to protease is (0.1-2): (0.1-4), more preferably (0.1-1): (0.1-1), more preferably 0.3:0.7. the typical, but non-limiting, mass ratio of lipase to protease is 0.1：0.1、0.1：0.5、0.1：1、0.1：1.5、0.1：2、0.1：2.5、0.1：3、0.1：3.5、0.1：4、0.3：0.1、0.3：0.5、0.3：0.7、0.3：1、0.5：0.1、1：0.1、1.5：0.1、2：0.1、1：0.5、1.5：0.5、2：0.5、1.5：1、1.8：1、2：1、2：2.5、2：3 or 2:4.
By further limiting the types and the dosage proportions of the complex enzymes, the respective optimal effects among the enzymes can be exerted.
As a preferred embodiment of the present invention, the enzyme activity-maintaining agent includes sodium citrate and ethoxylated polyethyleneimine.
Preferably, the mass ratio of sodium citrate to ethoxylated polyethyleneimine is (2.5-4): (0.1-4), more preferably (2.5-3): (0.2-2), more preferably 2.5:0.5. the mass ratio of sodium citrate to ethoxylated polyethyleneimine is typically, but not limited to 2.5：0.1、2.5：0.5、2.5：1、2.5：1.5、2.5：2、2.5：3、2.5：4、3：0.1、3：0.5、3：1、3：1.5、3：2、3：3、3：4、3.5：0.1、3.5：0.5、3.5：1、3.5：1.5、3.5：2、3.5：3、3.5：4、4：0.1、4：0.5、4：1、4：1.5、4：2、4：3 or 4:4.
By further limiting the types and the dosage proportion of the enzyme activity maintaining agent, the enzyme activity maintaining agent can not only fully maintain the activity of enzymes, but also avoid the interaction among various enzymes, thereby achieving better action effect.
As an alternative embodiment of the present invention, the active agent includes an anionic surfactant and a nonionic surfactant.
The active agent is compounded by adopting an anionic surfactant and a nonionic surfactant, so that the foaming and foam stabilizing effects of the active agent are maintained, the risk of enzymolysis is reduced, and the effect of the active agent can be improved.
As an alternative embodiment of the present invention, the anionic surfactant comprises sodium dodecyl sulfate and/or lauric acid. By "and/or" herein is meant that the anionic surfactant may comprise only sodium dodecyl sulfate, may comprise only lauric acid, and may also comprise both sodium dodecyl sulfate and lauric acid.
As an alternative embodiment of the present invention, the nonionic surfactant comprises any one or a combination of at least two of tea saponin, fatty alcohol polyoxyethylene ether, sodium fatty alcohol polyoxyethylene ether sulfate or nonylphenol polyoxyethylene ether.
As a preferred embodiment of the present invention, the active agent comprises tea saponin and sodium dodecyl sulfate;
preferably, the mass ratio of the tea saponin to the sodium dodecyl sulfate is (2-5): (2-5), more preferably (2-4): (2-4), more preferably 2:3.
The effect of the active agent can be exerted to the maximum extent by further limiting the type and the dosage proportion of the active agent.
As an alternative embodiment of the invention, the raw materials of the membrane cleaning agent composition further comprise an antifoaming agent, and the mass fraction of the antifoaming agent is 0.1-1%.
The defoamer is mainly used for inhibiting foam generated in the cleaning process and avoiding influencing the production workshop environment, and is typically but not limited to 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 0.9% or 1% by mass.
As an alternative embodiment of the present invention, the defoamer comprises polyoxyethylene polyoxypropylene pentaerythritol ether and/or polyoxypropylene polyoxyethylene glyceryl ether.
Preferably, the defoamer comprises polyoxypropylene polyoxyethylene glyceryl ether.
Through the further limitation to the type and the dosage proportion of the defoaming agent, the defoaming agent can control the foam of the cleaning water tank not to overflow and can not influence the cleaning effect.
According to a second aspect of the present invention, there is also provided a method for preparing the above membrane cleaning pharmaceutical composition, comprising the steps of:
and mixing the raw materials in the formula amount to obtain the membrane cleaning medicament composition.
The preparation method of the membrane cleaning medicament composition provided by the invention is simple to operate, stable in process and suitable for industrial scale production.
As an alternative embodiment of the present invention, a method of preparing a membrane cleaning pharmaceutical composition comprises the steps of:
mixing a formula amount of alkali and water, and heating to obtain a mixture A;
mixing the mixture A with chelating agent, active agent and defoamer in the formula amount to obtain a mixture B;
And mixing the mixture B with a formula amount of enzyme activity maintaining agent and complex enzyme to obtain the membrane cleaning medicament composition.
As a preferred embodiment of the present invention, the method for preparing the membrane cleaning pharmaceutical composition comprises the steps of:
Mixing and stirring the alkali and water in the formula amount for 15min, and heating to 30 ℃ to obtain a mixture A;
Mixing and stirring the mixture A with chelating agent, defoamer and defoamer in the formula amount for 20-30min to obtain a mixture B;
and mixing and stirring the mixture B with the enzyme activity maintaining agent and the complex enzyme in the formula amount for 15-25min to obtain the membrane cleaning medicament composition.
By further limiting the preparation method, the components of the membrane cleaning medicament composition can be fully dissolved and uniformly mixed, and the specific addition sequence can avoid interaction among the components, so that the effect of the membrane cleaning medicament composition is ensured.
According to a third aspect of the present invention there is also provided the use of a membrane cleaning agent composition as described above or a membrane cleaning agent composition prepared by a method as described above in the field of membrane system cleaning.
In view of the advantages of the membrane cleaning agent composition or the membrane cleaning agent composition prepared by the preparation method, the membrane cleaning agent composition has good application prospect in the field of membrane system cleaning.
As a preferred embodiment of the present invention, the membrane system comprises a nanofiltration membrane system or a reverse osmosis membrane system.
The use method of the membrane cleaning medicament composition or the membrane cleaning medicament composition prepared by adopting the preparation method comprises the following steps:
(a) Flushing the membrane system with reverse osmosis produced water or clean water;
(b) The membrane cleaning agent composition provided by the invention is configured in a cleaning water tank with the mass concentration of 1-15%, so as to form a cleaning liquid;
(c) Circularly mixing and heating the cleaning liquid to 30-35 ℃;
(d) Measuring the pH of the cleaning solution to be 10-11.5;
(e) Feeding the cleaning solution into the membrane for circulation for 30-60min;
(f) Soaking the membrane in the cleaning solution for 40-80min;
(g) The cleaning solution is put into the membrane again for circulation for 30-60min;
(h) The cleaning solution is emptied and the membrane system is flushed with reverse osmosis produced water or clean water until the flushing water has a pH of 7.
When in use, the proper temperature should be controlled at 30-35 ℃, so that the cleaning efficiency of the cleaning composition can be improved.
The present invention will be further described with reference to specific examples and comparative examples. Wherein the polyaspartic acid molecular weight is 12000; lipase activity was 10 u/g; protease activity was 20 u/g; cellulase activity is 10 ten thousand u/g; amylase activity was 10 u/g; the molecular weight of the ethoxylated polyethyleneimine is 36000; the molecular weight of tea saponin is 1203.
Example 1
The embodiment provides a membrane cleaning medicament composition, which comprises the following raw materials in percentage by mass:
chelating agent 21.5%, alkali 20%, complex enzyme 1%, enzyme activity maintaining agent 3%, active agent 5%, defoaming agent 0.5%, water balance to 100%; the prepared film cleaning composition was taken and a cleaning liquid was prepared at a concentration of 10%.
Wherein the chelating agent comprises hydroxyethyl ethylenediamine trisodium acetate and polyaspartic acid, and the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is 13.5:8, 8; the alkali is sodium hydroxide; the complex enzyme comprises lipase and protease, and the mass ratio of the lipase to the protease is 0.3:0.7; the enzyme activity maintaining agent comprises sodium citrate and ethoxylated polyethyleneimine, and the mass ratio of the sodium citrate to the ethoxylated polyethyleneimine is 2.5:0.5; the active agent comprises tea saponin and sodium dodecyl sulfate, and the mass ratio of the tea saponin to the sodium dodecyl sulfate is 2:3, a step of; the defoaming agent is polyoxypropylene polyoxyethylene glyceryl ether.
Example 2
This example provides a membrane cleaning agent composition, and the composition and proportions of the raw materials are the same as in example 1, except that the mass fraction of the complex enzyme in the raw materials is replaced by 0.1% and the amount of water is adjusted accordingly.
Example 3
This example provides a membrane cleaning agent composition, and the composition and proportions of the other materials are the same as in example 1, except that the mass fraction of the complex enzyme in the materials is changed from 1% to 5%, and the amount of water is adjusted accordingly.
Example 4
This example provides a membrane cleaning agent composition, and the composition and proportions of the other materials are the same as in example 1, except that the mass fraction of the complex enzyme in the materials is changed from 1% to 3%, and the amount of water is adjusted accordingly.
Example 5
This example provides a membrane cleaning pharmaceutical composition except that the mass ratio of lipase to protease in the complex enzyme in the raw materials is from 0.3:0.7 is replaced with 0.9:0.1, and the composition and the proportion of the rest raw materials are the same as those of the example 1.
Example 6
This example provides a membrane cleaning composition, and the composition and proportions of the materials are the same as in example 1, except that the lipase and protease (mass ratio of 0.3:0.7) are replaced with the lipase and amylase (mass ratio of 0.3:0.7) in the materials.
Example 7
This example provides a membrane cleaning composition, and the composition and proportions of the materials are the same as in example 1, except that the lipase and protease (mass ratio of 0.3:0.7) are replaced by lipase and amylase (mass ratio of 0.3:0.7) in the materials.
Example 8
This example provides a membrane cleaning composition, which has the same composition and proportions as in example 1, except that the lipase and protease (mass ratio of 0.3:0.7) are replaced by lipase, protease and amylase (mass ratio of 0.3:0.5:0.2) in the raw materials.
Example 9
This example provides a membrane cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the enzyme activity-maintaining agent in the raw materials is replaced with 2% from 3%, and the amount of water is adjusted accordingly.
Example 10
This example provides a membrane cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the enzyme activity-maintaining agent in the raw materials is replaced with 5% from 3%, and the amount of water is adjusted accordingly.
Example 11
This example provides a membrane cleaning pharmaceutical composition, the composition and proportions of which are the same as example 1, except that the enzyme activity-maintaining agent in the raw materials is replaced by sodium citrate and ethoxylated polyethyleneimine (mass ratio of 2.5:0.5) with sodium polyacrylate and ethoxylated polyethyleneimine (mass ratio of 2.5:0.5).
Example 12
This example provides a membrane cleaning pharmaceutical composition, the composition and proportions of which are the same as example 1, except that the enzyme activity-maintaining agent in the raw materials is replaced with sodium citrate and sodium polyacrylate (mass ratio of 2.5:0.5) by sodium citrate and ethoxylated polyethyleneimine (mass ratio of 2.5:0.5).
Example 13
This example provides a membrane cleaning pharmaceutical composition, the composition and proportions of the materials are the same as example 1, except that the enzyme activity-maintaining agent in the materials is replaced with sodium citrate, ethoxylated polyethylenimine and polyacrylate (mass ratio of 1:0.5:1.5) by sodium citrate and ethoxylated polyethylenimine (mass ratio of 2.5:0.5).
Example 14
This example provides a membrane cleaning pharmaceutical composition, which is identical to example 1 in composition and proportions except that the active agent in the raw materials is replaced with tea saponin, which is 5% by mass, by tea saponin and sodium dodecyl sulfate.
Example 15
This example provides a membrane cleaning pharmaceutical composition, except that the active agent in the raw materials is replaced by tea saponin and sodium dodecyl sulfate, the mass fraction of sodium dodecyl sulfate is 5%, and the composition and the proportion of the remaining raw materials are the same as those in example 1.
Example 16
This example provides a membrane cleaning pharmaceutical composition, which is identical to example 1 in composition and proportions except that the active agent in the raw materials is replaced by tea saponin and sodium dodecyl sulfate, the mass fraction of tea saponin is 2%.
Example 17
This example provides a membrane cleaning pharmaceutical composition, except that the active agent in the raw materials is replaced by tea saponin and sodium dodecyl sulfate, the mass fraction of sodium dodecyl sulfate is 3%, and the composition and the proportion of the remaining raw materials are the same as those in example 1.
Example 18
The embodiment provides a membrane cleaning medicament composition, which comprises the following raw materials in percentage by mass:
30% of chelating agent, 15% of alkali, 2.5% of complex enzyme, 4% of enzyme activity maintaining agent, 1.5% of active agent, 0.5% of defoaming agent and the balance of water to 100%;
Wherein the chelating agent comprises hydroxyethyl ethylenediamine trisodium acetate and polyaspartic acid, and the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is 10:3, a step of; the alkali is potassium hydroxide; the complex enzyme comprises lipase and protease, and the mass ratio of the lipase to the protease is 2:0.1; the enzyme activity maintaining agent comprises sodium citrate and ethoxylated polyethyleneimine, and the mass ratio of the sodium citrate to the ethoxylated polyethyleneimine is 2.5:4, a step of; the active agent comprises tea saponin and sodium dodecyl sulfate, and the mass ratio of the tea saponin to the sodium dodecyl sulfate is 2:5, a step of; the defoaming agent is polyoxypropylene polyoxyethylene glyceryl ether.
Example 19
The embodiment provides a membrane cleaning medicament composition, which comprises the following raw materials in percentage by mass:
15% of chelating agent, 18% of alkali, 3% of complex enzyme, 4% of enzyme activity maintaining agent, 4% of active agent and the balance of water to 100%;
Wherein the chelating agent comprises hydroxyethyl ethylenediamine trisodium acetate and polyaspartic acid, and the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is 25:14; the alkali is sodium hydroxide; the complex enzyme comprises lipase and protease, and the mass ratio of the lipase to the protease is 1:2; the enzyme activity maintaining agent comprises sodium citrate and ethoxylated polyethyleneimine, and the mass ratio of the sodium citrate to the ethoxylated polyethyleneimine is 2.5:0.5; the active agent comprises tea saponin and sodium dodecyl sulfate, and the mass ratio of the tea saponin to the sodium dodecyl sulfate is 2:3.
A method of preparing a membrane cleaning pharmaceutical composition provided in examples 1-19 comprising the steps of:
Mixing and stirring the alkali and water in the formula amount for 15min, and heating to 30 ℃ to obtain a mixture A;
mixing and stirring the mixture A with a chelating agent, an active agent and an optional defoaming agent in a formula amount for 25min to obtain a mixture B;
And mixing and stirring the mixture B with the enzyme activity maintaining agent and the complex enzyme in the formula amount for 25min to obtain the membrane cleaning medicament composition.
Comparative example 1
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that no complex enzyme is added to the raw materials (i.e., the mass fraction of complex enzyme is 0%), and the amount of water is adjusted accordingly.
Comparative example 2
This comparative example provides a membrane cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the complex enzyme in the raw materials is replaced by 0.05% by 1% and the amount of water is adjusted accordingly.
Comparative example 3
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that the mass fraction of the complex enzyme in the raw materials is changed from 1% to 7%, and the amount of water is adjusted accordingly.
Comparative example 4
This comparative example provides a membrane cleaning agent composition, except that the complex enzyme in the raw materials is replaced with lipase by lipase and protease, and the mass fraction of lipase is 1%, and the composition and ratio of the remaining raw materials are the same as those of example 1.
Comparative example 5
This comparative example provides a membrane cleaning agent composition, except that the complex enzyme in the raw materials is replaced with protease by lipase and protease, and the mass fraction of protease is 1%, and the composition and ratio of the remaining raw materials are the same as those of example 1.
Comparative example 6
This comparative example provides a membrane cleaning agent composition, except that the complex enzyme in the raw materials is replaced with lipase by lipase and protease, and the mass fraction of lipase is 0.3%, and the composition and ratio of the remaining raw materials are the same as those of example 1.
Comparative example 7
This comparative example provides a membrane cleaning agent composition, except that the complex enzyme in the raw materials is replaced with protease by lipase and protease, and the mass of protease is 0.7%, and the composition and ratio of the remaining raw materials are the same as those of example 1.
Comparative example 8
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that no enzyme activity-maintaining agent (i.e., the mass fraction of the enzyme activity-maintaining agent is 0%) is added to the raw materials, and the amount of water is adjusted accordingly.
Comparative example 9
This comparative example provides a membrane cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the enzyme activity-maintaining agent in the raw materials is replaced with 1% from 3%, and the amount of water is adjusted accordingly.
Comparative example 10
This comparative example provides a membrane cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the enzyme activity-maintaining agent in the raw materials is replaced with 7% by 3% and the amount of water is adjusted accordingly.
Comparative example 11
This comparative example provides a film cleaning agent composition, except that the enzyme activity-maintaining agent in the raw materials was replaced with sodium citrate by sodium citrate and ethoxylated polyethyleneimine, the mass fraction of the enzyme activity-maintaining agent was 3%, and the composition and the ratio of the remaining raw materials were the same as in example 1.
Comparative example 12
This comparative example provides a film cleaning agent composition, except that the enzyme activity maintaining agent in the raw materials was replaced with ethoxylated polyethyleneimine by sodium citrate and ethoxylated polyethyleneimine, the mass fraction of the enzyme activity maintaining agent was 3%, and the composition and the ratio of the remaining raw materials were the same as in example 1.
Comparative example 13
This comparative example provides a film cleaning pharmaceutical composition, except that the enzyme activity-maintaining agent in the raw materials was replaced with sodium citrate by sodium citrate and ethoxylated polyethyleneimine, the mass fraction of the enzyme activity-maintaining agent was 2.5%, and the composition and the ratio of the remaining raw materials were the same as in example 1.
Comparative example 14
This comparative example provides a membrane cleaning agent composition, except that the lipase and protease are replaced with lipase in the raw materials, and the mass of the lipase is 0.3%, and the water usage amount is adjusted adaptively, and the composition and ratio of the remaining raw materials are the same as those of comparative example 13.
Comparative example 15
This comparative example provides a membrane cleaning agent composition, except that the complex enzyme in the raw materials is replaced with protease by lipase and protease, and the mass of the complex enzyme is 0.7%, and the water usage amount is adjusted, and the composition and the ratio of the remaining raw materials are the same as those of comparative example 13.
Comparative example 16
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as comparative example 13, except that no complex enzyme is added to the raw materials (i.e., the mass fraction of complex enzyme is 0%), and the amount of water is adjusted accordingly.
Comparative example 17
This comparative example provides a film cleaning agent composition, the composition and proportions of which are the same as in example 1, except that no active agent (i.e., 0% active agent by mass) is added to the raw materials, and the amount of water is adjusted accordingly.
Comparative example 18
This comparative example provides a film cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the active agent in the raw material is 0.5%, and the amount of water is adjusted accordingly.
Comparative example 19
This comparative example provides a film cleaning agent composition, the composition and proportions of which are the same as in example 1, except that the mass fraction of the active agent in the raw materials is 7%, and the amount of water is adjusted accordingly.
Comparative example 20
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that the enzyme activity-maintaining agent and the complex enzyme (i.e., the mass fractions of the enzyme activity-maintaining agent and the complex enzyme are both 0%) are not added to the raw materials, and the amount of water is adjusted accordingly.
Comparative example 21
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that no enzyme activity-maintaining agent is added to the raw materials (i.e., the mass fraction of enzyme activity-maintaining agent is 0%), and the complex enzyme is replaced with protease by lipase and protease, and the mass fraction of protease is 1%, and the amount of water is adjusted accordingly.
Comparative example 22
This comparative example provides a membrane cleaning agent composition, and the composition and ratio of the raw materials are the same as in example 1, except that no enzyme activity-maintaining agent is added to the raw materials (i.e., the mass fraction of enzyme activity-maintaining agent is 0%), and the complex enzyme is replaced with lipase from lipase and protease, and the mass fraction of lipase is 1%, and the amount of water is adjusted accordingly.
Comparative example 23
The comparative example provides a membrane cleaning medicament composition which comprises the following raw materials in percentage by mass:
10% of chelating agent, 25% of alkali, 0.05% of complex enzyme, 3% of enzyme activity maintaining agent, 5% of active agent, 0.5% of defoaming agent and the balance of water to 100%;
The specific composition and ratio of the chelating agent, the base, the complex enzyme, the enzyme activity maintaining agent, the active agent and the antifoaming agent were the same as in example 1.
Comparative example 24
The comparative example provides a membrane cleaning medicament composition which comprises the following raw materials in percentage by mass:
35% of chelating agent, 10% of alkali, 8% of complex enzyme, 6% of enzyme activity maintaining agent, 5% of active agent, 0.5% of defoaming agent and the balance of water to 100%;
The specific composition and ratio of the chelating agent, the base, the complex enzyme, the enzyme activity maintaining agent, the active agent and the antifoaming agent were the same as in example 1.
Comparative example 25
The comparative example provides a membrane cleaning medicament composition which comprises the following raw materials in percentage by mass:
20% of sodium hydroxide, 30% of EDTA and 1% of sodium dodecyl benzene sulfonate, and the balance of water is up to 100%.
The preparation methods of the film cleaning agent compositions provided in comparative examples 1 to 25 are the same as those of examples 1 to 19, and are not repeated here.
In order to verify the technical effects of the above examples and comparative examples, the following experimental examples were specially set.
Experimental example 1
The membrane cleaning agent composition provided in each example and comparative example is used for cleaning a membrane element (reverse osmosis membrane of a certain chemical plant in quzhou, and the anatomical analysis of the membrane element is organic matters, microorganisms and oil composite fouling). The diaphragm machine is adopted for cleaning test, and the specific cleaning method comprises the following steps:
(a) Testing the initial flux and desalination rate of the membrane by using a membrane machine;
(b) Flushing the membrane machine with reverse osmosis produced water or clean water;
(c) The film cleaning agent composition provided in the embodiment 1 of the invention is arranged in a cleaning water tank according to the concentration of 10%, so as to form a cleaning liquid;
(d) Circularly mixing and heating the cleaning liquid to 35 ℃;
(e) Measuring the pH of the cleaning solution to be 11;
(f) Feeding the cleaning solution into the membrane and circulating for 45min;
(g) Soaking the membrane in the cleaning solution for 60min;
(h) The cleaning solution is put into the membrane again for circulation for 45min;
(i) Cleaning liquid is emptied, and the membrane system is flushed by reverse osmosis water or clean water until the pH of flushing water is 7;
(j) The membrane flux and the desalination rate after the completion of the washing were tested using a membrane machine.
The flux and desalination rate of the membrane machine before and after cleaning were measured according to GB T32373-2015, and the specific results are shown in Table 1.
TABLE 1
As can be seen from the cleaning data of each example and comparative example in table 1, the film cleaning agent composition provided by each example of the present invention has a good cleaning effect.
Specifically, examples 2 to 8 and comparative examples 1 to 7 are control experiments of example 1, and it can be seen from the data in Table 1 that the cleaning effect of the membrane cleaning agent composition is related to the amount of the complex enzyme added, the kind of the complex enzyme and the compounding ratio of the complex enzyme. The cleaning effect of the membrane cleaning agent composition added with lipase alone (comparative example 4) and the cleaning effect of the membrane cleaning agent composition added with protease alone (comparative example 5) were both stronger than those of the membrane cleaning agent composition without complex enzyme (comparative example 1). The cleaning effect of the membrane cleaning agent composition added with lipase is stronger than that of the membrane cleaning agent composition added with protease, and the cleaning effect of the membrane cleaning agent composition added with cellulase and amylase is mainly that of non-cellulose and starch.
Examples 9 to 13 are control experiments of example 1, and it can be seen from the data in Table 1 that the cleaning effect of the film cleaning agent composition is related to the kind of the enzyme activity maintaining agent, the addition amount of the enzyme activity maintaining agent, and the ratio of the enzyme activity maintaining agent.
Examples 14 to 17 and comparative example 17 are control experiments of example 1, and it can be seen from the data in table 1 that the cleaning effect of the film cleaning agent composition is related to the kind of active agent, the addition amount of the active agent, and the ratio of the active agent. The active agent is an anionic surfactant alone, and the anionic surfactant is stronger than the nonionic surfactant in terms of foaming and stabilizing effects, but the cleaning effect is general. This is because anionic surfactants are prone to react with the enzyme protein, often causing dissociation Cheng Yaji of the enzyme protein or denaturation of the peptide chain, ultimately leading to a reduction in cleaning performance. And the anionic surfactant is compounded with the nonionic surfactant, so that the foaming and foam stabilizing effects of the surfactant are maintained, the risk of enzymolysis is reduced, and the flux of the final membrane element is recovered to a better level. The film cleaning agent composition provided in comparative example 17 was free of an active agent, had no foaming and foam stabilizing effects of the active agent, was less likely to carry out of the film with a large amount of contaminants, and had a poor cleaning effect.
Comparative example 1, comparative example 8, comparative example 21 and comparative example 22 are all control experiments of example 1. As can be seen from the data in table 1, in the case where the enzyme activity maintaining agent was not added, the cleaning effect of the membrane cleaning agent composition (comparative example 8) to which the lipase and the protease were added as the complex enzyme was weaker than the cleaning effect of the membrane cleaning agent composition (comparative example 21) to which the protease was added alone and the cleaning agent composition (comparative example 22) to which the lipase was added alone. This is mainly due to the fact that the main component of the enzyme is protein, the lipase is decomposed by protease, and the enzymes interact with each other.
When the membrane cleaning agent composition (example 1) added with the enzyme activity maintaining agent is used for cleaning, the membrane flux is greatly increased, and the enzyme activity maintaining agent and the complex enzyme have better compatibility, so that the interaction between different enzyme preparations in the complex enzyme can be prevented, and the different enzyme preparations can play respective roles. In the case where no enzyme was added or only a single enzyme preparation was used, the addition of the enzyme activity maintaining agent (comparative example 1, comparative example 4, comparative example 5) had substantially no effect on the cleaning effect. Therefore, the addition of the enzyme activity maintaining agent and the complex enzyme have a synergistic effect in cleaning, thereby being beneficial to maintaining the activity of the complex enzyme.
Experimental example 2
The chemical plant in the state adopts reverse osmosis equipment to treat ammonium sulfate wastewater which contains oil and organic matters and has the temperature of 27 ℃ and frequent pollution and blockage in the operation process. The initial water flow rate is 6.5m 3/h and the pressure difference is 1.5bar. After 15 days of continuous operation, the water production flow rate was reduced to 3.2m 3/h and the pressure difference was increased to 2.9bar. The reverse osmosis membrane is oil and microbial fouling by sampling analysis, and the conventional cleaning agent is adopted, so that the water flow rate can only be recovered to about 5.0m/h, the pressure difference is recovered to about 2.4bar, and the flow rate pressure difference becomes the condition before cleaning after the reverse osmosis membrane runs for less than one week.
The membrane cleaning agent composition provided in example 1 was prepared with a cleaning solution I, a cleaning solution II and a cleaning solution III at a concentration of 8%, 10% and 12%, and a conventional cleaning agent formulation (comparative example 25 agent) was prepared with a cleaning solution IV at a concentration of 10%, and the reverse osmosis membrane was cleaned by the cleaning method comprising the steps of:
(a) Flushing the membrane system with reverse osmosis produced water or clean water;
(b) The film cleaning agent composition and the conventional cleaning agent provided in the embodiment 1 of the invention are prepared into a cleaning water tank according to the concentration specified in the experimental example 2 to form a cleaning liquid;
(c) Circularly mixing and heating the cleaning liquid to 35 ℃;
(d) Measuring the pH of the cleaning solution to be 11;
(e) Feeding the cleaning solution into the membrane and circulating for 45min;
(f) Soaking the membrane in the cleaning solution for 60min;
(g) The cleaning solution is put into the membrane again for circulation for 45min;
(h) The cleaning solution is emptied and the membrane system is flushed with reverse osmosis produced water or clean water until the flushing water has a pH of 7.
The cleaning data are shown in table 2.
TABLE 2
Experimental example 3
Reverse osmosis is adopted in a dye factory in Hangzhou, the organic matter content in the wastewater is high, membrane elements are frequently blocked, the water flow rate of a new membrane is 6.0m 3/h, the device continuously runs for only 72h, the water flow rate is reduced to about 2.0m 3/h, the pressure difference change is small, and the pressure difference is increased from 1.5bar to 1.8bar. Conventional cleaning agents have poor flux recovery and frequent cleaning, resulting in reduced membrane element life, requiring replacement of the membrane element for an average of 6 months. The membrane cleaning agent composition provided in example 1 was prepared with a cleaning solution I, a cleaning solution II and a cleaning solution III at a concentration of 8%, 10% and 12%, and a conventional cleaning agent formulation (comparative example 25 agent) was prepared with a cleaning solution IV at a concentration of 10%, and the reverse osmosis membrane was cleaned by the cleaning method comprising the steps of:
(a) Flushing the membrane system with reverse osmosis produced water or clean water;
(b) The film cleaning agent composition and the conventional cleaning agent provided in the embodiment 1 of the invention are prepared into a cleaning water tank according to the concentration specified in the experimental example 3 to form a cleaning liquid;
(c) Circularly mixing and heating the cleaning liquid to 35 ℃;
(d) Measuring the pH of the cleaning solution to be 11;
(e) Feeding the cleaning solution into the membrane and circulating for 45min;
(f) Soaking the membrane in the cleaning solution for 60min;
(g) The cleaning solution is put into the membrane again for circulation for 45min;
(h) The cleaning solution is emptied and the membrane system is flushed with reverse osmosis produced water or clean water until the flushing water has a pH of 7.
The cleaning data are shown in table 3.
TABLE 3 Table 3
Experimental example 4
A water works of an industry is prepared by adopting an immersion ultrafiltration and reverse osmosis process to treat water produced by municipal domestic sewage treatment plants, and microorganisms are bred due to the fact that bactericide is not added at the front end of the water works, so that the conventional medicament has poor cleaning effect.
The membrane cleaning agent composition provided in example 1 was prepared with a cleaning solution I, a cleaning solution II and a cleaning solution III at a concentration of 8%, 10% and 12%, and a cleaning solution IV was prepared at a concentration of a conventional cleaning agent formulation (comparative example 25 agent), and the reverse osmosis membrane was cleaned by the cleaning method comprising the steps of:
(a) Flushing the membrane system with reverse osmosis produced water or clean water;
(b) The film cleaning agent composition and the conventional cleaning agent provided in the embodiment 1 of the invention are prepared into a cleaning water tank according to the concentration specified in the experimental example 4 to form a cleaning liquid;
(c) Circularly mixing and heating the cleaning liquid to 35 ℃;
(d) Measuring the pH of the cleaning solution to be 11;
(e) Feeding the cleaning solution into the membrane and circulating for 45min;
(f) Soaking the membrane in the cleaning solution for 60min;
(g) The cleaning solution is put into the membrane again for circulation for 45min;
(h) The cleaning solution is emptied and the membrane system is flushed with reverse osmosis produced water or clean water until the flushing water has a pH of 7.
The cleaning data are shown in table 4.
TABLE 4 Table 4
As can be seen from the data in tables 2 to 4, the cleaning effect of the membrane cleaning agent composition of the present invention against fouling containing microorganisms, organics and oils is significantly better than that of the conventional cleaning composition, and the cleaning effect of the membrane cleaning agent composition of the present invention is better at a concentration of 10%.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (4)
1. The membrane cleaning medicament composition is characterized by comprising the following raw materials in percentage by mass:
Chelating agent 21.5%, alkali 20%, complex enzyme 1%, enzyme activity maintaining agent 3%, active agent 5%, defoaming agent 0.5%, water balance to 100%;
Wherein the chelating agent comprises hydroxyethyl ethylenediamine trisodium acetate and polyaspartic acid, and the mass ratio of the hydroxyethyl ethylenediamine trisodium acetate to the polyaspartic acid is 13.5:8, 8; the alkali is sodium hydroxide; the complex enzyme comprises lipase and protease, and the mass ratio of the lipase to the protease is 0.3:0.7; the enzyme activity maintaining agent comprises sodium citrate and ethoxylated polyethyleneimine, and the mass ratio of the sodium citrate to the ethoxylated polyethyleneimine is 2.5:0.5; the active agent comprises tea saponin and sodium dodecyl sulfate, and the mass ratio of the tea saponin to the sodium dodecyl sulfate is 2:3, a step of; the defoaming agent is polyoxypropylene polyoxyethylene glyceryl ether.
2. A method of preparing the membrane cleaning pharmaceutical composition of claim 1, comprising the steps of:
and mixing the raw materials in the formula amount to obtain the membrane cleaning medicament composition.
3. The preparation method according to claim 2, characterized by comprising the steps of:
mixing a formula amount of alkali and water, and heating to obtain a mixture A;
Mixing the mixture A with chelating agent, active agent and defoamer in the formula amount to obtain a mixture B; and mixing the mixture B with a formula amount of enzyme activity maintaining agent and complex enzyme to obtain the membrane cleaning medicament composition.
4. Use of the membrane cleaning pharmaceutical composition according to claim 1 or the membrane cleaning pharmaceutical composition produced by the production method according to claim 2 or 3 in the field of cleaning of reverse osmosis membrane systems.
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| JP2006055784A (en) * | 2004-08-23 | 2006-03-02 | Asahi Kasei Corp | Method for cleaning porous separation membrane |
| CN105705220A (en) * | 2013-03-12 | 2016-06-22 | 艺康美国股份有限公司 | Surfactant blends for cleaning filtration membranes |
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