CN103332796B - A kind of degradable without phosphorus composite slow-corrosion scale resistor - Google Patents
A kind of degradable without phosphorus composite slow-corrosion scale resistor Download PDFInfo
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- 238000005260 corrosion Methods 0.000 title claims abstract description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000011574 phosphorus Substances 0.000 title claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 alkyl glycoside Chemical class 0.000 claims abstract description 8
- 235000001014 amino acid Nutrition 0.000 claims abstract description 8
- 150000001413 amino acids Chemical class 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 7
- 229930182470 glycoside Natural products 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 6
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 102000016938 Catalase Human genes 0.000 claims description 27
- 108010053835 Catalase Proteins 0.000 claims description 27
- 108010015776 Glucose oxidase Proteins 0.000 claims description 27
- 239000004366 Glucose oxidase Substances 0.000 claims description 27
- 229940116332 glucose oxidase Drugs 0.000 claims description 27
- 235000019420 glucose oxidase Nutrition 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 102000004190 Enzymes Human genes 0.000 claims description 17
- 108090000790 Enzymes Proteins 0.000 claims description 17
- 229940088598 enzyme Drugs 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005576 amination reaction Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 239000008103 glucose Substances 0.000 claims description 13
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000006166 lysate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HOGDNTQCSIKEEV-UHFFFAOYSA-N n'-hydroxybutanediamide Chemical compound NC(=O)CCC(=O)NO HOGDNTQCSIKEEV-UHFFFAOYSA-N 0.000 claims description 3
- 230000003534 oscillatory effect Effects 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 12
- 230000005764 inhibitory process Effects 0.000 abstract description 9
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 19
- 108010093096 Immobilized Enzymes Proteins 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- NEEHYRZPVYRGPP-IYEMJOQQSA-L calcium gluconate Chemical compound [Ca+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O NEEHYRZPVYRGPP-IYEMJOQQSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical group [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- 238000011218 seed culture Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001677188 Coccus viridis Species 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical class OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 108010091086 Recombinases Proteins 0.000 description 1
- 102000018120 Recombinases Human genes 0.000 description 1
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960005069 calcium Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000011169 microbiological contamination Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The present invention relates to a kind of degradable without phosphorus composite slow-corrosion scale resistor, be prepared from by following raw materials in parts by weight number ratio: sodium sulfate 5-10 part, alkyl glycoside 3-5 part, poly aspartic acid 3-5 part, carboxymethyl cellulose 2-5 part, poly-epoxy succinic acid 8-20 part, polymeric amino acid 3-5 part, Sunmorl N 60S 3-5 part, xylogen 5-10 part, methyl benzotriazole 1-2 part and 40-50 part deionized water.The present invention adopts nontoxic, natural, renewable and degradable substance to be raw material, makes full use of the synergy of each component, greatly improves its corrosion and scale inhibition performance, effectively can reduce chemical feeding quantity, have nontoxic, biodegradable, steady performance.
Description
Technical field
The present invention relates to a kind of Scale inhibitors, especially relate to a kind of degradable without phosphorus composite slow-corrosion scale resistor.
Background technology
The calcium contained in water, magnesium plasma can, constantly in tube wall surface fouling, cause tube wall heat transfer efficiency to reduce in recirculating cooling water system, affect recirculated water flowing time serious.Form galvanic corrosion simultaneously, make tube wall thinning gradually, reduce work-ing life, have a strong impact on the safe operation of system.The traditional method addressed this problem adopts to add corrosion inhibiting and descaling agent.
At present, conventional organic phosphorous ingredient corrosion inhibiting and descaling agent, include 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), 2-phosphonobutane-1,2-phosphonobutane-2,4 one tri hydroxy acids (PBTCA) etc., relatively early stage phosphoric acid salt not only increases corrosion-mitigation scale-inhibition efficiency, and reduces phosphorus content, the pollution to water body can be reduced, but the impact on body eutrophication cannot be avoided.
These conventional corrosion inhibiting and descaling agents adopt poly carboxylic acid, poly-sulphonic acids makes dirt dispersion agent, and due to can not biological degradation, they be constantly accumulated, and certainly lead to detrimentally affect to water body.Along with environmental requirement is more and more higher, green scale corrosion inhibitor also more and more comes into one's own.
Calglucon is as one of water quality stabilizer component, and usual usage quantity is comparatively large, and yield is low, severe reaction conditions and the defect such as device structure is complicated to use traditional manufacture craft and catalyzer to exist.
Specifically: the production method of calglucon has electrolytic oxidation, bromination method, metal catalytic synthesis method, fermentation method etc.In industrialized production, main employing metal catalysed processes and fermentation method at present.
In recent years, Enzymes Industry develops along with the fast development of downstream industry, and kind and quality are all greatly improved.Enzyme method technique utilizes zymin directly conversion of glucose to be become gluconic acid exactly, then through the neutralizing effect of alkali, converts it into gluconate series product.Compared with fermentation method, the most outstanding feature of enzyme process is exactly do not need seed culture, eliminates the interference of the raw and auxiliary material such as microorganism and substratum to reaction system, improves the purity of reaction product, bring convenience to purifying.Without seed culture, thus reaction is more prone to control, and produces and also can become more steady.For the producer, enzyme method technique is easy, and equipment is simple, easy to operate, and do not have the danger of microbiological contamination, and product is single, purity is high, is easy to be separated and refine, and quality product and yield significantly improve, and product hierarchy reaches food grade and injection stage standard completely.For newly founding the factory, seeding tank and extracting section equipment can be saved, reduce facility investment.Compared with metal catalysed processes, enzyme process also has the high feature of security.
By being fixed of enzyme, the stability of enzyme can be significantly improved.Be not subject to the impact of external environment and inactivation.Immobilized enzyme is easy to and product separation, and owing to only having substrate in reaction system, product, immobilized enzyme, by immobilized enzyme Separation and Recovery from reaction system after reaction terminates, only exists product in system, is easy to carry out the refining of product, and product purity is high.Immobilized enzyme can repeat to recycle, and greatly reduces the cost of enzyme.
But still there are some shortcomings in these immobilized enzyme methods: such as carrier microballoons finite surface area, cannot the too much zymoprotein of load, make enzymatic activity recovery lower.In addition, due to the impact of resistance to mass transfer, the H generated in reaction process
2o
2can not decompose rapidly, thus cause GOD and CAT inactivation, immobilized enzyme just loses most enzymic activity after continued use very soon.
Summary of the invention
The present invention devises a kind of degradable without phosphorus composite slow-corrosion scale resistor, and its technical problem solved is: (1) existing Scale inhibitors is phosphorous, there is toxicity, and cannot degrade, easily to water body and environment; (2) existingly prepare calglucon technique by immobilized enzyme and there is carrier microballoons finite surface area, cannot the too much zymoprotein of load, make enzymatic activity recovery lower; (3) due to the impact of resistance to mass transfer, the H generated in reaction process
2o
2can not decompose rapidly, thus cause GOD and CAT inactivation, immobilized enzyme just loses most enzymic activity after continued use very soon.
In order to solve the technical problem of above-mentioned existence, present invention employs following scheme:
A kind of degradable without phosphorus composite slow-corrosion scale resistor, be prepared from by following raw materials in parts by weight number ratio: sodium sulfate 5-10 part, alkyl glycoside 3-5 part, poly aspartic acid 3-5 part, carboxymethyl cellulose 2-5 part, poly-epoxy succinic acid 8-20 part, polymeric amino acid 3-5 part, Sunmorl N 60S 3-5 part, xylogen 5-10 part, methyl benzotriazole 1-2 part and 40-50 part deionized water, it is characterized in that: described Sunmorl N 60S preparation process is as follows: step 1: there is polymethacrylic acid macroporous resin microspheres for carrier, the mean pore size of microballoon is between 100nm-200nm, be amination reagent with 1-5% (v/v) ethylenediamine solution, by carrier quality: amination reagent volume 1: 40-50 by support dispersion in amination reagent, at pH7-9, oscillatory reaction 1-10h at 40-90 DEG C, collect amination carrier, step 2: according to glucose oxidase (GOD): the vigor ratio of catalase (CAT) is the ratio of 1: 1-8, is dissolved in the phosphoric acid buffer of pH5-8 by glucose oxidase (GOD) and catalase (CAT), in enzyme lysate, add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide, at 0-8 DEG C, react 20-75min, then by amination support dispersion in enzyme liquid, stirring reaction 1-10h at 25-35 DEG C, step 3: add the acetone of 1-5 times of reaction solution volume and the mixture of 0.1-2.0% (v/v) linking agent in step 2 gained reaction solution, continue reaction 1-2h, the reaction solution generated after reaction is filtered, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing at least 4 times, drying obtains mixed immobilized glucose oxidase/catalase microspheres, step 4: be 20% preparation glucose solution according to mass percent, in the container that stirring rake is housed, add glucose solution and sodium hydroxide solution, glucose and sodium hydroxide mol ratio are 1: 1, mixed immobilized glucose oxidase/catalase microspheres is added according to 0.6% ~ 1% of glucose quality, carry out being oxidized the reaction carried out in gluconic acid and sodium hydroxide simultaneously and produce Sunmorl N 60S, oxidizing temperature 32-40 DEG C, ventilate 1: 0.14 ~ 0.15 (v/v/h, the ratio of air flow per hour and the actual material liquid volume of container), oxidization time 15 ~ 20 hours, ph5.5 ~ 7.5, residual sugar lower than 0.3% time oxidation terminate, obtain Sunmorl N 60S.
Further, glucose oxidase (GOD) in step 2: catalase (CAT): phosphoric acid buffer volume ratio is each other: 10-15: 1: 400-500.
Further, after oxidation terminates in step 4, reclaim immobilized glucose oxidase/catalase microballoon and reuse.
Further, the linking agent in step 3 is glutaraldehyde or Vanillin.
This degradable without phosphorus composite slow-corrosion scale resistor, compared with the degradable without phosphorus composite slow-corrosion scale resistor of tradition, has following beneficial effect:
(1) the present invention adopts nontoxic, natural, renewable and degradable substance to be raw material, make full use of the synergy of each component, greatly improve its corrosion and scale inhibition performance, effectively can reduce chemical feeding quantity, there is nontoxic, biodegradable, steady performance.
(2) the present invention can avoid the deposition of calcium carbonate, calcium sulfate, calcium phosphate containing the without phosphorus composite slow-corrosion scale resistor of natural biodegradable thing, and scale inhibition effect is obvious, and corrosion inhibition is excellent.
(3) the present invention is owing to having biodegradable feature, effectively can avoid the formation of body eutrophication, can reduce the consumption of Biocidal algae-killing agent, remarkable in economical benefits simultaneously.
(4) the present invention is that the required calglucon of water quality stabilizer preparation proposes novel process, and this yield of calcium gluconate is high, and reaction conditions is gentle, and equipment is simple and easy to get, is a kind of production technique of environmental protection.
(5) the present invention adopts polymethacrylic acid macroporous resin to be fixation support, cost is low, its aperture, particle diameter and epoxy group(ing) density are all controlled, because the charge capacity impact of the parameter such as aperture, particle diameter on enzyme of resin is very large, therefore polymethacrylic acid macroporous resin can be applicable to the immobilization of GOD/CAT to greatest extent according to real needs.
(6) the present invention adopts crosslinked for zymoprotein gathering, makes the limited more zymoprotein of carrier surface area energy load.In addition because carrier has suitable aperture, can overcome the impact of resistance to mass transfer, immobilized enzyme diffusion mass transfer resistance is very little, and speed of reaction is close to use resolvase.
(7) mixed immobilized glucose oxidase/catalase microspheres of the present invention effectively can promote the covalently bound of carrier and enzyme molecule, substantially increase immobilization efficiency, and significant prolongation work-ing life of co-immobilization GOD/CAT, can Reusability time, production cost is low, is conducive to Sustainable development.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Embodiment 1: a kind of degradable without phosphorus composite slow-corrosion scale resistor, is prepared from by following raw materials in parts by weight number ratio: 5 parts, sodium sulfate, alkyl glycoside 3 parts, poly aspartic acid 3 parts, carboxymethyl cellulose 5 parts, poly-epoxy succinic acid 20 parts, polymeric amino acid 5 parts, Sunmorl N 60S 5 parts, 10 parts, xylogen, methyl benzotriazole 2 parts and 50 parts of deionized waters.
Embodiment 2: a kind of degradable without phosphorus composite slow-corrosion scale resistor, is prepared from by following raw materials in parts by weight number ratio: 10 parts, sodium sulfate, alkyl glycoside 5 parts, poly aspartic acid 5 parts, carboxymethyl cellulose 2 parts, poly-epoxy succinic acid 8 parts, polymeric amino acid 3 parts, Sunmorl N 60S 5 parts, 10 parts, xylogen, methyl benzotriazole 1 part and 40 parts of deionized waters.
Alkyl glycoside (APG) contained by product of the present invention, synthesized by renewable resources natural fat alcohol and glucose, it is the more comprehensive new non-ionic surfactants of a kind of performance, having high surface, good ecological security and intermiscibility, is internationally recognized first-selection " green " functional surfactant.Its surface tension is low, compatibleness is strong, biological degradation is thorough rapidly, has stronger broad spectrum antibiotic activity, easy ten dilutions, gel-free phenomenon, composite with amino acids material, the scale inhibition/dissemination of such material can be promoted, promote corrosion inhibition, synergistic effect is obvious.
Alkyl glycoside and poly aspartic acid have obvious synergistic effect, and the excellent ten single poly aspartic acids of performance, have obvious lifting when ensureing scale-inhibiting properties to corrosion inhibition.
Carboxymethyl cellulose (CMC) is a kind of conventional foodstuff additive, and its sodium salt is the sodium salt of Mierocrystalline cellulose shuttle methyl ether, another name sodium cellulose glycolate.Carboxymethyl cellulose and poly-epoxy succinic acid have obvious synergistic effect, and performance is better than the scale-inhibiting properties of arbitrary one-component.
Polymeric amino acid is a kind of protein comprising amino acid group, polymeric amino acid can be prepared by natural product, such as soybean produces through biological fermentation, it is a kind of natural reproducible green corrosion inhibitor, its polymerization degree is 3000-1000000, there is good corrosion inhibition, to the generation of calcium sulfate scale, there is obvious restraining effect simultaneously.
Sunmorl N 60S mainly plays inhibition synergism.
Xylogen plays effect of dispersion, effectively avoids the formation of fouling, and environmental protection.
Wherein, the preparatory technology of calglucon is as follows:
Be amination reagent with 2% (v/v) ethylenediamine solution, carrier mean pore size is 100-200nm, by carrier quality: amination reagent volume 1: 40 by support dispersion in 2% (v/v) amination reagent, at pH8.0,200rpm oscillatory reaction 2h at 60 DEG C, collects amination carrier.
Be the ratio of 1: 2 according to the vigor ratio of GOD: CAT, GOD and CAT be dissolved in the phosphoric acid buffer of the 0.1mol/l of pH6.In enzyme lysate, add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide, react 60min at 8 DEG C, by amination support dispersion in enzyme liquid, 30 DEG C are reacted 2h under mixing speed 200rpm.In reaction solution, add acetone and 0.5% (v/v) the glutaraldehyde mixture of 2 times of reaction solution volumes, at 30 DEG C, continue reaction 1h.Filtered by above-mentioned reaction solution, abandon filtrate, collect solid substance, for the solid substance collected, wash 4 times with the 0.01mol/l phosphoric acid buffer of pH7.0,4 DEG C of dryings, just prepare epoxy resin co-immobilization GOD/CAT microballoon, enzyme activity is 111.9U/g.
Be 20% preparation glucose solution according to mass percent, in the container that stirring rake is housed, add glucose solution and sodium hydroxide solution, mixed immobilized glucose oxidase/catalase microspheres is added according to 0.6% ~ 1% of glucose quality, carry out being oxidized the reaction carried out in gluconic acid and sodium hydroxide simultaneously and produce calglucon, oxidizing temperature 32-40 DEG C; Ventilate 1: 0.14 ~ 0.15 (v/v/h); Oxidization time 15 ~ 20 hours, ph5.5 ~ 7.5, residual sugar lower than 0.3% time oxidation terminate, obtain Sunmorl N 60S.
Above in conjunction with the embodiments to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (2)
1. a degradable without phosphorus composite slow-corrosion scale resistor, be prepared from by following raw materials in parts by weight number ratio: sodium sulfate 5-10 part, alkyl glycoside 3-5 part, poly aspartic acid 3-5 part, carboxymethyl cellulose 2-5 part, poly-epoxy succinic acid 8-20 part, polymeric amino acid 3-5 part, Sunmorl N 60S 3-5 part, xylogen 5-10 part, methyl benzotriazole 1-2 part and 40-50 part deionized water, it is characterized in that: the preparation process of described Sunmorl N 60S is as follows: step 1: there is polymethacrylic acid macroporous resin microspheres for carrier, the mean pore size of microballoon is between 100nm-200nm, take concentration expressed in percentage by volume as the ethylenediamine solution of 1-5% be amination reagent, by carrier quality: amination reagent volume 1: 40-50 by support dispersion in amination reagent, at pH7-9, oscillatory reaction 1-10h at 40-90 DEG C, collect amination carrier, step 2: according to glucose oxidase (GOD): the vigor ratio of catalase (CAT) is the ratio of 1: 1-8, is dissolved in the phosphoric acid buffer of pH5-8 by glucose oxidase (GOD) and catalase (CAT), add in enzyme lysate mass percentage concentration be 0.2% carbodiimide and mass percentage concentration be the N-hydroxy-succinamide of 0.2%, 20-75min is reacted at 0-8 DEG C, then by amination support dispersion in enzyme liquid, stirring reaction 1-10h at 25-35 DEG C, step 3: add the mixture that the acetone of 1-5 times of reaction solution volume and concentration expressed in percentage by volume are 0.1-2.0% linking agent in step 2 gained reaction solution, continue reaction 1-2h, the reaction solution generated after reaction is filtered, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing at least 4 times, drying obtains mixed immobilized glucose oxidase/catalase microspheres, step 4: be 20% preparation glucose solution according to mass percent, in the container that stirring rake is housed, add glucose solution and sodium hydroxide solution, glucose and sodium hydroxide mol ratio are 1: 1, mixed immobilized glucose oxidase/catalase microspheres is added according to 0.6% ~ 1% of glucose quality, carry out being oxidized the reaction carried out in gluconic acid and sodium hydroxide simultaneously and produce Sunmorl N 60S, oxidizing temperature 32-40 DEG C, ventilate, wherein the ratio of air flow per hour and the actual material liquid volume of container is 1: 0.14 ~ 0.15, oxidization time 15 ~ 20 hours, pH5.5 ~ 7.5, residual sugar lower than 0.3% time oxidation terminate, obtain Sunmorl N 60S, glucose oxidase (GOD) in step 2: catalase (CAT): phosphoric acid buffer volume ratio is each other: 10-15: 1: 400-500, after oxidation terminates in step 4, reclaim mixed immobilized glucose oxidase/catalase microspheres and reuse.
2. degradable without phosphorus composite slow-corrosion scale resistor according to claim 1, is characterized in that: the linking agent in step 3 is glutaraldehyde or Vanillin.
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| CN104263766A (en) * | 2014-09-01 | 2015-01-07 | 郸城财鑫糖业有限责任公司 | Method for preparing sodium gluconate by using immobilized enzyme |
| CN104291453B (en) * | 2014-10-20 | 2016-08-24 | 南通纺都置业有限公司 | A kind of corrosion inhibiting and descaling agent for beer bottle washing machine |
| CN104445652A (en) * | 2014-10-22 | 2015-03-25 | 山东华亚环保科技有限公司 | Corrosion and scale inhibitor for beer bottle washing machine |
| CN104450806B (en) * | 2014-11-27 | 2018-01-16 | 江南大学 | A kind of method that enzyme process prepares sodium gluconate |
| CN104556426B (en) * | 2014-12-24 | 2016-08-24 | 广州市清顺环保科技有限公司 | The preparation method of without phosphorus compound corrosion inhibiting and descaling agent |
| CN104762844A (en) * | 2015-04-30 | 2015-07-08 | 陈朝民 | Papermaking stewing accessory ingredient and preparation method thereof |
| CN105883947B (en) * | 2016-06-29 | 2018-10-16 | 欣格瑞（山东）环境科技有限公司 | Environmentally protective medicament for recirculated water zero blowdown |
| CN107555622A (en) * | 2017-10-25 | 2018-01-09 | 成都凯米拉科技有限公司 | A kind of production technology of oil field water process composite scale inhibitor |
| CN108996714A (en) * | 2018-08-24 | 2018-12-14 | 广州科宝水处理科技有限公司 | A kind of recirculated cooling water phosphate-free corrosion inhibition antisludging agent |
| CN109987723B (en) * | 2019-04-29 | 2021-11-19 | 郑州轻工业学院 | Non-phosphorus scale and corrosion inhibitor and preparation method and application thereof |
| CN111138592A (en) * | 2019-12-31 | 2020-05-12 | 长江大学 | Carboxymethyl inulin graft polymer scale and corrosion inhibitor and preparation method thereof |
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