CN103332796A - Degradable phosphorus-free composite corrosion and scale inhibitor - Google Patents
Degradable phosphorus-free composite corrosion and scale inhibitor Download PDFInfo
- Publication number
- CN103332796A CN103332796A CN2013101079143A CN201310107914A CN103332796A CN 103332796 A CN103332796 A CN 103332796A CN 2013101079143 A CN2013101079143 A CN 2013101079143A CN 201310107914 A CN201310107914 A CN 201310107914A CN 103332796 A CN103332796 A CN 103332796A
- Authority
- CN
- China
- Prior art keywords
- parts
- reaction
- catalase
- glucose
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005260 corrosion Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 230000007797 corrosion Effects 0.000 title abstract description 14
- 239000002455 scale inhibitor Substances 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001413 amino acids Chemical class 0.000 claims abstract description 8
- 229920000805 Polyaspartic acid Polymers 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
- 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
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 5
- 108010064470 polyaspartate Proteins 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
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 3
- 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 22
- 102000004190 Enzymes Human genes 0.000 claims description 16
- 108090000790 Enzymes Proteins 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 229940088598 enzyme Drugs 0.000 claims description 16
- 238000005576 amination reaction Methods 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 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
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- 235000001014 amino acid Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl glycoside Chemical class 0.000 claims description 6
- 229930182470 glycoside Natural products 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-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
- 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
- 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
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 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 2
- 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
- 230000002401 inhibitory effect Effects 0.000 abstract description 7
- 239000003112 inhibitor Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 229920001529 polyepoxysuccinic acid Polymers 0.000 abstract 1
- 239000000176 sodium gluconate Substances 0.000 abstract 1
- 229940005574 sodium gluconate Drugs 0.000 abstract 1
- 235000012207 sodium gluconate Nutrition 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 10
- 108010093096 Immobilized Enzymes Proteins 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 8
- 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 7
- 230000000694 effects 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
- 239000004593 Epoxy Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 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
- 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 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
- 235000011044 succinic acid Nutrition 0.000 description 2
- 150000003444 succinic acids Chemical class 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
- 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
- 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
- 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
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- 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
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002950 deficient 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
- 239000000284 extract 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
- 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
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 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
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 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
Landscapes
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The invention relates to a degradable phosphorus-free composite corrosion and scale inhibitor. The inhibitor is prepared from following raw materials by weight: 5-10 parts of sodium sulfate, 3-5 parts of alkyl polyglycoside, 3-5 parts of polyaspartic acid, 2-5 parts of carboxymethylcellulose, 8-20 parts of polyepoxysuccinic acid, 3-5 parts of a polymerized amino acid, 3-5 parts of sodium gluconate, 5-10 parts of xylogen, 1-2 parts of methylbenzotriazole and 40-50 parts of deionized water. According to the invention, the raw materials of the inhibitor are nontoxic, natural, renewable and degradable. The synergistic effects of all compositions are fully utilized, and performance of corrosion and scale inhibiting is improved and dosage is reduced. The inhibitor has the advantages of no toxicity, no harm, biodegradability, stable performance, and the like.
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 that contains in the water, magnesium plasma can cause the tube wall heat transfer efficiency to reduce constantly in the tube wall surface fouling in recirculating cooling water system, influence recirculated water when serious and flow.Form galvanic corrosion simultaneously, make tube wall attenuation gradually, reduce work-ing life, have a strong impact on the safe operation of system.The traditional method that addresses this problem is to adopt to add corrosion inhibiting and descaling agent.
At present, organophosphorus prescription corrosion inhibiting and descaling agent commonly used, include 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), 2-phosphonic acids butane-1,2-phosphonic acids butane-2,4 one tri hydroxy acids (PBTCA) etc., early stage relatively phosphoric acid salt has not only improved corrosion-mitigation scale-inhibition efficient, and has reduced phosphorus content, the pollution to water body can be reduced, but the influence to body eutrophication can't be avoided.
These corrosion inhibiting and descaling agents commonly used adopt poly carboxylic acid, poly-sulfonic acid class to make dirt dispersion agent, because can not biological degradation, they are constantly accumulated, and water body is certainly led to detrimentally affect.Along with environmental requirement is more and more higher, green corrosion inhibiting and descaling agent also more and more comes into one's own.
Calglucon is as one of water quality stabilizer component, and usage quantity is bigger usually, uses that traditional manufacture craft and catalyzer exist that yield is low, defectives such as severe reaction conditions and device structure complexity.
Specifically: the production method of calglucon has electrolytic oxidation, bromination method, metal catalytic synthesis method, fermentation method etc.In industrialized production, mainly adopt metal catalytic method and fermentation method at present.
In recent years, zymin industry is accompanied by the fast development of downstream industry and develops, and all is greatly improved on kind and quality.Enzyme method technique utilizes zymin directly conversion of glucose to be become gluconic acid exactly, passes through the neutralizing effect of alkali again, converts it into the gluconate series product.Compare with fermentation method, the outstanding feature of enzyme process is exactly not need seed culture, has removed raw and auxiliary materials such as microorganism and substratum to the interference of reaction system, has improved the purity of reaction product, gives and extracts and refining bringing convenience.Do not had seed culture, thereby reaction is more prone to control, produces and also can become more steady.For the producer, enzyme method technique is easy, and equipment is simple, easy to operate, does not have the danger of microbiological contamination, and product is single, and the purity height is easy to separate and make with extra care, and quality product and yield significantly improve, and product hierarchy reaches food grade and injection stage standard fully.For newly founding the factory, can save seeding tank and extracting section equipment, reduced facility investment.Compare with the metal catalytic method, enzyme process also has safe characteristics.
Enzyme is carried out immobilization, can significantly improve the stability of enzyme.Be not subject to the influence of external environment and inactivation.Immobilized enzyme is easy to and product separation, owing to have only substrate in the reaction system, product, with immobilized enzyme Separation and Recovery from reaction system, only there is product in immobilized enzyme after reaction finishes in the system, be easy to carry out the refining of product, product purity height.Immobilized enzyme can repeat to recycle, and reduces the cost of enzyme greatly.
But still there are some shortcomings in these immobilized enzyme methods: limited such as the carrier microballoons surface-area, can't the too much zymoprotein of load, and make enzymatic activity recovery lower.In addition, since the influence of resistance to mass transfer, the H that generates in the reaction process
2O
2Can not decompose rapidly, thereby cause GOD and CAT inactivation, immobilized enzyme is very fast after using continuously just to lose most enzymic activity.
Summary of the invention
The present invention has designed a kind of degradable without phosphorus composite slow-corrosion scale resistor, and the technical problem of its solution is: (1) existing Scale inhibitors is phosphorous, has toxicity, and can't degrade, and easily water body and environment is polluted; (2) existingly prepare calglucon technology by immobilized enzyme and exist the carrier microballoons surface-area limited, can't the too much zymoprotein of load, make enzymatic activity recovery lower; (3) because the influence of resistance to mass transfer, the H that generates in the reaction process
2O
2Can not decompose rapidly, thereby cause GOD and CAT inactivation, immobilized enzyme is very fast after using continuously just to lose most enzymic activity.
In order to solve the technical problem of above-mentioned existence, the present invention has adopted following scheme:
A kind of degradable without phosphorus composite slow-corrosion scale resistor, counting ratio by following raw materials in parts by weight is prepared from: 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: be carrier to have polymethacrylic acid macroporous resin microballoon, the mean pore size of microballoon is between 100nm-200nm, be amination reagent with 1-5% (v/v) ethylenediamine solution, by the carrier quality: amination reagent volume 1: 40-50 is scattered in carrier in the amination reagent, at pH7-9,40-90 ℃ of following oscillatory reaction 1-10h collects the amination carrier; Step 2: according to glucose oxidase (GOD): the vigor ratio of catalase (CAT) is 1: the ratio of 1-8 is dissolved in glucose oxidase (GOD) and catalase (CAT) in the phosphoric acid buffer of pH5-8; Add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide in the enzyme lysate, 0-8 ℃ is reacted 20-75min down, then the amination carrier is scattered in the enzyme liquid 25-35 ℃ of following stirring reaction 1-10h; Step 3: in step 2 gained reaction solution, add the acetone of 1-5 times of reaction solution volume and the mixture of 0.1-2.0% (v/v) linking agent, continue reaction 1-2h, the reaction solution that the reaction back is generated filters, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing at least 4 times, drying obtains co-immobilization glucose oxidase/catalase microballoon; Step 4: according to mass percent be 20% the preparation glucose solution, in the container of stirring rake is housed, add glucose solution and sodium hydroxide solution, glucose and sodium hydroxide mol ratio are 1: 1, add co-immobilization glucose oxidase/catalase microballoon according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and the sodium hydroxide simultaneously and the reaction that produces Sunmorl N 60S, oxidizing temperature 32-40 ℃; 1: 0.14～0.15 (v/v/h, the per hour ratio of air flow and the actual material liquid volume of container) ventilates; Oxidization time 15～20 hours, ph5.5～7.5, residual sugar is lower than oxidation in 0.3% o'clock to be finished, and obtains Sunmorl N 60S.
Further, glucose oxidase (GOD) in the step 2: catalase (CAT): phosphoric acid buffer volume ratio each other is: 10-15: 1: 400-500.
Further, after oxidation finishes in the step 4, reclaim immobilized glucose oxidase/catalase microballoon and reuse.
Further, the linking agent in the step 3 is glutaraldehyde or Vanillin.
This degradable without phosphorus composite slow-corrosion scale resistor is 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 is raw material, takes full advantage of the synergy of each component, improves its corrosion and scale inhibition performance greatly, can effectively reduce to add dose, has nontoxic, biodegradable, steady performance.
(2) the present invention's without phosphorus composite slow-corrosion scale resistor of containing natural biodegradable thing can be avoided the deposition of calcium carbonate, calcium sulfate, calcium phosphate, and scale inhibition effect is obvious, the corrosion inhibition excellence.
(3) the present invention can effectively avoid the formation of body eutrophication owing to have biodegradable characteristics, can reduce the consumption of Biocidal algae-killing agent simultaneously, remarkable in economical benefits.
(4) required calglucon has proposed novel process for water quality stabilizer prepares in the present invention, this novel process is guaranteed calglucon yield height, the reaction conditions gentleness, and equipment is simple and easy to, and is a kind of production technique of environmental protection.
(5) to adopt the polymethacrylic acid macroporous resin be fixation support in the present invention, cost is low, its aperture, particle diameter and epoxy group(ing) density are all controlled, because parameters such as the aperture of resin, particle diameter are very big to the charge capacity influence of enzyme, so the 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 and zymoprotein to be assembled crosslinked, makes the limited carrier surface area can the more zymoprotein of load.Because carrier has suitable aperture, can overcome the influence of resistance to mass transfer in addition, immobilized enzyme diffusion mass transfer resistance is very little, and speed of reaction is close to using resolvase.
(7) co-immobilization glucose oxidase of the present invention/catalase microballoon can effectively promote the covalently bound of carrier and enzyme molecule, improved immobilization efficiency greatly, and significant prolongation the work-ing life of co-immobilization GOD/CAT, can use inferior repeatedly, 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, and count ratio by following raw materials in parts by weight and be prepared from: 5 parts in sodium sulfate, 3 parts of alkyl glycoside, 3 parts of poly aspartic acids, 5 parts of carboxymethyl celluloses, 20 parts of poly-epoxy succinic acids, 5 parts of polymeric amino acids, 5 parts of Sunmorl N 60Ss, 10 parts in xylogen, 2 parts and 50 parts deionized waters of methyl benzotriazole.
Embodiment 2: a kind of degradable without phosphorus composite slow-corrosion scale resistor, and count ratio by following raw materials in parts by weight and be prepared from: 10 parts in sodium sulfate, 5 parts of alkyl glycoside, 5 parts of poly aspartic acids, 2 parts of carboxymethyl celluloses, 8 parts of poly-epoxy succinic acids, 3 parts of polymeric amino acids, 5 parts of Sunmorl N 60Ss, 10 parts in xylogen, 1 part and 40 parts deionized waters of methyl benzotriazole.
The contained alkyl glycoside of product of the present invention (APG), synthetic by the pure and mild glucose of renewable resources natural fat, 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 surface promoting agent.Its surface tension is low, compatibleness is strong, biological degradation is thorough rapidly, has stronger broad spectrum antibiotic activity, easy ten dilutions, the gel-free phenomenon, composite with the amino acids material, can promote the scale inhibition/dissemination of such material, promote corrosion inhibition, synergistic effect is obvious.
Alkyl glycoside and poly aspartic acid have the obvious synergistic effect, and the poly aspartic acid that performance excellent ten is single has obvious lifting to corrosion inhibition under the situation that guarantees scale-inhibiting properties.
Carboxymethyl cellulose (CMC) is a kind of foodstuff additive commonly used, and its sodium salt is the sodium salt of Mierocrystalline cellulose shuttle methyl ether, the another name sodium cellulose glycolate.Carboxymethyl cellulose and poly-epoxy succinic acid have the obvious synergistic effect, and performance is better than the scale-inhibiting properties of arbitrary one-component.
Polymeric amino acid is a kind of protein that comprises amino acid group, polymeric amino acid can be prepared by natural product, for example soybean produces through biological fermentation, it is a kind of natural reproducible green corrosion inhibitor, its polymerization degree is 3000-1000000, have good corrosion inhibition, the generation to the calcium sulfate dirt simultaneously has the obvious suppression effect.
Sunmorl N 60S mainly plays the inhibition synergism.
Xylogen plays the 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, the carrier mean pore size is 100-200nm, and by the carrier quality: amination reagent volume 1: 40 is scattered in carrier in 2% (v/v) amination reagent, at pH8.0,60 ℃ of following 200rpm oscillatory reaction 2h collect the amination carrier.
Be 1: 2 ratio according to the vigor ratio of GOD: CAT, GOD and CAT be dissolved in the phosphoric acid buffer of 0.1mol/l of pH6.Add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide in the enzyme lysate, 8 ℃ are reacted 60min down, and the amination carrier is scattered in the enzyme liquid, and 30 ℃ are reacted 2h under mixing speed 200rpm.Acetone and 0.5% (v/v) the glutaraldehyde mixture that adds 2 times of reaction solution volumes in reaction solution, 30 ℃ are continued reaction 1h down.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, use the 0.01mol/l phosphoric acid buffer of pH7.0 to wash 4 times, 4 ℃ of dryings are just prepared Resins, epoxy co-immobilization GOD/CAT microballoon, and enzyme activity is 111.9U/g.
According to mass percent be 20% the preparation glucose solution, in the container of stirring rake is housed, add glucose solution and sodium hydroxide solution, add co-immobilization glucose oxidase/catalase microballoon according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and the sodium hydroxide simultaneously and the reaction that produces calglucon, oxidizing temperature 32-40 ℃; 1: 0.14～0.15 (v/v/h) ventilates; Oxidization time 15～20 hours, ph5.5～7.5, residual sugar is lower than oxidation in 0.3% o'clock to be finished, and obtains Sunmorl N 60S.
In conjunction with the embodiments the present invention has been carried out exemplary description above; obvious realization of the present invention is not subjected to the restriction of aforesaid way; as long as the various improvement of having adopted method design of the present invention and technical scheme to carry out; or without improving design of the present invention and technical scheme are directly applied to other occasion, all in protection scope of the present invention.
Claims (4)
1. degradable without phosphorus composite slow-corrosion scale resistor, counting ratio by following raw materials in parts by weight is prepared from: 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: be carrier to have polymethacrylic acid macroporous resin microballoon, the mean pore size of microballoon is between 100nm-200nm, be amination reagent with 1-5% (v/v) ethylenediamine solution, by the carrier quality: amination reagent volume 1: 40-50 is scattered in carrier in the amination reagent, at pH7-9,40-90 ℃ of following oscillatory reaction 1-10h collects the amination carrier; Step 2: according to glucose oxidase (GOD): the vigor ratio of catalase (CAT) is 1: the ratio of 1-8 is dissolved in glucose oxidase (GOD) and catalase (CAT) in the phosphoric acid buffer of pH5-8; Add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide in the enzyme lysate, 0-8 ℃ is reacted 20-75min down, then the amination carrier is scattered in the enzyme liquid 25-35 ℃ of following stirring reaction 1-10h; Step 3: in step 2 gained reaction solution, add the acetone of 1-5 times of reaction solution volume and the mixture of 0.1-2.0% (v/v) linking agent, continue reaction 1-2h, the reaction solution that the reaction back is generated filters, abandon filtrate, collect solid substance, with phosphoric acid buffer or water washing at least 4 times, drying obtains co-immobilization glucose oxidase/catalase microballoon; Step 4: according to mass percent be 20% the preparation glucose solution, in the container of stirring rake is housed, add glucose solution and sodium hydroxide solution, glucose and sodium hydroxide mol ratio are 1: 1, add co-immobilization glucose oxidase/catalase microballoon according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and the sodium hydroxide simultaneously and the reaction that produces Sunmorl N 60S, oxidizing temperature 32-40 ℃; 1: 0.14～0.15 (v/v/h, the per hour ratio of air flow and the actual material liquid volume of container) ventilates; Oxidization time 15～20 hours, ph5.5～7.5, residual sugar is lower than oxidation in 0.3% o'clock to be finished, and obtains Sunmorl N 60S.
2. according to the described degradable without phosphorus composite slow-corrosion scale resistor of claim 1, it is characterized in that: glucose oxidase in the step 2 (GOD): catalase (CAT): phosphoric acid buffer volume ratio each other is: 10-15: 1: 400-500.
3. according to the described degradable without phosphorus composite slow-corrosion scale resistor of claim 1, it is characterized in that: after oxidation finishes in the step 4, reclaim immobilized glucose oxidase/catalase microballoon and reuse.
4. according to the described degradable without phosphorus composite slow-corrosion scale resistor of claim 1, it is characterized in that: the linking agent in the step 3 is glutaraldehyde or Vanillin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310107914.3A CN103332796B (en) | 2013-04-01 | 2013-04-01 | A kind of degradable without phosphorus composite slow-corrosion scale resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310107914.3A CN103332796B (en) | 2013-04-01 | 2013-04-01 | A kind of degradable without phosphorus composite slow-corrosion scale resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103332796A true CN103332796A (en) | 2013-10-02 |
| CN103332796B CN103332796B (en) | 2016-04-20 |
Family
ID=49241025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310107914.3A Active CN103332796B (en) | 2013-04-01 | 2013-04-01 | A kind of degradable without phosphorus composite slow-corrosion scale resistor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103332796B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104291453A (en) * | 2014-10-20 | 2015-01-21 | 山东华亚环保科技有限公司 | Corrosion and scale inhibitor 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 |
| CN104450806A (en) * | 2014-11-27 | 2015-03-25 | 江南大学 | Method for preparing sodium gluconate with enzymatic method |
| CN104556426A (en) * | 2014-12-24 | 2015-04-29 | 芜湖协诚金属制品有限公司 | Preparation method for phosphorus-free compound corrosion and scale inhibitor |
| CN104556430A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Water treatment pharmaceutical composition and application thereof |
| CN104762844A (en) * | 2015-04-30 | 2015-07-08 | 陈朝民 | Papermaking stewing accessory ingredient and preparation method thereof |
| CN105883947A (en) * | 2016-06-29 | 2016-08-24 | 欣格瑞（山东）环境科技有限公司 | Green medicament used for zero discharge of circulating water |
| 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 |
| CN109987723A (en) * | 2019-04-29 | 2019-07-09 | 郑州轻工业学院 | A kind of non-phosphorus scale and corrosion inhibitor and its preparation method and application |
| CN111138592A (en) * | 2019-12-31 | 2020-05-12 | 长江大学 | Carboxymethyl inulin graft polymer scale and corrosion inhibitor and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7241391B1 (en) * | 2004-05-12 | 2007-07-10 | Cortec Corporation | Biodegradable scale and corrosion inhibitor composition |
| CN101693998A (en) * | 2009-09-29 | 2010-04-14 | 上海电力学院 | Corrosion inhibitor for stainless steel pipe condenser recirculating cooling water system and preparation method thereof |
| CN102134130A (en) * | 2011-01-24 | 2011-07-27 | 湖北中泰环境技术有限公司 | Scale and corrosion inhibitor for treating circulating cooling water |
| CN102627359A (en) * | 2012-04-24 | 2012-08-08 | 湖南省电力公司科学研究院 | Phosphorus-free composite corrosion and scale inhibitor containing natural biodegradable substances |
| CN102943069A (en) * | 2012-11-27 | 2013-02-27 | 北京化工大学 | Co-immobilization glucose oxidase/catalase microspheres and application thereof in production of gluconic acid or gluconic salt |
-
2013
- 2013-04-01 CN CN201310107914.3A patent/CN103332796B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7241391B1 (en) * | 2004-05-12 | 2007-07-10 | Cortec Corporation | Biodegradable scale and corrosion inhibitor composition |
| CN101693998A (en) * | 2009-09-29 | 2010-04-14 | 上海电力学院 | Corrosion inhibitor for stainless steel pipe condenser recirculating cooling water system and preparation method thereof |
| CN102134130A (en) * | 2011-01-24 | 2011-07-27 | 湖北中泰环境技术有限公司 | Scale and corrosion inhibitor for treating circulating cooling water |
| CN102627359A (en) * | 2012-04-24 | 2012-08-08 | 湖南省电力公司科学研究院 | Phosphorus-free composite corrosion and scale inhibitor containing natural biodegradable substances |
| CN102943069A (en) * | 2012-11-27 | 2013-02-27 | 北京化工大学 | Co-immobilization glucose oxidase/catalase microspheres and application thereof in production of gluconic acid or gluconic salt |
Non-Patent Citations (1)
| Title |
|---|
| 金栋等: "我国聚合物阻垢分散剂研究进展", 《四川化工与腐蚀控制》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556430A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Water treatment pharmaceutical composition and application thereof |
| 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 |
| CN104291453A (en) * | 2014-10-20 | 2015-01-21 | 山东华亚环保科技有限公司 | Corrosion and scale inhibitor 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 |
| CN104450806A (en) * | 2014-11-27 | 2015-03-25 | 江南大学 | Method for preparing sodium gluconate with enzymatic method |
| CN104450806B (en) * | 2014-11-27 | 2018-01-16 | 江南大学 | A kind of method that enzyme process prepares sodium gluconate |
| CN104556426A (en) * | 2014-12-24 | 2015-04-29 | 芜湖协诚金属制品有限公司 | Preparation method for phosphorus-free compound corrosion and scale inhibitor |
| 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 |
| CN105883947A (en) * | 2016-06-29 | 2016-08-24 | 欣格瑞（山东）环境科技有限公司 | Green medicament used for zero discharge of circulating water |
| 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 |
| CN109987723A (en) * | 2019-04-29 | 2019-07-09 | 郑州轻工业学院 | A kind of non-phosphorus scale and corrosion inhibitor and its preparation method and application |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103332796B (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103332796A (en) | Degradable phosphorus-free composite corrosion and scale inhibitor | |
| US4919845A (en) | Phosphate-free detergent having a reduced tendency towards incrustation | |
| CN102627359A (en) | Phosphorus-free composite corrosion and scale inhibitor containing natural biodegradable substances | |
| CA1037815A (en) | Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate | |
| CN102094205B (en) | Phosphorus-free oil removing powder and phosphorus-free oil removing process | |
| US8759397B2 (en) | Detergent composition | |
| FI64637B (en) | FOERFARANDE OCH MEDEL FOER TVAETTNING OCH BLEKNING AV TEXTILER | |
| CN101591155A (en) | Yeast protein concrete foaming agent and preparation method thereof | |
| CN104944603A (en) | Sewage treatment agent | |
| CN105037736A (en) | Chitosan grafted hyperbranched polymer polyamide-amine (PAMAM), and preparation method and application thereof | |
| CN101993257B (en) | Method for preparation of high-activity compound organic fertilizer by waste acid liquid of D-glucosamine hydrochloride | |
| CN103525595A (en) | Fatty acid-containing soap powder | |
| CN110803787A (en) | Nano composite material and preparation method and application thereof | |
| CN101016314A (en) | Preparing process adapted for electronic grade solid aminotrimethylene phosphonic acid | |
| CN102220693A (en) | Natural silk refining agent | |
| FI112508B (en) | Process for the production of cellulose and by-product | |
| CN106854603B (en) | A kind of room temperature ardealite cleaning agent and its application | |
| CN103145257B (en) | Water quality stabilizer | |
| CN103497849B (en) | A kind of liquid detergent containing lipid acid | |
| CN109437415A (en) | Without phosphorus reverse osmosis antisludging agent PER-PAMAM and preparation method thereof | |
| CN103754853A (en) | Method for preparing disodium hydrogen phosphate from wet-process phosphoric acid | |
| CN1103365C (en) | Bleach product | |
| CN107021467B (en) | A kind of preparation method of magnesium monohydrogen phosphate hydroxyapatite core-shell material | |
| CN112657338A (en) | Flexible anti-scaling composite filtering membrane and preparation method thereof | |
| CN112250513A (en) | Universal type slow-release fertilizer for green plants cultivated in a pot |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Chuzhou Xuzhong Chemical Co., Ltd. Document name: Notification of Decision on Request for Restoration of Right |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cai Xian Inventor after: Cai Xiying Inventor after: Yang Li Inventor before: Wang Hui Inventor before: Yin Li |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170619 Address after: 528437, Guangdong Industrial Zone, Zhongshan City Torch Development Zone, Hong Kong Road, creative industrial park, No. 3 business card 1601 Patentee after: Guangdong Environmental Protection Technology Co., Ltd. Bawofu Address before: 239001, room 1, building 103, building 1, hi tech Innovation Service Center, 82 Garden West Road, Anhui, Chuzhou Patentee before: Chuzhou Xuzhong Chemical Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Wu Xiang Document name: Notification of Passing Examination on Formalities |
|
| DD01 | Delivery of document by public notice | ||
| DD01 | Delivery of document by public notice |
Addressee: Chuzhou Asahi Chemical Co., Ltd. Finance Document name: Notification of Approving Refund |