CN103147080A - Corrosion inhibitor - Google Patents
Corrosion inhibitor Download PDFInfo
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- CN103147080A CN103147080A CN2013101079158A CN201310107915A CN103147080A CN 103147080 A CN103147080 A CN 103147080A CN 2013101079158 A CN2013101079158 A CN 2013101079158A CN 201310107915 A CN201310107915 A CN 201310107915A CN 103147080 A CN103147080 A CN 103147080A
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Abstract
The invention relates to a corrosion inhibitor. The corrosion inhibitor is prepared from the following raw materials in parts by weight: 1-2 parts of molybdate, 20-60 parts of calcium gluconate, 2-5 parts of polyphosphate, 2-5 parts of borate, and 2-5 parts of benzodiazole. A new process for preparing the required calcium gluconate for a water quality stabilizer is provided. The new process can guarantee the high yield of the calcium gluconate, the reaction condition is mild, the device is simple and available and an environment-friendly production process is provided.
Description
Technical field
The present invention relates to a kind of inhibiter, especially a kind of brine media inhibiter.
Background technology
Due to the character of aluminum self, the corrosion characteristics of aluminum alloy materials in brine media is different from acid, alkaline solution and neutral aqueous solution.Aluminium is active amphoteric metal, in acid, alkaline solution, forms uniform corrosion.In neutral aqueous solution, due to the passive state character of aluminum alloy surface, its corrosion is the local corrosion characteristic, and pitting is its typical local corrosion form.Aluminium alloy crevice corrosion in brine media seems particularly evident, and crevice corrosion is the local corrosion of aluminium alloy inside, and its extent of corrosion is serious than pitting attack and uniform corrosion, and therefore, the exploitation of brine media inhibiter comes into one's own day by day.
Adopt the anti-corrosion technology to compare with other inhibition anti-corrosion methods, it is more economical, flexible, convenient.Existing inhibiter has type oxide film, deposition membranous type and absorption membranous type inhibiter etc.Chromic salt, nitrite, molybdate, tungstate, vanadate, orthophosphoric acid salt, borate etc. all are counted as the type oxide film inhibiter.They mostly are anodic corrosion inhibitor or dangerous type inhibiter, because they will cause spot corrosion once underdosage (separately inhibition, process 1L water, and required dosage is often up to hundreds of, even cross thousand milligrams), make original not too serious etching problem, become on the contrary more serious.And chlorion, high temperature and high water flow velocity all can disruptive oxidation films.The carbonate of zinc, phosphoric acid salt and oxyhydroxide, the carbonate of calcium and phosphoric acid salt are modal precipitation membranous type inhibiter.Because the sedimentation type corrosion inhibiting film does not have and the direct combination in metallic surface, and be porous, often appear at metallic surface and adhere to bad phenomenon, corrosion mitigating effect is not as the oxidized form film.Absorption membranous type inhibiter mostly is organic inhibitor, and when metallic surface is clean or active condition, this type of inhibiter can form the gratifying adsorption film of corrosion mitigating effect.But if there is corrosion product metallic surface or has in the situation of dirt deposition, just be difficult to form respond well corrosion inhibiting film.
Existing brine media inhibiter exists the problems such as corrosion inhibition rate is on the low side, dosage is large, toxic and expensive.
Calglucon is as one of inhibiter component, and usage quantity is larger usually, uses that traditional manufacture craft and catalyzer exist that yield is low, the defects 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 at present metal catalytic method and fermentation method.
In recent years, Enzymes Industry is accompanied by the fast development of downstream industry and develops, and on kind and quality, all is greatly improved.Enzyme method technique utilizes zymin directly conversion of glucose to be become to gluconic acid exactly, then passes through the neutralizing effect of alkali, converts it into the gluconate series product.With fermentation method, compare, the outstanding feature of enzyme process is exactly not need seed culture, has removed the interference of the raw and auxiliary materials such as microorganism and substratum to reaction system from, has improved the purity of reaction product, to purifying, brings convenience.There is no 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, there is no the danger of microbiological contamination, and product is single, and purity is high, 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.With the metal catalytic method, compare, enzyme process also has safe characteristics.
By being fixed of enzyme, can significantly improve the stability of enzyme.Be not subject to the impact of external environment and inactivation.Immobilized enzyme is easy to and product separation, owing to only having substrate in reaction system, and product,, by immobilized enzyme Separation and Recovery from reaction system, only there is product in immobilized enzyme after reaction finishes in system, be 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 the carrier microballoons surface-area is limited, can't 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, thereby cause GOD and CAT inactivation, immobilized enzyme just loses very soon most enzymic activity after using continuously.
Summary of the invention
The present invention has designed a kind of inhibiter, and the technical problem of its solution is: (1) existing brine media inhibiter exists the problems such as corrosion inhibition rate is on the low side, dosage is large, toxic and expensive; (2) prepare the support of the catalyst microsphere surface that calglucon uses long-pending limited, can't 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, thereby cause GOD and CAT inactivation, immobilized enzyme just loses very soon most enzymic activity after using continuously.
In order to solve the technical problem of above-mentioned existence, the present invention has adopted following scheme:
A kind of inhibiter, counting ratio by following raw materials in parts by weight is prepared from: molybdate 1-2 part, calglucon 20-60 part, poly-phosphate 2-5 part, borate 2-5 part and benzodiazole 2-5 part, described calglucon preparation process is as follows: step 1: take and have the polymethacrylic acid macroporous resin microspheres as carrier, the mean pore size of microballoon is between 100nm-200nm, 1-5% (v/v) ethylenediamine solution of take is amination reagent, by the carrier quality: amination reagent volume 1: 40-50 is scattered in carrier in amination reagent, at pH7-9, 40-90 ℃ of lower oscillatory reaction 1-10h, collect 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, react 20-75min under 0-8 ℃, then the amination carrier is scattered in enzyme liquid to 25-35 ℃ of lower stirring reaction 1-10h, 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 of stirring rake is housed, add glucose solution and calcium carbonate, glucose and calcium carbonate mol ratio are 2: 1-1.3, add mixed immobilized glucose oxidase/catalase microspheres according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and calcium carbonate and the reaction that produces calglucon simultaneously, 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 oxidation lower than 0.3% time finishes, and obtains calglucon, and the reaction formula is: 2C
6h
12o
7+ CaCO
3=Ca (C
6h
11o
7)
2+ H
2o+CO
2.
Further, glucose oxidase (GOD) in step 2: catalase (CAT): phosphoric acid buffer volume ratio each other is: 10-15: 1: 400-500.
Further, after in step 4, oxidation finishes, reclaim immobilized glucose oxidase/catalase microballoon and reused.
Further, the linking agent in step 3 is glutaraldehyde or Vanillin.
This inhibiter is compared with existing inhibiter, has following beneficial effect:
(1) the present invention is that water quality stabilizer prepares required calglucon and proposed novel process, and this novel process guarantees that the calglucon yield is high, the reaction conditions gentleness, and equipment is simple and easy to get, is a kind of production technique of environmental protection.
(2) 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 the parameters such as the aperture of resin, particle diameter are very large on the charge capacity impact of enzyme, so the polymethacrylic acid macroporous resin can be applicable to greatest extent according to real needs the immobilization of GOD/CAT.
(3) the present invention adopts and zymoprotein to be assembled crosslinked, makes the limited more zymoprotein of carrier surface area energy load.Because carrier has suitable aperture, can overcome the impact 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.
(4) mixed immobilized glucose oxidase/catalase microspheres of the present invention can effectively promote the covalently bound of carrier and enzyme molecule, greatly improved immobilization efficiency, and significant prolongation the work-ing life of co-immobilization GOD/CAT, but Reusability, production cost is low, is conducive to Sustainable development.
(5) corrosion inhibitor formula of the present invention have economy, effectively, low toxicity and suitability strong, and protect original technical process not to be destroyed, need hardly the characteristics of optional equipment.In water dissolution, aluminate, calglucon and poly-phosphate have the characteristics of the lower and stable in properties of toxicity.Between aluminate, calglucon and poly-phosphate, act synergistically, they are as the mechanism of action difference of inhibiter, the action site difference, therefore in metallic surface, the polar molecule difference of having an effect in chemical action formation macromolecular compound adsorption layer occurs, improve surface coverage or form the mutual effect of multilayer adsorption phase, improved the stability of adsorption layer, reduced the working concentration of inhibiter, reduce toxicity, enlarged the scope of application.The experimental result surface, the corrosion inhibition rate of corrosion inhibitor formula of the present invention all reaches more than 95%.
Embodiment
Below in conjunction with embodiment, the present invention will be further described:
Embodiment 1: a kind of inhibiter, and count ratio by following raw materials in parts by weight and be prepared from: 2 parts of 1 part of molybdate, 20 parts of calglucons, 2 parts of poly-phosphate, 2 parts of borates and benzodiazoles.
Wherein, the preparatory technology of calglucon is as follows:
2% (v/v) ethylenediamine solution of take is amination reagent, the carrier mean pore size is 100-200nm, and by the carrier quality: the amination reagent volume is scattered in carrier in 2% (v/v) amination reagent, at pH8.0 at 1: 40,60 ℃ of lower 200rpm oscillatory reaction 2h, collect the amination carrier.
The ratio that is 1: 2 according to the vigor ratio of GOD: CAT, be dissolved in GOD and CAT in the phosphoric acid buffer of 0.1mol/1 of pH6.Add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide in the enzyme lysate, react 60min under 8 ℃, the amination carrier is scattered in enzyme liquid, 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, continue reaction 1h under 30 ℃.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, wash 4 times with the 0.01mol/l phosphoric acid buffer of pH7.0,4 ℃ of dryings, just prepare epoxy resin co-immobilization GOD/CAT microballoon, and enzyme activity is 111.9U/g.
According to mass percent, it is 20% preparation glucose solution, in the container of stirring rake is housed, add glucose solution, calcium carbonate, add mixed immobilized glucose oxidase/catalase microspheres according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and calcium carbonate and the reaction that produces calglucon simultaneously, oxidizing temperature 32-40 ℃; 1: 0.14～0.15 (v/v/h) ventilates; Oxidization time 15～20 hours, pH5.5～7.5, residual sugar oxidation lower than 0.3% time finishes, and obtains calglucon, the reaction formula:
2C
6H
12O
7+CaCO
3＝Ca(C
6H
11O
7)
2+H
2O+CO
2。
Embodiment 2: a kind of inhibiter, and count ratio by following raw materials in parts by weight and be prepared from: 5 parts of 2 parts of molybdates, 60 parts of calglucons, 5 parts of poly-phosphate, 5 parts of borates and benzodiazoles.
Wherein, the preparatory technology of calglucon is as follows:
2% (v/v) ethylenediamine solution of take is amination reagent, the carrier mean pore size is 400-500nm, and by the carrier quality: the amination reagent volume is scattered in carrier in 2% (v/v) amination reagent, at pH8.0 at 1: 40,60 ℃ of lower 200rpm oscillatory reaction 2h, collect the amination carrier.
The ratio that is 1: 2 according to the vigor ratio of GOD: CAT, be dissolved in GOD and CAT in the phosphoric acid buffer of 0.1mol/1 of pH6.Add 0.2% (w/v) carbodiimide and 0.2% (w/v) N-hydroxy-succinamide in the enzyme lysate, react 60min under 8 ℃, the amination carrier is scattered in enzyme liquid, 30 ℃ are reacted 2h under mixing speed 200rpm, acetone and 0.5% (v/v) glutaraldehyde that adds 2 times of reaction solution volumes in reaction solution, continue reaction 1h.Above-mentioned reaction solution is filtered, abandon filtrate, collect solid substance, for the solid substance of collecting, wash 5 times with the 0.01mol/1 phosphoric acid buffer of pH7.0,4 ℃ of dryings, just prepare epoxy resin co-immobilization GOD/CAT microballoon, and enzyme activity is 35.9U/g.
According to mass percent, it is 20% preparation glucose solution, in the container of stirring rake is housed, add glucose solution, calcium carbonate, add mixed immobilized glucose oxidase/catalase microspheres according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and calcium carbonate and the reaction that produces calglucon simultaneously, oxidizing temperature 32-40 ℃; 1: 0.14～0.15 (v/v/h) ventilates; Oxidization time 15～20 hours, pH5.5～7.5, residual sugar oxidation lower than 0.3% time finishes, and obtains calglucon, the reaction formula:
2C
6H
12O
7+CaCO
3＝Ca(C
6H
11O
7)
2+H
2O+CO
2。
This inhibiter is compared with existing inhibiter, has following beneficial effect:
(1) the present invention is that water quality stabilizer prepares required calglucon and proposed novel process, and this novel process guarantees that the calglucon yield is high, the reaction conditions gentleness, and equipment is simple and easy to get, is a kind of production technique of environmental protection.
(2) 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 the parameters such as the aperture of resin, particle diameter are very large on the charge capacity impact of enzyme, so the polymethacrylic acid macroporous resin can be applicable to greatest extent according to real needs the immobilization of GOD/CAT.
(3) the present invention adopts and zymoprotein to be assembled crosslinked, makes the limited more zymoprotein of carrier surface area energy load.Because carrier has suitable aperture, can overcome the impact 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.
(4) mixed immobilized glucose oxidase/catalase microspheres of the present invention can effectively promote the covalently bound of carrier and enzyme molecule, greatly improved immobilization efficiency, and significant prolongation the work-ing life of co-immobilization GOD/CAT, but Reusability, production cost is low, is conducive to Sustainable development.
(5) corrosion inhibitor formula of the present invention have economy, effectively, low toxicity and suitability strong, and protect original technical process not to be destroyed, need hardly the characteristics of optional equipment.In water dissolution, aluminate, calglucon and poly-phosphate have the characteristics of the lower and stable in properties of toxicity.Between aluminate, calglucon and poly-phosphate, act synergistically, they are as the mechanism of action difference of inhibiter, the action site difference, therefore in metallic surface, the polar molecule difference of having an effect in chemical action formation macromolecular compound adsorption layer occurs, improve surface coverage or form the mutual effect of multilayer adsorption phase, improved the stability of adsorption layer, reduced the working concentration of inhibiter, reduce toxicity, enlarged the scope of application.The experimental result surface, the corrosion inhibition rate of corrosion inhibitor formula of the present invention all reaches more than 95%.
Claims (4)
1. an inhibiter, counting ratio by following raw materials in parts by weight is prepared from: molybdate 1-2 part, calglucon 20-60 part, poly-phosphate 2-5 part, borate 2-5 part and benzodiazole 2-5 part, it is characterized in that: described calglucon preparation process is as follows: step 1: take and have the polymethacrylic acid macroporous resin microspheres as carrier, the mean pore size of microballoon is between 100nm-200nm, 1-5% (v/v) ethylenediamine solution of take is amination reagent, by the carrier quality: amination reagent volume 1: 40-50 is scattered in carrier in amination reagent, at pH7-9, 40-90 ℃ of lower oscillatory reaction 1-10h, collect 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, react 20-75min under 0-8 ℃, then the amination carrier is scattered in enzyme liquid to 25-35 ℃ of lower stirring reaction 1-10h, 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 of stirring rake is housed, add glucose solution and calcium carbonate, glucose and calcium carbonate mol ratio are 2: 1-1.3, add mixed immobilized glucose oxidase/catalase microspheres according to 0.6%～1% of glucose quality, carry out oxidation and carry out in gluconic acid and calcium carbonate and the reaction that produces calglucon simultaneously, 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 oxidation lower than 0.3% time finishes, and obtains calglucon, and the reaction formula is: 2C
6h
12o
7+ CaCO
3=Ca (C
6h
11o
7)
2+ H
2o+CO
2.
2. inhibiter according to claim 1, it is characterized in that: glucose oxidase in step 2 (GOD): catalase (CAT): phosphoric acid buffer volume ratio each other is: 10-15: 1: 400-500.
3. inhibiter according to claim 1, is characterized in that: after in step 4, oxidation finishes, reclaim immobilized glucose oxidase/catalase microballoon and reused.
4. inhibiter according to claim 1, it is characterized in that: the linking agent in step 3 is glutaraldehyde or Vanillin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101079158A CN103147080A (en) | 2013-04-01 | 2013-04-01 | Corrosion inhibitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101079158A CN103147080A (en) | 2013-04-01 | 2013-04-01 | Corrosion inhibitor |
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|---|---|
| CN103147080A true CN103147080A (en) | 2013-06-12 |
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ID=48545387
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543863A (en) * | 2015-12-28 | 2016-05-04 | 常州思宇环保材料科技有限公司 | Preparation method for natural green compound corrosion inhibitor |
| CN115522228A (en) * | 2022-04-25 | 2022-12-27 | 江苏双盛锌业股份有限公司 | Energy-saving environment-friendly high-purity zinc powder preparation method and preparation equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304716A (en) * | 2011-08-30 | 2012-01-04 | 吴江市精工铝字制造厂 | Corrosion inhibitor |
| 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 CN2013101079158A patent/CN103147080A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304716A (en) * | 2011-08-30 | 2012-01-04 | 吴江市精工铝字制造厂 | Corrosion inhibitor |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105543863A (en) * | 2015-12-28 | 2016-05-04 | 常州思宇环保材料科技有限公司 | Preparation method for natural green compound corrosion inhibitor |
| CN105543863B (en) * | 2015-12-28 | 2017-10-13 | 西安凯尔文石化助剂制造有限公司 | A kind of preparation method of natural green composite corrosion inhibitor |
| CN115522228A (en) * | 2022-04-25 | 2022-12-27 | 江苏双盛锌业股份有限公司 | Energy-saving environment-friendly high-purity zinc powder preparation method and preparation equipment |
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Application publication date: 20130612 |