CN1390982A - Process for preparing acid corrosion inhibitor by modifying azacyclic compound by natural plant gum powder - Google Patents
Process for preparing acid corrosion inhibitor by modifying azacyclic compound by natural plant gum powder Download PDFInfo
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- CN1390982A CN1390982A CN 02134350 CN02134350A CN1390982A CN 1390982 A CN1390982 A CN 1390982A CN 02134350 CN02134350 CN 02134350 CN 02134350 A CN02134350 A CN 02134350A CN 1390982 A CN1390982 A CN 1390982A
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Abstract
An acid corrosion inhibitor is prepared from natural plant gum powder through preparing the cationic etherifying agent from the azacyclo quaternary ammonium salt of pyridine or quinoline, weighing plant gum powder, wetting in with organic solvent, mixing with sodium (or potassium) hydroxide, alkalizing, mixing with said etherifying agent, etherifying reaction to obtain intermediate, mixing with deionized water, heating to a certain temp and holding the temp for a certain time. Its advantages are low dosage, easy biologic degradation, and low cost.
Description
(1) technical field:
The present invention utilizes natural plant gum powder to carry out the method that the nitrogen heterocyclic modification prepares acid inhibitor, belongs to the fine chemical technology field, particularly the technology of preparing of acid inhibitor.
(2) background technology:
In the acidization of the pickling of metal and oil gas well, all need to add the acid corrosion inhibiter, to slow down metal material surface pitting corrosion, hydrogen embrittlement and weight-loss corrosion.Mineral compound is adopted in the acid corrosion inhibition in early days, and arsenate is the inorganic inhibitor that uses the earliest, and it has good corrosion inhibition, and cheap, but because of its toxicity and the danger of serious pitting corrosion is arranged, seldom uses now; What generally use at present is organic inhibitor, organic inhibitor commonly used has following several big class: (1) nitrogenous compound: comprise monoamine, diamines, acid amides, alkynes oxygen methylamine, mannich base, alkynol, quaternary amine, heteroaromatic nitrogenous compound (as pyridine, quinoline and derivative thereof) etc., wherein the heteroaromatic nitrogenous compound uses at most, and effect is best; (2) aldehydes: as formaldehyde and phenylacrolein.Formaldehyde is lower concentration (＜15%) and the low temperature hydrochloric acid pickling corrosion inhibitor of using always.Phenylacrolein is an inhibiter of succeeding in developing and be applied to acidizing treatment in recent years, have advantages such as low toxicity, corrosion mitigating effect be good: (3) alkynol class: aliphatics alkynol such as propiolic alcohol, butynol, acetylene alcohol etc., especially propiolic alcohol is the crucial composition of the salt acid inhibitor that uses in the oil-gas field acidizing treatment.It can prevent corrosion and the hydrogen osmosis of medium carbon steel in hydrochloric acid effectively; (4) alpha-alkenes phenyl ketone: alpha-alkenes phenyl ketone or its parent are the novel acid corrosion inhibiter of developing in recent years of a class, and it is good that it has in high-temperature high concentration hydrochloric acid a corrosion mitigating effect, advantage such as nontoxic.Since the eighties, external in the research field of acid inhibitor, one of its main direction is exploitation pyridine quaternary amine, quinoline quaternary ammonium salts modified product.The advantage of this class improvement product is that the corrosion mitigating effect in high-temperature high concentration acid is good, and thermostability height, this type of medicament have inhibiter, emulsion splitter, cats product function concurrently, are a kind of multifunctional efficient inhibiter.In addition, exploitation is a basic components with pyridine quaternary amine or the quaternary ammonium salt modified product of quinoline, alpha-alkenes phenyl ketone, composite by selecting differing materials to carry out, make a series of heat resistance height, the composite corrosion inhibitor that corrosion inhibition is good is the very active field of foreign study work in recent years.Sum up the acid inhibitor of using at present both at home and abroad, the overwhelming majority is the chemosynthesis product, and dosage is bigger when generally using, and relatively difficulty of artifact degraded, the more high defective of use cost are used in existence.And certain toxicity is arranged, therefore, limited the use range of this class medicament to a certain extent.Consulting patent documentation still finds no and utilizes plant gum powder to carry out the relevant patent of the quaternary ammonium salt modified preparation acid inhibitor of nitrogen heterocyclic.
(3) summary of the invention:
Purpose of the present invention is the chemosynthesis product in order to overcome and to solve the existing acid inhibitor overwhelming majority exactly, dosage is bigger during general the application, and exist and use relatively difficulty of artifact degraded, use cost is higher, and certain toxicity arranged, the shortcoming and the problem of its use range etc. have been limited to a certain extent, the research invention is a kind of to overcome and solve existing acid inhibitor large usage quantity, difficult for biological degradation, toxic, shortcoming that cost is more high and problem, and main raw material adopts plant gum powder, with the back readily biodegradable, can not produce secondary pollution in the use, realize the exhaustion of people, wish to seek inexpensive along with mineral wealth, renewable, easily degraded, the natural phant that utilizes that use range is wide carries out the method that the nitrogen heterocyclic modification prepares acid inhibitor.
The present invention realizes by following method and technology scheme: its preparation methods steps is: (its each component all is weight percentage), step (1): the nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent that at first prepares pyridine or quinoline, it is the hydrochloride that generates nitrogen-containing heterocycle compound with 35～75% concentrated hydrochloric acid and equimolar pyridine or quinoline reaction, and then react with equimolar epoxy chloropropane, can form nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent; Step (2): after making nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent,------natural gum part or guar-bean rubber powder generation graft reaction: take by weighing plant gum powder earlier---gummy powder or guar-bean rubber powder 3～10% under the katalysis of sodium hydroxide or potassium hydroxide and plant gum powder at alkali, with 2～10% organic solvents---ethanol or Virahol are moistening with plant gum powder, take by weighing 4～14% concentration again and be 20～30% sodium hydroxid or potassium hydroxide, join by on the moistening plant gum powder, and stir, plant gum powder is carried out alkalinisation treatment, 0.3～1 hour alkalinisation treatment time; Step (3): add 7～25% nitrogen heterocyclic quaternary ammonium salt cationic etherifying agents that made at last, itself and alkalinisation treatment is good plant gum powder are mixed, begin to carry out etherification reaction, temperature of reaction is controlled at 30～40 ℃, 0.3～1 hour etherification reaction time; Step (4): add 50～82% deionized water in the intermediate product after etherificate, and stir, the temperature of reaction system is risen to 55～70 ℃, after being incubated 1～3 hour and carrying out slaking reaction, promptly make this product---acid inhibitor.
Ultimate principle of the present invention is: the at first synthetic etherifying agent of making quaternary ammonium reaction: nitrogen-containing heterocycle compound such as pyridine, quinoline belong to weak organic bases, it can with protonic acid---hydrochloric acid generation thermopositive reaction, generate salt; The hydrochloride and the epichlorohydrin reaction of the nitrogen heterocyclic that forms, get final product nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent; Synthetic nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent can make this product---acid inhibitor with generation graft reactions such as plant gum powder such as gummy powder, guar-bean rubber powders again under the katalysis of catalyzer alkali.
The present invention compared with prior art has following advantage and beneficial effect: (1) along with the exhaustion of mineral wealth, and people more wish to seek reproducible utilization, " green product " of reduced contamination.Synthetic medicament is a raw material with mineral wealth generally, and the natural macromolecule modification product is to be main raw material with the natural plant resource, has inexpensive, advantage such as can regenerate.So the natural macromolecule modification acid inhibitor is compared with synthetic medicament, has some clear superiorities, has the certain development prospect in future so can expect this class natural macromolecule modification medicament; (2) acid inhibitor of using at present both at home and abroad, the overwhelming majority is the chemosynthesis product, dosage is bigger during general the application, and exist and use relatively difficulty of artifact degraded, the more high defective of use cost, and be to be main raw material with the natural plant resource with the acid inhibitor of the natural plant gum powder modification of present method preparation has inexpensive, advantage such as can regenerate, so the natural macromolecule modification acid inhibitor is compared with synthetic medicament, has certain remarkable advantages; (3) it is few that application experiment research and use the result to show, the acid inhibitor of the natural plant gum powder modification that makes with present method also have an added amount of chemical, the advantage that corrosion mitigating effect is good.In the hydrochloric acid of 1M, added amount of chemical only needs 20～80mg/L, can reach the corrosion mitigating effect more than 96%; (4) further application experiment research and use result show, acid inhibitor of the present invention also has long lasting corrosion inhibition, be after medicament adds in the acid, even the time period of greater than two months of in acid, depositing, the acid inhibitor that the present invention makes still has corrosion inhibition preferably, and the generally synthetic medicament of this advantage does not possess.
(4) embodiment:
The contriver has a lot of successful embodiment through years of researches, test, existing only for three embodiment shown in following table table 1.Table 1:
Claims (1)
1, a kind of natural plant gum powder that utilizes carries out the method that the nitrogen heterocyclic modification prepares acid inhibitor, its method steps is: its each component all is weight percentage, step (1): the nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent that at first prepares pyridine or quinoline, it is the hydrochloride that generates nitrogen-containing heterocycle compound with 35～75% concentrated hydrochloric acid and equimolar pyridine or quinoline reaction, and then react with equimolar epoxy chloropropane, can form nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent; After step (2) makes nitrogen heterocyclic quaternary ammonium salt cationic etherifying agent, at alkali---under the katalysis of sodium hydroxide or potassium hydroxide again with plant gum powder---gummy powder or guar-bean rubber powder carry out graft reaction: take by weighing plant gum powder earlier---gummy powder or guar-bean rubber powder 3～10%, with 2～10% organic solvents---ethanol or Virahol are moistening with plant gum powder, take by weighing 4～14% concentration again and be 20～30% sodium hydroxide or potassium hydroxide, join by on the moistening plant gum powder, and stir, plant gum powder is carried out alkalinisation treatment, 0.3～1 hour alkalinisation treatment time; Step (3): add 7～25% nitrogen heterocyclic quaternary ammonium salt cationic etherifying agents that made then, itself and alkalinisation treatment is good plant gum powder are mixed, begin to carry out etherification reaction, temperature of reaction is controlled at 30～40 ℃, 0.3～1 hour etherification reaction time; Step (4): add 50～82% deionized water in the intermediates after etherificate, and stir, the temperature of reaction system is risen to 55～70 ℃, after being incubated 1～3 hour and carrying out slaking reaction, promptly make this product---acid inhibitor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02134350 CN1390982A (en) | 2002-07-15 | 2002-07-15 | Process for preparing acid corrosion inhibitor by modifying azacyclic compound by natural plant gum powder |
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| CN 02134350 CN1390982A (en) | 2002-07-15 | 2002-07-15 | Process for preparing acid corrosion inhibitor by modifying azacyclic compound by natural plant gum powder |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711579A (en) * | 2014-11-28 | 2015-06-17 | 武汉工程大学 | Pyridine derivative corrosion inhibitor for metals and preparation method thereof |
| CN105239076A (en) * | 2015-10-10 | 2016-01-13 | 中国海洋石油总公司 | Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof |
| CN105731853A (en) * | 2016-02-29 | 2016-07-06 | 冯丽娟 | Reinforcing bar rusty retardant agent produced by vegetable waste extracts and application method of rusty retardant agent |
| CN108611171A (en) * | 2018-05-07 | 2018-10-02 | 苏州捷德瑞精密机械有限公司 | A kind of cutting fluid and preparation method thereof for mechanical processing |
| CN110158099A (en) * | 2019-06-18 | 2019-08-23 | 陈团英 | A kind of metal surface oil-removing rust-removing agent |
-
2002
- 2002-07-15 CN CN 02134350 patent/CN1390982A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711579A (en) * | 2014-11-28 | 2015-06-17 | 武汉工程大学 | Pyridine derivative corrosion inhibitor for metals and preparation method thereof |
| CN105239076A (en) * | 2015-10-10 | 2016-01-13 | 中国海洋石油总公司 | Dissymmetric bis-quaternary ammonium carbon dioxide corrosion inhibitor and preparation method thereof |
| CN105731853A (en) * | 2016-02-29 | 2016-07-06 | 冯丽娟 | Reinforcing bar rusty retardant agent produced by vegetable waste extracts and application method of rusty retardant agent |
| CN105731853B (en) * | 2016-02-29 | 2018-07-10 | 潍坊科技学院 | A kind of application process of the reinforcing steel bar corrosion inhibitor made of vegetable waste extract and corrosion inhibitor |
| CN108611171A (en) * | 2018-05-07 | 2018-10-02 | 苏州捷德瑞精密机械有限公司 | A kind of cutting fluid and preparation method thereof for mechanical processing |
| CN110158099A (en) * | 2019-06-18 | 2019-08-23 | 陈团英 | A kind of metal surface oil-removing rust-removing agent |
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