CN105088252A - Benzimidazoline corrosion inhibitor prepared from refined swill-cooked dirty oil - Google Patents

Benzimidazoline corrosion inhibitor prepared from refined swill-cooked dirty oil Download PDF

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CN105088252A
CN105088252A CN201510509872.5A CN201510509872A CN105088252A CN 105088252 A CN105088252 A CN 105088252A CN 201510509872 A CN201510509872 A CN 201510509872A CN 105088252 A CN105088252 A CN 105088252A
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benzimidazoline
inhibiter
oil
reaction
corrosion
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CN105088252B (en
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袁斌
胡微
吕松
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The invention relates to the technical field of metal corrosion inhibition and particularly discloses a benzimidazoline corrosion inhibitor prepared from refined swill-cooked dirty oil, of which the chemical formula is as shown in the description, wherein R=C(16-20) saturated alkyl or unsaturated alkyl; and R1=H, CH3 and C6H5. The corrosion inhibitor is obtained in the way that saturated alkyl and unsaturated alkyl or phenyl, of different chain lengths, are added into benzimidazole molecules, so that the hydrophobicity of a protective film is improved while the density of pi electron cloud, capable of being coordinated with metals, in the molecules is increased, accordingly, the metal corrosion rate is greatly reduced, and the metal anticorrosiveness is increased. The corrosion inhibitor is an oil-soluble product, can be used for corrosion protection of oil field pipelines and industrial pickling, can form a compact and firm adsorption film on a metal surface, reduces the metal corrosion rate and achieves the purpose of metal corrosion protection.

Description

A kind of use refines the benzimidazoline inhibiter that sewer oil prepares
Technical field
The present invention relates to metallic corrosion suppression technology field, more specifically, relate to a kind of use and refine the benzimidazoline inhibiter that sewer oil prepares.
Background technology
In oil gas well mining and industrial heat power equipment acid cleaning process, in order to prevent acid solution to the corrosion of the equipment such as oil pipe, sleeve pipe, boiler, in acid solution, add inhibiter to be absolutely necessary anti-corrosion measure, nowadays imidazoline corrosion inhibitor is particularly extensive in the anticorrosion middle application of oil field pipe; At present, the synthesis of benzimidazoline mainly with organic carboxyl acid and substituted o-phenylenediamine for raw material, adopt ladder-elevating temperature technology, prepared by amidation, cyclodehydration.And utilize refining sewer oil to prepare the rare report of research of benzimidazoline class inhibiter for raw material.
In prior art, favourable sewer oil prepares inhibiter, can in practical situation, and general sewer oil impurity is a lot, and directly can not be used as raw material, the slow-release capability of its inhibiter prepared is very poor.
When raw material is O-Phenylene Diamine, above-mentioned preparation method comprises the following steps:
S1. refining sewer oil and O-Phenylene Diamine press the mass ratio of 1:1.1 ~ 1.5 under protection of inert gas, in reaction medium, in 138 ~ 145 DEG C of reaction 3 ~ 6h;
S2. again under 180 ~ 200mmHg decompression, in 170 ~ 180 DEG C of reflux 2 ~ 3h, then in the backflow of 20 ~ 25mmHg heated under reduced pressure, until do not have liquid to flow out;
S3. cool, add the NaCl aqueous solution in mixture, mixing post-heating to 60 ~ 80 DEG C are also incubated 1h, cooling, leave standstill, be separated oily matter, vacuum-drying, obtain benzimidazoline inhibiter.
When raw material is substituted o-phenylenediamine, comprise the following steps:
S1. refining sewer oil and substituted o-phenylenediamine press the mass ratio of 1:1.3 ~ 1.9 under protection of inert gas, in reaction medium, in 138 ~ 145 DEG C of reaction 3 ~ 6h;
S2. again under 180 ~ 200mmHg decompression, in 170 ~ 180 DEG C of reflux 2 ~ 3h, then in the backflow of 20 ~ 25mmHg heated under reduced pressure, until do not have liquid water to flow out;
S3. cool, add the NaCl aqueous solution in mixture, mixing post-heating to 60 ~ 70 DEG C are also incubated 1h, cooling, leave standstill, be separated oily matter, vacuum-drying, obtain substituted benzimidazole quinoline inhibiter.
Chemical equation involved in the present invention is:
In formula: C 16 ~ 20saturated alkyl or unsaturated alkyl; R 1=H, CH 3, C 6h 5.
More preferably, when raw material is substituted o-phenylenediamine, the concrete steps of above-mentioned preparation method are: refining sewer oil is placed in reactor, 1:1.3 ~ 1.9 add substituted o-phenylenediamine in mass ratio, under nitrogen protection, in dimethylbenzene medium, after 138 ~ 145 DEG C of reflux 4 ~ 6.5h, again under 180 ~ 200mmHg decompression, in 170 ~ 180 DEG C, reflux 2 ~ 3 hours, again under 20 ~ 25mmHg decompression, reflux 1h, until do not have liquid water to flow out, cooling, in mixture, add a certain proportion of 10%NaCl aqueous solution and stir, heated mixt to 60 ~ 80 DEG C are also incubated 1h, cooling, leave standstill 2 ~ more than 3h and make it layering, the yellow clear liquid of lower floor is isolated with separating funnel, by upper strata oily matter, wash 2 times with water, isolate water layer, oil phase vacuum-drying, obtain oil soluble fatty group benzimidazoline inhibiter.
Present invention also offers above-mentioned benzimidazoline inhibiter and prevent the application in metallic corrosion; Preferably, described metallic corrosion is caused by acidic aqueous media.
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of use and refine the benzimidazoline inhibiter that sewer oil prepares, be in benzoglyoxaline molecule, introduce the saturated alkyl of different chain length and unsaturated alkyl or phenyl after, increase molecule in can with the π-electron cloud density of metal-complexing while, also increase the hydrophobicity of protective membrane, thus substantially reduce rate of metal corrosion, add metals against corrosion ability, this inhibiter is oil-soluble products, can be used as oil filed pipeline anticorrosion and industrial acid-washed in inhibiter, closely and firmly adsorption film can be formed on the metal surface, reduce rate of metal corrosion, reach the object of anti-corrosion of metal.
Summary of the invention
Technical problem to be solved by this invention overcomes the above-mentioned defect existed in prior art, the benzimidazoline inhibiter providing a kind of use to refine sewer oil to prepare.
Second object of the present invention is to provide the preparation method of above-mentioned inhibiter.
3rd object of the present invention is to provide above-mentioned inhibiter and is preventing the application in metallic corrosion.
The object of the invention is to be achieved by the following technical programs:
Use refines the benzimidazoline inhibiter that sewer oil prepares, and its chemical formula is as follows:
Wherein, R=C 16 ~ 20saturated alkyl or unsaturated alkyl; R 1=H, CH 3, C 6h 5.
In acidic medium, to metal, there is good corrosion inhibition based on benzimidazoline compounds; propose and the molecule fragment of fatty group and benzimidazoline is engaged in a molecule; adsorption film with long chain hydrophobic group more can stop close to metallic surface of corrosive medium effectively, thus improves the protective capability to metal.
The present invention also provides the preparation method of above-mentioned inhibiter, for reaction raw materials with refining sewer oil and O-Phenylene Diamine or substituted o-phenylenediamine, react through amidation, cyclodehydration and obtain, the source of described refining sewer oil (35.3% animal oil, 64.7% vegetables oil) is the swill oil of catering industry.
Embodiment
Further illustrate content of the present invention below in conjunction with specific embodiment, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification do the inventive method, step or condition or replacement, all belong to scope of the present invention; If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
embodiment 1
In the there-necked flask being furnished with water trap, thermometer, prolong and whipping appts, add 20g and refine sewer oil, 25.0g o-Phenylene Diaminewith 60ml dimethylbenzene, pass into nitrogen, slowly be heated to 140 DEG C, reaction 3.5 ~ 4.0h, be warming up to 150 ~ 160 DEG C gradually, after steaming xylene solvent, remove water trap, change vacuum distillation apparatus into, pressure-controlling is under 200mmHg, stirring reaction 2 ~ 2.5h at 175 ~ 180 DEG C, water and superfluous reagent is constantly had to be distilled out of, then under system pressure is down to 20mmHg more gradually, continue isothermal reaction 1.0 ~ 1.5h again, until do not have low-boiling point liquid to steam in reaction process, after product cooling, in mix products, add the 10%NaCl aqueous solution of 80ml and stir, heated mixt to 80 DEG C is also incubated 1h, cooling, leave standstill 2.5h, upper strata oily matter is isolated with separating funnel, wash 2 times with water, isolate water layer, oil phase vacuum-drying obtains light yellow fatty group benzimidazoline cream solid, the heavy 40.8g of product.1634,1547,1453cm infrared spectra (KBr): -1(stretching vibration of phenyl ring skeleton); 1572,1456,1410cm -1(stretching vibration of tetrahydroglyoxaline ring skeleton); 3435,3114cm -1(tetrahydroglyoxaline ring N-H stretching vibration); 724cm -1[-(CH 2) n-stretching vibration].
embodiment 2
Is being furnished with water trap, thermometer, in the there-necked flask of prolong and whipping appts, add 30g and refine sewer oil, 39gN-methyl-o-phenylenediamine and 70ml dimethylbenzene, pass into nitrogen, after slow heating 140 DEG C of back flow reaction 6.5h, under 190 ~ 200mmHg, underpressure distillation 2.5 ~ 3h, again under 20 ~ 25mmHg, underpressure distillation 1 ~ 2h, until do not have liquid to flow out, after cooling, in mixture, add the 10%NaCl aqueous solution of 110ml and stir, heated mixt to 80 DEG C is also incubated 1h, cooling, leave standstill 2.0h, upper strata oily matter is isolated with separating funnel, wash 2 times with water, divide water-yielding stratum, oil phase vacuum-drying, obtain the inhibiter of paste oil soluble fatty group N-tolimidazole quinoline, heavy 48.3g.1636,1550,1450cm infrared spectra (KBr): -1(stretching vibration of phenyl ring skeleton); 1575,1455,1410cm -1(stretching vibration of tetrahydroglyoxaline ring skeleton); 2868,2890cm -1(CH 3, CH 2stretching vibration.720cm -1[-(CH 2) n-stretching vibration].
embodiment 3
Is being furnished with water trap, thermometer, in the there-necked flask of prolong and whipping appts, add 30g and refine sewer oil, 43.5gN-phenyl O-Phenylene Diamine and 80ml dimethylbenzene, pass into nitrogen, after slow heating 140 DEG C of back flow reaction 6.5h, under 190 ~ 200mmHg, underpressure distillation 2.5 ~ 3h, again under 20 ~ 25mmHg, underpressure distillation 1 ~ 2h, until do not have liquid to flow out, after cooling, in mixture, add the 10%NaCl aqueous solution of 120ml and stir, heated mixt to 80 DEG C is also incubated 1h, cooling, leave standstill 1.5h, upper strata oily matter is isolated with separating funnel, wash 2 times with water, isolate water layer, oil phase vacuum-drying, obtain oil soluble fatty group N-phenylbenzimidazol quinoline cream solid inhibiter, heavy 49.8g.1635,1545,1451cm infrared spectra (KBr): -1(stretching vibration of phenyl ring skeleton); 1568,1445,1410cm -1.2875,2891cm -1(CH 3, CH 2stretching vibration); 722cm -1[-(CH 2) n-stretching vibration].
The fatty group benzimidazoline inhibiter of gained of the present invention can form good adsorption film in metallic surface, is conducive to corrosion of metal protection.Just consider the anticorrosion corrosion inhibition test carried out of oil field pipe below.Due to oil field pipe mainly N80 steel, therefore N80 metallic substance is adopted to carry out simulated experiment, the performance of inspection inhibiter.The example of this invention is only in experiment, does not represent all tests, only for reference.
It is that 35% ethanolic soln is for subsequent use that the fatty group N-phenylbenzimidazol quinoline inhibiter that the fatty group benzimidazoline obtained by embodiment 1 and embodiment 3 obtain is made into mass percent respectively.
What prepare toward 1000ml contains 400mg/LH 2s and 10%NaCl solution (medium 1) and 1000ppmHCl+100ppmH 2s(medium 2) in add the obtained fatty group benzimidazoline of embodiment 1 and the obtained fatty group N-phenylbenzimidazol quinoline inhibiter 0.6ml of embodiment 3 respectively, N80 steel disc is hung in the solution, water bath with thermostatic control 60 DEG C, after placing 72h, measure steel disc quality, experimental result is as table 1.
comparative example 1
Experimental technique is with embodiment 3, unique is not refining sewer oil unlike what select, but general sewer oil, the method that preparation-obtained inhibiter Application Example 3 is identical carries out oil field pipe corrosion inhibition test, result shows: hung in the solution by N80 steel disc, water bath with thermostatic control 60 DEG C, after placing 72h, its corrosion inhibition rate is 82.5%.

Claims (5)

1., with the benzimidazoline inhibiter that refining sewer oil prepares, it is characterized in that, chemical formula is as follows:
Wherein, R=C 16-20saturated alkyl or unsaturated alkyl; R 1=H, CH 3, C 6h 5.
2. the preparation method of benzimidazoline inhibiter described in claim 1, is characterized in that, with refining sewer oil and O-Phenylene Diamine or substituted o-phenylenediamine for reaction raw materials, through amidation, cyclodehydration reaction and obtaining.
3. preparation method according to claim 2, is characterized in that, when raw material is O-Phenylene Diamine, comprises the following steps:
S1. refining sewer oil and O-Phenylene Diamine press the mass ratio of 1:1.1 ~ 1.5 under protection of inert gas, in reaction medium, in 138 ~ 145 DEG C of reaction 3 ~ 6h;
S2. again under 180 ~ 200mmHg decompression, in 170 ~ 180 DEG C of reflux 2 ~ 3h, then in the backflow of 20 ~ 25mmHg heated under reduced pressure, until do not have liquid water to flow out, benzimidazoline inhibiter is obtained;
Or when raw material is substituted o-phenylenediamine, comprise the following steps:
S1. refining sewer oil and substituted o-phenylenediamine press the mass ratio of 1:1.3 ~ 1.9 under protection of inert gas, in reaction medium, in 138 ~ 145 DEG C of reaction 3 ~ 6h;
S2. again under 180 ~ 200mmHg decompression, in 170 ~ 180 DEG C of reflux 2 ~ 3h, then in the backflow of 20 ~ 25mmHg heated under reduced pressure, until do not have liquid water to flow out;
S3. cool, add the NaCl aqueous solution in mixture, mixing post-heating to 60 ~ 70 DEG C are also incubated 1h, cooling, leave standstill, be separated oily matter, vacuum-drying, obtain substituted benzimidazole quinoline inhibiter.
4. benzimidazoline inhibiter described in claim 1 is preventing the application in metallic corrosion.
5. application according to claim 4, is characterized in that, described metallic corrosion is caused by acidic aqueous media.
CN201510509872.5A 2015-08-19 2015-08-19 A kind of benzimidazoline corrosion inhibiter being prepared with refined gutter oil Active CN105088252B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820156A (en) * 2016-04-21 2016-08-03 广东工业大学 Benzotriazole benzimidazoline as well as preparation method and application thereof
CN108383797A (en) * 2018-03-09 2018-08-10 浙江农林大学 A kind of corrosion preventive compound and the preparation method and application thereof
CN106083727B (en) * 2016-06-06 2019-04-19 广东工业大学 A kind of mixing-in fat base bis- (benzimidazole hyamines) and the preparation method and application thereof
CN110760858A (en) * 2019-10-15 2020-02-07 桂林理工大学 Schiff base waste cooking oil derivative corrosion inhibitor and preparation method and application thereof
CN110818640A (en) * 2019-11-19 2020-02-21 西安石油大学 Corrosion inhibition lubricant for alcohol-based clean fuel oil and preparation method thereof

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CN103012272A (en) * 2012-12-21 2013-04-03 张家港保税区超威电化技术服务有限公司 Preparation method of imidazoline compound

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820156A (en) * 2016-04-21 2016-08-03 广东工业大学 Benzotriazole benzimidazoline as well as preparation method and application thereof
CN106083727B (en) * 2016-06-06 2019-04-19 广东工业大学 A kind of mixing-in fat base bis- (benzimidazole hyamines) and the preparation method and application thereof
CN108383797A (en) * 2018-03-09 2018-08-10 浙江农林大学 A kind of corrosion preventive compound and the preparation method and application thereof
CN108383797B (en) * 2018-03-09 2020-07-21 浙江农林大学 Anticorrosive compound and preparation method and application thereof
CN110760858A (en) * 2019-10-15 2020-02-07 桂林理工大学 Schiff base waste cooking oil derivative corrosion inhibitor and preparation method and application thereof
CN110818640A (en) * 2019-11-19 2020-02-21 西安石油大学 Corrosion inhibition lubricant for alcohol-based clean fuel oil and preparation method thereof
CN110818640B (en) * 2019-11-19 2022-12-09 西安石油大学 Corrosion inhibition lubricant for alcohol-based clean fuel oil and preparation method thereof

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