CN104805444A - Low-temperature corrosion inhibitor and preparation method thereof - Google Patents
Low-temperature corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN104805444A CN104805444A CN201410047745.3A CN201410047745A CN104805444A CN 104805444 A CN104805444 A CN 104805444A CN 201410047745 A CN201410047745 A CN 201410047745A CN 104805444 A CN104805444 A CN 104805444A
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Abstract
The invention discloses a low-temperature corrosion inhibitor in the field of petrochemical engineering and a preparation method thereof. The low-temperature corrosion inhibitor comprises A, 10-80wt% of a polyacrylamide-amine compound, B, 1-30wt% of a thiourea compound and C, 10-70wt% of a solvent. The low-temperature corrosion inhibitor can be used for a corrosion environment containing HCl-H2S-H2O and low molecular weight organic acids such as formic acid and acetic acid in a distillation device top condensation cooling system. Compared with the same type of corrosion inhibitors, the low-temperature corrosion inhibitor has the characteristics of less use amount, high corrosion inhibition efficiency, good chemical stability, good heat stability, a wide application range, low cost and simple manufacturing processes.
Description
Technical field
The invention belongs to petrochemical industry, be specifically related to the Low-temperature corrosion inhibitor of a kind of crude oil for inhibiting water distilling apparatus overhead condensation cooling system equipment and pipeline corrosion.
Background technology
Atmospheric and vacuum distillation unit is the first operation of crude oil processing, and the safety and steady of atmospheric and vacuum distillation unit runs the productivity effect that direct relation whole refinery.Ratio such as crude oil with poor quality such as refinery processing in recent years high-sulfur, peracid etc. day by day increases, and electric desalting instability causes the problems such as the de-rear cl content rising of crude oil, water distilling apparatus overhead system is caused to corrode aggravation, cause equipment failure occurs, cause unplanned parking, be the major hidden danger of water distilling apparatus safe operation always.The reason that corrosion occurs water distilling apparatus " three tops " condensing cooling system is to contain HCl, H after water vapor condensation in oil gas
2the corrosive mediums such as S.HCl, H
2as long as S, from muriate in crude oil and sulfide decomposes, forms HCl-H with after water condensation
2s-H
2o corrosive environment.Part refinery finds that water distilling apparatus overhead system exists the low molecular organic acids of high level, as corrosive mediums such as formic acid, acetic acid, propionic acid, with HCl-H in addition
2s-H
2mechanism of corrosion under O corrosion types interacts is more complicated, makes tower top corrosion control comparatively difficulty.
The corrosion prevention policy of water distilling apparatus overhead condensation cooling system is based on Process anti-corrosion, and material antiseptic is auxiliary.Process cor-rosion-protection refers to traditional " de-three notes ", i.e. crude oil electric desalting and the water filling of overhead condensation cooling system, note neutralizing agent, note inhibiter.Wherein inhibiter have that cost is low, instant effect, the feature such as simple to operate, be one of safeguard procedures the most frequently used in water distilling apparatus overhead condensation cooling system.Be applied in water distilling apparatus tower top inhibiter at present and be mainly Long carbon chain acid amides, pyridine derivate, imidazolidine derivatives, quaternary ammonium salt type compound.
Although above-mentioned inhibiter has certain effect, at HCl-H at the anticorrosion tool of water distilling apparatus overhead condensation cooling system
2s-H
2the corrosion mitigating effect that O and the low molecular organic acids such as formic acid, acetic acid coexist under corrosive environment is undesirable, generally about 70%.
Summary of the invention
The object of this invention is to provide Low-temperature corrosion inhibitor of a kind of crude oil for inhibiting water distilling apparatus overhead condensation cooling system equipment and pipeline corrosion and preparation method thereof; this inhibiter can have good corrosion inhibition under HCl-H2S-H2O and the low molecular organic acids such as formic acid, acetic acid coexist corrosive environment, plays a good protection to the surface of metallic conduit and equipment.
The invention provides a kind of Low-temperature corrosion inhibitor, it is characterized in that this inhibiter is made up of following component:
(A) polyacrylamide-amine compound of 10 ~ 80 % by weight
(B) thiourea of 1 ~ 30 % by weight
(C) solvent of 10 ~ 70 % by weight
With inhibiter total weight.
Wherein, described polyacrylamide-amine compound is with methyl acrylate and polyethylene polyamine for prepared by raw material, and its structural formula is as follows:
In formula, m is 2 ~ 8; N is 0 ~ 5;
X is
Y is-H or-(CH
2-CH
2-NH)
p-CH
2-CH
2-NH
2; P is 0 ~ 4.
A kind of Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: described polyacrylamide-amine compound preferred content is 30 ~ 60 % by weight, described thiourea preferred content is 5 ~ 20 % by weight, and described solvent preferred content is 20 ~ 50 % by weight, with inhibiter total weight.
A kind of Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: described thiourea is any one or two kinds in thiocarbamide, methylthiourea, dimethyl thiourea, ethyl thiourea, diethyl thiourea, thiosinamine, phenylthiourea, tolylthiourea.
A kind of Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: described solvent is any one or two kinds in methyl alcohol, ethanol, propyl alcohol, Virahol, water.
The present invention also provides a kind of preparation method of described Low-temperature corrosion inhibitor, it is characterized in that:
(1) component (A) polyacrylamide-amine compound is prepared:
By polyethylene polyamine and methyl alcohol according to 1: 1 mass ratio at room temperature mix and blend, then slowly add methyl acrylate, in adition process, control temperature is no more than 50 DEG C, and methyl acrylate adds according to the mol ratio with polyethylene polyamine 1: 0.5 ~ 1: 2.Add complete under 30 ~ 50 DEG C of conditions stirring reaction 20 ~ 60 hours, then heat up solvent methanol distillation removing, 80 DEG C ~ 90 DEG C reactions 1 ~ 3 hour, be warming up to 115 ~ 125 DEG C of reactions 1 ~ 3 hour, be warming up to 145 ~ 155 DEG C of reactions 2 ~ 5 hours again, after cooling, namely obtain polyacrylamide-amine compound product.
Wherein said polyethylene polyamine be in diethylenetriamine, triethylene tetramine, tetraethylene pentamine any one.
(2) preparation of Low-temperature corrosion inhibitor:
Component (A) polyacrylamide-amine compound prepared by step (1) and component (B) thiourea and component (C) solvent, the mixture of above-mentioned three kinds of components is at 40 ~ 80 DEG C of temperature, and namely stirring reaction obtained Low-temperature corrosion inhibitor of the present invention after 2 ~ 6 hours.
The preparation method of a kind of described Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: the blending ratio of described three kinds of components is component (A) polyacrylamide-amine compound of 10 ~ 80 % by weight, component (B) thiourea component (B) of 1 ~ 30 % by weight, component (C) solvent of 10 ~ 70 % by weight, with inhibiter total weight.
The preparation method of a kind of described Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: described thiourea is any one or two kinds in thiocarbamide, methylthiourea, dimethyl thiourea, ethyl thiourea, diethyl thiourea, thiosinamine, phenylthiourea, tolylthiourea.
The preparation method of a kind of described Low-temperature corrosion inhibitor of the present invention, it is further characterized in that: described solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, water any one or two kinds.
Low-temperature corrosion inhibitor provided by the invention can be used for HCl-H in water distilling apparatus overhead condensation cooling system
2s-H
2o and the low molecular organic acids such as formic acid, acetic acid coexist corrosive environment.Compared with similar inhibiter, have that consumption is few, inhibition efficiency is high, chemical stability and Heat stability is good, applied range, with low cost and manufacture the features such as easy; Both there is the film forming properties good in metallic surface, had again in aqueous phase good solubility and dispersiveness.The inhibiter that invention provides is at water distilling apparatus overhead condensation cooling system HCl-H
2s-H
2o and the low molecular organic acids such as formic acid, acetic acid coexist in corrosive environment, and need only effectively can control the corrosion of carbon steel equipment and pipeline by 5 ~ 30mg/L, corrosion inhibition rate is more than 95%.
Embodiment
Below in conjunction with concrete embodiment, the present invention is described in further detail, but these embodiments are not for limiting the scope of the invention by any way.
Evaluation method
(1) appreciation condition: according to the situation at refinery low-temperature light oil position, laboratory preparation etchant solution is simulated actual corrosive environment and is carried out corrosion coupon experiment.Select carbon steel test piece to carry out corrosion experiment, adopt blank with add inhibiter and contrast, according to corrosion weight loss and the corrosion condition of test piece, calculate corrosion inhibition rate.
(2) evaluation procedure:
1. according to Different hypothermia light oil position situation preparation corrosion simulation solution;
2. carbon steel test piece pre-treatment, weighs;
3. (for inhibiter evaluation experimental, first test piece is 50mg/L at content to carry out corrosion experiment
Pre-membranization 2 hours in the etchant solution of corresponding inhibiter);
4. take out test piece, weigh after treatment, calculate corrosion inhibition rate.
Wherein embodiment 1 ~ embodiment 5 is synthesis and the preparation of inhibiter, and embodiment 6 and 7 is the corrosion inhibition evaluation of water soluble rust inhibitor.
Embodiment 1
By diethylenetriamine and methyl alcohol according to 1: 1 mass ratio at room temperature mix and blend, then slowly add methyl acrylate, in adition process, control temperature is no more than 50 DEG C, and methyl acrylate adds according to the mol ratio with polyethylene polyamine 1: 1.1.Add complete under 30 ~ 50 DEG C of conditions stirring reaction 40 hours, be then warming up to 80 DEG C of reactions 1.5 hours, then be warming up to 120 DEG C of reactions 2 hours, be warming up to 150 DEG C of reactions 3 hours.Namely polyacrylamide-amine compound a is obtained after cooling.
Embodiment 2
By triethylene tetramine and methyl alcohol according to 1: 1 mass ratio at room temperature mix and blend, then slowly add methyl acrylate, in adition process, control temperature is no more than 50 DEG C, and methyl acrylate adds according to the mol ratio with polyethylene polyamine 1: 0.8.Add complete under 30 ~ 50 DEG C of conditions stirring reaction 40 hours, be then warming up to 80 DEG C of reactions 1 hour, then be warming up to 120 DEG C of reactions 2.5 hours, be warming up to 150 DEG C of reactions 3 hours.Namely polyacrylamide-amine compound b is obtained after cooling.
Embodiment 3
By tetraethylene pentamine and methyl alcohol according to 1: 1 mass ratio at room temperature mix and blend, then slowly add methyl acrylate, in adition process, control temperature is no more than 50 DEG C, and methyl acrylate adds according to the mol ratio with polyethylene polyamine 1: 0.5.Add complete under 30 ~ 50 DEG C of conditions stirring reaction 40 hours, be then warming up to 80 DEG C of reactions 1.5 hours, then be warming up to 120 DEG C of reactions 3 hours, be warming up to 150 DEG C of reactions 4 hours.Namely polyacrylamide-amine compound c is obtained after cooling.
Embodiment 4
60 grams of polyacrylamides-amine compound a, 2 grams of methylthioureas, 5 grams of phenylthioureas, 20 grams of ethanol, 13 grams of water are uniformly mixed under 40 DEG C of conditions, obtained inhibiter CP01.
Embodiment 5
20 grams of polyacrylamides-amine compound a, 15 grams of thiocarbamides, 10 grams of thiosinamines, 30 grams of methyl alcohol, 25 grams of water are uniformly mixed under 40 DEG C of conditions, obtained inhibiter CP02.
Embodiment 6
70 grams of polyacrylamides-amine compound b, 15 grams of ethyl thioureas, 10 grams of methyl alcohol are uniformly mixed under 40 DEG C of conditions, obtained inhibiter CP03.
Embodiment 7
50 grams of polyacrylamides-amine compound b, 5 grams of ethyl thioureas, 5 grams of tolylthioureas, 20 grams of ethanol, 20 grams of Virahols are uniformly mixed under 40 DEG C of conditions, obtained inhibiter CP04.
Embodiment 8
45 grams of polyacrylamides-amine compound c, 10 grams of thiosinamines, 30 grams of ethanol, 10 grams of water are uniformly mixed under 40 DEG C of conditions, obtained inhibiter CP05.
Embodiment 9
According to the environment of Atmospheric vacuum tower top condensing cooling system, preparation corrosive medium is 800mg/LHCl+150mg/L HCOOH+200mg/L H
2the S aqueous solution investigates the corrosion inhibition of different water soluble rust inhibitor.Experimental result is in table 2.
Table 2 Different hypothermia inhibiter laboratory evaluation data
As shown in Table 1,5 kinds of inhibiter are in 5 ~ 20mg/L concentration range, and its corrosion inhibition rate is all more than 97%.
Embodiment 10
According to the environment at catalytic cracking unit stable absorption system hypothermia light oil position, preparation corrosive medium is 800mg/L HCl+150mg/L CH
3cOOH+200mg/L H
2the S aqueous solution, investigates the corrosion inhibition of different water soluble rust inhibitor.Experimental result is in table 3.
Table 3 Different hypothermia inhibiter laboratory evaluation data
As shown in Table 2,5 kinds of inhibiter are in 5 ~ 20mg/L concentration range, and its corrosion inhibition rate is all more than 97%.
Although be described in detail the present invention and quoted some specific exampless as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes and revise.
Claims (10)
1. a Low-temperature corrosion inhibitor, is characterized in that this inhibiter is made up of following component:
(A) polyacrylamide-amine compound of 10 ~ 80 % by weight,
(B) thiourea of 1 ~ 30 % by weight,
(C) solvent of 10 ~ 70 % by weight,
With inhibiter total weight;
Wherein, the structural formula of described polyacrylamide-amine compound is as follows:
In formula, m is 2 ~ 8; N is 0 ~ 5;
X is
Wherein Y is-H or-(CH
2-CH
2-NH)
p-CH
2-CH
2-NH
2; P is 0 ~ 4.
2. Low-temperature corrosion inhibitor according to claim 1, is characterized in that: described component (A) polyacrylamide-amine compound is prepared by raw material by methyl acrylate and polyethylene polyamine.
3. Low-temperature corrosion inhibitor according to claim 1, is characterized in that: described component (B) thiourea is any one or two kinds in thiocarbamide, methylthiourea, dimethyl thiourea, ethyl thiourea, diethyl thiourea, thiosinamine, phenylthiourea, tolylthiourea.
4. Low-temperature corrosion inhibitor according to claim 1, is characterized in that: described component (C) solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, water any one or two kinds.
5. Low-temperature corrosion inhibitor according to claim 1, it is characterized in that: described component (A) content is 30 ~ 60 % by weight, shown component (B) content is 5 ~ 20 % by weight, and described component (C) content is 20 ~ 50 % by weight, with inhibiter total weight.
6. a preparation method for Low-temperature corrosion inhibitor, is characterized in that, comprises following steps:
(1) prepare component (A) polyacrylamide-amine compound: by polyethylene polyamine and methyl alcohol according to 1: 1 mass ratio at room temperature mix and blend, then slowly methyl acrylate is added, in adition process, control temperature is no more than 50 DEG C, and methyl acrylate adds according to the mol ratio with polyethylene polyamine 1: 0.5 ~ 1: 2.Add complete under 30 ~ 50 DEG C of conditions stirring reaction 20 ~ 60 hours, then heat up solvent methanol distillation removing, 80 DEG C ~ 90 DEG C reactions 1 ~ 3 hour, be warming up to 115 ~ 125 DEG C of reactions 1 ~ 3 hour, be warming up to 145 ~ 155 DEG C of reactions 2 ~ 5 hours again, after cooling, namely obtain polyacrylamide-amine compound product.
(2) preparation of Low-temperature corrosion inhibitor: by step (
1) in component (A) polyacrylamide-amine compound of preparation and component (B) thiourea and component (C) solvent, the mixture of three kinds of components at 40 ~ 80 DEG C of temperature, stirring reaction 2 ~ 6 hours.
7. the preparation method of Low-temperature corrosion inhibitor according to claim 6, is characterized in that: wherein said polyethylene polyamine be in diethylenetriamine, triethylene tetramine, tetraethylene pentamine any one.
8. the preparation method of Low-temperature corrosion inhibitor according to claim 6, is characterized in that: described thiourea is any one or two kinds in thiocarbamide, methylthiourea, dimethyl thiourea, ethyl thiourea, diethyl thiourea, thiosinamine, phenylthiourea, tolylthiourea.
9. the preparation method of Low-temperature corrosion inhibitor according to claim 6, is characterized in that: described solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, water any one or two kinds.
10. the preparation method of Low-temperature corrosion inhibitor according to claim 6, it is characterized in that: the blending ratio of described three kinds of components is component (A) polyacrylamide-amine compound of 10 ~ 80 % by weight, component (B) thiourea component (B) of 1 ~ 30 % by weight, component (C) solvent of 10 ~ 70 % by weight.
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Cited By (4)
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| CN106478873A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106478874A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106478876A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106868512A (en) * | 2016-12-22 | 2017-06-20 | 新疆德蓝股份有限公司 | A kind of high temperature resistant acidification corrosion inhibitor and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478873A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106478874A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106478876A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of copolymer and preparation method and application |
| CN106478873B (en) * | 2015-08-31 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of copolymer and the preparation method and application thereof |
| CN106478874B (en) * | 2015-08-31 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of copolymer and the preparation method and application thereof |
| CN106868512A (en) * | 2016-12-22 | 2017-06-20 | 新疆德蓝股份有限公司 | A kind of high temperature resistant acidification corrosion inhibitor and preparation method thereof |
| CN106868512B (en) * | 2016-12-22 | 2019-03-19 | 德蓝水技术股份有限公司 | A kind of high temperature resistant acidification corrosion inhibitor and preparation method thereof |
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Application publication date: 20150729 |