CN102517589B - Film forming corrosion inhibitor and preparation method thereof - Google Patents
Film forming corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN102517589B CN102517589B CN 201110452271 CN201110452271A CN102517589B CN 102517589 B CN102517589 B CN 102517589B CN 201110452271 CN201110452271 CN 201110452271 CN 201110452271 A CN201110452271 A CN 201110452271A CN 102517589 B CN102517589 B CN 102517589B
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Abstract
The invention discloses a film forming corrosion inhibitor and a preparation method thereof, which is used for shutdown protection of furnaces in thermal power stations. The corrosion inhibitor includes 40-50mg/L of octadecylamine, 45-50mg/L of morpholine, 25-30mg/L of urotropin, 20-25mg/L of thiourea, 25-40mg/L of acetamide, 5mL/L of organic solvent and the balance water. The solid octadecylamine is dissolved into the organic solvent, the morpholine, the thiourea and the acetamide are dissolved and diluted by water to be the corrosion inhibitor. The corrosion inhibitor is fine in film forming effect and fine in water solubility at the room temperature, and the octadecylamine cannot be condensed and separated to block pipelines at low-temperature section of a moisture system and can be added into the moisture system through a water feeding and ammonia adding pump, the adding manner is simple, operation is simple and convenient, harmful substances to the moisture system, such as low-molecule organic acid, cannot be produced during cycling, and the film forming corrosion inhibitor is safe and reliable.
Description
Technical field
The present invention relates to a kind of novel thermal power plant protection of boiler during shutdown period film inhibitor and preparation method thereof.
Background technology
Using at present more widely, the protection of boiler during shutdown period inhibiter has two kinds: the first kind is the stearylamine inhibiter; stearylamine is a kind of long chain alkane amine; the amido of its molecular end can form Coordination Adsorption with the atoms metal of metallic surface, thereby forms the protective membrane of layer of hydrophobic at metal pipe-wall.The defective of stearylamine inhibiter is water-soluble very poor when low temperature, can't be in the metallic surface film forming, and the low-temperature zone equipment of water-steam system can not get good protection during protection of boiler during shutdown period.And stearylamine decomposes during the high temperature about 450 ℃, is not suitable for the protection of boiler during shutdown period of the very high ultra supercritical unit of main steam temperature, and the scope of application is restricted.Equations of The Second Kind is imidazoline inhibitor, and is the same with stearylamine, and tetrahydroglyoxaline can rely on also that the Coordination Adsorption of amido acts on the metallic surface film forming in the molecule.The low-temperature water-soluble of tetrahydroglyoxaline slightly is better than stearylamine, but its film-formation result does not have stearylamine good, and tetrahydroglyoxaline also exists the defective of pyrolytic decomposition, and is undesirable to the protection effect of unit.
Summary of the invention
One of purpose of the present invention is to provide a kind of novel thermal power plant protection of boiler during shutdown period film inhibitor, and the low temperature good filming that this inhibiter can be about 100 ℃ can have good film forming provide protection by the high temperature about 450 ℃ again.
The technical scheme that realizes above-mentioned purpose is as follows:
A kind of film inhibitor, it consists of: 40～50mg/L stearylamine, 45～50mg/L morpholine, 25～30mg/L urotropine, 20～25mg/L thiocarbamide, 25～40mg/L ethanamide, 4.5～5.5mL/L organic solvent, all the other are water.
Preferably, described organic solvent is the mixed solution of pyridine and Diisopropylamine, and wherein with pyridine: Diisopropylamine=3-5: 1 volume ratio is mixed, and most preferably is with pyridine: the volume ratio of Diisopropylamine=4: 1 is mixed.
Preferably, described stearylamine, morpholine, urotropine, thiocarbamide, ethanamide and organic solvent are technical pure or above chemical reagent, most preferably analytical reagent.
Wherein, the morpholine molecular formula is C
4H
9NO, morpholine contain one-NH
2, the same with stearylamine ,-NH
2Thereby in N can form coordinate bond with the metallic surface and form adsorption film in the metallic surface.External a lot of power plant carries out protection of boiler during shutdown period as the protection of boiler during shutdown period agent to unit with morpholine.The laboratory has the experiment of exploration to show that No. 20 carbon steel test pieces that are immersed in the morpholine solution are very faint in the time internal corrosion that reaches 2 months, do not observe obvious corrosion phenomenon.The proof morpholine has good corrosion inhibition, and secondly, morpholine solution has strong basicity (10g/L morpholine solution pH is about 10), and therefore, morpholine can also be as the medicine of regulating pH.
The urotropine molecular formula is C
6H
12N
4, contain 4 in the urotropine molecule with the N element of lone-pair electron, this so that urotropine when carrying out coordination with metal selectivity stronger, film-formation result strengthens, the space frame of urotropine is so that the obstructing capacity of film is strong than long alkyl chain simultaneously.Urotropine is the inhibiter of often testing in the experiment, and film-formation result is good.
The thiocarbamide molecular formula is CH
4N
2S has two-NH in the thiocarbamide molecule
2, and it is sterically hindered several all less than front, and absorption film-forming is more prone in the metallic surface.Because its molecule is less, can between the slit of stearylamine film, fill simultaneously, make protective membrane finer and close.
Ethanamide (C
2H
5NO) be a kind of organic cosolvent, can be used as the solubilizing agent of many water-soluble low materials.Next, in the ethanamide molecule-NH
2Certain absorption film-forming characteristic is also arranged.
Organic solvent is pyridine (C
5H
5N) and Diisopropylamine (C
6H
15N) mixed solution, pyridine are a kind of good organic solvents, and Diisopropylamine has strong basicity, can promote the dissolving of stearylamine in pyridine.
Another object of the present invention provides the preparation method of above-mentioned thermal power plant protection of boiler during shutdown period film inhibitor.
The technical scheme that realizes above-mentioned purpose is as follows:
A kind of preparation method of film inhibitor may further comprise the steps:
(1) it is for subsequent use to take by weighing in proportion stearylamine, morpholine, urotropine, thiocarbamide, ethanamide and preparation organic solvent;
(2) stearylamine is put in the organic solvent, made stearylamine dissolve to get solution fully;
(3) respectively morpholine, urotropine, thiocarbamide, ethanamide are put in the solution that step (2) obtains, being dissolved in water and being diluted to fixed volume namely gets described film inhibitor.
Preferably, the preparation method of described film inhibitor also comprises the pH of step (4) adjusting film inhibitor: the pH value to 9.4 of regulating film inhibitor with ammonia soln.
Preferably, first morpholine being added the morpholine solution that water is mixed with 10g/L in the described step (3) puts in the solution of step (2) again.
Advantage of the present invention and beneficial effect:
1, the simultaneously low temperature range about 100 ℃ and 450 ℃ high temperature range good filming of inhibiter provided by the invention can be realized the all-round protection to ultra supercritical unit water-steam system;
2, multiple auxiliary inhibiter composition is arranged in the inhibiter provided by the invention, can promote the film forming of stearylamine, better than the film-formation result of pure stearylamine;
3, inhibiter provided by the invention can add ammonia pump by feedwater and adds and enter water-steam system, and dosing method is simple, and is easy and simple to handle;
4, inhibiter provided by the invention is at room temperature water-soluble good, and stearylamine can not cause line clogging at the low temperature section curding out of water-steam system;
5, inhibiter provided by the invention circulation time in water-steam system does not have the product generations harmful to system such as low molecular organic acids, and is safe and reliable.
Description of drawings
Fig. 1 is the Electronic Speculum picture of test piece after the inhibiter effect of the embodiment of the invention 1;
Fig. 2 is the Electronic Speculum picture of test piece after the inhibiter effect of the embodiment of the invention 2;
Fig. 3 is the Electronic Speculum picture of test piece after the inhibiter effect of the embodiment of the invention 3.
Embodiment
Below in conjunction with embodiment, the invention will be further elaborated.
Present embodiment prepares the film inhibitor of 1L, and is composed as follows: 40mg stearylamine, 45mg morpholine, 25mg urotropine, 20mg thiocarbamide, 25mg ethanamide, 5mL organic solvent (pyridine 4mL and Diisopropylamine 1mL mixed solution), all the other are water.
The preparation method of the film inhibitor of present embodiment is as follows:
(1) it is for subsequent use to take by weighing in proportion stearylamine, morpholine, urotropine, thiocarbamide, ethanamide and preparation organic solvent;
(2) stearylamine is put in the organic solvent, smashed to pieces the stearylamine solid and constantly stir with glass stick and obtain solution until solid dissolves fully, if can promote with the warm water soaking beaker dissolving of stearylamine when room temperature is low;
(3) morpholine is dissolved in water is mixed with the 10g/L morpholine solution, respectively morpholine solution, urotropine, thiocarbamide, ethanamide are put in the solution that step (2) obtains, being dissolved in water and being diluted to 1L namely gets film inhibitor.
(4) pH to 9.4 with ammoniacal liquor adjusting film inhibitor saves backup.
Embodiment 2
Present embodiment prepares the film inhibitor of 1L, and is composed as follows: 50mg stearylamine, 50mg morpholine, 30mg urotropine, 25mg thiocarbamide, 40mg ethanamide, 5mL organic solvent (pyridine 4mL and Diisopropylamine 1mL mixed solution), all the other are water.
The preparation method of the film inhibitor of present embodiment is with embodiment 1.
Embodiment 3
Present embodiment prepares the film inhibitor of 1L, and is composed as follows: 45mg stearylamine, 48mg morpholine, 28mg urotropine, 23mg thiocarbamide, 34mg ethanamide, 5mL organic solvent (pyridine 4mL and Diisopropylamine 1mL mixed solution), all the other are water.
The preparation method of the film inhibitor of present embodiment is with embodiment 1.
Embodiment 4
The preparation-obtained film inhibitor solution of above-described embodiment 1-3 is added in the autoclave, and hang No. 20 carbon steel test pieces that to polish smooth, closed the autoclave letting nitrogen in and deoxidizing 1 hour.Be warming up to 130 ℃, constant temperature 3.5h takes out test piece.The pH of corrosion inhibitor solution behind the determination experiment.Observe test piece surface filming situation, and hydrophobic test, acid copper sulfate spot test and ac impedance measurement test are carried out in the film forming test piece.All there is dark yellow on the test piece surface of taking out, and evenly smooth organic protective film forms.Water droplet is hemispherical on the test piece surface, and the film hydrophobic nature is good.The first red time of cupric sulphate dropping test is all greater than 40 seconds.The ac impedance measurement as a result impedance spectrum of surface film is two sections continuous semi arches, and the test piece polarization resistance of embodiment 1 inhibiter effect is 58400 Ω cm
2, the test piece limit resistance of embodiment 2 inhibiter effects is 58000 Ω cm
2, the test piece limit resistance of embodiment 3 inhibiter effects is 58800 Ω cm
2, all be higher than not film forming test piece far away.The phenomenon that pH descends still on 9.0, does not occur in the corrosion inhibitor solution pH after the film forming.
Embodiment 5
The resulting film inhibitor solution of embodiment 1-3 is added in the autoclave, and hang No. 20 carbon steel test pieces that to polish smooth, closed the autoclave letting nitrogen in and deoxidizing 1 hour.Be warming up to 450 ℃, constant temperature 3.5h takes out test piece.Composition behind the determination experiment in the pH of corrosion inhibitor solution and the qualitative analysis solution.Observe test piece surface filming situation, and hydrophobic test, acid copper sulfate spot test, ac impedance measurement test and electron-microscope scanning analysis are carried out in the film forming test piece.The test piece surface of taking out has all formed the smooth protective membrane of the dimmed densification of one deck.Water droplet is hemispherical on the test piece surface, and the hydrophobic nature of film is very good.The first red time of cupric sulphate dropping test is all greater than 2 hours.The ac impedance measurement result shows that all the high frequency region of the impedance spectrum of film is one section semi arch, and low frequency range is one section skew lines, and the polarization resistance all reaches 10
7Ω cm
2More than.Corrosion inhibitor solution pH is higher than 9.0 after the film forming, and the phenomenon that pH descends does not occur.Analytical results to the gas chromatography combined with mass spectrometry (GC-MS) of corrosion inhibitor solution after the film forming shows, do not have the objectionable impurities such as low molecular organic acids to produce in the solution.The electron-microscope scanning analysis is carried out in test piece, Fig. 1, Fig. 2, Fig. 3 are respectively the Electronic Speculum picture of test piece after the inhibiter effect of the embodiment of the invention 1, embodiment 2 and embodiment 3, test piece surface film crystal grain was even after we can find out inhibiter effect provided by the invention from the Electronic Speculum figure, marshalling, fine and close seamless, this film-formation result that inhibiter provided by the invention is described is good.
Be specific embodiments of the invention only below, do not limit protection scope of the present invention with this; Any replacement and the improvement done on the basic structure plinth of not violating the present invention's think of all belong to protection scope of the present invention.
Claims (5)
1. film inhibitor, it is characterized in that, the composition of described inhibiter and concentration are: 40～50mg/L stearylamine, 45～50mg/L morpholine, 25～30mg/L urotropine, 20～25mg/L thiocarbamide, 25～40mg/L ethanamide, 4.5-5.5mL/L organic solvent, and all the other are water; Described organic solvent is the mixed solution of pyridine and Diisopropylamine, and wherein with pyridine: the volume ratio of Diisopropylamine=3-5:1 is mixed.
2. film inhibitor according to claim 1 is characterized in that, described organic solvent is the mixed solution that the volume ratio of pyridine: Diisopropylamine=4:1 is mixed.
3. the preparation method of each described film inhibitor of claim 1-2 is characterized in that, may further comprise the steps:
(1) it is for subsequent use to take by weighing in proportion stearylamine, morpholine, urotropine, thiocarbamide, ethanamide and preparation organic solvent;
(2) stearylamine is put in the organic solvent, made stearylamine dissolve to get solution fully;
(3) respectively morpholine, urotropine, thiocarbamide, ethanamide are put in the solution that step (2) obtains, being dissolved in water and being diluted to fixed volume namely gets described film inhibitor.
4. the preparation method of film inhibitor according to claim 3 is characterized in that, also comprises the pH of step (4) adjusting film inhibitor: the pH value to 9.4 of regulating film inhibitor with ammonia soln.
5. the preparation method of film inhibitor according to claim 3 is characterized in that, first morpholine is added the morpholine solution that water is mixed with 10g/L in the described step (3) and puts in the solution of step (2) again.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104629713B (en) * | 2013-11-08 | 2018-01-05 | 中国石油天然气股份有限公司 | A kind of high temperature resistant corrosion inhibitor and preparation method thereof |
| CN104328439A (en) * | 2014-10-28 | 2015-02-04 | 吉林省电力科学研究院有限公司 | Specific anti-corrosive agent for supercritical unit thermodynamic system |
| CN105420734B (en) * | 2015-11-03 | 2018-10-26 | 张啸 | A kind of high-temperature steam corrosion inhibiter and its application process |
| CN108048852B (en) * | 2017-11-30 | 2019-11-12 | 湖南省湘电试验研究院有限公司 | A kind of flexible protection of boiler during shutdown period medicament and preparation method thereof |
| CN111334802B (en) * | 2020-04-09 | 2022-05-24 | 苏州热工研究院有限公司 | Film-forming amine corrosion inhibitor suitable for nuclear power plant secondary circuit shutdown maintenance and method for reducing secondary circuit corrosion during nuclear power plant shutdown |
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| WO2010057976A1 (en) * | 2008-11-21 | 2010-05-27 | Thermphos Trading Gmbh | Liquid surface treatment composition with phosphonic acid derivatives neutralized with a binary amine system |
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| CN1179348A (en) * | 1996-10-10 | 1998-04-22 | 戴仁逊 | Vapour phase corrosion inhibitor for high-pressure boiler and preparing process thereof |
| CN1827858A (en) * | 2006-03-30 | 2006-09-06 | 武汉大学 | Film-forming inhibitor and preparation method thereof |
| CN101498001A (en) * | 2008-01-29 | 2009-08-05 | 上海洗霸科技有限公司 | Anti-corrosive protective film agent for marine boiler |
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