CN107541736B - A kind of station boiler pickling solid corrosion inhibitor - Google Patents
A kind of station boiler pickling solid corrosion inhibitor Download PDFInfo
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- CN107541736B CN107541736B CN201710760476.9A CN201710760476A CN107541736B CN 107541736 B CN107541736 B CN 107541736B CN 201710760476 A CN201710760476 A CN 201710760476A CN 107541736 B CN107541736 B CN 107541736B
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Abstract
A kind of station boiler pickling solid corrosion inhibitor, belong to corrosion inhibiter field, including 12-15 parts of methenamine, 6-8 parts of ammonium thiocyanate, 0.6-1 parts of bromogeramine, 0.1-0.2 parts of benzotriazole, 2-5 parts of stannous chloride, 2-5 parts of sodium thiosulfate, 1-3 parts of thiocarbamide, the overwhelming majority acid of solid corrosion inhibitor of the invention other than nitric acid, there is good inhibition efficiency to most metals other than zinc and aluminium, and the present invention fully considers H during acidity+Ion etching, H atom burn into Fe3+Burn into Cu2+Various corrosion and the security risks such as corrosion, have inhibition point more comprehensively, outstanding advantages of inhibition efficiency is higher, use scope is wider.
Description
Technical field
The present invention relates to corrosion inhibiter fields, more particularly to station boiler pickling solid corrosion inhibitor.
Background technique
The pickling descaling of station boiler is heated inner surface cleaning, prevents heating surface from causing accident because of corrosion and fouling
Requisite measure, while being also to improve boiler thermal efficiency, improve one of the effective measures of unit water and steam quality.Station boiler is pressure
Container, the selection of corrosion inhibiter are the key that one rings of pickling descaling, and most of restrainers mainly solve H in acidic cleaner+Inhibition, H atom burn into Fe3+Burn into Cu2+Corrosion, due to H in corrosion mechanism and acidic cleaner+Difference, to total etching extent
Influence is smaller, also smaller for the harm of conventional equipment, is often unaware of or rarely has specific aim solution, but for station boiler
Equal pressure vessels are that there are biggish security risks.
Hydrogen atom corrosion includes hydrogen embrittlement and hydrogen blister, in pickling in spite of corrosion inhibiter, it would still be possible to there is a small amount of H+It can restore
At H, then have the problem of characteristic of H causes.By taking chlorohydric acid pickling as an example, when HCL aqueous solution and Fe have an effect and generate two originals
Sub- hydrogen just generates a hydrogen molecule when they encounter together.
2HCl+Fe=FeCl2+H2
The atomic hydrogen of nascent state is very active, and volume is also small, can be at steel or other metals (such as copper) intrinsic silicon four sides
Diffusion is walked from all directions, when will cause twisted lattice, atom vacancy or other microdefects inside it is stranded in material, just to material
The ability that material generates plastic deformation under external force plays the role of " anchoring ", i.e., material cannot be slowed down with the method for deformation
Stress makes material become fragile, or even fracture suddenly.
When hydrogen atom is diffused into the gross imperfections such as stomata, the slag inclusion of material internal, just stays at this and build up into molecule
Hydrogen, at this moment volume just increases 20 times (because two hydrogen atoms of one hydrogen molecule of composition are mutually 120 ° of angle).With H2Accumulation,
Pressure at the gross imperfection is just continuously increased, and the stress inside forming material is reached the limit values and ruptured.It is anti-in many enamel
It answers in the acid cleaning process of kettle, it is exactly Hydrogen blister by caused that it is intact good, which just to have cleaned, but burst porcelain occurs after washing.
In acidity cleaning, as long as there is iron rust that will generate Fe3+, due to Fe3+Oxidisability is stronger, aggravates in Oxidation of Fe
There is the anode of formation electrochemical corrosion in the operation of the metal surface meeting equipment of spot corrosion in the spot corrosion for causing carbon steel metal surface,
The corrosion for continuing to accelerate the point leaves the security risk of equipment operation.
2Fe3++ Fe=3Fe2+
With Fe3+Corroding similar problem, there are also copper facing, and the oxide or salt of copper, are converted to Cu in acid cleaning process2+, Cu2+
Oxidation of Fe.The Cu of reduction is attached to the surface Fe, since electrochemical corrosion potential is higher than Fe, in the electrification with Fe in day-to-day operation
Learning becomes cathode in corrosion,
Accelerate by the corrosion of copper facing area peripheral edge.
Cu2++ Fe=Cu+Fe2+
In chemical cleaning practice, in the biggish equipment of cleaning copper material specific gravity, in condenser of central air conditioner, tradition
The cleaning agent of corrosion inhibiter often sees one layer of copper in carbon steel circulating slot, and copper facing phenomenon is fairly obvious.
Based on existing problem above, the present invention provides a kind of station boiler restrainer, exhausted other than nitric acid
Most metals other than zinc and aluminium are had good inhibition efficiency by most of acid.It is general to compare traditional restrainer
Only consider H+Ion etching, the present invention fully consider H during acidity+Ion etching, H atom burn into Fe3+Burn into Cu2+Corrosion
Etc. various corrosion and security risk, have inhibition point more comprehensively, outstanding advantages of inhibition efficiency is higher, use scope is wider.
Summary of the invention
Based on the above technical problem, it is an object of the invention to: a kind of station boiler pickling solid corrosion inhibitor is provided, is wrapped
It includes: 12-15 parts of methenamine, 6-8 parts of ammonium thiocyanate, 0.6-1 parts of bromogeramine, 0.1-0.2 parts of benzotriazole.
Preferably, being also added with stannous chloride, sodium thiosulfate, thiocarbamide.
Station boiler pickling solid corrosion inhibitor as a preferred technical solution, including 12-15 parts of methenamine, thiocyanic acid
6-8 parts of ammonium, 0.6-1 parts of bromogeramine, 0.1-0.2 parts of benzotriazole, 2-5 parts of stannous chloride, 2-5 parts of sodium thiosulfate, sulphur
1-3 parts of urea.
Station boiler pickling solid corrosion inhibitor as a preferred technical solution, including 12 parts of methenamine, ammonium thiocyanate 6
Part, 0.6 part of bromogeramine, 0.1 part of benzotriazole, 2 parts of stannous chloride, 2 parts of sodium thiosulfate, 1 part of thiocarbamide.
Station boiler pickling solid corrosion inhibitor as a preferred technical solution, including 15 parts of methenamine, ammonium thiocyanate 8
Part, 1 part of bromogeramine, 0.2 part of benzotriazole, 5 parts of stannous chloride, 5 parts of sodium thiosulfate, 3 parts of thiocarbamide.
Station boiler pickling solid corrosion inhibitor as a preferred technical solution, is 14 parts of methenamine, 7 parts of ammonium thiocyanate, new
0.8 part of geramine, 0.2 part of benzotriazole, 3 parts of stannous chloride, 3 parts of sodium thiosulfate, 2 parts of thiocarbamide.
Methenamine, ammonium thiocyanate, bromogeramine, phenylpropyl triazole combine and mutually promote, interact in the present invention, energy
Efficiently slow down various acidic cleaners in addition to nitric acid to the corrosion of metal in addition to aluminum and zinc, inhibition efficiency all 95% with
On；Bromogeramine can form fine and close protective film in metal surface, be that a kind of infiltration hydrogen inhibits well with phenylpropyl triazole cooperation
Agent inhibits the infiltration of hydrogen atom to greatest extent, avoids hydrogen embrittlement and hydrogen blister；Bromogeramine or one kind are fine in the present invention
Remover, auxiliary cleaning agent cleaning after dirt remove faster, increase the cleaning speed and cleaning effect of cleaning agent；Commonly
Corrosion inhibiter is to Fe3+Less, the present invention is used as a kind of Fe using stannous chloride and ammonium thiocyanate cooperation for this oxidation corrosion effect3+
Reducing agent restores rapidly Fe3+, effectively prevent Fe3+Oxidation corrosion；The present invention using sodium thiosulfate and thiourea combination as
A kind of Cu2+Reducing agent, sodium thiosulfate mutually promote with thiocarbamide, interact, and restore Cu rapidly2+, effect is much better than merely
Using the reduction effect of thiocarbamide, copper facing phenomenon is avoided, it is no longer necessary to increase subsequent except process for copper, eliminate security risk.
The pretreatment that station boiler pickling solid corrosion inhibitor of the invention can be used for before various acidic cleaner cleanings, this hair
It is bright in addition to the H in acid cleaning+It can be other than high-efficient corrosion inhibition type, also to hydrogen-type corrosion, Fe3+The security risks such as burn into copper facing are primary
Property solve, while further improving inhibition efficiency.
The invention has the following beneficial effects:
(1) performance is brilliant: after tested, 0.11% sheet is added in the mixed acid solution of+1.3% hydrofluoric acid of 10% hydrochloric acid
Solid pickling inhibitor, the rate of corrosion of No. 20 carbon steels are only 0.8-1g/m2H, this is not only advised well below Ministry of Water Resources and Power Industry and Ministry of Labour
Fixed boiler acid pickling rate of corrosion is not more than 10g/m2The requirement of h, while being also that other types of corrosion inhibiter is incomparable.
(2) performance is comprehensive: solid pickling inhibitor, can be with one containing the ingredients such as hydrogen inhibitor, ferric ion reducing agent are seeped
Secondary property solves a series of corrosion phenomenons such as hydrogen embrittlement, the ferric ion burn into copper facing during strip system acid-washing.
(3) performance is stablized: solid pickling inhibitor high temperature resistant of the invention, 95 DEG C of working environments below are able to maintain inhibition
Performance is stablized.Individually storage does not influence performance indicator in the cool throughout the year, after being re-dubbed acid cleaning with various acid or mixed acid
Storage nor affects on performance indicator throughout the year.
(4) facilitate inexpensive: solid pickling inhibitor of the invention is solid product, nontoxic, tasteless, does not influence environment.It takes
Band, storage and transportation, using more convenient than the corrosion inhibiter of liquid, while can avoid liquid corrosion inhibiter and being mistakened as cleaning agent use in construction.
And in use, 10% (quality) various acid below or mixed acid, the additive amount of solid pickling inhibitor of the invention is only
0.11% is needed, lower than 0.25% additive amount of lan-826 corrosion inhibiter commonly used in the art.
(5) have a wide range of application: solid pickling inhibitor of the invention can be in the cleaning of any acidic chemical in addition to nitric acid
It uses, the pickling including station boiler；For the ground end acidification in oil exploitation, acid grease after filling the water in secondary oil recovery is solved
Corrosion of the mixture to oil extraction pipeline.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the invention will be further described, the description of embodiment only for ease of understanding and
With the application of the invention, rather than to the limitation of the invention protected.
Prepare station boiler pickling solid corrosion inhibitor, including 14 parts of methenamine, 7 parts of ammonium thiocyanate, bromogeramine 0.8
Part, 0.2 part of benzotriazole, 3 parts of stannous chloride, 3 parts of sodium thiosulfate, 2 parts of thiocarbamide.
Following test experiments are the mass concentration progress for adding above-mentioned station boiler pickling solid corrosion inhibitor 0.15%, are made
For comparison, select to add mass fraction as 0.25% lan-826 corrosion inhibiter reference examples as a comparison.
Corrosion inhibition test experiments are as follows:
Experiment one: the synthesis rust inhibition for the cleaning agent that the solid corrosion inhibitor of the present invention that addition mass concentration is 0.15% configures
Can test experiments, since acid pickling agent is mainly acid corrosion to corrosion of metal, i.e., hydrionic corrosion, this experiment is mainly
The verifying present invention is to hydrionic corrosion inhibition.
200W circulation mouth piece is connected into a circulating slot, outlet connects old fan coil, one by hose
Root corrodes serious carbon steel pipe, then connects hose and returns to circulating slot, forms a closed circulation cleaning system.
Cleaning agent is configured in circulating slot in mass ratio: hydrochloric acid 10%, hydrofluoric acid 1.3%, solid corrosion inhibitor of the invention
0.15%, remaining is water.
Circulating pump wash cycles are opened, will weigh up quality on a ten thousandth digital display balance in advance is W1It (is accurate to
20# corrosion of carbon steel test piece 0.1mg), each three pieces of red copper corrosion coupon be put into circulating slot, test piece hanging wire is using there is plastic skin
Electric wire, each test piece, which should be avoided, to collide with each other, avoid and circulating slot collide.
After cleaning, takes out standard corrosion coupon and weigh up the test piece quality W after cleaning respectively2(it is accurate to 0.1mg, by
Same operator weighs on same balance), the rate of corrosion of cleaning experiment is calculated, detection data is organized into table 1.
Rate of corrosion K:g/ (m2·h)
K=(W1-W2)/(F*T)=(W1-W2)/0.002T[g/(m2·h)]
W1、W2--- it is respectively that standard test piece cleans forward and backward quality g
T --- scavenging period h
F --- standard corrosion coupon surface area 0.0028m2
Remarks: corrosion coupon meets HG5-1526 corrosion monitoring standard test piece requirement.
1. red copper corrosion coupon corrosion experiment of table, one monitoring record table
| Test piece number | Red copper 5091# | Red copper 5092# | Red copper 5093# | It is average |
| Quality (g) before cleaning | 21.3595 | 20.6210 | 20.9638 | 20.9814 |
| Quality (g) after cleaning | 21.3572 | 20.6188 | 20.9608 | 20.9789 |
| (g) of poor quality | 0.0023 | 0.0022 | 0.0030 | 0.0025 |
| Strip accumulates (m2) | 0.0028 | 0.0028 | 0.0028 | 0.0028 |
| Etching time (h) | 4 | 4 | 4 | 4 |
| Rate of corrosion [g/ (m2·h)] | 0.205 | 0.197 | 0.268 | 0.22 |
2. corrosion of carbon steel test piece corrosion experiment of table, one monitoring record table
| Test piece number | Carbon steel 2001# | Carbon steel 2002# | Carbon steel 2003# | It is average |
| Quality (g) before cleaning | 19.8012 | 19.7926 | 19.7654 | 19.7864 |
| Quality (g) after cleaning | 19.7743 | 19.7662 | 19.7395 | 19.7600 |
| (g) of poor quality | 0.0269 | 0.0264 | 0.0259 | 0.0264 |
| Strip accumulates (m2) | 0.0028 | 0.0028 | 0.0028 | 0.0028 |
| Etching time (h) | 4 | 4 | 4 | 4 |
| Rate of corrosion | 2.402 | 2.357 | 2.312 | 2.36 |
Experiment two: the corrosion inhibition test experiments of the cleaning agent for the lan-826 corrosion inhibiter that addition mass fraction is 0.25%.
According to the operation of experiment one, re-replace an old fan coil, a serious carbon steel pipe of corrosion and
Cleaning: hydrochloric acid 10% is reconfigured, hydrofluoric acid 1.3%, lan-826 corrosion inhibiter 0.25%, remaining is water.Re-start rate of corrosion
Detection, testing result is organized into table 3, table 4, then according to experiment one and two the case where, sort out corrosion mitigating effect contrast table 5.
3. red copper corrosion coupon corrosion experiment of table, two monitoring record table
4. corrosion of carbon steel test piece corrosion experiment of table, two monitoring record table
| Test piece number | Carbon steel 2004# | Carbon steel 2005# | Carbon steel 2006# | It is average |
| Quality (g) before cleaning | 19.8034 | 20.1675 | 19.7548 | 19.9086 |
| Quality (g) after cleaning | 19.7583 | 20.1221 | 19.7044 | 20.5283 |
| (g) of poor quality | 0.0451 | 0.0454 | 0.0504 | 0.04697 |
| Strip accumulates (m2) | 0.0028 | 0.0028 | 0.0028 | 0.0028 |
| Etching time (h) | 4 | 4 | 4 | 4 |
| Rate of corrosion | 4.027 | 4.054 | 4.500 | 4.20 |
The inhibition efficiency contrast table of the different corrosion inhibiter of table 5.
From the data in table 5, it can be seen that being added to the corrosion mitigating effect of the cleaning agent of solid corrosion inhibitor of the invention obviously due to market
The performance of upper common corrosion inhibiter, and solve the problems, such as copper facing.
Experiment three: the corrosion inhibition test of solid corrosion inhibitor of the present invention.
In order to verify Fe3+Influence and stannous chloride cooperation ammonium thiocyanate to bite rate is to Fe3+Reducing agent
Can, cleaning agent (specific composition and the operating condition are as follows: 3% lemon of control more representational lan-826 corrosion inhibiter configuration at present
Acid, pH value 3~3.5,90 DEG C of temperature), carry out static corrosion coupon test experience, experimental result such as table 6.
Table 6.Fe3+Inhibition test experience record sheet
Since copper ion corrosion and ferric ion corrosion are all oxidation corrosions, and the oxidisability of copper ion is less than ferric iron
Ion, it is significant as the reducing agent inhibition efficiency of copper ion that this experiment also sufficiently demonstrates stannous chloride cooperation ammonium thiocyanate.
Experiment four: the measure of merit for inhibiting hydrogen atom infiltration of solid corrosion inhibitor of the present invention.
In order to verify the presence of hydrogen embrittlement problem, and solid corrosion inhibitor of the present invention does following comparison to the effect for inhibiting to seep hydrogen
Experiment:
Prepare two same Enamel jars of first, second, the hydrochloric acid solution of 2 glass 10% of configuration adds in wherein 1 glass of solution
0.15% solid corrosion inhibitor of the invention.First Enamel jar is placed in simple hydrochloric acid solution, second Enamel jar is immersed in addition
In the solution for having solid corrosion inhibitor of the present invention.The Enamel jar in two solution is taken out after impregnating 8 hours, and is rinsed and done with tap water
Only, two Enamel jars are observed, following situation as a result occur: first Enamel jar starts occur sudden and violent porcelain phenomenon successively in third day, finally
Sudden and violent porcelain facing product is up to 50% or so；There is sudden and violent porcelain at the 5th day in second Enamel jar, and final sudden and violent porcelain facing product is less than 10%, and sudden and violent porcelain point is also remote
Less than first Enamel jar.
This experiment has absolutely proved the infiltration of the invention for inhibiting hydrogen atom to greatest extent, effectively reduces hydrogen embrittlement and hydrogen
It is bubbled.
By testing and compare above, absolutely prove that solution hydrogen-type corrosion of the invention, ferric ion burn into copper ion are rotten
Erosion inhibits to seep the validity of hydrogen.In addition to station boiler, other high-tension apparatuses, the equipment of interior dangerous medium, pipeline, conveying
Important medium (such as lubricating oil, Seal Oil, control oil, hydraulic medium, liquid H2, heavy water, high-energy fuel etc.) the equipment such as pipeline
It is related to the above problem, the necessity of innovative point of the present invention similarly exists.
The above is only preferred application implementation mode of the invention, it is noted that for the common skill of the art
For art personnel, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improve and
Retouching also should be regarded as protection scope of the present invention.
Claims (4)
1. a kind of station boiler pickling solid corrosion inhibitor characterized by comprising based on parts by weight, methenamine 12-15
Part, 6-8 parts of ammonium thiocyanate, 0.6-1 parts of bromogeramine, 0.1-0.2 parts of benzotriazole, 2-5 parts of stannous chloride, sodium thiosulfate
2-5 parts, 1-3 parts of thiocarbamide.
2. station boiler pickling solid corrosion inhibitor according to claim 1 characterized by comprising based on parts by weight,
12 parts of methenamine, 6 parts of ammonium thiocyanate, 0.6 part of bromogeramine, 0.1 part of benzotriazole, 2 parts of stannous chloride, sodium thiosulfate
2 parts, 1 part of thiocarbamide.
3. station boiler pickling solid corrosion inhibitor according to claim 1 characterized by comprising based on parts by weight,
15 parts of methenamine, 8 parts of ammonium thiocyanate, 1 part of bromogeramine, 0.2 part of benzotriazole, 5 parts of stannous chloride, sodium thiosulfate 5
Part, 3 parts of thiocarbamide.
4. station boiler pickling solid corrosion inhibitor according to claim 1 characterized by comprising based on parts by weight,
14 parts of methenamine, 7 parts of ammonium thiocyanate, 0.8 part of bromogeramine, 0.2 part of benzotriazole, 3 parts of stannous chloride, sodium thiosulfate
3 parts, 2 parts of thiocarbamide.
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| RU2170288C2 (en) * | 1999-08-18 | 2001-07-10 | Астраханский государственный технический университет | Metal corrosion inhibitor in sulfuric, hydrochloric acid orthophosphoric acids |
| CN101634030B (en) * | 2009-01-22 | 2011-03-30 | 湖南省湘电试验研究院有限公司 | Acid-cleaning inhibiter for cleaning boiler and use method thereof |
| CN102766876B (en) * | 2012-07-23 | 2014-04-09 | 辽宁科技大学 | Environment-friendly pickling inhibitor and application thereof in pickling of carbon steel |
| CN106032576B (en) * | 2015-03-20 | 2018-11-02 | 中国石油化工股份有限公司 | Restrainer composition and its application and the method that pickling is carried out to equipment |
| CN105951106A (en) * | 2016-06-06 | 2016-09-21 | 上海理工大学 | Special hydrochloric acid pickling corrosion inhibitor for spring steel |
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