CN101691662B - Carbon steel pickling corrosion inhibitor and preparation method and application thereof - Google Patents
Carbon steel pickling corrosion inhibitor and preparation method and application thereof Download PDFInfo
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- CN101691662B CN101691662B CN2009100353943A CN200910035394A CN101691662B CN 101691662 B CN101691662 B CN 101691662B CN 2009100353943 A CN2009100353943 A CN 2009100353943A CN 200910035394 A CN200910035394 A CN 200910035394A CN 101691662 B CN101691662 B CN 101691662B
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- inhibiter
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- thiadiazoles
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- carbon steel
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- 229910000975 Carbon steel Inorganic materials 0.000 title claims abstract description 27
- 239000010962 carbon steel Substances 0.000 title claims abstract description 27
- 230000007797 corrosion Effects 0.000 title claims abstract description 24
- 238000005260 corrosion Methods 0.000 title claims abstract description 24
- 239000003112 inhibitor Substances 0.000 title claims abstract description 16
- 238000005554 pickling Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 4
- KTWDTPBHCWJWGJ-UHFFFAOYSA-N 5-pyridin-4-yl-1,3,4-thiadiazol-2-amine Chemical compound S1C(N)=NN=C1C1=CC=NC=C1 KTWDTPBHCWJWGJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 14
- -1 compounds compound Chemical class 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000001117 sulphuric acid Substances 0.000 claims description 8
- 235000011149 sulphuric acid Nutrition 0.000 claims description 8
- 229910000627 Superloy Inorganic materials 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000837 restrainer Substances 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 16
- MCYHQUZTYSVDHW-UHFFFAOYSA-N 5-pyridin-3-yl-1,3,4-thiadiazol-2-amine Chemical compound S1C(N)=NN=C1C1=CC=CN=C1 MCYHQUZTYSVDHW-UHFFFAOYSA-N 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 5
- YEKAGFYXUIXUOH-UHFFFAOYSA-N [C].S1N=NC=C1 Chemical compound [C].S1N=NC=C1 YEKAGFYXUIXUOH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- ZLHDTOUWXDZDGO-UHFFFAOYSA-N 4-(5-amino-1,3,4-thiadiazol-2-yl)phenol Chemical compound S1C(N)=NN=C1C1=CC=C(O)C=C1 ZLHDTOUWXDZDGO-UHFFFAOYSA-N 0.000 abstract 1
- 235000021110 pickles Nutrition 0.000 description 56
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UPLPHRJJTCUQAY-WIRWPRASSA-N 2,3-thioepoxy madol Chemical compound C([C@@H]1CC2)[C@@H]3S[C@@H]3C[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@](C)(O)[C@@]2(C)CC1 UPLPHRJJTCUQAY-WIRWPRASSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Chemical group 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The invention relates to a steel pickling corrosion inhibitor, a preparation method and application thereof, in particular to a thiadiazole carbon steel pickling corrosion inhibitor, and a preparation method and application thereof, wherein the corrosion inhibitor is a mixture of any two or three compounds of 2-amino-5-p-hydroxyphenyl-1, 3, 4-thiadiazole, 2-amino-5- (4-pyridyl) -1, 3, 4-thiadiazole or 2-amino-5- (3-pyridyl) -1, 3, 4-thiadiazole. The corrosion inhibitor can effectively prevent the corrosion of sulfuric acid to carbon steel materials in the pickling process, and has the advantages of environmental friendliness, low consumption, high corrosion inhibition efficiency, stable performance and the like.
Description
Technical field
The present invention and a kind of acid washing rolled steel inhibiter and its production and application are specifically related in order to prevent that carbon steel and goods thereof are sour in the sulfuric acid washing process carbon steel material corrosion and the outspent a kind of thiadiazole carbon steel pickling corrosion inhibitor of acid solution and preparation method thereof be used.
Background technology
In industries such as metallic substance, machinery, metallurgy, chemical industry, sulfuric acid is commonly used to the corrosion and the dirt of metal material surface in the systems such as pipe blow-through and boiler, so pickling is significant to the normal operation of keeping equipment.
Because in acid cleaning process, strong acid also can have corrosive nature to hardware when having removed corrosion and dirt, therefore " crossing erosion " phenomenon often appears in the acid cleaning process, thereby cause Corrosion of Metallic Materials, a large amount of sour gas of being separated out in addition, labor condition is worsened, produce a large amount of acid solutions simultaneously, environment has been caused havoc.Therefore when pickling, to add inhibiter,, reduce the usage quantity of acid, improve pickling effect, prolong the work-ing life of equipment to suppress the corrosion of metal in acidic medium.
In the inhibiter commonly used at present, mineral compound such as chromic salt, nitrate, nitrite, because it has toxic side effect, environment friendly is poor, the dangerous easy generation pitting of the use that has, its application is being restricted and will progressively eliminating.And green organic inhibitor is not only in use environmentally friendly, also can not cause detrimentally affect to environment in production and manufacturing processed.Therefore, new is efficient, and the organic inhibitor of environmental protection just is being subjected to people and is more and more paying close attention to.
Summary of the invention
The object of the present invention is to provide a kind of efficient, environmental protection, cheapness, carbon steel pickling corrosion inhibitor that is easy to get and its production and application.
Technical scheme of the present invention is: the superloy restrainer, it is characterized in that described inhibiter is 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles or 2-amino-5-(3-pyridyl)-1,3, the mixture of any two or three compound in the 4-thiadiazoles.
When above-mentioned inhibiter was the mixture of two kinds of compounds, two kinds of compounds compound proportion by weight was: (1-100): (1-100); When above-mentioned inhibiter was the mixture of three kinds of compounds, three kinds of compounds compound proportion by weight was: (1-100): (1-100): (1-100).
The present invention also provides a kind of method for preparing above-mentioned carbon steel pickling corrosion inhibitor, its concrete steps are: take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles, 2-amino-5-(3-pyridyl)-1,3, in the 4-thiadiazoles any two or three mixes, and obtains inhibiter.
When above-mentioned inhibiter was the mixture of two kinds of compounds, two kinds of compounds compound proportion by weight was: (1-100): (1-100) take by weighing;
When above-mentioned inhibiter was the mixture of three kinds of compounds, three kinds of compounds compound proportion by weight was: (1-100): (1-100): (1-100) take by weighing.
The present invention also provides the application in carbon steel pickling of above-mentioned carbon steel pickling corrosion inhibitor.
By the amount that adds inhibiter in every liter of acid solution is 0.001g-2g, and inhibiter is added in the dilute hydrochloric acid or dilute sulphuric acid that concentration is 0.1mol/L-1mol/L; Clean steel with the acid solution submergence that is added with inhibiter, wherein submergence temperature is 10 ℃-60 ℃, and Immersion time is 2-4h.
Principle of the present invention is: inhibiter involved in the present invention is a kind of thiadiazole organic compound, and this compound molecule contains atom or atomic groups such as nitrogen, sulphur, oxygen, heterocycle, can be adsorbed in steel surface effectively, plays slow releasing function.
Beneficial effect:
1. environmental friendliness.Inhibiter of the present invention is a thiadiazole compound, is organic inhibitor, compares with inorganic inhibitor at present commonly used, and toxicity is little, and is environmentally friendly, does not have the environmental problem after the use, meets the development trend of green corrosion inhibitor.
2. cost is low.Inhibiter of the present invention is a thiadiazole compound, and synthesis step is simple, and raw material is cheap and easy to get.
2. consumption is low, and result of use is good.The present invention is used for the steel surface pickling, add a spot of inhibiter and just can suppress harmful corrosion and the consuming of acid solution of metallic substance in acid cleaning process effectively, with inhibiter at present commonly used relatively, it is low to have a consumption, the high outstanding advantage of corrosion mitigating effect.
3. corrosion inhibition is stable.Inhibiter of the present invention can bear the variation of cleaning condition, and as temperature, acid strength etc. do not influence the corrosion mitigating effect of inhibiter.
Embodiment
The present invention carries out the lacing film zero-G test according to GB10124-88 " metallic substance laboratory uniform corrosion total immersion test method ".
Raw material 2-amino required for the present invention-5-p-hydroxybenzene-1,3, the 4-thiadiazoles is according to " synthetic chemistry " 2008 the 16th volumes, and P233～236 methods are synthetic; 2-amino-5-(4-pyridyl)-1,3, the 4-thiadiazoles is according to " applied chemistry " the 22nd the 3rd phase of volume, and in March, 2005, the method for P334 page or leaf is synthetic; 2-amino-5-(3-pyridyl)-1,3, the 4-thiadiazoles is according to " Central China Normal University's journal (natural science edition) " the 39th the 3rd phase of volume, and in September, 2005, the method for P340-P341 page or leaf is synthetic.
Embodiment 1
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 1g and 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 30g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 0.5mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 20 ℃ of conditions.
Inhibition efficiency 91% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 2
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 10g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 20g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 0.5mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 20 ℃ of conditions.
Inhibition efficiency 93% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 3
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 0.5g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 25g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 1mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 20 ℃ of conditions.
Inhibition efficiency 92% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 4
Take by weighing 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 15g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 15g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 0.5mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 20 ℃ of conditions.
Inhibition efficiency 94% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 5
Take by weighing 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 0.5g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 40g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 0.8mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 30 ℃ of conditions.
Inhibition efficiency 91% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 6
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 20g and 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 20g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, concentration is 0.8mol/L, and pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 30 ℃ of conditions.
Inhibition efficiency 97% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 7
Take by weighing 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 1g and 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 20g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, concentration is 0.1mol/L, and pickle solution consumption 100L is immersed in 3h in the pickle solution with carbon steel to be cleaned under 30 ℃ of conditions.
Inhibition efficiency 92% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 8
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 15g and 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 20g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, concentration is 0.1mol/L, and pickle solution consumption 100L is immersed in 3h in the pickle solution with carbon steel to be cleaned under 30 ℃ of conditions.
Imitate 96% by the inhibition that experimental test obtains, be shown as inhibiter efficiently.
Embodiment 9
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 0.5g, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 10g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 25g mixes as inhibiter, be dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, and concentration is 0.1mol/L, pickle solution consumption 100L is immersed in 3h in the pickle solution with carbon steel to be cleaned under 40 ℃ of conditions.
Inhibition efficiency 97% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 10
Take by weighing 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 20g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 15g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, concentration is 0.1mol/L, and pickle solution consumption 100L is immersed in 2h in the pickle solution with carbon steel to be cleaned under 40 ℃ of conditions.
Inhibition efficiency 95% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 11
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 45g, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 20g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 0.5g mixes as inhibiter, be dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, and concentration is 0.5mol/L, pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 30 ℃ of conditions.
Inhibition efficiency 96% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 12
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 20g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 20g mixes as inhibiter, is dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, concentration is 0.1mol/L, and pickle solution consumption 100L is immersed in 2h in the pickle solution with carbon steel to be cleaned under 40 ℃ of conditions.
Inhibition efficiency 92% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 13
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 10g, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 40g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 0.5g mixes as inhibiter, be dissolved in the pickle solution, pickle solution is a dilute hydrochloric acid, and concentration is 0.8mol/L, pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 20 ℃ of conditions.
Inhibition efficiency 96% by experimental test obtains is shown as inhibiter efficiently.
Embodiment 14
Take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles 15g, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles 15g and 2-amino-5-(3-pyridyl)-1,3,4-thiadiazoles 15g mixes as inhibiter, be dissolved in the pickle solution, pickle solution is a dilute sulphuric acid, and concentration is 1mol/L, pickle solution consumption 100L is immersed in 4h in the pickle solution with carbon steel to be cleaned under 40 ℃ of conditions.
Inhibition efficiency 97% by experimental test obtains is shown as inhibiter efficiently.
Claims (4)
1. the superloy restrainer is characterized in that described inhibiter is 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles or 2-amino-5-(3-pyridyl)-1,3, the mixture of any two or three compound in the 4-thiadiazoles; When described inhibiter was the mixture of two kinds of compounds, two kinds of compounds compound proportion by weight was: (1-100): (1-100); When described inhibiter was the mixture of three kinds of compounds, three kinds of compounds compound proportion by weight was: (1-100): (1-100): (1-100).
2. one kind prepares the method for carbon steel pickling corrosion inhibitor according to claim 1, its concrete steps are: take by weighing 2-amino-5-p-hydroxybenzene-1,3,4-thiadiazoles, 2-amino-5-(4-pyridyl)-1,3,4-thiadiazoles, 2-amino-5-(3-pyridyl)-1,3, in the 4-thiadiazoles any two or three mixes, and obtains inhibiter; When wherein said inhibiter was the mixture of two kinds of compounds, two kinds of compounds compound proportion by weight was: (1-100): (1-100) take by weighing; When described inhibiter was the mixture of three kinds of compounds, three kinds of compounds compound proportion by weight was: (1-100): (1-100): (1-100) take by weighing.
3. application in carbon steel pickling of carbon steel pickling corrosion inhibitor according to claim 1.
4. application according to claim 3 is characterized in that: by the amount that adds inhibiter in every liter of acid solution is 0.001g-2g, and inhibiter is added in the dilute hydrochloric acid or dilute sulphuric acid that concentration is 0.1mol/L-1mol/L; Clean steel with the acid solution submergence that is added with inhibiter, wherein submergence temperature is 10 ℃-60 ℃, and Immersion time is 2-4h.
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| CN2009100353943A CN101691662B (en) | 2009-09-27 | 2009-09-27 | Carbon steel pickling corrosion inhibitor and preparation method and application thereof |
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| CN2009100353943A CN101691662B (en) | 2009-09-27 | 2009-09-27 | Carbon steel pickling corrosion inhibitor and preparation method and application thereof |
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