CN104775126A - Application of 1, 2-di (benzimidazole-2-sulfenyl) ethane in preparation of metal pickling solution - Google Patents
Application of 1, 2-di (benzimidazole-2-sulfenyl) ethane in preparation of metal pickling solution Download PDFInfo
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- CN104775126A CN104775126A CN201410817686.3A CN201410817686A CN104775126A CN 104775126 A CN104775126 A CN 104775126A CN 201410817686 A CN201410817686 A CN 201410817686A CN 104775126 A CN104775126 A CN 104775126A
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Abstract
The invention discloses application of 1, 2-di (benzimidazole-2-sulfenyl) ethane in preparation of a metal pickling solution, the 1, 2-di (benzimidazole-2-sulfenyl) ethane is added into inorganic pickling mediums with different concentrations to make the concentration 1*10<-5>-1*10<-3>mol / L, the purpose is to solve the problem that people's requirements for corrosion inhibitors are increasingly improved, and the kind of the corrosion inhibitors meeting the requirements is seriously lack, the 1, 2-di (benzimidazole-2-sulfenyl) ethane is simple in preparation method, low in production cost, and good in metal corrosion inhibiting effect, has the advantages of less dosage, good compatibility and the like, is capable of being compatible with almost all of the inorganic pickling mediums, the inhibition efficiency is slightly affected by time, acidity and the like, the 1, 2-di (benzimidazole-2-sulfenyl) ethane can be used for pickling of a variety of metals, and has a wide range of application, at the same time, the new application field of the 1, 2-di (benzimidazole-2-sulfenyl) ethane is extended.
Description
Technical field
The present invention relates to metal pickling corrosion and protection field, especially a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is preparing the application in metal pickle liquor.
Background technology
Corrosion is the important destructive factor in modern industry and life, wherein with metallic corrosion to modern industry and the loss that causes of living the most serious.According to estimates, China accounts for the 3-4% of gross national product because of direct economic loss that steel corrosion causes.In the technique of chemical pickling hardware and component, pickle solution, while dissolution of metals oxide compound (such as iron rust, oxide skin etc.), also can make metallic matrix corrode and cause the hydrogen embrittlement of hardware to corrode, cause the huge waste of metals resources.In pickle solution, adding inhibiter, effectively can reduce metallic corrosion, is a kind of simple process protected metallic substance and equipment, the method that with low cost, suitability is strong.The inhibiter used in chemical pickling requires not reduce cleaning speed and quality, can not cause the local corrosion of metal, high in the fast fraction of coverage of hardware surface adsorption, and change and the corrosion inhibition that can bear acid washing conditions can not extend in time and decline.
All the time, be applied to life and produce in pickle solution more, in acid cleaning process, the mass concentration of pickle solution generally lower than 20%, the mainly organism of its its corrosion inhibition of inhibiting solution.But meanwhile, it is low to there is inhibition efficiency in existing organic inhibitor, the problems such as the toxicity of part inhibiter is comparatively large, production cost is high, range of application is narrow.The corrosion mitigating effect of the amine inhibitor being widely used in pickle solution at present when one-component is general, generally need to carry out composite, and amine inhibitor has irritating smell mostly; Pyridine derivate has irritating smell mostly; Imidazolidine derivatives class inhibiter is low without special irritating smell, Heat stability is good, toxicity, but needs multistep to synthesize, and synthesis technique is complicated; The inhibition efficiency of thiourea process is large by structure influence, and the concentration of inhibiter exists optimized scope, and range of application is narrow; The application performance of natural rosin is poor, usually need through modified, could as inhibiter.
For existing inhibiter Problems existing, applicant has synthesized a kind of benzimidazoles inhibiter---1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, and its rust inhibition is far above the 2-mercaptobenzimidazole under the same terms; At 30 DEG C, concentration is 5 × 10
-4the 1mol/L sulfuric acid pickling solution of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane of mol/L reaches 99.47% to the corrosion inhibition rate in Q235 steel.
People require day by day to improve for inhibiter, and the kind famine of the inhibiter that meets the demands.Therefore, in the urgent need to open new inhibiter, to meet the demand of people for inhibiter, effectively reduce metallic corrosion during metal pickling simultaneously, reduce financial loss.Applicant is in synthesis 1, while 2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, also synthesize 1,3-bis-(benzimidazolyl-2 radicals-sulfenyl) propane and 1,4-bis-(benzimidazolyl-2 radicals-sulfenyl) butane, test their corrosion inhibition, find that they have good corrosion mitigating effect equally to metal pickling.
Summary of the invention
Goal of the invention of the present invention is: day by day improve for the requirement of inhibiter effect for people, and the problem of the inhibiter kind famine met the demands, the application of a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane in metal pickle liquor is provided.The metal pickle liquor adopting the present invention to prepare has good corrosion inhibition for metal effect, and there is good consistency, can be compatible with nearly all inorganic pickling medium, and inhibition efficiency is less by the impact of time, acidity etc., can be used for various metals pickling, applied range, the present invention simultaneously is also that 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane has expanded new Application Areas.
To achieve these goals, the present invention adopts following technical scheme:
The structural formula of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is as follows:
1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is preparing the application in metal pickle liquor, adds 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane in the inorganic pickling medium of different concns, makes its concentration be 1 × 10
-5~ 1 × 10
-3mol/L, as preferably, concentration is 1 × 10
-4~ 1 × 10
-3mol/L, most preferable concentrations is 1 × 10
-4~ 5 × 10
-4mol/L, wherein, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane makes restrainer in pickle solution.
Described mineral acid be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid one or more.
Based on above application, a kind of metal pickle liquor can be prepared, comprise the pickling medium and 1 of various different concns, 2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane works as restrainer, and preferably adding 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 1 × 10
-5~ 1 × 10
-3mol/L.
For the existing problem that can meet the inhibiter kind famine that people require, the application provides a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane preparing the application in metal pickle liquor.1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) provided by the invention ethane, in metal pickle liquor, it is good to have with metal pickle liquor media compatibility, the advantage that corrosion mitigating effect is high.Contriver is proved by lot of experiments, by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane joins in the pickling medium such as hydrochloric acid, sulfuric acid by certain concentration, effective corrosion inhibition for metal effect can be obtained, wherein, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is joined in the inorganic pickling medium of different concns, the concentration of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-5~ 1 × 10
-3mol/L; As preferably, its concentration is 1 × 10
-4~ 1 × 10
-3mol/L; Most preferably, its concentration is 1 × 10
-4~ 5 × 10
-4mol/L.
Contriver is by experimental results demonstrate, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane and nearly all inorganic pickling medium all have good consistency, and inhibiter of the present invention can be used in various metals pickling, has wider range of application.By 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane adds metal pickle liquor obtained in the metal pickling medium of various different concns to according to described concentration, there is good corrosion inhibition for metal effect, and its inhibition efficiency is less by the impact of time, acidity etc.
The invention provides a kind of preparation method of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, its cheaper starting materials is easy to get simultaneously, preparation method is simple, and production cost is low, is applied to prepare metal pickle liquor, there is advantage with low cost, be suitable for commercial introduction application.Meanwhile, the present invention is also that 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane has expanded a kind of new Application Areas.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is in embodiment 1, and temperature is 30 DEG C, in 1mol/L HCl pickle solution, and the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate.
Fig. 2 is in embodiment 2, and temperature is 30 DEG C, at 1mol/L H
2sO
4in pickle solution, the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate.
Fig. 3 is in embodiment 3, and temperature is 30 DEG C, at 1mol/L H
3pO
4in pickle solution, the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate.
Fig. 4 is in embodiment 4, and in 1mol/L HCl pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and temperature.
Fig. 5 is in embodiment 5, at 1mol/L H
2sO
4in pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and temperature.
Fig. 6 is in embodiment 6, at 1mol/L H
3pO
4in pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and temperature.
Fig. 7 is in embodiment 7, and in 1mol/L HCl pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and time of repose.
Fig. 8 is in embodiment 8, at 1mol/L H
2sO
4in pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and time of repose.
Fig. 9 is in embodiment 9, at 1mol/L H
3pO
4in pickle solution, 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10
-4during mol/L, the graph of a relation of corrosion inhibition rate and time of repose.
Embodiment
All features disclosed in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this specification sheets, unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Below in conjunction with embodiment, foregoing invention content of the present invention is described in further detail.
Embodiment 1
The present embodiment is the different impact on hydrochloric acid pickler corrosion inhibition rate of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration.
The present embodiment concentration of hydrochloric acid identical (1mol/L, volumetric molar concentration, lower with) when, add 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, the concentration making 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-5~ 1 × 10
-3mol/L.At 30 DEG C, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of each pickle solution, result is as shown in table 1.And with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L hydrochloric acid pickler, 1, the graph of a relation of 2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate, as shown in Figure 1.
Table 11,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is on the impact of hydrochloric acid pickler corrosion inhibition rate
According to the above results, 1 × 10
-5~ 1 × 10
-3in mol/L concentration range, hydrochloric acid pickler corrosion inhibition rate raises along with the increase of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration, and when 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is more than 5 × 10
-4after mol/L, corrosion inhibition rate change is little.
Embodiment 2
The present embodiment is the different impact on sulfuric acid pickling solution corrosion inhibition rate of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration.
The present embodiment sulfuric acid concentration identical (1mol/L, volumetric molar concentration, lower with) when, add 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, the concentration making 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-5~ 1 × 10
-3mol/L.At 30 DEG C, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of each pickle solution, result is as shown in table 2.And with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L sulfuric acid pickling solution, 1, the graph of a relation of 2-bis-(benzimidazolyl-2 radicals-sulfenyl) concentration and corrosion inhibition rate, as shown in Figure 2.
Table 21,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is on the impact of sulfuric acid pickling solution corrosion inhibition rate
According to the above results, 1 × 10
-5~ 1 × 10
-3in mol/L concentration range, sulfuric acid pickling solution corrosion inhibition rate raises along with the increase of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration, and when 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is more than 5 × 10
-4after mol/L, corrosion inhibition rate change is little.
Embodiment 3
The present embodiment is the different impact on phosphoric acid washing lotion corrosion inhibition rate of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration.
The present embodiment phosphoric acid concentration identical (1mol/L, volumetric molar concentration, lower with) when, add 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, the concentration making 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-5~ 1 × 10
-3mol/L.At 30 DEG C, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of each pickle solution, result is as shown in table 3, and with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtains in 1mol/L sulfuric acid pickling solution, 1, the graph of a relation of 2-bis-(benzimidazolyl-2 radicals-sulfenyl) concentration and corrosion inhibition rate, as shown in Figure 3.
Table 31,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is on the impact of phosphoric acid washing lotion corrosion inhibition rate
And with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L phosphoric acid washing lotion, 1, the graph of a relation of 2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate, as shown in Figure 3.
According to the above results, 1 × 10
-5~ 1 × 10
-3in mol/L concentration range, the corrosion inhibition rate of phosphoric acid washing lotion first raises rear reduction, when 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration is 5 × 10 along with the increase of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration
-4mol/L, corrosion inhibition rate reaches 90.02%.
Embodiment 4
The present embodiment is the impact of temperature on hydrochloric acid pickler corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) join in the HCl solution (1mol/L) of same concentrations, under condition of different temperatures, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of pickle solution during differing temps, result is as shown in table 4.
Table 4 temperature is on the impact of hydrochloric acid pickler corrosion inhibition rate
| Temperature (DEG C) | 20 | 25 | 30 | 35 | 40 |
| Inhibition efficiency (%) | 98.22 | 98.32 | 99.75 | 98.86 | 99.15 |
Meanwhile, with pickle solution temperature T (DEG C) for X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtains in 1mol/L sulfuric acid pickling solution, the graph of a relation of temperature and pickle solution corrosion inhibition rate, as shown in Figure 4.
The above results shows, restrainer of the present invention is within the scope of 20 ~ 40 DEG C at chlorohydric acid pickling liquid temp, and corrosion inhibition rate change is little.
Embodiment 5
The present embodiment is the impact of temperature on sulfuric acid pickling solution corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) H of same concentrations is joined
2sO
4in solution (1mol/L), under condition of different temperatures, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of pickle solution during differing temps, result is as shown in table 5.
Table 5 temperature is on the impact of sulfuric acid pickling solution corrosion inhibition rate
| Temperature (DEG C) | 30 | 35 | 40 | 45 | 50 |
| Inhibition efficiency (%) | 99.47 | 98.92 | 98.55 | 97.40 | 95.46 |
Meanwhile, with pickle solution temperature T (DEG C) for X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtains in 1mol/L sulfuric acid pickling solution, the graph of a relation of temperature and pickle solution corrosion inhibition rate, as shown in Figure 5.
The above results shows, restrainer of the present invention is that within the scope of 30 ~ 50 DEG C, corrosion inhibition rate slightly declines at sulfuric acid washing liquid temp, but change is little.
Embodiment 6
The present embodiment is the impact of temperature on phosphoric acid washing lotion corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) H of same concentrations is joined
3pO
4in solution (1mol/L), under condition of different temperatures, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of pickle solution during differing temps, result is as shown in table 6.
Table 6 temperature is on the impact of phosphoric acid washing lotion corrosion inhibition rate
| Temperature (DEG C) | 20 | 30 | 40 | 50 | 60 |
| Inhibition efficiency (%) | 91.32 | 90.02 | 89.13 | 88.25 | 87.93 |
Meanwhile, with pickle solution temperature T (DEG C) for X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtains in 1mol/L phosphoric acid washing lotion, the graph of a relation of temperature and pickle solution corrosion inhibition rate, as shown in Figure 6.
The above results shows, restrainer of the present invention is that within the scope of 20 ~ 60 DEG C, corrosion inhibition rate is downtrending slightly at phosphoric acid wash temperature, but rangeability is within 3.3%.
Embodiment 7
The present embodiment is the impact of time of repose on hydrochloric acid pickler corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) join in the HCl solution (1mol/L) of same concentrations, under 30 DEG C and different time of repose conditions, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of different time of repose pickle solution, result is as shown in table 7.
Table 7 time of repose is on the impact of hydrochloric acid pickler corrosion inhibition rate
| Time (h) | 0 | 24 | 48 | 72 | 96 | 120 |
| Inhibition efficiency (%) | 93.50 | 93.67 | 93.44 | 93.52 | 93.54 | 93.60 |
Simultaneously, with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L hydrochloric acid pickler, the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate, as shown in Figure 7.
According to the above results, be within the scope of 0 ~ 120h in the pickle solution time, hydrochloric acid pickler corrosion inhibition rate changes little along with the growth corrosion inhibition rate of time, and the growth of inhibition efficiency along with the time of restrainer of the present invention is described, changes little, can use for a long time.
Embodiment 8
The present embodiment is the impact of time of repose on sulfuric acid pickling solution corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) H of same concentrations is joined
2sO
4in solution (1mol/L), under 30 DEG C and different time of repose conditions, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of different time of repose pickle solution, result is as shown in table 8.
Table 8 time of repose is on the impact of sulfuric acid pickling solution corrosion inhibition rate
| Time (h) | 0 | 24 | 48 | 72 | 96 | 120 |
| Inhibition efficiency (%) | 95.45 | 95.33 | 95.98 | 95.52 | 95.53 | 95.54 |
Simultaneously, with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L sulfuric acid pickling solution, the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate, as shown in Figure 8.
According to the above results, be within the scope of 0 ~ 120h in the pickle solution time, sulfuric acid pickling solution corrosion inhibition rate along with the growth corrosion inhibition rate change of time little, the growth of inhibition efficiency along with the time of restrainer of the present invention is described, change is little, can use for a long time, use convenient.
Embodiment 9
The present embodiment is the impact of time of repose on phosphoric acid washing lotion corrosion inhibition rate.
The present embodiment by 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane according to same concentrations (5 × 10
-4mol/L) H of same concentrations is joined
3pO
4in solution (1mol/L), under 30 DEG C and different time of repose conditions, be respectively used to the pickling of Q235 steel, measure the corrosion inhibition rate of different time of repose pickle solution, result is as shown in table 9.
Table 9 time of repose is on the impact of phosphoric acid washing lotion corrosion inhibition rate
| Time (h) | 0 | 24 | 48 | 72 | 96 | 120 |
| Inhibition efficiency (%) | 90.02 | 90.47 | 90.12 | 89.82 | 89.45 | 89.30 |
Simultaneously, with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration C (mol/L) is X-coordinate, corrosion inhibition rate IE (%) is ordinate zou, obtain in 1mol/L phosphoric acid washing lotion, the graph of a relation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane concentration and corrosion inhibition rate, as shown in Figure 9.
According to the above results, be within the scope of 0 ~ 120h at pickle solution time of repose, phosphoric acid washing lotion corrosion inhibition rate changes little along with the growth corrosion inhibition rate of time, illustrates that the inhibition efficiency of restrainer of the present invention changes little along with the growth of time, can use for a long time.
In addition, contriver also will add the obtained various pickle solutions of different concns 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane and be used for other metal of pickling, as aluminium, copper, magnesium, zinc, aluminum magnesium alloy etc., by measuring, it has corrosion mitigating effect good equally.
The mensuration of corrosion inhibition rate IE (%) in the various embodiments described above, static suspension weight-loss method conventional in industry is adopted to carry out: to consider at different temperatures, by the different metal materials prints such as the Q235 steel after weighing respectively static suspension be soaked in blank pickle solution and be added with 1, in the pickle solution of 2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, take out after leaving standstill certain hour, wipe corrosion product with vulcanite, deionized water rinsing, acetone cleans, and weighs after drying.According to its corrosion inhibition rate of weight loss data IE (%), calculation formula is as follows:
IE＝[(V
0-V
corr)/V
0]×100％
In formula, V
0and V
corrrepresent respectively blank pickle solution and be added with 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane pickle solution in the weight loss rate of print, unit is mg/cm
2.h.
Embodiment 11
The present embodiment is the preparation of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane
In reactor, add 2-mercaptobenzimidazole, make 2-mercaptobenzimidazole be dissolved in KOH solution, under being warming up to reflux state, start to drip glycol dibromide, drip 1, after 2-ethylene dibromide, then reflux 2 ~ 3 hours, after a large amount of white solid of rear precipitation, terminate reaction, be cooled to room temperature, suction filtration, washs by massive laundering, vacuum-drying, ethyl alcohol recrystallization obtains white powder 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane.Fusing point: 256 ~ 258 DEG C, productive rate 85.5 ~ 93.2%.
In 1mol 2-mercaptobenzimidazole, the quality of KOH is 50 ~ 70g, and the volume of glycol dibromide is 0.07 ~ 0.10L, and the volume of dehydrated alcohol is 0.3 ~ 1.0L, and the time for adding of glycol dibromide is 10 ~ 40min.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (5)
1. one kind 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is preparing the application in metal pickle liquor, it is characterized in that: in the inorganic pickling medium of different concns, add 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, make its concentration be 1 × 10
-5~ 1 × 10
-3mol/L.
2. a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, preparing the application in metal pickle liquor, is characterized in that according to claim 1, and the concentration of described 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-4~ 1 × 10
-3mol/L.
3. a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, preparing the application in metal pickle liquor, is characterized in that according to claim 2, and the concentration of described 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane is 1 × 10
-4~ 5 × 10
-4mol/L.
4. a kind of 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane, preparing the application in metal pickle liquor, is characterized in that according to claim 1, described mineral acid be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid one or more.
5. a metal pickle liquor, is characterized in that: comprise pickling medium and 1,2-bis-(benzimidazolyl-2 radicals-sulfenyl) ethane.
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