CN109208005A - A kind of pre- film corrosion inhibiter of the B30 corronil suitable for Seawater and preparation method thereof - Google Patents
A kind of pre- film corrosion inhibiter of the B30 corronil suitable for Seawater and preparation method thereof Download PDFInfo
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- CN109208005A CN109208005A CN201710535006.2A CN201710535006A CN109208005A CN 109208005 A CN109208005 A CN 109208005A CN 201710535006 A CN201710535006 A CN 201710535006A CN 109208005 A CN109208005 A CN 109208005A
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- corrosion inhibiter
- linseed oil
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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Abstract
The invention belongs to metallic material corrosions and protection field, are related to a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater.The pre- film corrosion inhibiter of B30 corronil proposed by the present invention suitable for Seawater is made of benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and deionized water.It has the advantages that one side corrosion inhibiter host agent benzotriazole linseed oil amide derivatives raw material sources extensively and linseed oil is green plants oil, there is environment friendly；Synthetic method is simple, and product need not purifying post-processing.On the other hand the homogeneous corrosion and spot corrosion that can inhibit cupronickel B 30 material simultaneously are used in compounding with other reagents.Pre-filming treatment need to be only carried out before B30 materials'use again, additionally addition corrosion inhibiter is not had to again in use process, greatlys save cost.
Description
Technical field
The invention belongs to metallic material corrosions and protection field, and in particular to a kind of B30 cupro-nickel suitable for Seawater
Pre- film corrosion inhibiter of alloy and preparation method thereof.
Background technique
The cupronickel B 30 outstanding advantages good with its electric conductivity and thermal conductivity are widely used in each of military project and civilian department
Field, for making the machinery such as heat-exchange apparatus, container, valve, pump, turbine, axis and component.However the shadow by various factors
It rings, is particularly present Cl-When erosion, it may occur that serious corrosion.
The pre- film of corrosion inhibiter is a kind of metal material pre-treatment step, can under very low pre- film corrosion inhibiter effective concentration,
Stable protective film is formed in metal surface, to effectively inhibit destruction corrosion of the metal in corrosive medium.There is report at present
Road " novel corrosion inhibitor 3- amino-1,2,4-triazol and compounding study the inhibition of copper " uses the conduct of triazole derivative
Corrosion inhibiter of the B30 copper-nickel alloy to simulated seawater corrosive medium；Also have been reported that poly-aspartate and sodium tungstate compounding as B30 copper-nickel alloy
To the corrosion inhibiter of 3% NaCl solution；Or the inhibition as B30 corronil is compounded with sodium tungstate using poly-epoxy succinic acid
Agent, although there is certain corrosion mitigating effect, corrosive medium (using 3% NaCl solution or simulation aqueous solution when test) and reality
Seawater corrosion medium is simultaneously different, and there is not yet report is directed to the pre- film corrosion inhibiter and preparation method thereof of B30 copper-nickel alloy.
With the reinforcement of people's environmental consciousness, active development green high-efficient corrosion inhibiter becomes inexorable trend.With linseed oil
Document report " protecting metallic surface coating assessment and inhibiter technology research " has been seen for Material synthesis imidazoline corrosion inhibitor
And patent 201410238332.3 and 201410238349.9, however the linseed oil corrosion inhibiter reported in the document or patent
It is to be directed to steel in the inhibition protection of different medium (acidity, sewage, seawater), and is addition type corrosion inhibiter, i.e., in reality
Corrosion inhibiter is quantitatively adding by metering pump under the operating condition of border, this process may have an impact the normal operation of operating condition.Therefore, it grinds
The B30 corronil that is directed to for making a kind of environmentally protective, high efficiency and direct pre- film pre-treatment is applied to seawater corrosion medium
The pre- film corrosion inhibiter of Compositional type has Important Economic meaning and social effect.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention proposes a kind of efficient, environmental protection and direct pre- film pre-treatment
Be suitable for Compositional type pre- film corrosion inhibiter and preparation method thereof of the B30 corronil in seawater corrosion medium, the pre- film of the Compositional type
Corrosion inhibiter is particularly suitable for protection of the B30 corronil in seawater corrosion medium.
The present invention proposes that a kind of pre- film corrosion inhibiter of B30 corronil suitable for Seawater, the pre- film of the Compositional type are slow
Erosion agent by benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and go from
Sub- water composition, mass fraction are respectively as follows: benzotriazole linseed oil amide derivatives 25% -35%, sodium gluconate 10% -
15%, white vitriol 5% -15%, sodium molybdate 10% -15%, dehydrated alcohol 5% -15%, deionized water 30% -50%, respectively
The sum of component percentage composition is 100%.
The molecular structural formula of the benzotriazole linseed oil amide derivatives are as follows:
Wherein R includes R1, R2, R3 and R4；
。
According to B30 copper-nickel alloy sample area when the application of the pre- film corrosion inhibiter of Compositional type proposed by the present invention: pre- film corrosion inhibiter body
The ratio of product=1:50 impregnates pre- film, pre- film condition are as follows: 25 °C of temperature, the time 36 hours.The B30 copper-nickel alloy sample of pre- film pre-treatment
It is directly placed into corrosive medium and is tested.
As preferred: the corrosive medium is simulated seawater corrosive medium In The East China Sea testing result: distilled water+2.5
% NaCl+0.2 % CaCl2+0.6 % MgCl2.6H20+0.5 % Na2SO4+0.15 % NaHC03+0.08 % KCl。
This preparation method suitable for Compositional type pre- film corrosion inhibiter of the B30 corronil in seawater corrosion medium: including
Following steps:
Step 1: the preparation of benzotriazole linseed oil amide derivatives.
To be dissolved in dimethylbenzene molten for example 1:1-1:3 linseed oil and triethylene tetramine in molar ratio in 250 ml four-hole bottles
Agent, it is 20-40 ml that dimethylbenzene volume, which is added, in every mole of linseed oil, is heated slowly to 100-150 ° under nitrogen protection
C, while concentrated sulfuric acid catalyst is added, it is reacted 3-4 hours under 100-150 °C, the additional amount of the catalyst is every
0.1-0.5 ml is added in mole linseed oil, distills out dimethylbenzene after reaction.It cools and obtains product to room temperature
For linseed oil amide derivatives.
Linseed oil amide derivatives and benzo three is added in example 1:1-1:1.05 in molar ratio in 250 ml four-hole bottles
Azoles sodium is heated to 60-80 °C to four-hole bottle magnetic agitation, and 80% acetum is slowly added dropwise, the acetum
Additional amount is that 15.2 g are added in every mole of linseed oil amide derivatives, is washed with distilled water after reaction, then vacuum is steamed
It evaporates, finally obtaining transparent liquid product is benzotriazole linseed oil amide derivatives.
Wherein, linseed oil raw material is purchased from Zhangjiakou City Xin Te vegetable oil Co., Ltd, and main ingredient see the table below:
| Fatty acid species | Content |
| Saturated fatty acid | 9%-11% |
| Oleic acid | 13%-29% |
| Linoleic acid | 15%-30% |
| Linolenic acid | 40%-60% |
Reaction equation are as follows:
Step 2: the preparation of the pre- film corrosion inhibiter of Compositional type.
By benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and
Deionized water is respectively 25% -35%, 10% -15%, 5% -15%, 10% -15%, 5% -15%, 30% by its mass fraction
- 50% is mixed, the sum of each component percentage composition be 100% to get arrive the pre- film corrosion inhibiter of Compositional type.
The beneficial effects of the present invention are:
1. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, at present
The pre- film corrosion inhibiter that there is not been reported researches and develops in seawater corrosion medium for cupronickel B 30；
2. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, wherein
The benzotriazole linseed oil amide derivatives of preparation, which have both, independently forms stable protective film layer to copper and mickel；
3. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, wherein
Each raw material sources are extensively and linseed oil is green plants oil, have environment friendly；
4. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, wherein
The polyamine used is triethylene tetramine, and activity is higher compared with diethylenetriamine；
5. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, synthesis
Final product benzotriazole linseed oil amide derivatives corrosion inhibiter do not need purification process, by-product is basic to inhibition efficiency
Without influence；
6. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, merely
Benzotriazole linseed oil amide derivatives it is water-soluble and bad, compound with dehydrated alcohol and significantly improves its dissolubility and disperse
Property；
7. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, benzo
Triazole linseed oil amide derivatives compound the homogeneous corrosion and spot corrosion that can inhibit cupronickel B 10 material simultaneously with sodium molybdate；
8. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, application
When according to copper-nickel alloy sample area: the ratio of pre- film corrosion inhibiter volume=1:50 impregnates pre- film, pre- film condition are as follows: 25 °C of temperature, when
Between 36 hours.
9. the present invention provides a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater,
Use deionized water for solvent.
10. the present invention provides pre- film corrosion inhibiter and its preparation side of a kind of B30 corronil suitable for Seawater
Method greatlys save the increased cost of subsequent addition corrosion inhibiter only for the pre- film pre-treatment of cupronickel B 30 sample.
Detailed description of the invention
The electrochemical impedance in simulated seawater that Fig. 1: B30 corronil is handled before without the pre- film corrosion inhibiter of Compositional type
Test result；
Electrochemical impedance test knot in the simulated seawater that Fig. 2: B30 corronil is handled before by the pre- film corrosion inhibiter of Compositional type
Fruit；
Polarization curve in the simulated seawater that Fig. 3: B30 corronil is handled before without the pre- film corrosion inhibiter of Compositional type tests knot
Fruit；
Polarization curve test knot in the simulated seawater that Fig. 4: B30 corronil is handled before by the pre- film corrosion inhibiter of Compositional type
Fruit.
Specific embodiment
The present invention is described further with reference to the accompanying drawings and examples.Although the present invention will in conjunction with preferred embodiment into
Row description, it should be understood that being not offered as limiting the invention in the embodiment.On the contrary, it may include having that the present invention, which will cover,
Alternative, modified and the equivalent in the scope of the present invention that appended claims limits.
Embodiment 1:
The present invention proposes a kind of pre- film corrosion inhibiter and preparation method thereof of B30 corronil suitable for Seawater, specific to wrap
Include following steps:
Step 1: the preparation of benzotriazole linseed oil amide derivatives.
To be dissolved in dimethylbenzene molten for example 1:1-1:3 linseed oil and triethylene tetramine in molar ratio in 250 ml four-hole bottles
Agent, it is 20-40 ml that dimethylbenzene volume, which is added, in every mole of linseed oil, is heated slowly to 100-150 ° under nitrogen protection
C, while concentrated sulfuric acid catalyst is added, it is reacted 3-4 hours under 100-150 °C, the additional amount of the catalyst is every
0.1-0.5 ml is added in mole linseed oil, distills out dimethylbenzene after reaction.It cools and obtains product to room temperature
For linseed oil amide derivatives.
Linseed oil amide derivatives and benzo three is added in example 1:1-1:1.05 in molar ratio in 250 ml four-hole bottles
Azoles sodium is heated to 60-80 °C to four-hole bottle magnetic agitation, and 80% acetum is slowly added dropwise, the acetum
Additional amount is that 15.2 g are added in every mole of linseed oil amide derivatives, is washed with distilled water after reaction, then vacuum is steamed
It evaporates, finally obtaining transparent liquid product is benzotriazole linseed oil amide derivatives.
Wherein, linseed oil raw material is purchased from Zhangjiakou City Xin Te vegetable oil Co., Ltd, and main ingredient see the table below:
| Fatty acid species | Content |
| Saturated fatty acid | 9%-11% |
| Oleic acid | 13%-29% |
| Linoleic acid | 15%-30% |
| Linolenic acid | 40%-60% |
Reaction equation are as follows:
Step 2: the preparation of the pre- film corrosion inhibiter of Compositional type.
By benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and
Deionized water is respectively that 25%, 10%, 5%, 10%, 15% and 35% are mixed by its mass fraction, the sum of each component percentage composition
For 100% to get arrive the pre- film corrosion inhibiter of Compositional type.
The pre- film corrosion inhibiter of the Compositional type is in use, according to B30 copper-nickel alloy sample area: pre- film corrosion inhibiter volume=1:
50 ratio impregnates pre- film, pre- film condition are as follows: 25 °C of temperature, the time 36 hours.B30 copper-nickel alloy sample by pre- film pre-treatment is straight
It connects to be soaked into seawater corrosion medium and be tested.The corrosive medium is (the In The East China Sea detection of simulated seawater corrosive medium
As a result :+2.5 % NaCl+0.2 % CaCl2+0.6 % MgCl2.6H20+0.5 % Na2SO4+0.15 % of distilled water
NaHC03+0.08 % KCl).Respectively to B30 corronil sample without with carry out the pre- pre- film of film corrosion inhibiter of this Compositional type before
Processing is placed in progress electrochemical impedance test after impregnating 30 days in simulated seawater solution, as a result such as Fig. 1 and Fig. 2 and table 1
It is shown, it is significantly increased by the charge transfer resistance of this B30 corronil for compounding the pre- film pre-treatment of pre- film corrosion inhibiter, illustrates this
Pre- film corrosion inhibiter has excellent corrosion mitigating effect.
Table 1
Embodiment 2:
The main distinction of the present embodiment and embodiment 1 is step 2, specifically:
By benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and go from
Sub- water is respectively 35%, 10%, 10%, 10%, 5% and 30% to be mixed to get to the pre- film corrosion inhibiter of Compositional type by its mass fraction.
The pre- film corrosion inhibiter of the Compositional type is in use, according to B30 copper-nickel alloy sample area: pre- film corrosion inhibiter volume=1:
50 ratio impregnates pre- film, pre- film condition are as follows: 25 °C of temperature, the time 36 hours.B30 copper-nickel alloy sample by pre- film pre-treatment is straight
It connects to be soaked into seawater corrosion medium and be tested.The corrosive medium is (the In The East China Sea detection of simulated seawater corrosive medium
As a result :+2.5 % NaCl+0.2 % CaCl2+0.6 % MgCl2.6H20+0.5 % Na2SO4+0.15 % of distilled water
NaHC03+0.08 % KCl).Respectively to B30 corronil sample without with carry out the pre- pre- film of film corrosion inhibiter of this Compositional type before
Processing is placed in progress polarization curve test after impregnating 30 days in simulated seawater solution, as a result such as 2 institute of Fig. 3 and Fig. 4 and table
Show, after pre-filming treatment, B30 corronil corrosion current is obviously reduced, and illustrates that this pre- film corrosion inhibiter has excellent delay
Lose effect.
Table 2
Embodiment 3:
By benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and go from
Sub- water is respectively 25%, 10%, 5%, 10%, 5% and 45% to be mixed to get to the pre- film corrosion inhibiter of Compositional type by its mass fraction.
The pre- film corrosion inhibiter of the Compositional type is in use, according to white B30 sample area: pre- film corrosion inhibiter volume=1:50
Ratio impregnate pre- film, pre- film condition are as follows: 25 °C of temperature, the time 36 hours.B30 copper-nickel alloy sample by pre- film pre-treatment is direct
It is soaked into seawater corrosion medium and is tested.The corrosive medium is simulated seawater corrosive medium (In The East China Sea detection knot
Fruit :+2.5 % NaCl+0.2 % CaCl2+0.6 % MgCl2.6H20+0.5 % Na2SO4+0.15 % NaHC03+ of distilled water
0.08 % KCl).Respectively to B30 corronil sample without with carry out the pre- film pre-treatment of the pre- film corrosion inhibiter of this Compositional type,
It is placed in after being impregnated 30 days in simulated seawater solution and carries out weightless test, the results are shown in Table 3, after pre-filming treatment, B30 copper
Nickel alloy illustrates that this pre- film corrosion inhibiter has excellent corrosion mitigating effect substantially without weightlessness.
Table 3
Claims (4)
1. a kind of pre- film corrosion inhibiter of the B30 corronil suitable for Seawater and preparation method thereof, it is characterised in that: this is multiple
The pre- film corrosion inhibiter of distribution type is by benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, anhydrous
Ethyl alcohol and deionized water composition, mass fraction are respectively as follows: benzotriazole linseed oil amide derivatives 25% -35%, grape
Sodium saccharate 10% -15%, white vitriol 5% -15%, sodium molybdate 10% -15%, dehydrated alcohol 5% -15%, deionized water
30% -50%, the sum of each component percentage composition is 100%；The molecular structural formula of the benzotriazole linseed oil amide derivatives
Are as follows:
Wherein R includes R1, R2, R3 and R4；
。
2. it is a kind of it is described in claim 1 suitable for B30 corronil in the pre- film corrosion inhibiter of Compositional type of seawater corrosion medium and
Preparation method, it is characterised in that: according to cupronickel B 30 sample area: the ratio of pre- film corrosion inhibiter volume=1:50 impregnates pre- film,
Pre- film condition are as follows: 25 °C of temperature, the time 36 hours.
3. it is according to claim 2 suitable for B30 corronil seawater corrosion medium the pre- film corrosion inhibiter of Compositional type and
Preparation method, it is characterised in that: the corrosive medium is Seawater.
4. it is a kind of it is described in claim 1 suitable for B30 corronil in the pre- film corrosion inhibiter of Compositional type of seawater corrosion medium and
Preparation method, it is characterised in that: including the following steps:
Step 1: the preparation of benzotriazole linseed oil amide derivatives:
Example 1:1-1:3 linseed oil and triethylene tetramine are dissolved in xylene solvent in molar ratio in 250 ml four-hole bottles, often
It is 20-40 ml that dimethylbenzene volume, which is added, in mole linseed oil, is heated slowly to 100-150 °C under nitrogen protection, simultaneously
Concentrated sulfuric acid catalyst is added, is reacted 3-4 hours under 100-150 °C, the additional amount of the catalyst is every mole of Asia
0.1-0.5 ml is added in flaxseed oil, distills out dimethylbenzene after reaction, cooling and obtaining product to room temperature is flax
Seed oleoyl amine derivative,
Linseed oil amide derivatives and benzotriazole sodium is added in example 1:1-1:1.05 in molar ratio in 250 ml four-hole bottles,
60-80 °C is heated to four-hole bottle magnetic agitation, and 80% acetum is slowly added dropwise, the additional amount of the acetum
For 15.2 g are added in every mole of linseed oil amide derivatives, it is washed with distilled water after reaction, then be evaporated in vacuo, finally
Obtaining transparent liquid product is benzotriazole linseed oil amide derivatives, reaction equation are as follows:
R includes R1, R2, R3 and R4；
Step 2: the preparation of the pre- film corrosion inhibiter of Compositional type；
By benzotriazole linseed oil amide derivatives, sodium gluconate, white vitriol, sodium molybdate, dehydrated alcohol and go from
Sub- water is respectively 25% -35%, 10% -15%, 5% -15%, 10% -15%, 5% -15% and 30%-by its mass fraction
50% is mixed, the sum of each component percentage composition be 100% to get arrive the pre- film corrosion inhibiter of Compositional type.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710535006.2A CN109208005A (en) | 2017-07-04 | 2017-07-04 | A kind of pre- film corrosion inhibiter of the B30 corronil suitable for Seawater and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115279946A (en) * | 2020-01-27 | 2022-11-01 | 阿迪控股(2008)有限公司 | Corrosion inhibitor for central heating system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107470A (en) * | 1994-08-19 | 1995-08-30 | 辽宁省化工研究院 | Method for preparing benzotriazole aliphatic amine derivative |
| CN103993321A (en) * | 2014-05-30 | 2014-08-20 | 杭州央力科技有限公司 | Compound corrosion inhibitor suitable for seawater corrosion medium and preparation method of compound corrosion inhibitor |
-
2017
- 2017-07-04 CN CN201710535006.2A patent/CN109208005A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107470A (en) * | 1994-08-19 | 1995-08-30 | 辽宁省化工研究院 | Method for preparing benzotriazole aliphatic amine derivative |
| CN103993321A (en) * | 2014-05-30 | 2014-08-20 | 杭州央力科技有限公司 | Compound corrosion inhibitor suitable for seawater corrosion medium and preparation method of compound corrosion inhibitor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115279946A (en) * | 2020-01-27 | 2022-11-01 | 阿迪控股(2008)有限公司 | Corrosion inhibitor for central heating system |
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