CN110184610A - A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor and preparation method thereof - Google Patents
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN110184610A CN110184610A CN201910586968.XA CN201910586968A CN110184610A CN 110184610 A CN110184610 A CN 110184610A CN 201910586968 A CN201910586968 A CN 201910586968A CN 110184610 A CN110184610 A CN 110184610A
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- carbon steel
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- phosphonic acid
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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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- 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
- C23F11/10—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 using organic inhibitors
- C23F11/173—Macromolecular compounds
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Abstract
The invention discloses a kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitors, are made of the raw material of following mass percent concentration: 0.1 ~ 1% poly-epoxy succinic acid, and molecular weight is 400 ~ 800；0.1 ~ 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the mass ratio of the two are 1:3 ~ 5；0.1 ~ 1% sodium molybdate；0.1 ~ 0.5% methylbenzotrazole；0.1 ~ 0.3% zinc gluconate；Surplus is water.Compared with the prior art, corrosion inhibiter of the invention has excellent corrosion mitigating effect to the carbon steel in briny environment, and corrosion inhibiter is up to 99.2% under the low concentration of 0.5wt%, to the corrosion inhibition rate of A3 carbon steel.
Description
Technical field
The invention belongs to corrosion inhibitor of sea water fields, and in particular to a kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor and its
Preparation method.
Background technique
Currently, more and more carbon steel equipments or building are applied in marine environment.It is due to existing in seawater with NaCl
The solution of main electrolyte, and it is dissolved in a certain amount of oxygen, most metals are all easy oxygen depolaxization corrosion in the seawater, and extra large
These are conducive to the environmental condition of oxygen supply for wave, splashing, flow velocity etc., and the cathodic depolarization of oxygen but will be promoted to react, promote the corruption of metal
Erosion.Huge loss is caused to industry and economy as a result,.
Currently, adding corrosion inhibiter in Seawater is to carry out one of protection effective measures to carbon steel.Corrosion inhibitor of sea water
It can effectively prevent or slow down seawater to corrosion of metal speed, and is easy to use, it is adding less, it is quick, it is at low cost,
Therefore neutralization technology has become main anti-corrosion means.For example, prior art discloses the technical solutions of some corrosion inhibiter, such as
Publication No. is the Chinese patent application of CN 1880244A, discloses a kind of composite water treating agent for central air conditioner cooling water comprising
The component of following parts by weight: 1 ~ 10 part of poly-epoxy succinic acid；1 ~ 10 part of phosphonate；In terms of molybdenum acid ion, 1 ~ 10 part
Molybdate；The salt of 0.1 ~ 10 part of rare earth element；1 ~ 5 part of copper inhibitor；In terms of zinc ion, 0 ~ 3 part of zinc salt.The invention
For low-phosphorous, environment-friendly type formula, scale inhibition, corrosion inhibition are excellent, and raw material is easy to get, and develop application of the rare earth element in water process
Range, the rare earth cause for developing China have very positive meaning.But the corrosion inhibiter is only applicable to the carbon in fresh water
Steel protection, it is unexcellent for the protective performance in the high seawater medium carbon steel of salt content.This is because being in seawater and fresh water
Under environment, due to conductivity difference, the chemical property significant difference of metal.Therefore, in the central air-conditioner cooling water Compound Water
The environment-friendly type carbon steel corrosion inhibitor that a kind of suitable briny environment is developed on the basis of inorganic agent has critically important application value.
Summary of the invention
The object of the present invention is to provide a kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitors and preparation method thereof, for reality
Existing above-mentioned purpose the present invention adopts the following technical scheme:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.1 ~ 1% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
0.1 ~ 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the mass ratio of the two
For 1:3 ~ 5；
0.1 ~ 1% sodium molybdate；
0.1 ~ 0.5% methylbenzotrazole；
0.1 ~ 0.3% zinc gluconate；
Surplus is water.
A kind of preparation method of seawater circulation water environmental protection carbon steel composite corrosion inhibitor: the raw material is added to the water, stirring
Uniformly to get the environment-friendly type carbon steel composite corrosion inhibitor.
The application method of seawater circulation water environmental protection carbon steel composite corrosion inhibitor of the present invention: quality hundred is added in seawater circulation water
Divide the corrosion inhibiter of the present invention than 0.1 ~ 1%.
Compared with the prior art, corrosion inhibiter of the invention has excellent corrosion mitigating effect to the carbon steel in briny environment, delays
Agent is lost under the low concentration of 0.5wt%, and 99.2% is up to the corrosion inhibition rate of A3 carbon steel.
Specific embodiment:
The present invention is further described below with reference to embodiment.
Embodiment 1:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
The mass ratio of 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two is 1:
3；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Embodiment 2:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
1% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
0.5% 2- phosphonic acid butane -1,2, the mass ratio of the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two are
1:4；
0.5% sodium molybdate；
0.3% methylbenzotrazole；
0.2% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Embodiment 3:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.1% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
0.8% 2- phosphonic acid butane -1,2, the mass ratio of the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two are
1:5；
0.7% sodium molybdate；
0.5% methylbenzotrazole；
0.1% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 1:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% 2- phosphonic acid butane -1,2,4- tricarboxylic acids；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 1 difference from example 1 is that, organic phospho acid is only with 2- phosphonic acid butane -1,2,4- tricarboxylic
Acid.
Comparative example 2:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% ethylene diamine tetra methylene phosphonic acid；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 2 difference from example 1 is that, organic phospho acid is only with ethylene diamine tetra methylene phosphonic acid.
Comparative example 3:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
The mass ratio of 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two is 1:
1；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 3 difference from example 1 is that, organic phospho acid use 2- phosphonic acid butane -1,2,4- tricarboxylic acids
With the mixture of ethylene diamine tetra methylene phosphonic acid, the mass ratio of the two is 1:1.
Comparative example 4:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
The mass ratio of 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two is 1:
10；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 4 difference from example 1 is that, organic phospho acid use 2- phosphonic acid butane -1,2,4- tricarboxylic acids
With the mixture of ethylene diamine tetra methylene phosphonic acid, the mass ratio of the two is 1:10.
Comparative example 5:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% 2- phosphonic acid butane -1,2,4- tricarboxylic acids；
1% cerous nitrate；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% monohydrate zinc sulphate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 5 difference from example 1 is that, organic phospho acid is only with 2- phosphonic acid butane -1,2,4- tricarboxylic
Acid；It is added to 1% cerous nitrate；Zinc salt replaces zinc gluconate using monohydrate zinc sulphate.
Comparative example 6:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% 2- phosphonic acid butane -1,2,4- tricarboxylic acids；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% monohydrate zinc sulphate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 6 difference from example 1 is that, organic phospho acid is only with 2- phosphonic acid butane -1,2,4- tricarboxylic
Acid；Zinc salt replaces zinc gluconate using monohydrate zinc sulphate.
Comparative example 7:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and aminotrimethylenephosphonic acid, the mass ratio of the two are 1:3；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 7 difference from example 1 is that, organic phospho acid use 2- phosphonic acid butane -1,2,4- tricarboxylic acids
With the mixture of aminotrimethylenephosphonic acid, the mass ratio of the two is 1:1.
Comparative example 8:
A kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, is made of the raw material of following mass percent concentration:
0.5% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and 1- carboxyl ethylidine -1,1 di 2 ethylhexyl phosphonic acid, the quality of the two
Than for 1:3；
1% sodium molybdate；
0.1% methylbenzotrazole；
0.3% zinc gluconate；
Surplus is water.
Preparation method: the raw material is added to the water, stir evenly to get.
Comparative example 8 difference from example 1 is that, organic phospho acid use 2- phosphonic acid butane -1,2,4- tricarboxylic acids
With the mixture of 1- carboxyl ethylidine -1,1 di 2 ethylhexyl phosphonic acid, the mass ratio of the two is 1:1.
1-3 of the embodiment of the present invention, comparative example 1-8 corrosion inhibiter the corrosion mitigating effect of the carbon steel in simulated seawater is tested:
The preparation of simulated seawater: NaCl 26.518g, KCl 0.725g, CaCl21.141g MgCl22.447g MgSO4
3.305g NaHCO30.202g, NaBr 0.083g add water to total weight 1000g.
According to method as defined in " the measurement rotary hanging plate method of GBT18175-2000- water treatment agent corrosion inhibition ", by A3 carbon
Steel test piece is linked into the simulated seawater containing 0.5wt% corrosion inhibiter and respectively not plus in the simulated seawater of corrosion inhibiter, in constant temperature 40 ± 1
DEG C, 75 revs/min of revolving speed, run 72 hours progress corrosion tests, every group of test takes three parallel samples.Test piece is then taken out, is passed through
It is weighed after cleaning-drying processing, corrosion inhibition rate is calculated by the mass loss of test piece.Test result is shown in Table 1 ~ 3:
Corrosion inhibition rate (%) of the 1 embodiment 1-3 corrosion inhibiter of table to A3 carbon steel
| Density of corrosion inhibitor | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 0.5 wt% | 99.2% | 97.4% | 96.7% |
Corrosion inhibition rate (%) of the 2 comparative example 1-4 corrosion inhibiter of table to A3 carbon steel
| Density of corrosion inhibitor | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| 0.5wt% | 79.1% | 73.5% | 83.6% | 80.3% |
Corrosion inhibition rate (%) of the 3 comparative example 5-8 corrosion inhibiter of table to A3 carbon steel
| Density of corrosion inhibitor | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 |
| 0.5wt% | 69.1% | 47.5% | 68.5% | 63.6% |
Pass through above-mentioned test result, it is seen then that on the basis of present invention corrosion inhibiter disclosed in the prior art, although not adding rare earth
Salt, but monohydrate zinc sulphate is replaced by using the organic phospho acid mixture of extra fine quality ratio, simultaneously using zinc gluconate, make
Obtaining improved corrosion inhibiter has excellent corrosion mitigating effect, well beyond those skilled in the art to the carbon steel in briny environment
Expection.Especially embodiment 1 is preferred embodiment of the invention, and corrosion inhibiter is under the low concentration of 0.5wt%, to A3 carbon steel
Corrosion inhibition rate be up to 99.2%.
However, the organic phospho acid in 1 corrosion inhibiter of comparative example is only with 2- phosphonic acid butane -1,2,4- tricarboxylic acids, to A3 carbon
The corrosion inhibition rate of steel is down to 79.1%；Organic phospho acid in 2 corrosion inhibiter of comparative example is only with ethylene diamine tetra methylene phosphonic acid, to A3 carbon steel
Corrosion inhibition rate be down to 73.5%；Organic phospho acid in 3 corrosion inhibiter of comparative example uses 2- phosphonic acid butane -1,2,4- tricarboxylic acids and second
The mass ratio of the mixture of four methylenephosphonic acid of diamines, the two is 1:1, is down to 83.6% to the corrosion inhibition rate of A3 carbon steel；Comparative example 4 is slow
The organic phospho acid lost in agent uses 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the two
Mass ratio be 1:10,80.3% is down to the corrosion inhibition rate of A3 carbon steel；Organic phospho acid in 5 corrosion inhibiter of comparative example is only with 2- phosphine
Acidic group butane -1,2,4- tricarboxylic acids, be added to 1% cerous nitrate, zinc salt using monohydrate zinc sulphate replace zinc gluconate, to A3
The corrosion inhibition rate of carbon steel is down to 69.1%；Organic phospho acid in 6 corrosion inhibiter of comparative example is only with 2- phosphonic acid butane -1,2,4- tricarboxylic
Acid, zinc salt replace zinc gluconate using monohydrate zinc sulphate, are down to 47.5% to the corrosion inhibition rate of A3 carbon steel；In 7 corrosion inhibiter of comparative example
Organic phospho acid use 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and aminotrimethylenephosphonic acid, the mass ratio of the two
For 1:1,68.5% is down to the corrosion inhibition rate of A3 carbon steel；Organic phospho acid in 8 corrosion inhibiter of comparative example uses phosphonic acid butane -1 2-,
The mass ratio of the mixture of 2,4- tricarboxylic acids and 1- carboxyl ethylidine -1,1 di 2 ethylhexyl phosphonic acid, the two is 1:1, to the corrosion inhibition rate of A3 carbon steel
It is down to 63.6%.
Claims (3)
1. a kind of seawater circulation water environmental protection carbon steel composite corrosion inhibitor, which is characterized in that by the raw material of following mass percent concentration
It is made:
0.1 ~ 1% poly-epoxy succinic acid, molecular weight are 400 ~ 800；
0.1 ~ 1% 2- phosphonic acid butane -1,2, the mixture of 4- tricarboxylic acids and ethylene diamine tetra methylene phosphonic acid, the mass ratio of the two
For 1:3 ~ 5；
0.1 ~ 1% sodium molybdate；
0.1 ~ 0.5% methylbenzotrazole；
0.1 ~ 0.3% zinc gluconate；
Surplus is water.
2. a kind of preparation method of seawater circulation water environmental protection carbon steel composite corrosion inhibitor according to claim 1, feature exist
In the raw material is added to the water, is stirred evenly to get the environment-friendly type carbon steel composite corrosion inhibitor.
3. a kind of application method of seawater circulation water environmental protection carbon steel composite corrosion inhibitor according to claim 1, feature exist
In the corrosion inhibiter of addition mass percent 0.1 ~ 1% in seawater circulation water.
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Cited By (1)
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| CN113773804A (en) * | 2021-10-18 | 2021-12-10 | 广州阿美新材料有限公司 | Special debonder for environment-friendly anaerobic adhesive and preparation method and application thereof |
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